ES2269409T3

Aqueous pesticide formulations and novel surfactants

Abstract

A formulation useful for retarding the growth of vegetation, which comprises an aqueous mixture containing a surfactant, glyphosate salt selected from sodium and potassium salts, ammonium salts, diamonium salts, ethanolamine salts and alkylsulfonium salts, and an acid dicarboxylic, the nature of said surfactant and the composition of said formulation being such that after application of the formulation to a plant anisotropic aggregates are formed comprising said surfactant on the foliage of said plant.

ES2269409T3, drawing sheet 1 — Sheet 1 of 75

Term

Term ended

Projected expiry passed 21 May 2021, 5.3 years ago.

16 claims: 5 independent, 11 dependent

1
ES 2 269 409 T3 REIVINDICACIONES 1. Una formulación útil para retrasar el crecimiento de vegetación, que comprende una mezcla acuosa que contiene un tensioactivo, sal de glifosato seleccionada de sales de sodio y potasio, sales de amonio, sales de diamonio, sales de etanolamina y sales de alquilsulfonio, y un ácido dicarboxílico, siendo la naturaleza de dicho tensioactivo y la composición de dicha formulación tal que tras la aplicación de la formulación a una planta se forman agregados anisotrópicos que comprenden dicho tensioactivo sobre el follaje de dicha planta.
2
Una formulación de la reivindicación 1, en la que el ácido dicarboxílico se selecciona del grupo constituido por ácido oxálico, ácido malónico, ácido succínico, ácido glutárico, ácido maleico, ácido adípico y ácido fumárico, y combinaciones o mezclas de los mismos.
3
Una formulación como se expone en la reivindicación 1, en la que la naturaleza de dicho tensioactivo y la composición de dicha formulación son tales que tras la aplicación de la formulación a una planta se forman cristales líquidos que comprenden dicho tensioactivo en el follaje de dicha planta.
4
Una formulación como se expone en la reivindicación 1, en la que la naturaleza de dicho tensioactivo y la composición de dicha formulación son tales que tras la aplicación de la formulación a una planta, los cristales líquidos que comprenden dicho tensioactivo forman canales hidrófilos transcuticulares a través de la cutícula de dicha planta.
5
Una formulación como se expone en la reivindicación 1, que carece sustancialmente de cristales líquidos que comprenden dicho tensioactivo, pero que tiene una composición tal que tras la aplicación de la formulación a una planta, se forman cristales líquidos que comprenden dicho tensioactivo, en una capa acuosa sobre la superficie del follaje de la planta.
6
Una formulación como se expone en la reivindicación 1, en la que dichos cristales se forman tras la evaporación del agua a partir de dicha formulación, tras la aplicación a dicho follaje.
7
Un concentrado herbicida estable durante el almacenamiento, que se puede diluir con agua para proporcionar una mezcla de aplicación herbicida acuosa para aplicar al follaje de una planta, comprendiendo dicho concentrado glifosato o una sal o éster del mismo, a una concentración de al menos aproximadamente 500 g de e.a./l de equivalente ácido de glifosato, y un componente tensioactivo, siendo la naturaleza y concentración de dicho componente tensioactivo en dicho concentrado tales que tras la aplicación de dicha mezcla de aplicación al follaje de una planta, se forman agregados anisotrópicos que comprenden dicho tensioactivo, sobre dicho follaje de la planta.
8
Un concentrado como se expone en la reivindicación 7, que carece sustancialmente de cristales líquidos que comprenden dicho tensioactivo, pero tiene una composición tal que tras la aplicación a una planta de dicho concentrado o dicha mezcla de aplicación, se forman cristales líquidos que comprenden dicho tensioactivo en o sobre dicho follaje de la planta.
9
Un concentrado como se expone en la reivindicación 7, en el que la naturaleza y la concentración de dicho componente tensioactivo son tales que tras la aplicación de dicha mezcla de aplicación al follaje de una planta, se forman cristales líquidos que comprenden dicho tensioactivo sobre el follaje de la planta.
10
Un concentrado como se expone en la reivindicación 7, en el que los agregados anisotrópicos se forman en dicho follaje de la planta tras la aplicación a dicho follaje de dicha mezcla de aplicación y la evaporación del agua a partir de la mezcla de aplicación sobre dicho follaje.
11
Una formulación o concentrado como se expone en las reivindicaciones 1-3, en la que la concentración de glifosato es de aproximadamente 400 g de e.a./l a aproximadamente 600 g de e.a./l.
12
Una formulación o concentrado como se expone en la reivindicación 11, en la que la concentración de glifosato es de aproximadamente 500 g de e.a./l a aproximadamente 600 g de e.a./l.
13
Una formulación o concentrado como se expone en cualquiera de las reivindicaciones precedentes, en la que la formulación o concentrado comprende una sal de glifosato seleccionada del grupo constituido por glifosato potásico, glifosato de monoamonio, glifosato de diamonio, glifosato sódico, glifosato de monoetanolamina, glifosato de n-propilamina, glifosato de etilamina, glifosato de etilendiamina, glifosato de hexametilendiamina, glifosato de trimetilsulfonio y mezclas de las mismas.
14
Una formulación o concentrado como se expone en la reivindicación 13, en la que la formulación o concentrado comprende glifosato potásico.
15
Una formulación o concentrado de cualquier reivindicación precedente, en la que la formulación o concentrado tiene un punto de enturbiamiento de al menos aproximadamente 50°C y un punto de cristalización no mayor que aproximadamente 0°C. 148 ES 2 269 409 T3
16
Una formulación o concentrado de la reivindicación 15, en la que la formulación o concentrado tiene un punto de enturbiamiento de al menos aproximadamente 60°C y un punto de cristalización no mayor que aproximadamente -10°C. 149

Independent claims16

2,079 paragraphs in 116 sections, as filed

ES 2 269 409 T3

DESCRIPTION

Aqueous pesticidal formulations and new surfactants.

Field of the invention

The present invention relates to pesticidal aqueous formulations containing high concentrations of a herbicide, such as the potassium salt of glyphosate, together with surfactants or other adjuvants, including formulations that form anisotropic aggregates (AA) or liquid crystals (CL) on or in the foliage of a plant. More specifically, the present invention relates to glyphosate-containing herbicidal formulations containing one or more surfactants that form anisotropic aggregates and / or liquid crystals that facilitate the introduction, absorption, and translocation of glyphosate throughout the plant. Procedures for killing or controlling unwanted vegetation using such formulations are also described. The invention also relates to new surfactants and pesticidal compositions containing such surfactants.

Background of the invention

Glyphosate is well known in the art as a foliar-applied post-bud herbicide. In its acid form, glyphosate has a structure represented by the formula (1):

and it is relatively insoluble in water (1.16% by weight at 25 ° C). For this reason it is typically formulated in the form of a water soluble salt.

Monobasic, dibasic, or tribasic glyphosate salts can be made. However, it is generally preferred to formulate the glyphosate and apply the glyphosate to the plants in the form of a monobasic salt. The most widely used glyphosate salt is the mono (isopropylammonium) salt, often abbreviated as IPA salt. Monsanto herbicides that have the IPA salt of glyphosate as an active ingredient include the herbicides Roundup®, Roundup® Ultra, Roundup® Xtra, and Rodeo®. All of these are concentrated aqueous solution (SL) formulations and are generally diluted in water prior to application to plant foliage. Other salts of glyphosate that have been formulated commercially as SL formulations include the trimethylphosphonium salt, often abbreviated as TMS, used, for example, in the herbicide Touchdown® from Zeneca (Syngenta).

Various glyphosate salts, processes for preparing glyphosate salts, formulations of glyphosate or its salts, and methods of using glyphosate or its salts to kill and control weeds and other plants are described in US Patent No. 4,507,250 to Bakel, US Patent No. 4,481,026 to Prisbylla, US Patent No. 4,405,531 to Franz, US Patent No. 4,315,765 to Large, US Patent No. US Pat. No. 4,140,513 to Prill, US Pat. No. 3,977,860 to Franz, US Patent No. 3,853,530 to Franz, and US Patent No. 3,799,758 to Franz. The aforementioned patents are incorporated herein in their entirety by reference.

Among the water-soluble salts of glyphosate known in the literature, but which have never been used commercially before the date of presentation of this document, is the potassium salt, which has a structure represented by the formula (2):

present predominantly in ionic form in aqueous solution at a pH of about 4. The glyphosate potassium salt has a molecular weight of 207. This salt is described, for example, by Franz in US Patent No. 4,405. 531 cited above as one of the "alkali metal" salts of glyphosate useful as a herbicide, potassium being specifically described as one of the alkali metals, along with lithium, sodium, cesium and rubidium. Example C describes the preparation of the monopotassium salt by reacting specified amounts of glyphosate acid and potassium carbonate in an aqueous medium.

ES 2 269 409 T3

Very few herbicides have been marketed as their potassium salts. In The Pesticide Manual, 11to Edition, 1997, the herbicides of the auxin type 2,4-DB ((2,4-dichlorophenoxy) butanoic acid), dicamba (3,6-dichloro-2-methoxybenzoic acid), dichlorprop (acid 2 - (2,4-dichlorophenoxy) propanoic), MCPA ((4-chloro-2-methylphenoxy) acetic acid), and picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid), the active substance of some herbicidal products marketed by Dow Agrosciences under the Tordon trademark.

The solubility of the potassium glyphosate salt in water is described in pending patent application Serial No. 09 / 444,766, filed November 22, 1999, the disclosure of which is incorporated in its entirety herein by reference. As described therein, the glyphosate potassium salt has a solubility in pure water at 20 ° C of about 54% by weight, which is about 44% glyphosate acid equivalent (ae) by weight. This is very similar to the solubility of the IPA salt. Concentrations expressed as percent by weight herein refer to parts by weight of the salt or acid equivalent per 100 parts by weight of solution. Thus, a simple aqueous solution concentrate of glyphosate potassium salt can easily be provided with a concentration, for example 44% by weight of ae, comparable to that commercially available with the IPA salt of glyphosate, as in the aqueous solution concentrate available from Monsanto under the name Roundup® D-Pak®. Somewhat higher concentrations can be obtained by a slight over-neutralization, for example 5 to 10%, of an aqueous solution of potassium glyphosate salt with potassium hydroxide.

A major advantage of the IPA salt over many other salts of glyphosate has been the good compatibility in aqueous solution concentrate formulations of this salt with a wide variety of surfactants. As used herein, the term "surfactant" is intended to include a wide variety of adjuvants that can be added to glyphosate herbicidal compositions to enhance their herbicidal efficacy, compared to the activity of the glyphosate salt in the absence of said adjuvant, the stability, formulation capacity or other beneficial properties of the solution, regardless of whether such adjuvants meet a more traditional definition of "surfactant."

Glyphosate salts in general require the presence of a suitable surfactant for the best herbicidal performance. The surfactant can be provided in the concentrated formulation, or it can be added by the end user in the dilute spray composition. The choice of surfactant has a major influence on herbicidal performance. For example, in a large study described in Weed Science, 1997, volume 25, pages 275-287, Wyrill and Burnside found wide variation among surfactants in their ability to enhance the herbicidal efficacy of glyphosate, applied as the IPA salt.

Beyond some broad generalizations, the relative ability of different surfactants to enhance the herbicidal efficacy of glyphosate is highly unpredictable.

The surfactants that tend to most usefully enhance the herbicidal efficacy of glyphosate are generally, but not exclusively, cationic surfactants, including surfactants that form cations in aqueous solution or dispersion at pH levels around 4-5, characteristic of SL formulations. monobasic salts of glyphosate. Examples are long chain tertiary alkylamine surfactants (typically C12 to C18) and quaternary alkyl ammonium surfactants. A tertiary alkylamine surfactant especially commonly used in formulations of IPA glyphosate salt aqueous solution concentrates has been the highly hydrophilic polyoxyethylene (15) tallowamine surfactant, that is, tallowamine having a total of about 15 moles of ethylene oxide in two polymerized ethylene oxide chains attached to the amine group as shown in formula (3):

(CH2CH2OR)mH (3) (CHaCHaOJnH where R is a mixture of predominantly C alkyl and alkenyl chains16 and C18 derived from tallow and the total of m + n is a mean number of about 15.

For some applications, it has been found convenient to use a somewhat less hydrophilic alkylamine surfactant, such as one having less than about 10 moles of ethylene oxide, as suggested in US Patent No. 5,668,085 to Forbes. et al., for example, polyoxyethylene (2) -cocoamine. The patent describes illustrative aqueous compositions comprising said surfactant together with the IPA, ammonium or potassium salts of glyphosate. The highest glyphosate concentration in the potassium salt formulations shown in Table 3 of the 085 patent is 300 g glyphosate ae / L, with a glyphosate ae to surfactant weight ratio of 2: 1.

A class of alkoxylated alkylamines is disclosed in WO 00/59302 for use in herbicidal spray compositions. Potassium glyphosate solutions are described therein, including different Jeffamine® EO / POpropylamines or propyldiamines.

ES 2 269 409 T3

A wide variety of quaternary ammonium surfactants have been described as components of IPA glyphosate salt aqueous solution concentrate formulations. Illustrative examples are N-methylpolyoxyethylene (2) -cocoammonium chloride, described in European patent No. 0274369, N-methylpolyoxyethylene (15) -cocoammonium chloride, described in US patent No. 5,317,003, and different quaternary ammonium compounds having the formula (4):

(R1) (R2) (R3) N + - CH2CH2O - (CH2CH (CH3) O)nHCÍ- (4) in which R1, R2 and R3 are each C alkyl groups1-3 and n is an average number from 2 to 20, described in US Patent No. 5,464,807.

PCT Publication No. WO 97/16969 describes concentrated aqueous glyphosate solution compositions, in the form of IPA, methylammonium and diammonium salts, comprising a quaternary ammonium surfactant and an acid salt of a primary, secondary or alkylamine compound. tertiary.

Other cationic surfactants that have been reported to be useful in concentrated compositions of aqueous glyphosate salts solution include those described in PCT Publication No. WO 95/33379. Furthermore, PCT Publication No. WO 97/32476 describes that highly concentrated aqueous compositions of glyphosate salts can be made with some of the same cationic surfactants, with the addition of a defined component that enhances the stability of the compositions. The glyphosate salts exemplified therein are the IPA salt and the mono and diammonium salts.

Among the amphoteric or zwitterionic surfactants described as useful components of glyphosate IPA salt aqueous solution concentrate formulations are alkylamine oxides such as polyoxyethylene (10-20) tallowamine, described in US Pat. U.S. No. 5,118,444.

Nonionic surfactants are generally described as less effective in enhancing herbicidal activity than cationic or amphoteric surfactants when used as the sole surfactant component of the SL formulations of the IPA salt of glyphosate; and exceptions appear to include some alkyl polyglycosides, as described for example in Australian Patent No. 627503, and alkyl ethers (C16-22) of polyoxyethylene (10-100), as described in PCT Publication No. WO 98/17109. Anionic surfactants, except in combination with cationic surfactants as described in US Patent No. 5,389,598 and US Patent No. 5,703,015, generally have little interest in SL formulations of the glyphosate salt of IPA. Patent 5,703,015 describes a surfactant mixture of a dialkoxylated alkylamine and an anionic eye irritation reducing compound. The surfactant mixture is described as being suitable for preparing aqueous solution concentrate formulations of different glyphosate salts, the potassium salt being included in the list of salts mentioned. The concentrates of the '015 patent contain from about 5 to about 50%, preferably from about 35% to about 45% ae of glyphosate and from about 5 to about 25% surfactant. Furthermore, PCT Publication No. WO 00/08927 describes the use of certain polyalkoxylated phosphate esters in combination with certain polyalkoxylated amidoamines in glyphosate-containing formulations. Glyphosate is identified as one of several glyphosate salts that are indicated to be "suitable."

Recently, a class of alkyl ether amine, alkyl ether ammonium salt and alkyl ether amine oxide surfactants has been described in US Patent No. 5,750,468 as suitable for preparing formulations. aqueous solution concentrates of different glyphosate salts, the potassium salt being included in the list of salts mentioned. It is disclosed therein that an advantage of these surfactants when used in an aqueous composition with glyphosate salts is that these surfactants allow the glyphosate concentration of the composition to be increased to very high levels.

Serious consideration of the glyphosate potassium salt as a herbicidal active ingredient has likely been stopped because of its relative difficulty in formulating this salt as a highly concentrated SL product in conjunction with the preferred types of surfactants. For example, a surfactant widely used in the IPA salt of glyphosate compositions, specifically the polyoxyethylene (15) tallowamine of formula (3) above, is highly incompatible in aqueous solution with the glyphosate potassium salt. Furthermore, PCT Publication No. WO 00/15037 indicates the low compatibility of alkoxylated alkylamine surfactants in general with high concentration glyphosate concentrates. As described therein, in order to "build" an effective level of surfactant, an alkylpolyglucoside surfactant is required in combination with an alkoxylated alkylamine surfactant to obtain very high concentrations containing the potassium salt of glyphosate.

The addition of such alkylpolyglucosides resulted in formulations with higher viscosity (compared to formulations without alkylpolyglucosides). Such increased viscosity of these high concentration formulations is undesirable for a number of reasons. In addition to being more difficult to conveniently pour from the container or wash residue from the container, the detrimental effects that result from higher viscosity formulations are seen most dramatically relative to pumping requirements. End users purchase increasing volumes of aqueous liquid glyphosate products in large refillable containers sometimes known as shuttles, which typically have a built-in pump or connector for external pumping to allow liquid transfer. Aqueous liquid glyphosate products are also shipped in large, bulky tanks that have a capacity of up to approximately 100,000 liters. Usually the liquid is transferred by pumping to a storage tank in a facility run by a wholesaler, mayoris4

ES 2 269 409 T3 ta or cooperative, of which can be transferred back to shuttles or smaller containers for later distribution. Because large quantities of glyphosate formulations are purchased and shipped in early spring, the low temperature pumping characteristics for such formulations are extremely important.

When such alkylpolyglucosides (eg, Agrimul® APG-2067 and 2-ethylhexylglucoside) are added to a glyphosate concentrate, the formulated product is dark brown in color. It is desirable for a formulated glyphosate product to be lighter in color than alkylpolyglucoside-containing products as described in WO 00/15037, which has a color value of 14 to 18 as measured by a Gardner colorimeter. When colorant is added to a formulated glyphosate product that has a Gardner color greater than about 10, the concentrate remains dark brown. Concentrates having a Gardner color value of 10 are difficult to stain blue or green, as is often desired to distinguish the glyphosate product from other herbicidal products.

It would be desirable to provide a storage-stable aqueous concentrate composition (ie formulation) of the potassium salt of glyphosate, or other glyphosate salts other than IPA glyphosate, which has an agriculturally useful surfactant content, or is "completely loaded ”with surfactant. These formulations have a lower viscosity so that they can be pumped with conventional bulky pumping equipment at 0 ° C at rates of at least 28 liters per minute, usually more than 38 liters per minute and preferably more than 47.3 liters per minute. An "agriculturally useful surfactant content" means that it contains one or more surfactants of one or more types and in an amount that the user of the composition achieves a benefit in terms of herbicidal efficacy compared to an otherwise similar but yet similar composition. does not contain surfactant. By "fully loaded" is meant having a sufficient concentration of a suitable surfactant to provide, after conventional dilution in water and application to foliage, herbicidal efficacy on one or more weed species without the need to add additional surfactant to the diluted composition. .

By "storage stable" in the context of a concentrated aqueous glyphosate salt composition that additionally contains a surfactant, it is meant that it does not exhibit phase separation when exposed to temperatures up to about 50 ° C for 14-28 days, and preferably does not form crystals of glyphosate or salt thereof when exposed to a temperature of about 0 ° C for a period of up to about 7 days (i.e. the composition must have a crystallization point of 0 ° C or less). For aqueous solution concentrates high temperature storage stability is often indicated by a cloud point of about 50 ° C or more. The cloud point of a composition is normally determined by heating the composition until the solution becomes cloudy, and then allowing the composition to cool with stirring while continuously monitoring the temperature. A temperature reading taken when the solution becomes clear is an average of the cloud point. A cloud point of 50 ° C or more is normally considered acceptable for most commercial purposes for a glyphosate SL formulation. If possible, the cloud point should be 60 ° C or more, and the composition should withstand temperatures as low as about -10 ° C for up to about 7 days without crystal development, even in the presence of seed crystals of glyphosate salt. .

A surfactant described herein as "compatible" with a glyphosate salt at the specified glyphosate surfactant and ae concentrations is one that provides a storage stable aqueous concentration as defined immediately above, which contains that surfactant and salt at the specified concentrations.

Users of liquid herbicidal products typically measure dosage by volume rather than weight, and such products are typically labeled with instructions for appropriate use rates expressed in volume per unit area, e.g. Eg liters per hectare (l / ha) or fluid ounces per acre (oz / acre). Thus, the concentration of herbicidal active ingredient that matters to the user is not the percentage by weight, but the weight per unit volume, e.g. eg, grams per liter (g / l) or pounds per gallon (lb / gal). For glyphosate salts, the concentration is often expressed in grams of acid equivalent per liter (g ae / l).

Historically, surfactant-containing IPA glyphosate salt products such as Monsanto's Roundup® and Roundup® Ultra herbicides have more commonly been formulated with a glyphosate concentration of approximately 360 g ae / L. Zeneca's Touchdown® surfactant TMS salt product of glyphosate has been formulated with a glyphosate concentration of approximately 330 g ae / l. Products with a concentration of ea lower, that is, more diluted, they are also sold in some markets, but have a cost penalty per unit of glyphosate they contain, which mainly reflects the costs of packaging, transport and storage.

Additional benefits in cost savings and user convenience can be found if a "fully loaded" aqueous concentrate composition, or at least one having an agriculturally useful surfactant content, can be provided with a glyphosate concentration of at least about 320 g ea / l, 340 g ea / l, or significantly more than 360 g ea / l. for example, at least about 420 g ea / l or more, or at least 440, 450, 460, 470, 380, 490, 500, 510, 520, 530, 540, 550, or 600 g ea / l or more.

ES 2 269 409 T3

With very high glyphosate ae concentrations like these, a major problem usually occurs. It is the difficulty in pouring and / or pumping the aqueous concentrate due to the high viscosity of the concentrate, which is especially evident at low temperatures. It would therefore be very convenient to have a highly concentrated aqueous solution of glyphosate potassium salt fully loaded with an agriculturally useful surfactant, said formulation preferably being less viscous than glyphosate potassium salt formulations containing alkylpolyglycoside surfactants, such as described in PCT Publication No. WO 00/15037.

Finally, another prior art considered important in the context of the invention described hereinafter includes US 5,863,863 and EP-A- 0290416. US 5,863,863 describes a stable herbicidal liquid composition based on a glyphosate solution. isopropylamine, and an enhancer composition comprising a surfactant and an oxalate. EP-A-0290416 describes a solubilized glyphosate concentrate and an alkoxylated amine surfactant.

There is still a need for surfactants that are compatible with a pesticidal formulation, such as an aqueous glyphosate herbicidal concentrate. Surfactants include new surfactants as well as known surfactants not previously used in pesticidal formulations. Surfactants that are particularly compatible with glyphosate potassium or other glyphosate salts other than glyphosate IPA have been identified to formulate concentrates that have better viscosity, storage stability and loading compared to known glyphosate concentrates.

As will be clear from the following description, these and other benefits are provided by the present invention.

Summary of the invention

The invention is directed to formulations that form anisotropic aggregates comprising a surfactant, on the waxy cuticle of the plant foliage after application of the formulation. Other herbicidal formulations of the present invention form liquid crystals comprising the surfactant, on the waxy cuticle of the plant foliage after application of the formulation. Still other herbicidal formulations of the present invention form liquid crystals comprising the surfactant, on the waxy cuticle of the foliage and within the plant after application of the formulation. It has been found that the formation of both epicuticular and intracuticular anisotropic aggregates and liquid crystals is not dependent on the presence or absence of a second surfactant and significantly enhances the performance of the herbicidal formulations of the present invention.

More specifically, the invention provides a formulation useful for retarding the growth of vegetation comprising an aqueous mixture containing a surfactant, glyphosate salt selected from sodium and potassium salts, ammonium salts, diammonium salts, ethanolamine salts, salts of alkylsulfonium, and a dicarboxylic acid, the nature of said surfactant and the composition of said formulation being such that after application of the formulation to a plant anisotropic aggregates comprising said surfactant are formed on the foliage of said plant.

The invention also provides a shelf stable herbicidal concentrate which can be diluted with water to provide an aqueous herbicidal application mixture for application to the foliage of a plant, said concentrate comprising glyphosate or a salt or ester thereof in a concentration of about 500 g ea / l, acid equivalent of glyphosate, and a surfactant component, the nature and concentration of said surfactant component in said concentrate being such that after application of said application mixture to the foliage of a plant, anisotropic aggregates comprising said surfactant are formed on the foliage of said plant. Brief description of the drawings

Figures A1 and A2 show a birefringence pattern (A1 with polarized light at 100x magnification; A2 with polarized light at 200x magnification) of negative fan units, which are typical of hexagonal phase liquid crystals. The formulation that produces these epicuticular liquid crystals was comprised of potassium glyphosate and a mixture of surfactants. Specifically, the formulation comprised a 3: 1 weight ratio of glyphosate to surfactant with potassium glyphosate and a mixture of the surfactants Tomah 1816 E20PA and Witcamine 405.

Figures B1 and B2 show a birefringence pattern (B1 in polarized light at 100x magnification; B2 in polarized light at 200x magnification) of fine mosaic patterns, which are typical of laminar phase liquid crystals. The formulation that produces these epicuticular liquid crystals was comprised of isopropylamine glyphosate and a surfactant. Specifically, the formulation comprised a 3: 1 weight ratio of glyphosate to surfactant with glyphosate isopropylamine and Plurafac A38 surfactant.

Detailed description of the invention

The pesticidal compositions of the invention include herbicidal compositions of the potassium salt of glyphosate or another glyphosate salt other than IPA glyphosate and a herbicidal efficacy enhancing amount of one or more surfactants. The compositions of the present invention are stable on storage over a wide temperature range. The compositions of the present invention also exhibit characteristics of

ES 2 269 409 T3 enhanced viscosity and significantly lighter color compared to glyphosate potassium salt compositions containing an alkylpolyglucoside surfactant combined with an alkoxylated alkylamine surfactant. Such "viscosity enhanced" and "color enhanced" formulations are made possible by the selection of a surfactant system that does not include an alkylpolyglucoside surfactant, although such formulations are still fully loaded so that after dilution in water no additional surfactant is necessary. before foliar application to reach commercial performance level. It has also been discovered that alkyl polyglycoside surfactants in combination with surfactants other than alkoxy-alkylamine surfactants can be used to provide useful glyphosate potassium salt compositions, although without some of the enhanced viscosity characteristics of the more preferred compositions of the present invention that do not contain alkylpolyglucoside surfactants. In addition, by controlling the amount of alkyl polyglucosides present in the glyphosate potassium salt composition, a sufficient amount of alkoxylated alkylamine, or other surfactant described herein, can be used to prepare a suitable formulation. In general, the ratio of alkyl polyglucoside to another surfactant should be between about 1: 5 and 5: 1, preferably between about 1: 5 and 1: 1.1, more preferably between about 1: 5 and 1: 1.2, and more preferably between about 1: 5 and 1: 1.5. The color of such concentrates is considerably less than that of concentrates containing greater amounts of alkylpolyglucosides, and is less than 14, preferably less than about 13, 12, 11, 10, 9, 8, 7, 6, or 5.

The herbicidal formulations of the present invention may optionally contain one or more additional surfactants, one or more additional herbicides, and / or other adjuvants or ingredients such as, for example, a dicarboxylic acid such as oxalic acid or a salt or ester thereof. The formulations of the present invention can be prepared on site by the end user just prior to application to the foliage of vegetation or weeds to be eliminated or controlled by diluting the herbicidal formulations of aqueous concentrate, or by dissolving or dispersing solid particles. containing glyphosate. Alternatively, the herbicidal formulations of the present invention can be supplied to the end consumer on a "ready to use" basis.

The present invention takes advantage of the high relative density of concentrated aqueous solutions of the glyphosate potassium salt. Accordingly, at a given concentration weight percent, an aqueous concentrate glyphosate potassium salt composition provides the user with a significantly greater weight of active ingredient per unit volume of the composition than the corresponding IPA salt composition of glyphosate.

In one embodiment of the invention, it has been discovered that in an aqueous concentrate formulation, an unexpectedly high weight / volume concentration of glyphosate potassium salt can be obtained in the presence of an agriculturally useful surfactant content, the resulting composition exhibiting characteristics viscosity and stability during storage acceptable or in some cases better. Surfactant choice has been found to be extremely important in achieving these results.

Accordingly, in said embodiment, the present invention provides a herbicidal composition comprising:

(1) N-phosphonomethylglycine, predominantly in the form of the potassium salt thereof, in solution in water in an amount of greater than about 360 grams of acid equivalent of N-phosphonomethylglycine per liter of the composition; and (2) a water-stable dispersion or solution surfactant component comprising one or more surfactants present in an agriculturally useful amount. It is preferred that the surfactant component is selected such that the composition has a viscosity of no greater than about 100 centipoise at 10 ° C, a cloud point of not less than about 50 ° C, and preferably that it exhibits substantially no crystallization of glyphosate or salt. of the same when stored at a temperature of about 0 ° C for a period of up to about 7 days. More preferably, the composition has a viscosity of no greater than about 500 centipoise at 45 reciprocal seconds at 10 ° C, with more preferred that it is no greater than 250, 225, 200, 175, 150, 125, or 100 centipoise. However, in some cases higher viscosities may be acceptable, such as, for example, when low temperature pumping considerations are important. The surfactant component added to the aqueous herbicidal concentrate composition is in solution or is a stable suspension, emulsion or dispersion.

The word "predominantly" in the above context means that at least about 50%, preferably at least about 75% and more preferably at least about 90% by weight of glyphosate, expressed in ea, is present as the potassium salt. The remainder can be made up with other salts and / or glyphosate acid, but it is preferred that the viscosity, cloud point and non-crystallization properties of the composition remain within the stated limits.

As a further aspect of the present invention, a particular class of surfactants has been identified with which compatibility with concentrations of the glyphosate potassium salt greater than 300 g ae / l to about 600 g ae / l is unexpectedly high. Accordingly, one embodiment of the invention is a surfactant-containing herbicidal composition as described above, wherein the surfactant component predominantly comprises one or more surfactants, each with a molecular structure comprising:

(1) a hydrophobic moiety comprising at least one hydrocarbyl or substituted hydrocarbyl group; Y

ES 2 269 409 T3 (2) a hydrophilic moiety comprising (i) an amino, ammonium or amine oxide group comprising hydrocarbyl or substituted hydrocarbyl substituents; and / or (ii) a carbohydrate group.

The carbohydrate of the hydrophilic moiety is preferably a sugar such as a monosaccharide, disaccharide, or polysaccharide. Preferred sugars include glycosides such as alkyl glucosides, alkyl polyglycosides, and aminoglycosides. Surfactants containing on average no more than about two carbohydrate groups per surfactant molecule are preferred.

In such surfactants, the hydrophobic moiety is attached to the hydrophilic moiety in one of the following ways. The terminal atom of the hydrophobic moiety is attached (a) directly to the nitrogen in an amino, ammonium, or amine oxide group if present, or (b) directly to the carbohydrate group if present.

In a preferred embodiment, the hydrophobic moiety of the surfactant is a substituted hydrocarbyl group comprising at least one oxyalkylene group in the main chain. Such substituted hydrocarbyl groups include, for example, alkyloxyalkylene and alkenyloxyalkylene groups containing from one to thirty RO oxyalkylene groups where each R in each of the RO groups is independently C alkylene.2-C4.

In one embodiment of the invention, the surfactant component predominantly comprises one or more surfactants each having a molecular structure comprising:

(1) a hydrophobic moiety having one or a plurality of hydrocarbyl or hydrocarbylidene groups C3-18 aliphatic, alicyclic or aromatic, branched or linear, saturated or unsaturated, linked together by 0 to about 7 bonds independently selected from ether, thioether, sulfoxide, ester, thioester and amide bonds, this hydrophobic moiety in total having a J number carbon atoms, where J is from about 8 to about 30; Y (2) a hydrophilic moiety comprising:

(i) an amino group which is cationic or which can be protonated to become cationic, having directly attached to it from 0 to 3 oxyethylene groups or polyoxyethylene chains, said oxyethylene groups and polyoxyethylene chains comprising an average of no more than an E number of oxyethylene units per surfactant molecule, such that E + J <50; and / or (ii) an alkyl sugar derived unit, such as a glucoside, polyglucoside, or aminoglycoside group comprising an average of no more than about 2 of the alkyl sugar derived units per surfactant molecule.

In such surfactants the hydrophobic moiety is attached to the hydrophilic moiety in one of the following ways: (a) directly to an amino group, if present, (b) by an ether bond incorporating an oxygen atom from one of the oxyethylene groups , if present, or from a terminal oxyethylene unit of one of the polyoxyethylene chains, if present, or (c) by an ether bond to one of the units derived from alkyl sugar, if present.

In a preferred embodiment, J is from about 8 to about 25, and E + J is no more than 45, preferably no more than 40, and more preferably no more than 28. For example, compound JJJ in Table 4 includes a a hydrophobic moiety having a total number of carbon atoms of 24 and a hydrophilic moiety that includes 9 oxyethylene units in total, such that E + J = 33. Compound C includes 18 carbon atoms (J) in its hydrophobic moiety, and 7 oxyethylene units in total (E) so that E + J = 25.

In one embodiment of the invention, the surfactant component predominantly comprises one or more surfactants, each with a molecular structure comprising:

(1) a hydrophobic moiety having one or a plurality of hydrocarbyl or hydrocarbylidene groups C3-18 aliphatic, alicyclic or aromatic, branched or linear, independently saturated or unsaturated, linked together with from 0 to about 7 bonds independently selected from ether, thioether, sulfoxide, ester, thioester and amide bonds, this hydrophobic moiety in total having a J number of carbon atoms, where J is from about 8 to about 18; and (2) a hydrophilic moiety comprising:

(i) an amino group that is cationic or that can be protonated to become cationic, having directly attached to it from 0 to 3 oxyethylene groups or polyoxyethylene chains, said oxyethylene groups and polyoxyethylene chains comprising an average of no more than an E number of oxyethylene units per surfactant molecule, such that E + J <22; and / or (ii) an alkyl sugar derived unit, such as a glucoside, polyglucoside, or aminoglycoside group comprising an average of no more than about 2 of the alkyl sugar derived units per surfactant molecule.

ES 2 269 409 T3

In the context of surfactant content, the term "predominantly comprises" means that at least about 50%, preferably at least about 75%, and more preferably at least about 90% by weight of the surfactant component is composed of surfactants having the characteristics of specified molecular structure. For the present purpose, the weight or concentration of the surfactant component as defined herein does not include essentially non-surfactant compounds that are sometimes introduced with the surfactant component, such as water, isopropanol, or other solvents, or glycols (such as ethylene glycol, propylene glycol, polyethylene glycol, etc.).

Without in any way limiting the scope of the present invention, different subclasses of surfactants, defined by the following formulas (5) and (6), are particularly useful in the compositions of the invention.

One embodiment of the invention is a herbicidal concentrate composition as described above, wherein the surfactant component predominantly comprises one or more chemically stable surfactants having the formula (5):

[R1 - (XR2) m - (NR3) n - (R8O) p - (R4) q - (NR5R6 - (CH2)r)s - (NR7)t(sugar)orOH]v [TO]w (5) in which R1 is hydrogen or C1-18 hydrocarbyl, each X is independently an ether, thioether, sulfoxide, ester, thioester or amide bond, each R2 is independently C2-6 hydrocarbylidene, m is an average number from 0 to about 8, the total number of carbon atoms in R1- (XR2) m is from about 8 to about 24, n is 0 or 1, p is a mean number from 0 to about 5, R3, R4, R5, R6 and R7 are independently hydrogen or C1-4 hydrocarbyl, R8 is independently alkylene C2-C4, q is 0 or 1, r is 0 or 4, s is 0 or 1, t is 0 or 1, sugar is (i) an open or cyclic structure derived from sugars, such as, for example, glucose or sucrose (called herein a sugar unit), or (ii) a hydroxyalkyl, polyhydroxyalkyl or poly (hydroxyalkyl) alkyl group, u is an average number from 1 to about 2. A is an anionic entity, and v is an integer of 1 a 3 and w is 0 or 1, so that electrical neutrality is maintained. An example of a preferred compound of the type defined by formula 5 is a glucosamine in which R1 is C8H17 hydrocarbyl, m, p, q, s, t and w are 0, n, u and v are 1, R3 is hydrogen and sugar is an open glucose derivative that has the structure

CH (OH) CH (OH) CH (OH) CH (OH) CH2

Another embodiment of the invention is a herbicidal concentrate composition as described above wherein the surfactant component predominantly comprises one or more surfactants having the formula (6):

in which R1 is hydrogen or C1-18 hydrocarbyl, each X is independently an ether, thioether, sulfoxide, ester, thioester or amide bond, each R2 is independently C2-6 hydrocarbylidene, each R8 independently is C2-C alkylene4; m is an average number from 0 to about 9, the total number J of carbon atoms in R1- (XR2) m is from about 8 to about 24, n is a mean number from 0 to about 5, R5 is hydrogen, C1-4 alkyl, benzyl, an anionic oxide group or an anionic group - (CH2)orC (O) O where u is 1 to 3, R6 and R7 are independently hydrogen, C1-4 alkyl or C2-4 acyl, x and y are mean numbers such that x + y + n is not greater than the number E as defined above, A is an anionic entity and s is an integer from 1 to 3, and t is 0 or 1, so that electrical neutrality is maintained.

It will be appreciated that surfactants according to formulas (5) or (6) above include but are not limited to those which can be described as alkylpolyglycosides, alkylaminoglycosides, polyoxyalkylene-alkylamines, polyoxyalkylene-alkyl-ether-amines, alkyltrimethylammonium salts, salts alkyldimethylbenzylammonium, polyoxyalkylene-N-methyl-alkylammonium salts, polyoxyalkylene-N-methyl-alkyl ether-ammonium salts, alkyldimethylamine oxides, polyoxyalkylene-alkylamine oxides, polyoxyalkylene alkyl ether amine oxides, alkyl betaines, alkylamidopropylamines, and the like. In one embodiment of the invention, the average number of oxyalkylene units, such as oxyethylene units, if present, per surfactant molecule is not greater than 22-J where J is as defined above, and the average number glucose units, if present, per surfactant molecule is not

ES 2 269 409 T3 greater than about 2. In another embodiment of the invention, the average number of oxyalkylene units, such as oxyethylene units, if present, per surfactant molecule is not greater than 50-J where J is as has been defined above, and the average number of glucose units, if present, per surfactant molecule is no greater than about 42.

Illustrative types of surfactants found to be useful in compositions of the invention include the following:

(A) Surfactants corresponding to formula (5) in which R1 is a C hydrocarbyl chain8-18 aliphatic, saturated or unsaturated, linear or branched, m, n, p, s, t and w are 0, and v is 1. This group includes various commercial surfactants generally known in the art or referred to herein as "alkylpolyglucosides" or "APGs. ”. Suitable examples are sold from Henkel as Agrimul® PG-2069 and Agrimul® PG-2076.

(B) Surfactants corresponding to formula (6) in which R1 is a C hydrocarbyl chain8-18 aliphatic, saturated or unsaturated, linear or branched and m is 0. In this group R1 it only forms the hydrophobic moiety of the surfactant and is attached directly to the amino function, as in alkylamines, or through an ether bond formed by the oxygen atom of an oxyalkylene group or the terminal oxygen atom of a polyoxyalkylene chain, as in some alkyl ether amines. Illustrative subtypes that have different hydrophobic moieties include:

(1) Surfactants where x and y are 0, R4 5 and R6 are independently C alkyl1-4, R7 is hydrogen and t is 1. This subtype includes (when R5 and R6 are each methyl) various commercial surfactants known in the art or referred to herein as "alkyldimethylamines". Suitable examples are dodecyldimethylamine, available for example from Akzo as Armeen® DM12D, and cocodimethylamine and sebodimethylamine, available for example from Ceca as Noram® DMC D and Noram® DMS D respectively. Such surfactants are generally provided in a non-protonated form, with the anion A not supplied with the surfactant. However, in a glyphosate potassium salt formulation at a pH of about 4-5, the surfactant will be protonated and it will be recognized that the anion A may be glyphosate, which is capable of forming dibasic salts.

(2) Surfactants where x and y are 0, R5, R6 and R7 are independently C alkyl1-4 yt is 1. This subtype includes (when R5, R6 and R7 are each methyl and A is a chloride ion) various commercial surfactants known in the art or referred to herein as "alkyltrimethylammonium chlorides". A suitable example is cocoalkyl trimethylammonium chloride, available for example from Akzo as Arquad® C.

(3) Surfactants where x + y is 2 or greater, R6 and R7 are hydrogen and t is 1. This subtype includes commercial surfactants known in the art or referred to herein as polyoxyalkylene alkylamines "(where n is 0 and R5 is hydrogen), some "polyoxyalkylene alkyl ether amines" (where n is 1-5 and R5 is hydrogen), "polyoxyalkylene-methyl-alkylammonium chlorides" (where n is 0 and R5 is methyl), and some ”polyoxyalkylene-methyl-alkyl-ether-ammonium chlorides). Suitable examples are polyoxyethylene (2) -cocoamine, polyoxyethylene (5) -seboamine and polyoxyethylene (10) -cocoamine, available for example from Akzo as Ethomeen® C / 12, Ethomeen® T / 15 and Ethomeen® C / 20 respectively; when its amine group is not protonated, a surfactant according to formula (7):

(CHjCHaOyd, /

R1- (C »Qr- N (ΟΗϋΡΗζΟί, Η σι in which R1 is C alkyl12-15, X is ethyl, propyl, methyl ethyl, and x + y is 5, as described in US Patent No. 5,750,468; and polyoxyethylene (2) -N-methyl-cocoammonium chloride and polyoxyethylene (2) -N-methyl-stearylammonium chloride, available for example from Akzo as Ethoquad® C / 12 and Ethoquad® 18/12, respectively. In cases where R5 is hydrogen, that is, in tertiary versus quaternary ammonium surfactants, the anion A is typically not supplied with the surfactant. However, in a glyphosate potassium salt formulation at a pH of about 4-5, it will be recognized that the anion A may be glyphosate, which is capable of dibasic salt forms.

(4) Surfactants in which R5 is an anionic oxide group and t is 0. This subtype includes commercial surfactants known in the art or referred to herein as "alkyldimethylamine oxides" (where n, x and y are 0, and R6 and R7 are methyl), some "alkyl ether dimethylamine oxides" (where n is

1-5, x and y are 0 and R6 and R7 are methyl), "polyoxyalkylene alkyl amine oxides" (where n is 0, x + y is

ES 2 269 409 T3 or higher and R6 and R7 are hydrogen), and some "polyoxyalkylene-alkyl-ether-amine oxides" (where n is 1-5, x + y is 2 or greater, and R6 and R7 are hydrogen). Suitable examples are cocodimethylamine oxide, sold by Akzo as Aromox® DMC, and polyoxyethylene (2) -cocoamine oxide sold by Akzo as Aromox® C / 12.

(5) Surfactants in which R5 is an anionic group -CH2C (O) O (acetate), x and y are 0 and t is 0. This subtype includes commercial surfactants known in the art or referred to herein as "alkyl betaines" (where n is 0, R5 is acetate and R6 and R7 are methyl) and some "alkyl ether betaines" (where n is 1-5, R5 is acetate and R6 and R7 are methyl). A suitable example is cocobetaine, sold for example by Henkel as Velvetex® AB-45.

(C) Surfactants corresponding to formula (6) in which R1 is a C hydrocarbyl chain8-18 aliphatic, saturated or unsaturated, straight or branched, m is 1, X is an ether bond, R2 is n-propylene and n is 0. In this group R1 together with OR2 form the hydrophobic moiety of the surfactant that is directly attached via the R bond2 to the amino function. These surfactants are a subclass of alkyl ether amines as described in US Patent No. 5,750,468. Illustrative subtypes have the different hydrophilic moieties exemplified in (B-1) through (B-5) above. Suitable examples are a surfactant according to formula (8), when its amino group is not protonated:

(ΟΗζΟΗζΟμ)

R1- (OCHzCttín— / (CrfeCHjOJyH (8).

a surfactant according to formula (9):

(CHjCHjOLH

R1-OCCHÜ, - N+- CHj CT (9)And a surfactant according to formula (10):

, L

R1—HEAR — N+_O '(CHjCHzOJyH (10).

where, in each of the formulas (8), (9) and (10), R1 is C alkyl12-15 yx + y is 5, as described in US Patent No. 5,750,468.

ES 2 269 409 T3 (D) Surfactants corresponding to formula (6) in which R1 is a C8-18 aliphatic, saturated or unsaturated, straight or branched hydrocarbyl chain, m is 1-5, each XR2 is a -OCH (CH3) CH group2- yn is 0. In this group R1 together with the groups OCH (CH3) CH2- forms the hydrophobic moiety of the surfactant which is

(CHaCHaOJyH linked directly to the amino function. These surfactants are an additional subclass of alkyl ethermines as described in US Patent No. 5,750,468. Illustrative subtypes have the various hydrophilic moieties exemplified above in (B- 1) to (B-5).

(E) Surfactants corresponding to formula (6) in which R1 is a C8-18 aliphatic, saturated or unsaturated, straight or branched hydrocarbyl chain, m is 1, X is an amide bond, R2 is n-propylene and n is 0. In this group R1 along with XR2 form the hydrophobic moiety of the surfactant that is directly attached via the R bond2 to the amino function. In the preferred surfactants of this group, x and y are 0, R5 is hydrogen or C1-4 alkyl, R6 and R7 independently are C alkyl1-4 and t is 1. A suitable example is cocoamidopropyl dimethylamine propionate, sold, for example, by McIntyre as Mackalene.® 117.

(F) Surfactants corresponding to formula (6) in which R1 is hydrogen, m is 3-8 and each XR2 is an OCH (CH3) CH2- group. In this group the polyether chain of the -OCH (CH3) CH2- groups (a polyoxypropylene chain) forms the hydrophobic moiety of the surfactant which is linked directly or by one or more oxyethylene units to the amino function. In the preferred surfactants of this group, x and y are 0, R5, R6 and R7 independently are C1-4 alkyl and t is 1. These surfactants are a subclass of the polyoxypropylene quaternary ammonium surfactants described in US Pat. 5,652,197. In a suitable example, m is 7, n is 1, R5, R6 and R7 they are each methyl, and A is chloride.

In surfactants where t is 1, A can be any agriculturally acceptable anion but is preferably chloride, bromide, iodide, sulfate, ethosulfate, phosphate, acetate, propionate, succinate, lactate, citrate, or tartrate, or as noted above. , glyphosate.

In one embodiment of the invention, the composition contains a class of alkyl ether amine surfactants described in US Patent No. 5,750,468, the disclosure of which is incorporated herein by reference. In a further embodiment, the present surfactants are other than alkyl ether amines as described in US Patent No. 5,750,468, the disclosure of which is incorporated herein by reference.

In another embodiment of the invention, the composition contains a surfactant having the general formula (11):

R1R2RN (CH2)nNR3R '(11) in which R1 and R2 are independently a C hydrocarbyl chain4-18 aliphatic, saturated or unsaturated, linear or branched, R3 and R4 are independently a C alkyl1-4 or hydrogen, and n is greater than 2. A particularly preferred compound of this description is where R1 and R2 are C8H17, n is 3, and R3 and R4 they are hydrogen.

In still another embodiment of the invention, the composition contains a surfactant having the general formula (12):

R1R2RN (CH2CH2Ü)nR3 (12) in which R1 is a C hydrocarbyl chain8-18 aliphatic, saturated or unsaturated, linear or branched, R2 and R3 are independently C alkyl1-10 preferably C1-4 or hydrogen, and n is 1 or greater, preferably 2 to 15. It is believed that at least one compound of this formula has hitherto not been described in the prior art, and is therefore a novel compound. The structure of this compound is

CH3 (CH2) 17N (CH3) (CH2CH2O) 7CH:

This novel compound, as well as its use as a pesticidal adjuvant, and in particular with glyphosate, and even more in particular with the glyphosate potassium salt, is within the scope of this invention. Additionally, the hydroxy analogs of the above compound show good compatibility with glyphosate potassium salt formulations.

ES 2 269 409 T3

In other embodiments of the invention, the composition contains a surfactant having one or more of the following formulas:

R1R2R3N + (CH2)nNR4R5 (13) in which R1 is a C8-18 aliphatic, saturated or unsaturated, straight or branched hydrocarbyl chain, R2, R3, R4 and R5 are independently C1-4 alkyl or hydrogen, X is an anionic entity, and n is 2 or greater;

R1O (CH2)nNR2R3 (14) in which R1 is a C hydrocarbyl chain4-18 aliphatic, saturated or unsaturated, linear or branched, R2 and R3 they are independently C1-4 alkyl or hydrogen, and n is equal to 2 or greater;

R1O (CH2) mNR2(CH2) nNR3R4 (15) in which R1 is a C hydrocarbyl chain4-18 aliphatic, saturated or unsaturated, linear or branched, R2, R3 and R4 are independently C1-4 alkyl or hydrogen, and m and n are independently equal to 2 or greater;

R1O (CH2) mNR2(CH2)nNR3R4 (16) in which R1 is a C hydrocarbyl chain4-18 aliphatic, saturated or unsaturated, linear or branched, R2, R3 and R4 are independently polyoxyethylene chains having combined total of 3 or more moles of ethylene oxide, and m and n are independently equal to 2 or greater;

R1O (CH2) mN [CH2CH2O) nR2] (CH2) p [CH2CH2O)whatR3] (17) in which R1 is a C hydrocarbyl chain4-18 aliphatic, saturated or unsaturated, linear or branched, R2 and R3 are independently methyl or hydrogen, m and p are independently equal to or greater than about 2 and equal to or less than about 6, n and q are independently equal to about 1-10;

R1 - X - (CH2)n - NR2R3 (18) in which R1 is a C4-18 aliphatic, saturated or unsaturated, straight or branched hydrocarbyl chain, R2 and R3 they are independently C1-4 alkyl or hydrogen, X is an amide bond and n is equal to 2 or greater;

R1R2R3(N + O-) (19) in which R1 is a C4-18 aliphatic, saturated or unsaturated, straight or branched hydrocarbyl chain, R2 and R3 are independently C1-4 alkyl;

R1 - NR2 - carbohydrate (20) in which R1 is a C4-18 aliphatic, saturated or unsaturated, straight or branched hydrocarbyl chain, and R2 is a C alkyl1-4 or hydrogen and "carbohydrate" is a carbohydrate, for example -CH2CH (OH) CH (OH) CH (OH) CH (OH) CH2OH. In addition, other derivatives are of particular interest, such as for example ethoxylated or non-ethoxylated alkyl or amide derivatives of amino sugars (in particular 2-aminoglucose) in glyphosate or other herbicide / pesticide formulations. In this connection, the di-sugar-amines are also of particular interest.

R1 - N - [(CH2)nNR2R3L (21) in which R1 is a C4-18 aliphatic, saturated or unsaturated, straight or branched hydrocarbyl chain, and R2 and R3 they are independently C1-4 alkyl or hydrogen, and n is 2 or greater, preferably n is 2 or 3;

R1 R2N (CH2) m-O - (CH-CH-O). - (CH2)P - NR3R4 (22) in which R1, R2, R3 and R4 are independently C1-4 alkyl, polyoxyethylene, or hydrogen, and m and p are independently 2 or greater, preferably 2-3, ynes1 or greater, preferably 1.

ES 2 269 409 T3

New surfactants have been discovered that are particularly suitable for use in formulating pesticidal compositions, such as herbicides. Surfactants have been found to be highly compatible with various water soluble glyphosate salts, especially potassium, ammonium and diammonium glyphosate. Suitable cationic surfactants for formulating pesticidal formulations include:

(a) monoalkoxylated amines having the formula:

in which R1 is hydrogen or hydrocarbyl or substituted hydrocarbyl having at least 7 carbon atoms (preferably containing 8 to about 30 carbon atoms); R2 in each of the groups x (R2O) ey (R2O) is independently C2-C4 alkylene; R3 is a hydrocarbylene or substituted hydrocarbylene having 2 to about 6 carbon atoms; R4 and R5 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having from 1 to about 30 carbon atoms, - (R6) n- (R2O) and R7 or R4 and R5, together with the nitrogen atom to which they are attached, form a cyclic or heterocyclic ring; R8 is hydrocarbylene or substituted hydrocarbylene containing 1 to about 6 carbon atoms, R7 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, nes0, 1, and x and y are independently an average number of 1 to about 60, however provided that when R2 and R3 in each of the groups x (R2O) is ethylene, R1 is other than unsubstituted alkyl or R4 is other than hydrogen or unsubstituted alkyl when R5 is hydrogen or unsubstituted alkyl, and when R2 and R3 are isopropylene and x is 1, R1 is other than unsubstituted alkyl or R4 is different from - (R2O) and R7. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R4, R5 and R6 Preferred groups include straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene), or aralkyl (aralkylene) groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 25 carbon atoms, R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R3 is an ethylene or 2-hydroxypropylene group, R4 and R5 are each independently hydrogen or a linear or branched alkyl group having 1 to about 6 carbon atoms, and x is an average number of 1 to about 30. More preferably, R1 is a straight or branched alkyl group having from about 12 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is an ethylene or 2-hydroxypropylene group, R4 and R5 are each independently hydrogen, methyl, or tris (hydroxymethyl) methyl, and x is an average number from about 2 to about 30. Even more preferably, R1 is a straight or branched alkyl group having from about 12 to about 18 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is an ethylene or 2-hydroxypropylene group, R4 and R5 are each independently hydrogen or methyl, and x is an average number from about 4 to about 20. More preferably, R1 is a straight or branched alkyl group having from about 12 to about 18 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is an ethylene or 2-hydroxypropylene group, R4 and R5 are methyl, and x is an average number from about 4 to about 20.

(b) alkoxylated poly (hydroxyalkyl) amines having the formula:

R3

Go1 - (OR2jx - (R4) and - N —R5 (24) in which R1 and R3 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R2 in each of the groups (R2O) is independently alkylene C2 -C4; R4 is hydrocarbylene or substituted hydrocarbylene having 1 to about 30 carbon atoms, R5 is hydroxyalkyl, polyhydroxyalkyl, or poly (hydroxyalkyl) alkyl; x is an average number from 0 to about 30, and y is 0 or 1. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R3 and R4 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. The alkoxylated poly (hydroxyalkyl) amines have the formula:

ES 2 269 409 T3

in which R1 and R3 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, R2 in each of the groups x (R2O) is independently alkylene C2-C4, R4 is hydrocarbylene or substituted hydrocarbylene having 1 to about 30 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is not more than about 7, p is an integer from 1 to about 8 , x is an average number from 0 to about 30, and y is 0 or 1. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R3 and R4 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 is a linear or branched alkyl group or linear or branched alkylene group having from about 8 to about 30 carbon atoms; R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R4 is a linear or branched alkylene having 1 to about 30 carbon atoms, m and n are independently integers from 0 to about

7, the sum of m and n is not more than about 3 to 7, p is an integer from 1 to about 8, x is a mean number from 0 to about 30, and y is 0 or 1. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms; R2 in each of the groups x (R2O) is independently ethylene or propylene; R3 is hydrogen, or a linear or branched alkyl group having 1 to about 6 carbon atoms; R4 is a linear or branched alkylene having 1 to about 6 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, p is an integer from 1 to about 8, x is an average number from 0 to about 30, and y is 0 or 1. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms; R2 in each of the groups x (R2O) is independently ethylene or propylene; R3 is hydrogen, or methyl; m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, p is an integer from 1 to about

8, x is a middle number from 0 to about 30, and y is 0.

R4 - N - R2 - N - R5

R1 R3 (27) in which R1 and R3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 22 carbon atoms, R2 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, R4 and R5 are independently hydroxyalkyl, polyhydroxyalkyl, or poly (hydroxyalkyl) alkyl, however provided that when R1 and R3 are methyl, R2 it is other than octylene. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2 and R3 Preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferred di-poly (hydroxyalkyl) amine groups have the formula:

(28)

ES 2 269 409 T3 in which R1 and R3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 22 carbon atoms, R2 is hydrocarbylene or substituted hydrocarbylene having 2 to about 18 carbon atoms, and m and n are independently integers from 1 to about 8, however, provided that when R1 and R3 are methyl, R2 it is other than octylene. In this context, the hydrocarbyl (hydrocarbylene) groups R1 , R2 and R3 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl groups. In one embodiment, R1 and R3 are independently hydrogen or a linear or branched alkyl group having 1 to about 6 carbon atoms, R2 is a linear or branched alkylene, linear or branched alkenylene, linear or branched alkynylene, arylene and alkylarylene group having from 9 to about 18 carbon atoms, and m and n are as defined above. In another embodiment, R1 and R3 are independently hydrogen or a linear or branched alkyl group having from 2 to about 22 carbon atoms, R2 is a linear or branched alkylene, linear or branched alkenylene, linear or branched alkynylene, arylene and alkylarylene group having 2 to 7 carbon atoms, and m and n are as defined above. Preferably R1 and R3 are independently hydrogen or a linear or branched alkyl group having 1 to about 18 carbon atoms, R2 is a linear or branched alkylene or linear or branched alkenylene group having from 2 to about 8 carbon atoms. More preferably, R1 and R3 are independently hydrogen or a linear or branched alkyl group having 6 to about 12 carbon atoms, R2 is a linear or branched alkylene group having 2 to about 6 carbon atoms, and m and n are independently integers from about 4 to about 8; or R1 and R3 are independently hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R2 is a linear or branched alkylene group having from 2 to about 16 carbon atoms, and m and n are independently integers from about 4 to about 8. Most preferably, R1 and R3 are independently hydrogen or a linear or branched alkyl group having 6 to about 12 carbon atoms, R2 is ethylene or propylene, and m and n are independently integers from about 4 to about 8; or R1 and R3 are independently hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R2 is a linear or branched alkylene group having 2 to about 12 carbon atoms, and m and n are independently integers from about 4 to about 8.

(d) alkoxylated triamines having the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, R2, R3, R4 and R5 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R8)Mr7-O) nR6; R6 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms; R7 in each of the groups n (R7O) is independently C2-C4 alkylene; R8 is hydrocarbylene or substituted hydrocarbylene having 1 to about 6 carbon atoms; n is an average number from 1 to about 10; s is 0 or 1; and x and y are independently an integer from 1 to about 4; however, provided that when R1 is alkyl, R2 is other than hydrogen, x is 3 or 4, or R4 is different from - (R7-O) nR6. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R3, R4, R5 and R8 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. In one embodiment, R2 is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl group having 1 to about 30 carbon atoms, or - (R8)Mr7-O) nR6 and the rest of the groups are as described above. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R2, R3, R4 and R5 are independently hydrogen, a linear or branched alkyl, or linear or branched alkenyl group having 1 to about 30 carbon atoms, or - (R7-O) nR6; R6 is hydrogen, methyl or ethyl; R7 in each of the groups n (R7O) is independently C2-C4 alkylene; n is an average number from 10 to about 10, and x and y are independently an integer from 1 to about 4. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, R2, R3, R4 and R5 are independently hydrogen, a linear alkyl group having 1 to about 6 carbon atoms, or - (R7-O) nR6; R6 is hydrogen or methyl; R7 in each of the groups n (R7O) is independently ethylene or propylene, n is an average number from 1 to about 5, and x and y are independently an integer from 1 to about 4. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, R2, R3, R4 and R5 are independently hydrogen or - (R7-OR)nR6; R6 is hydrogen, R7 in each of the groups n (R7OR)

ES 2 269 409 T3 is independently ethylene or propylene; n is a mean number from 1 to about 5, and x and y are independently an integer from 1 to about 4.

(e) monoalkoxylated amines having the formula:

in which R1 is a hydrocarbyl or substituted hydrocarbyl group having from 1 to about 30 carbon atoms, R2 is C2-C4 alkylene, R3 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R4 is a linear or branched alkynyl, aryl, or aralkyl group having 1 to about 30 carbon atoms, and x is an average number of 1 to about 60. In this context, the hydrocarbyl or substituted hydrocarbyl groups R1 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from 1 to about 25 carbon atoms, R2 is C alkylene2 -C4, R3 is hydrogen, methyl or ethyl, R4 is a straight or branched alkynyl, aryl, or aralkyl group having 1 to about 25 carbon atoms, and x is an average number of 1 to about 40. More preferably, R1 is a straight or branched alkyl group having from 8 to about 22 carbon atoms, R2 is ethylene or propylene, R3 is hydrogen, methyl or ethyl, R4 is a straight or branched alkynyl, aryl or aralkyl group having 1 to about 6 carbon atoms, and x is an average number of 1 to about 20. In one embodiment, the compound has the formula shown in Table 4, C.

(f) amine oxides having the formula:

OR

I

R1 - N - R3 I R2 (31) in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 8 to about 30 carbon atoms, R2 and R3 are independently - (R4O) xR5, R4 in each of the groups x (R4O) is independently C2-C4 alkylene, R5 is hydrogen, or a hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, x is an average number of 1 to about 50. In this context, the R groups1 and R5 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 22 carbon atoms, R2 and R3 are independently - (R4O) xR5, R4 in each of the groups x (R4O) is independently C2-C4 alkylene, R5 is hydrogen, or is a linear or branched alkyl or linear or branched alkenyl group having from 1 to about 30 carbon atoms; and x is an average number from 1 to about 20. More preferably, R1 is a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R2 and R3 are independently - (R4O) xR5, R4 in each of the groups x (R4O) is independently ethylene or propylene; R5 is hydrogen, or is a linear or branched alkyl or linear or branched alkenyl group having from about 1 to about 30 carbon atoms; and x is an average number from 1 to about 10. More preferably, R1 is a linear or branched alkyl group having from about 8 to about 18 carbon atoms, R2 and R3 are independently - (R4OR)xR5, R4 in each of the groups x (R4O) is independently ethylene or propylene; R5 is hydrogen, or is an alkyl group of about 8 to about 18 carbon atoms; and x is a mean number from 1 to about 5.

(g) an alkoxylated amine oxide having the formula:

ES 2 269 409 T3 in which R1 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms; R2 in each of the groups x (R2O) ey (R2O) is independently C2-C4 alkylene; R3 is a hydrocarbylene or substituted hydrocarbylene having 2 to about 6 carbon atoms; R4 and R5 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having from 1 to about 30 carbon atoms, - (R6) n- (R2O) and R7; R6 is hydrocarbylene or substituted hydrocarbylene containing 1 to about 6 carbon atoms, R7 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, n is 0 or 1, and x and y are independently an average number of 1 to about 60. In this context, hydrocarbyl (hydrocarbylene) groups R3, R4, R5 and R8 Preferred groups include straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 is a linear or branched alkyl group or linear or branched alkenyl group having from 8 to about 25 carbon atoms, R2 in each of the groups x (R2O) is independently C2-C4 alkylene; R3 is a linear or branched alkylene or alkenylene group having from 2 to about 6 carbon atoms; R4 and R5 are each independently hydrogen, or a linear or branched alkyl group having 1 to about 6 carbon atoms, and x is an average number of 1 to about

30. More preferably, R1 is a straight or branched alkyl group having 12 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is a linear or branched alkylene or alkenylene group having from 2 to about 6 carbon atoms; R4 and R5 are each independently hydrogen, methyl, or tris (hydroxymethyl) methyl, and x is an average number from about 2 to about 30. Even more preferably, R1 is a straight or branched alkyl group having 12 to about 18 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is an ethylene, propylene or 2-hydroxypropylene group, R4 and R5 are each independently hydrogen or methyl, and x is an average number from about 4 to about 20. More preferably, R1 is a straight or branched alkyl group having from about 12 to about 18 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is an ethylene, propylene or 2-hydroxypropylene group, R4 and R5 are methyl, and x is an average number from about 4 to about 20.

(h) alkoxylated diamines having the formula:

in which R1 is a hydrocarbyl or substituted hydrocarbyl group having from about 8 to about 30 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently C2-C4 alkylene; R3, R5 and R6 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R2O) and R7; R4 is hydrocarbylene or substituted hydrocarbylene having 2 to about 6 carbon atoms, -C (= NR11) NR12R13-, -C (= O) NR12R13, -C (= S) NR12R13-, -C (= NR12) -, -C (S) - or -C (O) -; R7 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms; R11, R12 and R13 they are hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, x is an average number of 1 to about 30; ey is a mean number from 1 to about 50, however, provided that at least one of R3, R5 and R6 is - (R2O) and R7, at least one of R2 is other than ethylene, R4 is other than unsubstituted propylene, R1 is other than unsubstituted alkyl, ox is from 2 to about 30. In this context, hydrocarbyl (hydrocarbylene) groups R1, R3, R4, R5 and R6 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 is a linear or branched alkyl group or linear or branched alkenyl group having from 8 to about 22 carbon atoms, R2 in each of the groups x (R2O) and the groups and (R2O) is independently alkylene C2-C4; R3, R5 and R6 they are independently hydrogen, a linear or branched alkyl or linear or branched alkylene group having from 1 to about 22 carbon atoms; or - (R2O) and R7, R4 is a linear or branched alkylene, linear or branched alkenylene group having 2 to about 6 carbon atoms, R7 is hydrogen, methyl, or ethyl, x is an average number from 1 to about 20, and y is an average number from 1 to about 20. More preferably, R1 is a linear or branched alkyl group or linear or branched alkenyl group having from 8 to about 18 carbon atoms, R2 in each of the groups x (R2O) and the groups and (R2O) is independently ethylene or propylene; R3, R5 and R6 they are independently hydrogen, a linear or branched alkyl group having from 1 to about 6 carbon atoms; or - (R2O) and R7, R4 is ethylene, propylene, or 2-hydroxypropylene, R7 is hydrogen or methyl, x is an average number from 1 to about 15, and y is an average number from 1 to about 10. More preferably, R1 is a linear or branched alkyl group or linear or branched alkenyl group having from 8 to about 18 carbon atoms, R2 in each of the groups x (R2O) and the groups and (R2O) is independently ethylene or propylene; R3, R5 and R6 are independently hydrogen, methyl, or - (R2O) and R7, R4 is ethylene, propylene, or 2-hydroxypropylene, R7 is hydrogen, x is a mean number from 1 to about 10, and y is a mean number from 1 to about 5.

ES 2 269 409 T3 (i) dialkoxylated amines having the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 6 to about 30 carbon atoms, or -R4MR5, R4 and R2 in each of the groups x (R2O) ey (R2O) is independently alkylene C2C4; R3 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R5 is a straight or branched alkyl group having from about 4 to about 15 carbon atoms, and x and y are independently an average number from 1 to about 40. In this context, the hydrocarbyl groups R1 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1 is a linear or branched alkynyl, aryl, or aralkyl group having from about 8 to about 30 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently C2-C4 alkylene; R3 is hydrogen, methyl or ethyl, and x and y are independently an average number from 1 to about 20. More preferably, R1 is a linear or branched alkynyl, aryl, or aralkyl group having from about 8 to about 25 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x and y are independently an average number from 1 to about 30. Even more preferably, R1 is a linear or branched alkynyl, aryl, or aralkyl group having from about 8 to about 22 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x and y are independently an average number from 1 to about 5.

Nonionic surfactants for use in pesticidal formulations include dialkoxylated alcohols having the formula:

R1(OR2) XO - R3 - O - (R2O) and R1 (35) in which R1 independently hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R2 in each of the groups x (R2O) and and (R2O) is independently alkylene C2-C4; R3 is hydrocarbylene or substituted hydrocarbylene having 2 to about 30 carbon atoms, and x and y are independently an average number of 1 to about 60. In this context, hydrocarbylene groups R3 preferred are linear or branched alkylene, linear or branched alkenylene, linear or branched alkynylene, arylene or aralkylene groups. Preferably R1 is hydrogen, methyl or ethyl, R2 in each of the groups x (R2O) and the and (R2O) is independently C2-C4 alkylene; R3 is a linear or branched alkylene or linear or branched alkenylene group having from about 8 to about 25 carbon atoms, and x and y are independently an average number from about 1 to about 20. More preferably, R1 is hydrogen or methyl, R2 in each of the groups x (R2O) and and (R2O) is independently ethylene or propylene; R3 is a linear or branched alkylene or linear or branched alkenylene group having from about 8 to about 18 carbon atoms, and x and y are independently an average number from 1 to about 10. Even more preferably, R1 is hydrogen, R2 in each of the groups x (R2O) and and (R2O) is independently ethylene or propylene; R3 is a linear or branched alkylene group having from about 8 to about 18 carbon atoms, and x and y are independently an average number from 1 to about 5.

Other surfactants for use in pesticidal compositions include compounds of the formula:

ES 2 269 409 T3

ES 2 269 409 T3

in which R1, R9 and R12 are independently hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R2O) pR13; R2 in each of the groups m (R2O), n (R2O), p (R2O) and q (R2O) is independently hydrogen, or a hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R4 is - (CH2) yOR13 or - (CH2)YO (R2O) qR3; R5, R6 and R7 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or R4; R10 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms; R14 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (CH2)zO (R2O) PR3; m, n, p and q are independently an average number from 1 to about 50; X is -O-, -N (R14) -, -C (O) -, -C (O) O-, -OC (O) -, -N (R15) C (O) -, -C (O) N (R15), -S-, -SO- or -SO2-; t is 0 or 1; A- is an agriculturally acceptable anion, e and yz are independently an integer from 0 to about 30. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R3 and R5-R15 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 , R9 and R12 are independently linear or branched alkyl or alkenyl groups having 1 to about 22 carbon atoms, or - (R2O) PR13; R2 in each of the groups m (R2O), n (R2O), p (R2O) and q (R2O) is independently C2-C alkylene4; R3 is hydrogen, methyl or ethyl; R4 is - (CH2) yOR13 or - (CH2)YO (R2O) qR3; R8, R11, R13 and R15 they are independently hydrogen, or linear or branched alkyl or alkenyl groups having 1 to about 22 carbon atoms; R4 is - (CH2)YOR13 o - (CH2) and O (R2O) qR3; R5, R6 and R7 are independently hydrogen, linear or branched alkyl or alkenyl groups having 1 to about 22 carbon atoms, or R4; R10 is a linear or branched alkylene or alkenylene group having from 2 to about 18 carbon atoms; R14 is a linear or branched alkyl or alkenyl group having 1 to about 22 carbon atoms, or - (CH2) zO (R2O) PR3; m, n, p and q are independently an average number from 1 to about 30; X is -O-, -N (R14) -, -C (O) -, -C (O) O-, -OC (O) -, -N (R15) C (O) -, -C (O) N (R15), -S-, -SO- or -SO2-; t is 0 or 1; A- is an agriculturally acceptable anion, e and z are independently an integer from 0 to about 30. More preferably, R1 is a linear or branched alkyl or alkenyl group having from about 8 to about 18 carbon atoms, or - (R2O) PR13; R9 and R12 are independently linear or branched alkyl or alkenyl groups having 1 to about 22 carbon atoms, or - (R2O) PR13; R2 in each of the groups m (R2O), n (R2O), p (R2O) and q (R2O) is independently ethylene or propylene; R3 is hydrogen or methyl; R4 is - (CH2)YOR13 o - (CH2) and O (R2O) qR3; R8, R11 and R15 they are independently hydrogen, or linear or branched alkyl or alkenyl groups having 1 to about 22 carbon atoms; R4 is - (CH2)YOr13 o - (CH2) and O (R2O) q R3; R5, R6 and R7 are independently hydrogen, linear or branched alkyl or alkenyl groups having 1 to about 22 carbon atoms, or R4; R10 is a linear or branched alkylene or alkenylene group having from 2 to about 6 carbon atoms; R13 is hydrogen or linear or branched alkyl or alkenyl groups having from about 6 to about 22 carbon atoms; R14 is a linear or branched alkyl or alkenyl group having 1 to about 22 carbon atoms, or - (CH2) zO (R2O) PR3; m, n, p and q are independently an average number from 1 to about 20; X is -O-, -N (R14) -, -C (O) -, -C (O) O-, -OC (O) -, -N (R15) C (O) -, -C (O) N (R15), -S-, -SO- or -SO2-; t is 0 or 1; A- is an agriculturally acceptable anion, e and z are independently an integer from 0 to about 10. More preferably, R1 is a linear or branched alkyl or alkenyl group having from about 12 to about 18 carbon atoms, or - (R2O) PR13; R9 and R12 are independently linear or branched alkyl or alkenyl groups having 1 to about 6 carbon atoms, or - (R2OR)PR13; R2 in each of the groups m (R2O), n (R2O), p (R2O) and q

ES 2 269 409 T3 (R2O) is independently ethylene or propylene; R3 is hydrogen; R4 is - (CH2)YOR13 o - (CH2) and O (R2O) qR3; R8, R11, R15 they are independently hydrogen, or linear or branched alkyl or alkenyl groups having 1 to about 6 carbon atoms; R4 is - (CH2) yOR13 o - (CH2) and O (R2O) qR3 ; R5, R6 and R7 are independently hydrogen, linear or branched alkyl or alkenyl groups having 1 to about 22 carbon atoms, or R4; R10 is a linear or branched alkylene or alkenylene group having from 2 to about 6 carbon atoms; R13 is hydrogen or linear or branched alkyl or alkenyl groups having from about 6 to about 22 carbon atoms; R14 is a linear or branched alkyl or alkenyl group having 1 to about 22 carbon atoms, or - (CH2)zO (R2OR)pR3; m, n, p and q are independently an average number from 1 to about 5; X is -O-, or -N (R14) -, t is 0 or 1; A- is an agriculturally acceptable anion, e and z are independently an integer from 1 to about 3.

A surfactant composition of the invention comprises any individual combination of the novel surfactants described above. The surfactant composition is particularly preferred for use in formulating potassium, diammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine and / or trimethylsulfonium glyphosate formulations, such as in aqueous concentrates. The surfactant composition can be incorporated into a formulation comprising any combination of these glyphosate salts.

Various surfactants not previously used in the formulation of pesticidal compositions have been found to be effective, particularly in the formulation of aqueous herbicidal concentrates containing potassium or ammonium glyphosate. Cationic surfactants effective in forming pesticidal formulations include:

(a) alkoxylated amino alcohol having the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl containing at least 7 carbon atoms (preferably containing 8 to about 30 carbon atoms); R2 in each of the groups x (R2O) ey (R2O) is independently C2-C4 alkylene; R3 and R6 are each independently hydrocarbylene or substituted hydrocarbylene having 1 to about 6 carbon atoms; R4 is hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, hydroxy-substituted hydrocarbyl, - (R6) n- (R2O) and R7, -C (= NR11) NR12R13, -C (= O) NR12R13, -C (= S) NR12R13 or together with R5 and the nitrogen atom to which they are attached, form a cyclic or heterocyclic ring; R5 is hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, hydroxy-substituted hydrocarbyl, - (R6) n- (R2O) and R7, -C (= NR11) NR12R13, -C (= O) NR12R13, -C (= S) NR12R13 or together with R4 and the nitrogen atom to which they are attached, form a cyclic or heterocyclic ring; R7 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms; R11, R12 and R13 are hydrocarbyl or substituted hydrocarbyl, R14 is hydrogen, hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, hydroxy substituted hydrocarbyl, - (R6) n- (R2O) and R7, -C (= NR11) NR12R13, -C (= O) NR12R13, or -C (= S) NR12R13, n is 0 or 1, x and y are independently a mean number from 1 to about 60, and A- is an agriculturally acceptable anion, however, provided that when R2 and R3 are isopropylene and x is 1, R1 is other than alkyl or R4 is different from - (R2O) and R7. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R3, R4, R5, R6, R11, R12 and R13 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. In one embodiment, R3 is linear alkylene, preferably ethylene, and R1, R2, R4 and R5 they are as previously defined. In another embodiment, R4 is H, alkyl, or -R2OR7 and R1, R2, R3, R5 and R7 they are as previously defined. In still another embodiment, R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 25 carbon atoms, R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R3 is a linear or branched alkylene group having 1 to about 6 carbon atoms, R4 and R5 are each independently hydrogen or a linear or branched alkyl group having 1 to about 6 carbon atoms, and x is an average number of about 2 to about 30. More preferably, R1 is a linear or branched alkyl group having about

ES 2 269 409 T3 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is a linear or branched alkylene group having 1 to about 4 carbon atoms, R4 and R5 are each independently hydrogen, methyl, or tris (hydroxymethyl) methyl, and x is an average number from about 2 to about 30. Even more preferably, R1 is a straight or branched alkyl group having from about 12 to about 18 carbon atoms, R2 in each of the groups x (R2 O) is independently ethylene or propylene, R3 is ethylene, R4 and R5 are each independently hydrogen or methyl, and x is an average number from about 4 to about 20. More preferably, R1 is a straight or branched alkyl group having from about 12 to about 18 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is ethylene, R4 and R5 are methyl, and x is an average number from about 4 to about 20. Compounds of formula (45) have the preferred groups described above and R14 preferably it is hydrogen or a linear or branched alkyl or alkenyl group, more preferably alkyl, and most preferably methyl. Preferred monoalkoxylated amines include PEG (13 or 18) -ether (C14-15) -propylamines and PEG (7, 10, 15 or 20) -ether (C16-18) -propylamines (from Tomah) and PEG (13 or 18) -ether (C14-15) -dimethylpropylamines and PEG (10, 15 or 20 or 25-ether (C16-18) -propylamines (from Tomah).

(b) hydroxylated amines having the formula:

OR

II

R1 - N - C - R3

IR2 (46) in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, R2 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, and R3 is hydroxyalkyl, polyhydroxyalkyl, or poly (hydroxyalkyl) alkyl. In this context, the hydrocarbyl groups R1 and R2 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably, the hydroxylated amines have the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, R2 is hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, and n is 1 to about 8. In this context, the hydrocarbyl groups R1 and R2 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R2 is hydrogen, a linear or branched alkyl or linear or branched alkenyl group having from about 1 to about 30 carbon atoms, and n is from about 4 to about 8; or R1 and R2 are independently linear or branched alkyl or linear or branched alkenyl groups having from about 4 to about 30 carbon atoms, and n is from about 4 to about 8. More preferably, R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 1 to about 6 carbon atoms, n is from about 4 to about 8; or R1 and R2 are independently linear or branched alkyl or linear or branched alkenyl groups having from about 4 to about 8 carbon atoms, and n is from about 4 to about 8.

R1 - Xm - N —R3 - N —R5

R2 R4 (48) in which R1 , R2 and R5 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or -R8(OR9)nOR10, R3 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, R8 and R9 are individually hydrocarbyl or hydrocarbyl

ES 2 269 409 substituted T3 having 2 to about 4 carbon atoms, R4 and R10 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, m is 0 or 1, n is an average number from 0 to about 40, X is -C (O) - or -SO2- , and A is an agriculturally acceptable anion. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R3, R4 and R5 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1, R2, R4 and R5 are independently hydrogen, a linear or branched alkyl or alkenyl group having 1 to about 6 carbon atoms, and R3 it is a linear or branched alkylene having from 2 to about 6 carbon atoms. More preferably, R1 , R2, R4 and R5 are independently hydrogen, or a linear or branched alkyl group having 1 to about 6 carbon atoms, and R3 it is a linear or branched alkylene having 1 to about 6 carbon atoms. More preferably, R1 , R2, R4 and R5 are independently hydrogen or methyl, and R3 it is ethylene or propylene.

(d) salts of mono or diammonium having the formula:

in which R1 , R2, R4, R5 and R7 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, or -R8(OR9) nOR10, R9 is hydrocarbyl or substituted hydrocarbyl having from about 1 to about 30 carbon atoms, R3 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, R8, R9 and R11 are individually hydrocarbylene or substituted hydrocarbylene having 2 to about 4 carbon atoms, R10 is hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, m is 0 or 1, n is an average number from 0 to about 40, X is -C (O) - or -SO2-, Z is -C (O) and A- it is an acceptable anion in agriculture. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R3, R4, R5 and R7 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1, R2, R4, R5 and R7 are independently hydrogen, a linear or branched alkyl or alkenyl group having 1 to about 6 carbon atoms, R6 is a linear or branched alkyl or alkenyl group having from about 8 to about 30 carbon atoms, m is 0 or 1, and R3 it is a linear or branched alkylene having from 2 to about 6 carbon atoms. More preferably, R1, R2, R4, R5 and R7 are independently hydrogen, a linear or branched alkyl group having from 1 to about 6 carbon atoms, R6 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms, m is 0 or 1, and R3 it is a linear or branched alkylene having 1 to about 6 carbon atoms. More preferably, R1, R2, R4, R5 and R7 are independently hydrogen or methyl, R6 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, m is 0 or 1, and R3 it is ethylene or propylene.

(e) poly (hydroxyalkyl) amines having the formula:

R1 - N - R3

R (51) in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, or -R4OR5, R2 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R3 is hydroxyalkyl, polyhydroxyalkyl, or poly (hydroxyalkyl) alkyl, R4 is hydrocarbylene or

ES 2 269 409 T3 substituted hydrocarbylene having 2 to about 18 carbon atoms, and R5 it is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms. Preferably, the poly (hydroxyalkyl) amines have the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, or -R3OR4, R2 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R3 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, R4 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from about 1 to about 30 carbon atoms m and n are independently integers from 0 to about 7, the sum of m and n is not greater than about 7, and p is an integer from 1 to about 8. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R3 and R4 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably, it is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, or -R3OR4, R2 is hydrogen, a linear or branched alkyl or linear or branched alkenyl group having 1 to about 30 carbon atoms, R3 is a linear or branched alkylene or alkenylene group having from 2 to about 6 carbon atoms, R4 is a linear or branched alkyl or alkenyl group having from about 8 to about 22 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, and p is an integer from about 4 to about 8; or R1 and R2 are independently linear or branched alkyl or linear or branched alkenyl groups having from about 4 to about 30 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, and p is an integer from about 4 to about 8. More preferably, R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 22 carbon atoms, or -R3OR4, R2 is hydrogen, a linear or branched alkyl or linear or branched alkenyl group having 1 to about 6 carbon atoms, R3 is a linear or branched alkylene or alkenylene group having from 2 to about 6 carbon atoms, R4 is a linear or branched alkyl or alkenyl group having from about 8 to about 18 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, and p is an integer from about 4 to about 8; or R1 and R2 are independently linear or branched alkyl or linear or branched alkenyl groups having from about 4 to about 8 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, and p is an integer from about 4 to about 8. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, or -R3OR4, R2 is hydrogen or methyl, m and n are independently integers from 0 to about 4, R3 is a linear or branched alkylene group having from 2 to about 6 carbon atoms, R4 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, the sum of m and n is about 4, and p is an integer of about 4. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, or -R3OR4, R2 is methyl, R3 is ethylene, propylene, hydroxyethylene, or 2-hydroxypropylene, R4 is an alkyl group

Linear or branched ES 2 269 409 T3 having from about 8 to about 18 carbon atoms, m and n are independently integers from 0 to about 4, the sum of m and n is about 4, and p is an integer of about 4. Such compounds are commercially available from Aldrich and Clariant.

(f) di-poly (hydroxyalkyl) amine having the formula:

R4 - N - R2 - N - R5

R1 R3 (54) in which R1 and R3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 22 carbon atoms, R2 is hydrocarbylene or substituted hydrocarbylene having 2 to about 18 carbon atoms, and R4 and R5 they are independently hydroxyalkyl, polyhydroxyalkyl or poly (hydroxyalkyl) alkyl. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2 and R3 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably, the di-poly (hydroxyalkyl) amine has the formula:

in which R1 and R3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 22 carbon atoms, R2 is hydrocarbylene or substituted hydrocarbylene having 2 to about 18 carbon atoms, and m and n are independently integers from 1 to about 8. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2 and R3 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 and R3 are independently hydrogen or a linear or branched alkyl group having 1 to about 18 carbon atoms, R2 is a linear or branched alkylene or linear or branched alkenylene group having 2 to about 18 carbon atoms, and m and n are independently integers from 1 to about 8. More preferably, R1 and R3 are independently hydrogen or a linear or branched alkyl group having 6 to about 12 carbon atoms, R2 is a linear or branched alkylene group having 2 to about 6 carbon atoms, and m and n are independently integers from about 4 to about 8; or R1 and R3 are independently hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R2 is a linear or branched alkylene group having 2 to about 16 carbon atoms, and m and n are independently integers from about 4 to about 8. More preferably, R1 and R3 are independently hydrogen or a linear or branched alkyl group having 6 to about 12 carbon atoms, R2 is ethylene or propylene, and m and n are independently integers from about 4 to about 8; or R1 and R3 are independently hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R2 is a linear or branched alkylene group having 2 to about 12 carbon atoms, and m and n are independently integers from about 4 to about 8.

(g) quaternary poly (hydroxyalkyl) amine salts having the formula:

ES 2 269 409 T3 in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, R2 and R3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, and R4 is hydroxyalkyl, polyhydroxyalkyl, or poly (hydroxyalkyl) alkyl. In this context, the hydrocarbyl groups R1, R2 and R3 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl. Preferably, the quaternary poly (hydroxyalkyl) amine salts have the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, R2 and R3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is not greater than about 7, and p is an integer from 1 to about 8. In this context, the hydrocarbyl groups R1, R2 and R3 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R2 and R3 are independently hydrogen or a linear or branched alkyl or linear or branched alkenyl group having 1 to about 30 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, and p is an integer from about 4 to about 8; or R1, R2 and R3 are independently linear or branched alkyl or linear or branched alkenyl groups, having from about 4 to about 30 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is not more than about 7 , and p is an integer from about 4 to about 8. More preferably, R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 22 carbon atoms, R2 and R3 are independently hydrogen or a linear or branched alkyl or linear or branched alkenyl group having 1 to about 6 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is about 3 to 7, and p is an integer from about 4 to about 8; or R1, R2 and R3 are independently linear or branched alkyl or linear or branched alkenyl groups, having from about 4 to about 8 carbon atoms, m and n are independently integers from 0 to about 7, the sum of m and n is not about 3 to 7, and p is an integer from about 4 to about 8. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, R2 and R3 are independently hydrogen or methyl, m and n are independently integers from 0 to about 4, the sum of m and n is about 4, and p is an integer of about 4. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, R2 and R3 are methyl, m and n are independently integers from 0 to about 4, the sum of m and n is about 4, and p is an integer of about 4.

ES 2 269 409 T3 (h) triamines having the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms; R2, R3, R4 and R5 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R8)Mr7O) nR6; R6 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R7 in each of the groups n (R7O) is independently C2-C4 alkylene; R8 is hydrocarbylene or substituted hydrocarbylene having 1 to about 6 carbon atoms, n is an average number from 1 to about 10, ses0 or 1, and x and y are independently an integer from 1 to about 4. In this context, hydrocarbyl groups (hydrocarbylene) R1, R2, R3, R4, R5 and R8 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R2, R3, R4 and R5 are independently hydrogen, a linear or branched alkyl, or linear or branched alkenyl group having 1 to about 30 carbon atoms, or - (R7-O) nR6, R6 is hydrogen, methyl or ethyl; R7 in each of the groups n (R7O) is independently C2-C4 alkylene; n is an average number from 1 to about 10, and x and y are independently an integer from 1 to about 4. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, R2, R3, R4 and R5 are independently hydrogen, a linear or branched alkyl group having 1 to about 6 carbon atoms, or - (R7-O) nR6, R6 is hydrogen or methyl, R7 in each of the groups n (R7O) is independently ethylene or propylene; n is a mean number from 1 to about 5, and x and y are independently an integer from 1 to about 4. R1 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, R2, R3, R4 and R5 are independently hydrogen, or - (R7-O) nR6, R6 is hydrogen, R7 in each of the groups n (R7O) is independently ethylene or propylene; n is a mean number from 1 to about 5, and x and y are independently an integer from 1 to about 4. Commercially available triamines include Acros and Clariant Genamin 3119.

Another effective cationic surfactant in any of the glyphosate formulations is:

(i) diamines having the formula:

R1 - N - (R6O) and - R2 - N - R3R4 R5 (60) in which R1 , R3, R4 and R5 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R6O) xR7, R2 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently C2-C4 alkylene; R7 is hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms, and y is an average number from 3 to about 60, however provided that when R2 is ethylene, any and is greater than 4, R3, R4 and R5 are independently hydrogen, a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl group, having 1 to about 30 carbon atoms, or - (R6O) xR7, R6 is other than ethylene, or not more than one of R1, R3, R4 and R5 is alkyl or - (R6OR)xR7. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R3, R4 and R5 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1, R3, R4 and R5 are independently hydrogen or a linear or branched alkyl or alkenyl group having from about 1 to about 22 carbon atoms, or - (R6O) xR7, R2 is a linear or branched alkylene or alkenyl group having from about 1 to about 6 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently C2-C4 alkylene; R7 is hydrogen, or a linear or branched alkyl group having 1 to about 30 carbon atoms, and y is an average number of 1 to about. More preferably, R1, R3, R4 and R5 are independently hydrogen or a linear or branched alkyl group having from about 1 to about 18 carbon atoms, or - (R6O) xR7, R2 is a linear or branched alkylene group having from about 1 to about 6 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently ethylene or propylene; R7 is hydrogen, or a linear or branched alkyl group having from 1 to about 4 atto28

ES 2 269 409 T3 mos of carbon, x is a mean number from 1 to about 10, and y is a mean number from 1 to about 60. Most preferably, R1 and R3 are independently linear or branched alkyl groups having from about 8 to about 18 carbon atoms, and R4 and R5 are independently hydrogen, R2 is a linear or branched alkylene group having from about 1 to about 6 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently ethylene or propylene; R7 is hydrogen, or a straight or branched alkyl group having 1 to about 4 carbon atoms, x is an average number from 1 to about 10, and y is an average number from 10 to about 50.

(j) Quaternary mono and diammonium salts having the formula:

in which R1, R3, R4, R5, R8 and R9 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R6O) xR7, R2 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently C2-C4 alkylene; R7 is hydrogen, or a linear or branched alkyl group having 1 to about 4 carbon atoms, x is an average number from 1 to about 30, and is an average number from about 3 to about 60, and X is an acceptable anion in agriculture. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R3, R4, R5, R8 and R9 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 , R3, R4, R5, R8 and R9 are independently hydrogen or a linear or branched alkyl or alkenyl group having from about 1 to about 22 carbon atoms, or - (R6O) xR7, R2 is a linear or branched alkylene or alkenyl group having from about 1 to about 6 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently C2-C4 alkylene; R7 is hydrogen, or a linear or branched alkyl group having 1 to about 4 carbon atoms, x is an average number of 1 to about 30, and y is an average number of 1 to about 60. More preferably, R1, R3, R4, R5, R8 and R9 are independently hydrogen or a linear or branched alkyl group having from about 1 to about 18 carbon atoms, or - (R6OR)xR7, R2 is a linear or branched alkylene group having from about 1 to about 6 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently ethylene or propylene; R7 is hydrogen, or a linear or branched alkyl group having 1 to about 4 carbon atoms, x is an average number of 1 to about 10, and y is an average number of 1 to about 60. Most preferably, R1 and R3 are independently linear or branched alkyl groups having from about 8 to about 18 carbon atoms, and R4, R5, R8 and R9 are independently hydrogen or methyl, R2 is a linear or branched alkylene group having from about 1 to about 6 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently ethylene or propylene; R7 is hydrogen, or a linear or branched alkyl group having 1 to about 4 carbon atoms, x is an average number from 1 to about 4, x is an average number from 1 to about 10, and y is an average number of 10 to about 50.

Effective surfactants in the formulation of potassium, diammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine, and / or trimethylsulfonium glyphosate include the nonionic, cationic, anionic and amphoteric surfactants described below and mixtures thereof.

ES 2 269 409 T3

Effective cationic surfactants in such glyphosate formulations include:

(a) a secondary or tertiary amine having the formula:

in which R1 and R2 are hydrocarbyl having from 1 to about 30 carbon atoms, and R3 it is hydrogen or hydrocarbyl having 1 to about 30 carbon atoms. In this context, the hydrocarbyl groups R1, R2 and R3 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, and R2 and R3 they are independently hydrogen, or a linear or branched alkyl or linear or branched alkenyl group having from 1 to about 6 carbon atoms. More preferably, R1 is a straight or branched alkyl group having 12 to about 22 carbon atoms, and R2 and R3 they are independently hydrogen, methyl or ethyl. In one embodiment of the amine of formula (CC), R1 is a straight or branched alkyl group having from about 12 to about 22 carbon atoms, and R2 and R3 they are independently linear or branched hydroxyalkyl groups having 1 to about 6 carbon atoms.

In one embodiment, the surfactant has formula (48) where R1 is hydrocarbyl or substituted hydrocarbyl having from about 8 to about 30 carbon atoms, R2 is a hydroxyalkyl, polyhydroxyalkyl or poly (hydroxyalkyl) alkyl group, and R3 is hydrogen, hydroxyalkyl, polyhydroxyalkyl or poly (hydroxyalkyl) alkyl. In this context, the hydrocarbyl groups R1 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. In one embodiment, R1 is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl group having from about 8 to about 30 carbon atoms, R2 is a linear or branched hydroxyalkyl group having 1 to about 6 carbon atoms, and R3 it is hydrogen, or a linear or branched hydroxyalkyl group having 1 to about 6 carbon atoms. Preferably R1 is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl group having from about 8 to about 22 carbon atoms, R2 is a linear or branched hydroxyalkyl group having 1 to about 4 carbon atoms, and R3 it is hydrogen, or a linear or branched hydroxyalkyl group having 1 to about 4 carbon atoms. More preferably, R1 is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl group having from about 8 to about 18 carbon atoms, R2 is hydroxymethyl or hydroxyethyl, and R3 it is hydrogen, hydroxymethyl or hydroxyethyl.

In one embodiment, secondary and tertiary amines are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine glyphosate. , hexamethylenediamine, dimethylamine, or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360,400,420,440, 460, 480, 500, 520 or 540 g ea / l.

(b) monoalkoxylated amines having the formula:

in which R1 and R4 are independently hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or -R5MR6, R2 in each of the groups x (R2O) is independently alkylene C2-C4, R3 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R5 is a straight or branched alkyl group having from about 6 to about 30 carbon atoms, R6 is a hydrocarbyl or substituted hydrocarbyl group having from 4 to about 15 carbon atoms, and x is an average number from 1 to about 60. In this context, the hydrocarbyl groups R1, R4 and R6 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. In one embodiment, R1 includes from about 7 to about 30 carbon atoms, preferably from about 8 to about 22 carbon atoms, and the remainder of the groups are as described above. Preferably R1 and R4 are independently a linear or branched alkyl or linear or branched alkenyl group having 1 to about 25 carbon atoms, R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R3 is hydrogen, methyl, or ethyl, and x is an average number from 1 to about

ES 2 269 409 T3

40. More preferably, R1 and R4 are independently a linear or branched alkyl group having 1 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is an average number from 1 to about 30. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms and R4 is a straight or branched alkyl group having 1 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is an average number from 1 to about 10. Most preferably, R1 is a linear or branched alkyl group having from about 16 to about 22 carbon atoms and R4 is methyl, R2 in each of the groups x (R2O) is ethylene, R3 is hydrogen, and x is an average number from 1 to about 5, or R1 is a straight or branched alkyl group having from about 8 to about 15 carbon atoms and R4 is methyl, R2 in each of the groups x (R2O) is ethylene, R3 is hydrogen, and x is an average number from about 5 to about 10.

In one embodiment, monoalkoxylated amines are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing glyphosate potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360, 400, 420, 440, 460,480, 500, 520 or 540 g ea / l.

in which R1 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently C2-C4 alkylene, R3 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R4 is hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, x and y are independently an average number of 1 to about 40, and X- it is an acceptable anion in agriculture. In this context, the hydrocarbyl groups R1 and R4 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1 and R4 are independently a linear or branched alkyl or linear or branched alkenyl group having 1 to about 25 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently C2-C4 alkylene, R3 is hydrogen, methyl, or ethyl, and the sum of x and y is an average number from about 2 to about 30. More preferably, R1 and R4 are independently a linear or branched alkyl group having 1 to about 22 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and the sum of x and y is an average number from about 2 to about 20. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms and R4 is a straight or branched alkyl group having 1 to about 22 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is an average number from about 2 to about 20. Most preferably, R1 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms and R4 is a straight or branched alkyl group having 1 to about 6 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is an average number from about 2 to about 15, or R1 and R4 are independently a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R2 in each of the groups x (R2O) ey (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is an average number from about 5 to about 15. Preferred dialkoxylated quaternary ammonium surfactants include Ethoquad® C12 (a PEG-2-cocomethylammonium chloride from Akzo Nobel), PEG-5-cocomethylammonium chloride, PEG-5-sebomethylammonium chloride, PEG-5-ditallowammonium bromide and PEG-10-ditallowammonium bromide.

In one embodiment, the dialkoxylated quaternary ammonium salts are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine glyphosate. , hexamethylenediamine, dimethylamine, or trimethylsulfonium

ES 2 269 409 T3 and mixtures thereof, containing at least about 20% by weight glyphosate ae, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360, 400, 420, 440, 460, 480, 500, 520 or 540 g of ae / l.

(d) monoalkoxylated quaternary ammonium salts having the formula:

in which R1 and R5 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, R4 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R3 is hydrogen or a linear or branched alkyl group having 1 to about 30 carbon atoms, x is an average number of 1 to about 60, and X- it is an acceptable anion in agriculture. In this context, the hydrocarbyl groups R1, R4 and R5 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1, R4 and R5 are independently a linear or branched alkyl or linear or branched alkenyl group having 1 to about 25 carbon atoms, R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R3 is hydrogen, methyl, or ethyl, and x is an average number from 1 to about 40. More preferably, R1, R4 and R5 are independently a linear or branched alkyl group having 1 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is an average number from 1 to about 30. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, R4 and R5 are independently linear or branched alkyl having from about 1 to about 22 carbon atoms and x is an average number from 1 to about 30. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, R4 and R5 are independently linear or branched alkyl having 1 to about 6 carbon atoms and x is an average number of about 5 to about 25. Most preferably, R1 is a straight or branched alkyl group having from about 16 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, R4 and R5 are independently linear or branched alkyl having 1 to about 3 carbon atoms and x is an average number of about 5 to about 25. Preferred monoalkoxylated quaternary ammonium surfactants include PEG-7- (C18) -dimethylammonium and PEG-22- (C18) -dimethylammonium.

In one embodiment, the monoalkoxylated quaternary ammonium salts are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine glyphosate. , hexamethylenediamine, dimethylamine or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360,400,420,440,460,480, 500, 520 or 540 g ea / l.

(e) quaternary ammonium salts having the formula:

ES 2 269 409 T3 in which R1 , R3 and R4 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R2 is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, and X- it is an acceptable anion in agriculture. In this context, the hydrocarbyl groups R1, R2, R3 and R4 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1, is a linear or branched alkyl or linear or branched alkenyl group having from 8 to about 30 carbon atoms, and R2, R3 and R4 they are independently a linear or branched alkyl or linear or branched alkenyl group having from 1 to about 30 carbon atoms. More preferably, R1 is a linear or branched alkyl or linear or branched alkenyl group having from 8 to about 22 carbon atoms, and R2, R3 and R4 they are independently a linear or branched alkyl or linear or branched alkenyl group having 1 to about 6 carbon atoms. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 16 carbon atoms, and R2, R3 and R4 they are independently linear or branched alkyl having from about 1 to about 6 carbon atoms. Most preferably, R1 is a straight or branched alkyl group having from 8 to about 14 carbon atoms, and R2, R3 and R4 they are methyl. Preferred commercially available quaternary ammonium surfactants include Arquad® C-50 (a dodecyltrimethylammonium chloride from Akzo Nobel) and Arquad® T-50 (a tallow-trimethylammonium chloride from Akzo Nobel).

In one embodiment, the quaternary ammonium salts are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing glyphosate potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine, or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360, 400, 420, 440, 460,480, 500, 520 or 540 g ea / l.

(f) ether-amines having the formula:

in which R1 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms; R2 is hydrocarbyl or substituted hydrocarbyl having from 2 to about 30 carbon atoms; R3 and R4 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R5O) xR6, R5 in each of the groups x (R5O) is independently C2-C4 alkylene, R6 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, and x is an average number of 1 to about 50. In this context, hydrocarbyl (hydrocarbylene) groups R1, R2, R3 and R4 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl group having from 8 to about 25 carbon atoms, R2 is a linear or branched alkylene or alkenylene group having 2 about 30 carbon atoms, R3 and R4 are independently hydrogen, a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl group having from 1 to about 30 carbon atoms, or - (R5O) xR6, R5 in each of the groups x (R5O) is independently C2-C4 alkylene, R6 is hydrogen, methyl, or ethyl, and x is an average number from 1 to about 30. More preferably, R1 is a linear or branched alkyl or alkenyl group, having from 8 to about 22 carbon atoms, R2 is a linear or branched alkylene or alkenylene group having from 2 to about 6 carbon atoms, R3 and R4 are independently hydrogen, a linear or branched alkyl or alkenyl group, having 1 to about 6 carbon atoms, or - (R5OR)xR6, R5 in each of the groups x (R5O) is independently ethylene or propylene, R6 is hydrogen or methyl, and x is an average number from 1 to about 15. Most preferably, R1 is a linear or branched alkyl or alkenyl group, having from 8 to about 18 carbon atoms, R2 is ethylene or propylene, R3 and R4 are independently hydrogen, methyl, or - (R5O) xR6, R5 in each of the groups x (R5O) is independently ethylene or propylene, R6 is hydrogen, and x is an average number from 1 to about 5.

In one embodiment, ether amines are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing glyphosate potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine. or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360, 400, 420, 440, 460, 480, 500, 520 or 540 g ea / l.

ES 2 269 409 T3 (g) diamines having the formula:

in which R1, R3, R4 and R5 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R6O) xR7; R2 and R8 are independently hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms, R6 in each of the groups x (R6O) ey (R6O) is independently C2 -C alkylene4; R7 is hydrogen or a linear or branched alkyl group having 1 to about 30 carbon atoms, x is an average number of 1 to about 30, X is -O-, -N (R6) -, -C (O) -, -C (O) O-, -N (R9) C (O) -, -C (O) N (R9) -, -S-, -SO-, or -SO2-, y is 0 or an average number from 1 to about 30, n and z are independently 0 or 1, and R9 it is hydrogen or hydrocarbyl or substituted hydrocarbyl. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R3, R4, R5 and R6 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 and R4 are independently a linear or branched alkyl or linear or branched alkenyl group having from about 1 to about 22 carbon atoms, R2 and R8 are independently linear or branched alkylene groups having from about 2 to about 25 carbon atoms, R3 and R5 are each independently hydrogen or a linear or branched alkyl group having from about 1 to about 6 carbon atoms, and n, y, and z are 0; R1, R2, R3 and R4 are independently hydrogen or a linear or branched alkyl or alkenyl group having from about 1 to about 6 carbon atoms, R2 is a linear or branched alkylene or alkenylene group having from about 8 to about 25 carbon atoms, and n, y, and z are 0; or R1, R2, R3 and R4 are independently hydrogen or a linear or branched alkyl or alkenyl group having from about 1 to about 6 carbon atoms, R2 is a linear or branched alkylene or alkenylene group having from about 1 to about 6 carbon atoms, R6 in each of the groups and (R6O) is independently C2C4 alkylene, and is an average number from 1 to about 20, and n and z are 0; or R1 and R3 are independently a linear or branched alkyl or linear or branched alkenyl group, having from 8 to about 22 carbon atoms, R2 is a linear or branched alkylene group having from about 2 to about 25 carbon atoms; and R4 and R5 are independently hydrogen, a linear or branched alkyl or alkenyl group, having 1 to about 6 carbon atoms, or - (R6O) xR7, R6 in each of the groups x (R6O) is independently C2-C4 alkylene, R7 is hydrogen, or a linear or branched alkyl group having 1 to about 4 carbon atoms, x is an average number of 1 to about 30, and n, y, and z are 0; or R1 is a linear or branched alkyl or linear or branched alkenyl group, having from about 1 to about 22 carbon atoms, R2 is a linear or branched alkylene group having from about 2 to about 25 carbon atoms, R3, R4 and R5 are each independently hydrogen or a linear or branched alkyl group having 1 to about 6 carbon atoms, X is -C (O) - or -SO2-m, and n and z are 0 and z is 1. More preferably, R1 and R4 are independently a linear or branched alkyl or linear or branched alkenyl group, having from about 4 to about 18 carbon atoms, R2 is a linear or branched alkylene group having from about 2 to about 6 carbon atoms, and R3 and R5 are each independently hydrogen or a linear or branched alkyl group having 1 to about 6 carbon atoms, and n and z are 0; or R1, R2, R3 and R4 are independently hydrogen or a linear or branched alkyl group having from about 1 to about 6 carbon atoms, R2 is a linear or branched alkylene group having from about 8 to about 25 carbon atoms, and y is 0; or R1 , R2, R3 and R4 are independently hydrogen or a linear or branched alkyl group having from about 1 to about 6 carbon atoms, R2 is a linear or branched alkylene group having from about 1 to about 6 carbon atoms, R6 in each of the groups and (R6O) is independently ethylene or propylene, and is an average number from 1 to about 10 and n and z is 0; or R1 and R3 are independently a linear or branched alkyl group having from about 8 to about 22 carbon atoms, R2 is a linear or branched alkylene group having from about 2 to about 6 carbon atoms, and R4 and R5 are each independently hydrogen or a linear or branched alkyl group having from 1 to about 6 carbon atoms, or - (R6O) xR7, R6 in each of the groups x (R6O) is independently ethylene or propylene, R2 is hydrogen or methyl, x is an average number from 1 to about 15, and n, y, and z are 0; or R1 is a straight or branched alkyl group having from about 1 to about 22 carbon atoms, R2 is a linear or branched alkylene group having from about 2 to about 6 carbon atoms, R3, R4 and R5 are each independently hydrogen, X is -C (O) - or -SO2-, n, and y are 0 and z is 1. Preferred diamines include Gemini 14-2-14, Gemini 14-3-14, Gemini 10-2-10, Gemini 10-3-10, Gemini 10-4-10, and Gemini 16-2-16 (C10, C14 or C16-ethylene, propylene or butylene-N-methyl diamines from Monsanto), Ethoduomeens® and Jeffamine® EDR-148.

In one embodiment, diamines are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing glyphosate potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine. or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of glyphosate ae, more preferably at least about34

ES 2 269 409 T3 25%, 30%, 35%, 40%, 45%, 50% or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360, 400, 420, 440, 460, 480, 500, 520 or 540 g ea / l.

(h) amine oxides having the formula:

R1 - N + - R3R2 (70) in which R1, R2 and R3 are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl, or - (R4OR)xR5, or

-R6 (OR4 ) xOR5; R4 in each of the groups x (R4 O) is independently C2-C alkylene4, R5 is hydrogen or a linear or branched alkyl group having 1 to about 30 carbon atoms, R6 is hydrocarbyl or substituted hydrocarbyl having 2 to about 6 carbon atoms, x is an average number of 1 to about 50, and the total number of carbon atoms in R1, R2 and R3 is at least 8. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R3 and R6 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 and R2 are independently hydrogen, a linear or branched alkyl, or linear or branched alkenyl group having 1 to about 30 carbon atoms, or - (R4O) xR5; R3 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R4 in each of the groups x (R4O) is independently C2 -C4 alkylene; R5 is hydrogen, methyl, or ethyl, and x is an average number from 1 to about 30. More preferably, R1 and R2 are independently hydrogen, or a linear or branched alkyl group having 1 to about 6 carbon atoms, and R3 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms; or R1 and R2 are independently - (R4O) xR5; R3 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms, R4 in each of the groups x (R4O) is independently ethylene or propylene; R5 is hydrogen or methyl, and x is an average number from 1 to about 10. More preferably, R1 and R2 are independently methyl, and R3 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms; or R1 and R2 are independently - (R4O) xR5; R3 is a straight or branched alkyl group having from about 8 to about 18 carbon atoms, R4 in each of the groups x (R4O) is ethylene or propylene; R5 is hydrogen, and x is an average number from 1 to about 5. Commercially available amine oxide surfactants include Chemoxide L70.

In one embodiment, amine oxides are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing glyphosate potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine. or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360, 400, 420, 440, 460, 480, 500, 520 or 540 g ea / l.

(h) dialkoxylated amines having the formula:

(R2OR)XR3 (F ^ OJyR3 in which R1 is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl group having from about 6 to about 30 carbon atoms, or -R4SH, R2 in each of the groups x (R2O) and and (R2O) is independently C2-C4 alkylene; R3 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, R4 is a straight or branched alkyl group having from about 6 to about 30 carbon atoms, and x and y are independently an average number from 1 to about 40. Preferably, R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R2 in each of the groups x (R2O) and and (R2O) is independently C2-C4 alkylene. R3 is hydrogen, methyl, or ethyl, and x and y are independently an average number from 1 to about 20. More preferably, R1 is a straight or branched alkynyl group having from about 8 to about 25 carbon atoms, R2 in each of the groups x (R2O) and and (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x and y are independently an average number from 1 to about 10. Even more preferably, R1 is a straight or branched alkyl group having from about 8 to about 22 carbon atoms, R2 in each

ES 2 269 409 T3 one of the groups x (R2O) and and (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x and y are independently an average number from 1 to about 5. Commercially available dialkoxylated amines include Trymeen® 6617 (from Cognis) and Ethomeen® C / 12, C / 15, C / 20, C / 25, T / 12, T / 15, T / 20 and T / 25 (from Akzo Nobel).

Said dialkoxylated amines are preferably used in glyphosate potassium concentrates containing at least 550 grams of ae per liter of glyphosate potassium, and more preferably at least 560, 570 or 580 grams of ae per liter of glyphosate potassium. It is preferred that such glyphosate potassium concentrates contain from about 550 to about 600 grams of ae per liter of glyphosate potassium.

Alternatively, the dialkoxylated amines are preferably formulated in potassium glyphosate concentrates that contain at least 320 grams of ae per liter of potassium glyphosate, that do not have alkyl polyglycosides, or that only contain alkyl polyglycosides that have a light color less than 10, preferably less than 9, 8, 7, 6 or 5 measured using a Gardner colorimeter. In one embodiment, said concentrates include at least 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 430, 460, 470, 480, 490, 500, 510, 520, 530 , 540, 550,560, 570 or 580 grams of ae per liter of potassium glyphosate. It is preferred that such potassium glyphosate concentrates contain from about 400 to about 600 grams of ea per liter of potassium glyphosate, more preferably about 450 to about 600, about 500 to about 600, about 540 to about 600, or about 550 to about 600 grams of ae per liter of potassium glyphosate.

Alternatively, the dialkoxylated amines are preferably incorporated into potassium glyphosate concentrates containing from about 20 to about 130 grams per liter. In another embodiment, the dialkoxylated amines are incorporated into potassium glyphosate concentrates containing from about 20 to about 150 grams per liter of total surfactant in the formulation and at least 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 430, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550,560, 570, or 580 grams of ae per liter of potassium glyphosate. It is preferred that such potassium glyphosate concentrates contain from about 400 to about 600 grams of ae per liter of potassium glyphosate, more preferably from about 450 to about 600, from about 500 to about 600, from about 540 to about 600, or from about 550 to about 600 grams of ae per liter of potassium glyphosate.

and (j) amino alkoxylated alcohols having the following chemical structure:

in which R1, R7, R8 and R9 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having from about 1 to about 30 carbon atoms, - (R11)MR3O) VR10; X is -O-, -OC (O) -, -C (O) O-, -N (R12) C (O) -, -C (O) N (R12) -, -S-, -SO-, -SO2- or -N (R9) -; R3 in each of the groups n (R3O) and the groups v (R3O) is independently C2-C4 alkylene; R10 is hydrogen, or a linear or branched alkyl group having from about 1 to about 30 carbon atoms; n is an average number from 1 to about 60; v is an average number from 1 to about 50; R2 and R11 are each independently hydrocarbylene or substituted hydrocarbylene having 1 to about 6 carbon atoms; R6 is hydrocarbylene or substituted hydrocarbylene having 2 to about 6 carbon atoms; R12 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 2 to about 30 carbon atoms, -C (= NR12) -, -C (S) - or -C (O) -; q is an integer from 0 to 5; and R5 it is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R4, R5, R6, R7, R8, R9, R11 and R12 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups.

In one embodiment, the amino and alkoxylated alcohols are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing glyphosate potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine, or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360,400,420,440, 460, 480, 500, 520 or 540 g ea / l.

ES 2 269 409 T3

A subclass of such cationic surfactants includes a monoalkoxylated amine having the formula:

in which R1 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R2 in each of the groups x (R2O) and and (R2O) is independently C2-C4 alkylene; R3 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms; R4 and R5 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having from 1 to about 30 carbon atoms, - (R6). - (R2O) and R7, or R4 and R5 together with the nitrogen atom to which they are attached, they form a cyclic or heterocyclic ring; R6 is hydrocarbylene or substituted hydrocarbylene having 1 to about 30 carbon atoms; R7 is hydrogen, or a linear or branched alkyl group having from about 1 to about 4 carbon atoms, nes0 or 1, x and y are independently an average number from 1 to about 60. In this context, hydrocarbyl (hydrocarbylene) groups R1, R3, R4, R5 and R6 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 25 carbon atoms, R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R4 and R5 are independently hydrogen or a linear or branched alkyl group having 1 to about 6 carbon atoms, and x is an average number of 1 to about 30. More preferably, R1 is a straight or branched alkyl group having from about 12 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is a linear or branched alkylene group having from 2 to about 6 carbon atoms, R4 and R5 are independently hydrogen, methyl, or tris (hydroxymethyl) methyl, and x is an average number from about 2 to about 30. Even more preferably, R1 is a straight or branched alkyl group having from about 12 to about 18 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is ethylene or propylene, R4 and R5 are independently hydrogen, methyl, or tris (hydroxymethyl) methyl, and x is an average number from about 4 to about 20. More preferably, R1 is a straight or branched alkyl group having from about 12 to about 18 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is ethylene, R4 and R5 are methyl, and x is an average number from about 4 to about 20. Preferred monoalkoxylated amines include PEG 13 or 18-C14-15 ether-propylamines and PEG 7, 10, 15, or 20-C16-18-ether-propylamines (from Tomah) and PEG 13 or 18-C14-15-ether-dimethyl-propylamines and PEG 10, 15 or 20 or 25-C16-18-ether dimethylpropylamines (from Tomah) and Surfonic® AGM-550 from Huntsman.

Quaternary ammonium, sulfonium, and sulfoxonium salts are also effective cationic surfactants in the formation of potassium glyphosate concentrates, and they have a chemical structure:

ES 2 269 409 T3 (76)

,m- (R3Of „—R4- (NR ')what—N + —R8 A '(77) in which R1, R7, R8, R9, R10 and R11 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R13)MR3O) VR12; X is -O-, -OC (O) -, -N (R14) C (O) -, -C (O) N (R14) -, -C (O) O- or -S-, -SO-; R3 in each of the groups n (R3O) and the groups v (R3O) is independently C2-C4 alkylene; R12 is hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms; n is an average number from 1 to about 60; v is an average number from 1 to about 50; R2 and R13 are each independently hydrocarbylene or substituted hydrocarbylene having 1 to about 6 carbon atoms; mys are each independently 0 or 1; R4 is hydrocarbylene or substituted hydrocarbylene having 2 to about 6 carbon atoms; R6 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms; -C (= NR12) -, -C (S) - or -C (O) -; R14 is hydrogen or hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, q is an integer from 0 to 5; and R5 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; and each A- it is an acceptable anion in agriculture. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R2, R4, R5, R6, R7, R8, R9, R10, R11, R13 and R14 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups.

Another effective cationic surfactant in any glyphosate formulations is a diamine or diammonium salt having the formula:

Ri- - f

- <R2-Q) n— R4 (78) σ9) where R1 , R4, R5, R6, R7 and R8 they are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R2 in each of the groups m (R2O) and n (R2O) and R9 is independently C2-C4 alkylene; R3 is hydrocarbylene or substituted hydrocarbylene having approximately

ES 2 269 409 T3 to about 6 carbon atoms or - (R2OR)pR9-, m and n are individually an average number from 0 to about 50, and p is an average number from 0 to about 60. In this context, the hydrocarbyl (hydrocarbylene) groups R1, R3, R4, R5, R6, R7 and R8 preferred are straight or branched alkyl (alkylene), straight or branched alkenyl (alkenylene), straight or branched alkynyl (alkynylene), aryl (arylene) or aralkyl (aralkylene) groups. In one embodiment of formula (DA), R3 is hydrocarbylene having from about 2 to about 6 carbon atoms, and the rest of the groups are as defined above.

Preferred nonionic surfactants for such glyphosate concentrates include alkoxylated alcohols having the formula:

R1O - (R2OR)xR3 (80) in which R1 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms; R2 in each of the groups x (R2O) is independently C2-C4 alkylene; R3 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, and x is an average number of 1 to about 60. In this context the hydrocarbylene groups R1 preferred are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl groups. Preferably R1 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R2 in each of the groups x (R2O) is independently alkylene C2 -C4; R3 is hydrogen, methyl, or ethyl, and x is an average number from about 5 to about 50. More preferably, R1 is a straight or branched alkyl group having from about 8 to about 25 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene; R3 is hydrogen or methyl, and x is an average number from about 8 to about 40. Even more preferably, R1 is a straight or branched alkyl group having from about 12 to about 22 carbon atoms, R2 in each of the groups x (R2 O) is independently ethylene or propylene; R3 is hydrogen or methyl, and x is an average number from about 8 to about 30. Preferred commercially available alkoxylated alcohols include Procol® LA-15 (ex Portameen), Brij® 35, Brij® 76, Brij® 78, Brij® 97 and Brij® 98 (from Sigma Chemical Co), Neodol® 25-12 (from Shell), Hexotol® CA-10, Hexotol® CA-20, Hexotol® CS-9, Hexotol® CS-15, Hexotol® CS- 20, Hexotol® CS-25, Hexotol® CS-30, and Plurafac® A38 (from BASF), ST-8303 (from Cognis), CS-30, and Arosurf® 66 E20 (from Witco / Crompton).

In one embodiment, the alkoxylated alcohols are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing glyphosate potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360, 400, 420, 440, 460,480, 500, 520 or 540 g ea / l.

Other nonionic surfactants for use in such glyphosate formulations include alkoxylated dialkylphenols having the formula:

in which R1 and R4 are independently hydrogen or a linear or branched alkyl group having from 1 to about 30 carbon atoms and at least one of R1 and R4 is an alkyl group, R2 in each of the groups x (R2O) is independently C2-C4 alkylene, R3 is hydrogen, methyl, or ethyl, and x is an average number from about 5 to about 50. More preferably, R1 and R4 are independently linear or branched alkyl groups having from about 8 to about 22 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is an average number from about 8 to about 40. Even more preferably, R1 and R4 are independently linear or branched alkyl groups having from about 8 to about 16 carbon atoms, R2 in each of the groups x (R2O) is independently ethylene or propylene, R3 is hydrogen or methyl, and x is a number

ES 2 269 409 T3 means from about 10 to about 30. Preferred commercially available alkoxylated dialkylphenols include ethoxylated dinonyl phenols such as Surfonic® DNP 100, Surfonic® DNP 140 and Surfonic® DNP 240 (ex Huntsman).

In one embodiment, phenols are included in glyphosate concentrates other than IPA glyphosate, such as glyphosate concentrates containing potassium, di-ammonium, ammonium, sodium, monoethanolamine, n-propylamine, methylamine, ethylamine, hexamethylenediamine, dimethylamine. or trimethylsulfonium and mixtures thereof, containing at least about 20% by weight of ea of glyphosate, more preferably at least about 25%, 30%, 35%, 40%, 45%, 50%, or 55% by weight of ae, or at least about 270 g of glyphosate ae per liter, more preferably at least 300, 360,400,420, 440, 460, 480, 500, 520 or 540 g ea / l.

Preferred anionic surfactants effective in forming potassium glyphosate formulations include saturated carboxylic acids such as butyric, caproic, caprylic, capric, lauric, palmitic, myristic, or stearic acid, and unsaturated carboxylic acids such as palmitic, oleic, or stearic acid. Preferred carboxylic acids include palmitic, oleic, or stearic acid. Other preferred anionic surfactants include alkyl sulfate such as sodium lauryl sulfate, and alkoxylated alkyl phosphates having the formula:

in which R1 and R3 they are independently a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl or aralkyl group having from about 4 to about 30 carbon atoms; R2 in each of the groups m (R2O) and the n (R2O) is C2-C4 alkylene form; ymyn are independently from 1 to about 30; or

in which R1 is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl group having from about 8 to about 30 carbon atoms; R2 in each of the groups m (R2O) is in alkylene form C2-C4; and m is from 1 to about 30. Representative alkoxylated alkyl phosphates include oleth-10 phosphate, oleth-20 phosphate, and oleth-25 phosphate.

Exemplary surfactants that can be used in accordance with the present invention include the following species:

ES 2 269 409 T3

Either in aqueous concentrated formulations or in dry formulations of the present invention, the ratio (by weight) of the ea of glyphosate to surfactant typically is in the range of about 1: 1 to about 20: 1, preferably about 2: 1 to about 10: 1, more preferably about 2: 1 to about 8: 1, still more preferably about 2 : 1 to about 6: 1, and still more preferably from about 3: 1 to about 6: 1.

The density of any glyphosate-containing formulation of the formulation of the invention is preferably at least 1,210 grams / liter, more preferably at least about 1,215, 1,220, 1,225, 1,230, 1,235, 1,240, 1,245, 1,250, 1,255, 1,260, 1,265, 1,270, 1,275, 1,280, 1,285, 1,290, 1,295, 1,300, 1,305, 1,310, 1,315, 1,320, 1,325, 1,330, 1,335, 1,340, 1,345, 1,350, 1,355, 1,360, 1,365, 1,370, 1,375, 1,380,1,385, 1,390, 1,395, 1,400, 1,405, 1,410, 1,415, 1,420, 1,425, 1,430, 1,435, 1,440, 1,445, or 1,450 grams / liter.

As discussed in more detail herein, other additives, adjuvants, or ingredients may be introduced into the formulations in the formulation of the present invention to improve certain properties of the resulting formulations. Although the formulations of the present invention generally show good overall stability and viscosity properties without the addition of any additional additives, the addition of a solubilizer (also commonly referred to as a cloud point enhancer or stabilizer) can significantly improve the properties of the compounds. formulations of the present invention. Stabilizers suitable for use with the new formulations of the present invention include, for example, cocoamine (Armeen C), dimethylcocoamine (Arquad DMCD), cocoammonium chloride (Arquad C), PEG 2-cocoamine (Ethomeen C12), PEG 5- tallow-amine (Ethomeen T15), and PEG 5-cocoamine (Ethomeen C15), all manufactured by Akzo Nobel (California).

Additionally, the addition of a (C4 to C16) alkyl or aryl amine compound, or the corresponding quaternary ammonium compound, has been found to greatly enhance the compatibility of certain glyphosate salts (e.g., potassium or isopropylamine) with surfactants that otherwise have low or negligible compatibility with a given glyphosate loading. Suitable alkyl or aryl amine compounds may also contain 0 to about 5 EO groups. Preferred alkylamine compounds include (C6 to C12) alkyl amines having 0 to 2 EO groups. Likewise, ether amine compounds having 4 to 12 carbons and 0 to about 5 EO groups, as well as the corresponding quaternary ammonium compounds, also enhance the compatibility of such formulations. In one embodiment, compounds that enhance the compatibility of said surfactants include amines or quaternary ammonium salts having the formulas:

ES 2 269 409 T3

in which R1 is a linear or branched alkyl or aryl having from about 4 to about 16 carbon atoms, R2 is hydrogen, methyl, ethyl or - (CH2CH2O) xH, R3 is hydrogen, methyl, ethyl, or - (CH2CH2O) and H in which the sum of X and y is not more than about 5; R4 is hydrogen or methyl; R6 is hydrocarbylene or substituted hydrocarbylene having 2 to about 6 carbon atoms; and A- is an agriculturally acceptable anion.

The present invention also provides a herbicidal method which comprises diluting a herbicidally effective volume of a composition as provided herein with a suitable volume of water to form an application composition, and applying the application composition to the foliage of a plant or plants. Definitions

The terms "hydrocarbon" and "hydrocarbyl" as used herein describe organic compounds or radicals consisting exclusively of the elements carbon and hydrogen. These moieties include alkyl, alkenyl, alkynyl, and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl, and alkynyl. Unless otherwise indicated, these moieties preferably comprise 1 to 30 carbon atoms.

The term "hydrocarbylene" as used herein describes radicals attached at both ends to other radicals in an organic compound, and consisting exclusively of the elements carbon and hydrogen. These moieties also include alkyl, alkenyl, alkynyl, and aryl groups substituted with other aliphatic or cyclic groups, such as alkaryl, alkenaryl, and alkynyl. Unless otherwise indicated, these moieties preferably comprise 1 to 30 carbon atoms.

The "substituted hydrocarbyl" moieties described herein are hydrocarbyl moieties that are substituted with at least one atom other than carbon, including moieties in which a carbon chain atom is replaced by a heteroatom such as a nitrogen atom, oxygen, silicon, phosphorus, boron, sulfur, or halogen. These substituents include halogen, heterocycle, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected hydroxy, ketal, acyl, acyloxy, nitro, amino, amido, cyano, thiol, acetal, sulfoxide, ester, thioester, ether, thioether, hydroxyalkyl, urea, guanidine, amidine, phosphate, amine oxide, and quaternary ammonium salts.

The "substituted hydrocarbylene" moieties described herein are hydrocarbylene moieties that are substituted with at least one atom other than carbon, including moieties in which a carbon atom in the chain is replaced by a hetero atom such as a nitrogen atom, oxygen, silicon, phosphorus, boron, sulfur, or halogen. These substituents include halogen, heterocycle, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected hydroxy, ketal, acyl, acyloxy, nitro, amino, amido, cyano, thiol, acetal, sulfoxide, ester, thioester, ether, thioether, hydroxyalkyl, urea, guanidine, amidine, phosphate, amine oxide, and quaternary ammonium salts.

Unless otherwise indicated, the alkyl groups described herein are preferably lower alkyl containing from one to 18 main chain carbon atoms and up to 30 carbon atoms. They can be straight or branched chain or cyclic, and include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, hexyl, 2-ethylhexyl, and the like.

ES 2 269 409 T3

Unless otherwise indicated, the alkenyl groups described herein are preferably lower alkenyl containing from two to 18 carbon atoms in the main chain and up to 30 carbon atoms. They can be straight or branched chain or cyclic, and include ethenyl, propenyl, isopropenyl, n-butenyl, isobutenyl, hexenyl, and the like.

Unless otherwise indicated, the alkynyl groups described herein are preferably lower alkynyl containing from two to 18 carbon atoms in the main chain and up to 30 carbon atoms. They can be straight or branched chain, and include ethynyl, propynyl, butynyl, isobutynyl, hexynyl, and the like.

The term "aryl" as used herein, alone or as part of another group indicates optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing 6 to 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. Phenyl and substituted phenyl are the most preferred aryl.

The term "aralkyl" as used herein indicates a group containing both alkyl and aryl structures such as benzyl.

As used herein, alkyl, alkenyl, alkynyl, aryl, and aralkyl groups can be substituted with at least one atom other than carbon, including moieties in which one atom in the carbon chain is substituted for such a heteroatom. such as nitrogen, oxygen, silicon, phosphorus, boron, sulfur or a halogen atom. These substituents include hydroxy, nitro, amino, amido, nitro, cyano, sulfoxide, thiol, thioester, thioether, ester and ether, or any other substituent that can increase the compatibility of the surfactant and / or its enhancement of the effectiveness in the formulation of potassium glyphosate without adversely affecting the storage stability of the formulation.

The term "halogen" or "halo" as used herein, alone or as part of another group, refers to chlorine, bromine, fluorine, and iodine. Fluoro substituents are often preferred in surface active compounds.

Unless otherwise indicated, the term "hydroxyalkyl" includes alkyl groups substituted with at least one hydroxy group, and includes bis (hydroxyalkyl) alkyl, tris (hydroxyalkyl) alkyl, and poly (hydroxyalkyl) alkyl groups. Preferred hydroxyalkyl groups include hydroxymethyl (-CH2OH), and hydroxyethyl (-C2H4OH), bis (hydroxymethyl) methyl (-CH (CH2OH) 2), and tris (hydroxymethyl) methyl (-C (CH2OH) 3).

The term "cyclic" as used herein, alone or as part of another group indicates a group that has at least one closed ring, and includes alicyclic, aromatic (arene), and heterocyclic groups.

The terms "heterocycle" or "heterocyclic" as used herein, alone or as part of another group, indicate fully saturated or unsaturated, optionally substituted, aromatic or non-aromatic, monocyclic or bicyclic groups having at least one heteroatom. in at least one ring, and preferably 5 or 6 atoms in each ring. The heterocyclic group preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms, and / or 1 to 4 nitrogen atoms in the ring, and may be attached to the rest of the molecule by a carbon or heteroatom. Exemplary heterocycles include heteroaromatics such as furyl, thienyl, pyridyl, oxazolyl, pyrrolyl, indolyl, quinolinyl, or isoquinolinyl) and the like, and non-aromatic heterocycles such as tetrahydrofuryl, tetrahydrothienyl, piperidinyl, pyrrolidino, etc. Exemplary substituents include one or more of the following groups: hydrocarbyl, substituted hydrocarbyl, keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro, cyano, thiol, thioester , thioether, ketal, acetal, ester and ether.

The term "heteroaromatic" as used herein, alone or as part of another group indicates optionally substituted aromatic groups having at least one heteroatom in at least one ring, and preferably 5 or 6 atoms in each ring. The heteroaromatic group preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms and / or 1 to 4 nitrogen atoms in the ring, and can be attached to the rest of the molecule by a carbon or heteroatom. Exemplary heteroaromatics include furyl, thienyl, pyridyl, oxazolyl, pyrrolyl, indolyl, quinolinyl, or isoquinolinyl and the like. Exemplary substituents include one or more of the following groups: hydrocarbyl, substituted hydrocarbyl, keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro, cyano, thiol, thioether , thioester, ketal, acetal, ester and ether.

The term "acyl" as used herein, alone or as part of another group indicates the residue formed by removal of the hydroxyl group from the -COOH group of an organic carboxylic acid, e.g. e.g., R (C (O) -, where R is R1, R1O-, R1R2N- or R1MR1 is hydrocarbyl, heterosubstituted hydrocarbyl, or heterocycle and R2 it is hydrogen, hydrocarbyl or substituted hydrocarbyl.

The term "acyloxy" as used herein, alone or as part of another group, indicates an acyl group as described above attached via an oxygen linker (-O-), eg. eg, RC (O) O- where T is as defined in relation to the term "acyl".

The term "pesticide" includes chemical and microbiological agents used as active ingredients in products to control crop and lawn pests and diseases, ectoparasites in animals, and other public health pests. The term also includes plant growth regulators, pest repellants, synergists, photoprotectors against herbicides (which reduce the phytotoxicity of herbicides to crop plants) and

ES 2 269 409 T3 preservatives, the delivery of which to the target can expose dermal tissue and especially eye tissue to the pesticide. Such exposure can be caused by movement of the delivery medium to the person applying the pesticide or who is present near an application.

When a maximum or minimum "average number" is cited herein with respect to a structural characteristic such as oxyethylene units or glucoside units, those of skill in the art will understand that the integer number of such units in the individual molecules in a Surfactant preparation will typically vary over a range that includes integers greater than the maximum "average number" or less than the minimum "average number". The presence in a composition of individual surfactant molecules having an integer of such units outside the range stated in the "mean number" does not take the composition out of the scope of the present invention, as long as the "mean number" is within the range of the present invention. set interval and other requirements are met.

As noted above, concentrated aqueous solutions of glyphosate potassium salt have been found to have an exceptionally high specific gravity. Table 1 shows, by way of example, relative densities measured for solutions of potassium salt of glyphosate at 30% by weight of glyphosate ae, by comparison with organic ammonia and other salts of current or previous commercial interest.

Relative densities are measured using a DA-300 Mettler Relative Density / Density Meter.

TABLE 1

Relative density (20 / 15.6 ° C) of 30% by weight solutions of glyphosate monobasic salt ae

<td>Salt</td><td>Relative density</td>

<td>potassium</td><td> 1,2539</td>

<td>monoethanolamine (MEA)</td><td> 1,2357</td>

<td>isopropylammonium (IPA)</td><td> 1,1554</td>

<td>n-propylammonium</td><td> 1,1429</td>

<td>ethylammonium</td><td> 1,1667</td>

<td>ethylammonium</td><td> 1,1599</td>

<td>ammonium</td><td> 1,1814</td>

<td>trimethylsulfonium</td><td> 1,1904</td>

Therefore, 1 liter of glyphosate potassium salt solution at 30% by weight of ae at 20 ° C contains approximately 376 g of glyphosate ae / liter, while 1 liter of glyphosate salt solution of 30% IPA by weight ae at 20 ° C it contains approximately 347 g glyphosate ae / l. In other words, with the same weight concentration of ae, the potassium salt solution supplies approximately 8% more glyphosate ae per liter.

The higher relative density of potassium salt solutions has a particular value in solutions containing surfactant, in which the maximum glyphosate concentration is restricted not only by the solubility limit of the potassium salt in water but also by the compatibility limits of the surfactant. In such solutions, the advantages of the potassium salt may mean that (a) a maximum concentration by weight / volume of ea is achieved. of glyphosate higher than with the IPA salt in the presence of the same surfactant compatible with the same percentage of surfactant concentration, (b) at given concentrations in weight / volume of glyphosate and surfactant ae, better stability is achieved during storage against to a corresponding composition prepared with the IPA salt, and / or (c) at given concentrations by weight / volume of ea of glyphosate and surfactant, better pouring and pumping properties are achieved compared to a corresponding composition prepared with the IPA salt.

The advantages of the compositions of the present invention are reduced when the glyphosate concentration is decreased and are only minimal with a glyphosate concentration less than about 360 g ae / l, less than the concentration found in glyphosate salt products. IPA such as Roundup® herbicide. In preferred compositions of the invention, the glyphosate concentration is not less than 400 g ea / l or about 420 g ea / l, in particularly preferred compositions not less than about 440, 460 or 480 g ea / l, for example from about 480 to about 540 g ea / l. It is believed that the upper limit of glyphosate concentration in a composition of the invention containing surfactant stable for

ES 2 269 409 T3 storage is greater than approximately 650 g ea / l, this being a consequence of this limit of the solubility limit of the potassium glyphosate salt in water, aggravated by the limitation due to the presence of surfactant.

It is expected that the closer the glyphosate concentration is to this upper limit, the less the amount of surfactant that can be accommodated. In some cases, this small amount of surfactant is likely to be inadequate to give a reliable enhancement of the herbicidal efficacy of glyphosate to acceptable quality. However, in some special purpose applications where the composition must be diluted with a relatively small amount of water, for treating plants with a volume, for example, from about 10 to about 50 l / ha, the surfactant concentration In a concentrate composition of the invention it can be usefully as low as about 20 g / l. Such special purpose applications include rope wicking, controlled dripping, and ultra-low volume aerial spraying. For general purpose applications, typically for spraying after dilution with about 50 to about 100 L / ha, more usually about 100 to about 400 L / ha of water, the concentration of surfactant in the concentrate composition of the composition of the invention preferably is about 60 to about 300 g / l, and more preferably about 60 to 200 g / l.

The herbicidal formulation of the present invention includes at least one surfactant that, combined with glyphosate or a salt or ester thereof and after application of the formulation to a plant or an application mixture prepared by diluting the formulation with water, forms anisotropic aggregates that They comprise the surfactant, on the foliage of the plant (epicuticular wax). In some formulations of the present invention, a surfactant combined with a glyphosate or a salt or ester thereof and after application of the formulation to a plant or an application mixture prepared by diluting the formulation with water, forms liquid crystals comprising the surfactant, on the foliage of the plant (epicuticular wax). In other formulations of the present invention, a surfactant combined with a glyphosate or a salt or ester thereof and after application of the formulation to a plant or an application mixture prepared by diluting the formulation with water, forms liquid crystals comprising the surfactant, both on the foliage of the plant (epicuticular wax) and on the plant itself (intracuticular liquid crystals). In other formulations of the present invention, a herbicidal formulation comprising an aqueous mixture containing glyphosate or a salt or ester thereof and a surfactant, contains liquid crystals comprising the surfactant.

Suitable glyphosate salt forms that can be used in accordance with the formulations of the present invention include, for example, alkali metal salts, for example sodium and potassium salts, ammonium salts, diammonium salts such as dimethylammonium , alkylamine salts, for example dimethylamine and isopropylamine salts, alkanolamine salts, for example ethanolamine salts, alkylsulfonium salts, for example trimethylsulfonium salts, sulfoxonium salts, and mixtures or combinations thereof. Different commercial glyphosate formulations sold so far by the Monsanto company include ammonium salts, sodium salts, and isopropylamine salts. Glyphosate formulations sold so far by Zeneca have included trimethylsulfonium salts. Especially preferred glyphosate salts useful in the novel formulations of the present invention include the potassium salt, isopropylamine salt, ammonium salt, diammonium salt, sodium salt, monoethanolamine salt, and trimethylsulfonium salt. Potassium salt, sodium salt, ammonium salt, and diammonium salts are preferred, since formulations of these glyphosate salts have the highest probability of forming liquid crystals.

In addition to the glyphosate or salt or ester thereof, the herbicidal formulations of the present invention also comprise at least one surfactant. In one embodiment of the present invention, the nature of the surfactant and the composition of the herbicidal formulation is such that upon application of the formulation to a plant or an application mixture prepared by diluting the formulation with water, anisotropic aggregates are formed which comprise the surfactant in the waxy (epicuticular) cuticle of the plant. These anisotropic aggregates form on the foliage of the plant regardless of whether a second surfactant is present in the formulation. Anisotropic aggregates can be formed immediately after application to the plant foliage, or they can be formed when water from the formulation present on the foliage after application evaporates. In addition, anisotropic aggregates can also form in concentrated herbicide formulations.

To determine whether a herbicidal formulation comprising glyphosate or a salt or ester thereof and a surfactant forms anisotropic aggregates on the foliage of a plant comprising surfactant, the following birefringence test can be used.

First, a wax-coated slide is prepared. A preferred wax for preparing the slide is a mixture of carnauba wax and beeswax in a weight / weight ratio of about 10: 1, respectively. A clear wax mixture is prepared consisting of approximately 5% carnauba wax and approximately 0.5% beeswax in isopropanol, and is maintained at a temperature of approximately 82 ° C. The end of a 2.4 cm x 7.2 cm microscope slide is immersed perpendicularly into the wax mixture to a depth of approximately one third of the length of the slide. After approximately 10 to 15 seconds, the slide is removed very slowly and steadily from the wax mixture and allowed to cool, leaving a layer of wax deposited on both sides of the slide.

Visual examination of the slide can give a preliminary indication of the thickness and uniformity of the wax coating. If there are obvious imperfections, the slide is rejected. If the slide shows no obvious imperfections, carefully remove the wax coating from one side of the slide by cleaning with acetone. The

ES 2 269 409 T3 Further evaluation of the acceptability of the wax coated slide for testing is done by examining the slide under the microscope. The slide is selected for use in the assay, if upon examination under the microscope using a 4.9x objective, the wax coating has a uniform thickness and there is a uniform density of the wax particles throughout the slide. A slide that has few observable wax particles and exhibits a very dark field when viewed with polarized light is preferred.

The next stage in the procedure is to carry out the test. For this purpose, samples of glyphosate herbicidal formulation containing one or more surfactants are diluted, if necessary up to 15% to 20% by weight of glyphosate acid equivalent. A reference sample is prepared consisting of 41% by weight IPA glyphosate salt in aqueous solution.

The following instrumentation items, or equivalents, are necessary or useful for the test procedure:

Nikon SMZ-10A stereo microscope equipped for polarized light observation, photomicrography, and video observation and recording.

3CCD MTI camera.

Diagnostic Instruments 150 IL-PS with Power Supply.

Sony Trinitron Color Video Monitor, model PVM-1353MD.

Mitsubishi Time Lapse Video Tape Recorder, model HS-S5600.

Hewlett Packard Pavillion 7270 computer, with Windows 95 and Image-Pro.

Installed electronic imaging program version 2.0 plus.

Hewlett Packard Deskjet 870Cse Printer.

For the assay, a wax-coated slide, prepared and selected as described above, is placed on the microscope stage, with the system set to provide both direct and polarized transmitted light. A 1 microliter drop of the sample to be tested is applied to the wax surface using a clean 1 microliter Hamilton syringe. This and the following operations are followed by the microscope with the 5.9x objective. Duplicate and triplicate tests are done for each composition. Multiple assays can be run simultaneously on a single slide. The evolution of the change in the appearance of the sample is observed under the microscope through the microscope and recorded at designated time intervals. Useful time intervals are 1 minute, 10 minutes, 2 hours, and more than 24 hours after applying the drop to the wax surface. Observations can also be made at intermediate times to capture possible significant transitions that occur at those times.

The temperature of the wax layer tends to increase with prolonged exposure to microscope light. In many cases it has been determined that this does not significantly interfere with the results obtained. However, in some cases the temperature affects the test result, and in such cases it is preferred to illuminate the sample only for the short periods necessary to make observations, so that the temperature of the wax layer remains close to room temperature.

In dark field (polarized light) the birefringence in the wax layer is observed and in bright field the character of the drop surface is observed, at each time interval. Preferably the following records are made:

birefringence (s / n);

time of initial onset of birefringence; character of birefringence;

appearance of the drop surface when the composition "dries"; extent of gout;

effects of temperature (heating of the slide), if any; other noticeable changes.

Optionally, the images are recorded at significant times using a 3CCD MTI camera and the Image-Pro Plus program as documentation of the observed changes. If desired, the rehearsals can also be videotaped, especially during the first 15 minutes. In addition to images captured using the lens

ES 2 269 409 T3 at 4.9x, all views can be recorded using the 0.75 objective to provide clear comparisons of different samples tested on the same slide. A particularly useful parameter for observing anisotropic aggregates is the observation of birefringence (s / n) 5-20 minutes after deposition of the test drop on the wax-coated slide.

Herbicidal formulations of the present invention that form epicuticular anisotropic aggregates have substantially better performance compared to currently available herbicidal formulations. Without being bound by any particular theory, it is believed that epicuticular anisotropic aggregates can create or enlarge hydrophobic channels through the epicuticular waxy surface of the plant cuticle. These transcuticular created or enlarged channels through the waxy surface can facilitate glyphosate mass transfer through the epicuticular wax of the plant cuticle already within the plant more rapidly than in a system without the anisotropic aggregates. Furthermore it is believed that most of the anisotropic aggregates present on the epicuticular surface are present in a form other than a simple micelle, such as a bilayer or multilamellar structure as they tend to form complex structures such as cylindrical, disk-like or headband. The "majority" means that more than 50% by weight of the structure is present as complex aggregates other than simple micelles. Preferably more than 75% by weight of the surfactant is present as complex aggregates other than single micelles. The anisotropic aggregates of the present invention typically have a diameter of at least about 20 gauges, preferably at least about 30 nanometers.

Regarding the formation of anisotropic aggregates that comprise a surfactant in the presence of glyphosate, the critical packaging parameter (P), which is defined as:

P = V / IA where V is the volume of the hydrophobic tail of the molecule, I is the effective length of the hydrophobic tail, and A is the area occupied by the hydrophilic head group, can be an important aspect. Amphiphilic substances useful in the formation of anisotropic aggregates are believed to have a critical packaging parameter greater than about 1/3.

In a preferred embodiment in which anisotropic aggregates are formed on the epicuticular wax of the plant cuticle, the surfactant that makes up the anisotropic aggregates is an amphiphilic substance comprising a compound having a cationic head group and a hydrophobic tail. Without being bound by any particular theory, it is believed that the cationic group enhances initial adhesion to the sheet surface, since most of these surfaces carry an overall negative charge. Furthermore, the cationic group is believed to contribute to the hydrophilicity of the transcuticular channels in the epicuticular wax formed or enlarged by the surfactants of the present invention. The cationic groups attract water molecules that further increase the hydrophilic channels and thus provide a better route for the entry of glyphosate, which is polar.

Surfactants that are effective in forming anisotropic aggregates in the presence of glyphosate include nonionic, cationic, anionic, and amphoteric surfactants and mixtures thereof.

Surfactant mixtures as described above are also effective in forming anisotropic aggregates. Preferred mixtures include an alkoxylated alcohol nonionic surfactant and a cationic surfactant of dialkoxylated quaternary ammonium, monoalkoxylated quaternary ammonium, quaternary ammonium, dialkoxylated amine, diamine, or alkyl choline halide (eg, lauryl choline chloride) . Other preferred mixtures contain: a phospholipid amphoteric surfactant and a dialkoxylated quaternary amine or dialkoxylated amine cationic surfactant, a fluorinated quaternary ammonium surfactant such as Fluorad® 754, or an alkoxylated alcohol nonionic surfactant; or a carboxylic acid anionic surfactant and a dialkoxylated amine cationic surfactant. Examples of such preferred mixtures include Hetoxol® cS-20 (a PEG 20-alcohol C16-C18 Heterene) and Ethomeen® T / 20 (an EO 10-tallow-amine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 25 (an EO 15-tallow-amine from Akzo Nobel), Hetoxol® CS- 25 (a PEG 25-alcohol C16-C18 Heterene) and Ethomeen® T / 20, Hetoxol® CS-25 and Ethomeen® T / 25, Brij® 78 (a PeG 20-alcohol C18 from Sigma Chemical Company) and Ethomeen® T / 20, Brij® 78 and Ethomeen® T / 25, Brij® 78 and Ethoquad® T / 20 (a PEG 10-tallow-methylammonium chloride from Akzo Nobel), Brij® 78 and Ethoquad® T / 25 (a PEG 15-tallow-methylammonium chloride from Akzo Nobel), Plurafac® A38 (a PEG 27-alcohol C16-C18 de Basf) and Ethomeen® T / 20, Plurafac® A38 and Ethomeen® T / 25, Plurafac® A38 and Ethoquad® T / 20, Plurafac® A38 and Ethoquad® T / 25, ST 8303 (a PEG 14-alcohol C18 from Cognis) and Ethoquad® T / 25, Arosurf® 66 E10 (a PEG 10-alcohol isoC18 from Witco / Crompton) and Ethoquad® T / 25, Arosurf® 66 E20 (a PEG 20-alcohol-isoC18 from Witco / Crompton) and Ethoquad® T / 25, Arosurf® 66 E20 and Ethomeen® T / 25, Hetoxol® CS-20 and Ethomeen® T / 15 (an EO 5-tallow-amine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 30 (an EO 20-tallow-amine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 35 (an EO 25-tallow-amine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 40 (an EO 30-tallow-amine from Akzo Nobel), Hetoxol® ™ CS-20 and Trymeen® 6617 (a PEG 50-stearylamine from Cognis), Hetoxol® CS-15 (a PEG 15 C16-C alcohol18 Heterene) and Ethomeen® T / 25, Hetoxol® CS-20 and a PEG 22-quaternary dimethylammonium chloride, Hetoxol® CS-20 and lecithin, Hetoxol® CS-25 and lecithin, Hetoxol® CS-20O and Arquad® C -50 (a dodecyltrimethylammonium chloride from Akzo Nobel), Hetoxol® CS-20 and lauryl-choline chloride, Hetoxol® CS-15 and lauryl-choline chloride, Procol® LA 15 (a PEG 15-alcohol C12 from Protameen) and Ethoquad® T25, Hetoxol® CS-20 and a PEG 7-quaternary dimethylammonium chloride, Hetoxol® CS-20 and Gemini® 10-2-10 (an ethylene C10-N-methyl-diamine from Monsanto), Hetoxol® CS-20 and Gemini® 10-3-10 (a propylene-C10-N-methyl-diamine from Monsanto), Hetoxol® CS-20 and Gemini® 10-4-10 (a butylene-C10-N-methyl-diamine from Monsanto), Hetoxol® CS-20 and Gemini® 14-2-14 (an ethylene C14-N-methyl47

ES 2 269 409 T3 diamine from Monsanto), Hetoxol® CS-20 and Gemini® 14-3-14 (a propylene-C14-N-methyl-diamine from Monsanto), palmitic acid and Ethomeen® T / 25, lecithin and Ethomeen® T / 25, lecithin and Ethoquad® T / 25, lecithin and Ethomeen® T / 20, lecithin and Ethoquad® T / 20, and lecithin and Fluorad® FC 754 (a 3M quaternary fluorinated alkyl ammonium chloride). Some of the above mixtures are synergistic in that there are surfactant mixtures that when tested individually do not form anisotropic aggregates.

The herbicidal formulations of the present invention include glyphosate and a surfactant that forms anisotropic aggregates on a waxy plant surface, can be prepared as concentrated aqueous formulations comprising at least about 50 g glyphosate ae / l, more preferably at least about 250 g glyphosate ae / l, still more preferably at least about 300, 360, 380,400,440,480, 500, 540, or 600 g glyphosate ae / l. An example of a concentrated aqueous glyphosate formulation contains the isopropylamine or potassium salt of glyphosate in an amount of 360 g glyphosate ae / L, or approximately the same level currently used by Monsanto Corporation in their commercial formulation of Roundup herbicide®. Another preferred concentrated aqueous glyphosate formulation contains the isopropylamine or potassium salt of glyphosate in an amount of from about 300 to about 600, preferably from about 400 to about 600, from about 440 to about 600, from about 440 to about 480, from about 480 to about 600, or from about 480 to about 540 g glyphosate ae / l.

On a weight basis, the stable concentrated aqueous compositions of the present invention that include a surfactant that forms anisotropic aggregates on the cuticle surface can be prepared with glyphosate at a concentration of at least about 35, 40, 41, 42, 43 , 44, 45, 46, 47, 48, 49 or 50% ea A concentration of about 35 to about 50% ae, about 40 to about 50% ae, about 45 to about 50% ae, in particular for potassium glyphosate.

In another embodiment, the concentrated formulations that form anisotropic aggregates on the waxy surfaces of plants can be dry formulations that can be in the form of powders, pellets, tablets or granules. Typically these dry formulations are dispersed or dissolved in water before use. These dry formulations are typically dispersed or dissolved in water before use. Preferably, there are no substantially water-insoluble constituents present at substantial levels in such formulations, so the formulations are substantially water-soluble. The water-soluble or water-dispersible dry formulations of the present invention typically comprise from about 20% to about 80% (by weight) glyphosate ae, preferably from about 50% to about 80% (by weight) ae. glyphosate, and most preferably from about 60% to about 75% (by weight) glyphosate ae.

In the dry formulations of the present invention, glyphosate itself may provide the support for other constituents of the formulation, or there may be additional inert ingredients that provide such support. An example of an inert carrier ingredient that can be used in accordance with the present invention is ammonium sulfate. One skilled in the art will recognize that as used herein, the term "dry" does not imply that the dry formulations of the present invention are 100% free of water. Typically, the dry formulations of the present invention comprise from about 0.5% to about 5% (by weight) of water. It is preferred that the dry formulations of the present invention contain less than about 1% (by weight) of water.

Dry water soluble or dispersible formulations according to the present invention can be produced by any method known in the art, including spray drying, fluid bed agglomeration, pan granulation, or extrusion. In dry formulations, glyphosate can be present in the form of a salt or in the form of an acid. Formulations containing glyphosate acid may optionally contain an acid acceptor such as an alkali metal or ammonium carbonate or bicarbonate, ammonium dihydrogen phosphate, or the like, so that upon dissolution or dispersion in water by the user a water soluble glyphosate salt.

Typically, herbicidal compositions of the present invention that are ready for direct application to foliage can be made with a glyphosate concentration of from about 1 to about 40 grams of acid equivalent per liter, preferably from about 2 to about 18 grams of acid equivalent per liter, more preferably from about 4 to about 11 grams of acid equivalent per liter. One skilled in the art will recognize that different factors influence the rate of glyphosate application necessary for the desired result.

Any convenient herbicidal activity enhancing amount of the surfactant that forms the anisotropic aggregates on the waxy plant surface can be used in the glyphosate formulations of the present invention. Preferably, the surfactant is present in the glyphosate concentrate formulations of the present invention in a concentration of from about 25 to about 250 g / L, more preferably from about 50 to about 200 g / L. Although higher concentrations of the surfactant can be incorporated into the glyphosate formulations of the present invention, for economic reasons it is generally more appropriate to use the concentration ranges set forth above. Herbicidal formulations of the present invention that are ready to be applied directly to foliage can be made with a surfactant concentration of about 0.1 g / l to about 10 g / l, preferably about 1 g / l to about 5 g / l.

ES 2 269 409 T3

In some herbicidal formulations of the present invention, the nature of the surfactant and the composition of the herbicidal formulation is such that upon application of the formulation to a plant or an application mixture prepared by diluting the formulation with water, liquid crystals are formed. comprising the surfactant on the foliage of the plant (epicuticular liquid crystals). In other words, the liquid crystals that comprise the surfactant are formed to create or enlarge the hydrophilic channels through the epicuticular wax of the plant cuticle. An important feature of the herbicidal formulations of the present invention is that the surfactant can form liquid crystals in the presence of glyphosate on a porous, waxy substrate, such as a leaf cuticle, to produce epicuticular transcuticular hydrophilic channels through the waxy cuticle. One feature that differentiates the surfactants that make up liquid crystals in the presence of glyphosate is the tendency of the surfactant molecules to align themselves along the common axis in an orderly fashion. Typically, liquid crystals have a higher degree of order than isotropic solutions and are much more fluid than solid crystals. The fluidity of the liquid crystals can be an important factor in the best translocation of glyphosate throughout the plant.

Many of the surfactants discussed herein that form liquid crystals on the cuticle surface in the presence of glyphosate to facilitate translocation of glyphosate throughout the plant infrastructure, do not form liquid crystals in concentrated glyphosate solutions with the concentrations that are typically found to be commercially viable. Typically, these surfactants form liquid crystals in the dried glyphosate / surfactant reservoir that is formed from droplets or by spraying the diluted formulation onto the surface of the plant cuticle. In general, and without wanting to be linked to a particular theory, it seems that the formation of liquid crystals in the concentrated glyphosate solution itself is not necessarily important or is related (although on some occasions it can be useful) with the formation of liquid crystals on and on the surface of the plant. Typically, it is more important that the liquid crystals composed of surfactant form as a dry deposit on the surface of the sheet. However, in some formulations liquid crystals can form in the concentrated glyphosate / surfactant solutions and on and on the leaf, but not in the dilute spray mix.

As previously mentioned, the formation of epicuticular liquid crystals can be the result of drying of glyphosate and surfactant contained in drops applied to plants. There are several environmental factors, including air temperature, humidity, and wind speed, which can affect how quickly liquid crystals form in and on the plant. In some situations, liquid crystals can actually be formed by phase separation of the main droplet on the foliage. Although the surfactants listed herein form liquid crystals in the presence of glyphosate, it is believed that it is preferred that the surfactant molecules have a molecular weight of less than about 2,500. When the molecular weight of the surfactant is greater than 2500, liquid crystals can still form but may not be as effective and efficient in translocation of glyphosate as the lower molecular weight surfactants.

Liquid crystals comprising a surfactant in the presence of glyphosate in epicuticular form are typically lyotropic liquid crystals; that is, the formation of liquid crystals is typically induced by the presence of a solvent, in this case water. The mesophases of liquid crystals depend not only on the solvent present, but also on the temperature. Lyotropic liquid crystals comprising a surfactant in the presence of glyphosate that form transcuticular hydrophilic channels have been observed in hexagonal formation, reverse hexagonal formation, lamellar and multilamellar formations having at least about 20 to about 30 or more separate different layers. It may also be possible to have lyotropic liquid crystals in a cubic form. Semetic and nemetic forms of liquid crystals composed of a surfactant have also been observed in the presence of glyphosate. In the herbicidal formulations of the present invention, liquid crystals are formed regardless of the presence or absence of a second surfactant.

In addition, some surfactants in the presence of glyphosate can form worm-like micelles, another class of organized structures in liquid form that can facilitate glyphosate translocation through the waxy cuticle to the plant. Worm-like micelles are typically less organized than liquid crystals but still have sufficient organization to form hydrophilic channels on and in the plant to facilitate glyphosate translocation by the plant. Typically surfactants that are sufficiently "flexible" will form these types of worm-like micelles.

To determine the onset of glyphosate and surfactant concentration in dry tanks that are liquid crystal type, the following test procedure can be used. The experiments are carried out at 50% relative humidity and 24 ° C. Isolated cuticles are prepared according to the protocol described herein. A liquid crystal formulation of glyphosate, containing a specified amount of glyphosate salts (eg. potassium), a liquid crystal forming surfactant (e.g. ether C16-18-15EO-dimethylpropylamine), is placed on previously prepared isolated leaf cuticles in the form of 1 microliter drops and the onset of birefringence is observed with a polarized light microscope. In a separate experiment, these droplets showing birefringence are examined and confirmed to show the characteristic liquid crystal patterns.

Once birefringence is observed, the droplets are scraped from the cuticles as quickly as possible, dissolved in 1 ml of 99.9% (nominal) D2O, and transferred to a 5 mm NMR tube. The spectrum can be acquired using a Varian Unity Inova 400 MHz spectrometer equipped with a 5 mm Nalorac pulse probe. For example, a 30 degree pulse can be used to acquire sweeps with a suitable regeneration time. The determination can be made by integrating the glyphosate doublet signal and the water signal.

ES 2 269 409 T3

The glyphosate concentration in these drops was determined to be 37% (+/- 6%) according to this procedure. However, it should be noted that the evaporation of the water from the drying drops is relatively fast (in minutes). Therefore, results can vary from 37% to 50% w / w depending on the skill of the technician performing the task of transferring the cuticle to the MRI tube.

To determine whether a herbicidal formulation comprising glyphosate or a salt or ester thereof and a surfactant forms liquid crystals comprising the surfactant on plant foliage, the following high resolution polarized light microscopy birefringence test can be used. The high resolution birefringence test can distinguish liquid crystal phase formations and their characteristic microfine textures from other types of anisotropic aggregates or liquid crystals that precipitate out of solution due to evaporation of water. The test procedure is as follows.

Before testing for birefringence, a greenhouse grown marshmallow cuticle (Abutilon theophrasti) is isolated for testing. Other suitable plants that can be used to supply a test cuticle include horse mallow, giant ragweed, and morning glory. To isolate the cuticle, stock solutions of glacial acetic acid and sodium acetate are prepared. The glacial acetic acid stock solution has a concentration between about 1 and about 5% (weight / weight), and the sodium acetate stock solution has a concentration between about 1 and about 5% (weight / weight). The stock solutions are mixed together to form a buffered solution having a pH of about 4.2 to about 4.6.

After preparing the buffer solution, an enzyme solution is prepared. Typically, the enzyme solution will be prepared very close to cuticle isolation for maximum effectiveness. The enzyme solution is prepared by adding about 1 to about 5% (w / w) and about 0.1 to about 0.5% (w / w) of cellulase in water. Typically pectinase has an activity of 3,600 units / gram and cellulase has an activity of approximately 10,600 units / gram. The enzyme solution is then sterilized by filtration and prepared for use or storage.

A healthy leaf is taken from the original plant and its back face is scraped with sea sand. The leaf is then rinsed well with the buffer solution prepared earlier and a healthy section of the leaf is cut to isolate the cuticle. The cut portion of the sheet is infiltrated with the freshly prepared enzyme solution and held at a temperature of about 30 ° C to about 35 ° C, for about 1 hour or until the cuticle of the sheet is detached from the tissue substrate of the sheet. After peeling off, the cuticle is carefully removed from the buffer solution and rinsed well with deionized water and stored in a buffer solution having a pH of about 4 to 6 in an area that has a humidity of about 30% at approximately 75%, and at a temperature of approximately 20 to approximately 30 ° C, until use. Typically, the cuticle is stored in the controlled environment for at least about 24 hours to allow it to come into balance with its environment.

After isolating the cuticle, it is used for testing to determine whether a specific herbicidal formulation containing glyphosate and a surfactant forms liquid crystals comprising the surfactant, on the waxy cuticle. The cuticle is transferred to a glass slide and examined under the microscope (without polarized light) for cracks and other damage. If cracks or other damage to the cuticle surface is identified, the cuticle is discarded. Once a suitable cuticle has been observed, it is further examined under a microscope (7.5x magnification) under polarized light to ensure that a dark field was observed. If small areas of crystalline wax are noted on the cuticle surface, these areas are carefully avoided during the test.

After observing the cuticle defects, the glass slide is connected to a heating / cooling circuit that can regulate the temperature of the glass plate during the test. Heat is applied to the glass plate and the cuticle is allowed to equilibrate with the temperature of the glass plate from 15 ° C to about 35 ° C. After reaching equilibrium, a sample of the test solution is prepared. The sample can be in diluted or concentrated form, although it is preferred that the sample is in diluted form such that the glyphosate (ea) concentration is in the range of about 1% to about 10% (w / w) in the sample. and the ratio of glyphosate to surfactant is in the range of about 1 to 1 to about 10: 1 (weight / weight), preferably about 3: 1 (weight / weight). A drop of the aqueous test sample is placed on the cuticle and viewed with polarized light (7.5x magnification) transmitted through the cuticle. The images of the sample drops on the cuticle are recorded and saved on a computer connected to a video monitor using Flash Point 128 software in the present time interval. The images are then digitized using Image Pro from Media Cybernetics.

In each test, a few drops of sample are duplicated on two nearly identical cuticles. If birefringence is observed under the polarized light microscope at 7.5x magnification, the sample is immediately transferred to a polarized light microscope that is capable of magnification from 100x to 400x magnification. With this microscope, at 200x magnification, characteristic liquid crystal patterns can be seen and can be distinguished from solid crystals or other birefringent materials. If liquid crystals are observed at high power magnification, the sample formulation forms epicuticular liquid crystals on the plant foliage.

Herbicidal formulations of the present invention containing glyphosate or a salt or ester thereof, which form epicuticular liquid crystals, have substantially better performance over herbicidal formulations.

ES 2 269 409 T3 currently available, and may be superior to herbicidal formulations that simply form epicuticular anisotropic aggregates. Without being restricted to any particular theory, it appears that the formation of liquid crystals in the epicuticular part of a plant forms or enlarges hydrophilic channels through the waxy canopy of the foliage. Hydrophilic channels created or enlarged can substantially increase glyphosate mass transfer through the waxy cuticle and into the plant.

Surfactants that are effective to form epicuticular liquid crystals in the presence of glyphosate include nonionic, cationic, and amphoteric surfactants and mixtures thereof.

Surfactant mixtures as described above are also effective in forming epicuticular liquid crystals. Preferred mixtures include an alkoxylated alcohol nonionic surfactant and a dialkoxylated quaternary ammonium, monoalkoxylated quaternary ammonium, or dialkoxylated amine cationic surfactant. Other preferred mixtures contain a phospholipid amphoteric surfactant and an alkoxylated alcohol nonionic surfactant. Examples of such preferred mixtures include Hetoxol® CS-20 (a PEG 20-alcohol C16-C18 from Heterene) and Ethomeen® T / 20 (an EO 10-tallow-amine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 25 (an EO 15-tallow-amine from Akzo Nobel), Hetoxol® CS- 25 (a PEG 25-alcohol C16-C1S de Heterene) and Ethomeen® T / 20, Hetoxol® CS-25 and Ethomeen® T / 25, Brij® 78 (a PEG 20-alcohol C18 from Sigma Chemical Company) and Ethomeen® T / 20, Brij® 78 and Ethomeen® T / 25, Brij® 78 and Ethoquad® T / 20 (a PEG 10-tallow-methylammonium chloride from Akzo Nobel), Brij® 78 and Ethoquad® T / 25 (a PEG 15-tallow-methylammonium chloride from Akzo Nobel), Plurafac® A38 (a PEG 27-alcohol C16-C18 from Basf) and Ethomeen® T / 20, Plurafac® A38 and Ethomeen® T / 25, Plurafac® A38 and Ethoquad® T / 20, Plurafac® A38 and Ethoquad® T / 25, ST 8303 (a PEG 14-alcohol C16 from Cognis) and Ethoquad® T / 25, Arosurf® 66 E10 (a PEG 10-alcohol isoC18 from Witco / Crompton) and Ethoquad® T / 25, Arosurf® 66 E20 (a PEG 20-alcohol isoC18 from Witco / Crompton) and Ethoquad® T / 25, Arosurf® 66 E20 and Ethomeen® T / 25, Hetoxol® CS-20 and Ethomeen® T / 15 (an EO 5-tallowamine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 30 (an EO 20-tallowamine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 35 (an EO 25-tallowamine from Akzo Nobel), Hetoxol® CS-20 and Ethomeen® T / 40 (an EO 30-tallowamine from Akzo Nobel), Hetoxol® CS-20 and Trimeen® 6617 ( a PEG 50-stearylamine from Cognis), Hetoxol® CS-15 (a PEG 15 alcohol C16-C18 Heterene) and Ethomeen® T / 25, Hetoxol® CS-20 and a PEG 22-quaternary dimethylammonium chloride, Hetoxol® CS-20 and Lecithin, and Hetoxol® CS-25 and lecithin. Some of the above mixtures are synergistic in that they are surfactant mixtures which, when tested individually, do not form anisotropic aggregates and / or epicuticular liquid crystals.

In some herbicidal formulations of the present invention, the nature of the surfactant and the composition of the herbicidal formulation is such that upon application of the formulation to a plant or an application mixture prepared by diluting the formulation with water, liquid crystals are formed. comprising the surfactant, both on the plant foliage (epicuticular liquid crystals) and on the plant foliage (intracuticular liquid crystals). In other words, the liquid crystals that comprise the surfactant are formed to create or enlarge hydrophilic channels through the epicuticular wax of the plant cuticle and are also formed within the plant (intracuticular) to form pathways deep within the plant. that can significantly enhance glyphosate translocation through plant pathways. These transcuticular pathways may be responsible for the increased efficacy provided by such formulations. An important feature of herbicidal formulations of the present invention that form both epicuticular and intracuticular liquid crystals is that the surfactant can form liquid crystals both on and within the plant.

Many of the surfactants discussed herein that form liquid crystals on the cuticle surface and within the plant in the presence of glyphosate to facilitate glyphosate translocation through the plant infrastructure may not form liquid crystals in solutions. glyphosate concentrates in concentrations typically found to be commercially viable. Typically, these surfactants form liquid crystals in the dry glyphosate / surfactant reservoir that are formed from droplets or sprays of the diluted formulation onto the surface of the plant cuticle. In general, and are wanting to be bound to a particular theory, it seems that the formation of liquid crystals in the concentrated glyphosate solution is not by itself necessarily important or is related (although in some cases it may be useful) for the formation of liquid crystals. on the surface or on the plant. Typically, it is more important that the liquid crystals comprising the surfactant form as a dry deposit on the surface of the sheet. However, in some formulations liquid crystals can form in the concentrated glyphosate / surfactant solutions and on and on the leaf, but not in the dilute spray mix.

As previously mentioned, epicuticular and intracuticular liquid crystal formation can be the result of drying of drops containing glyphosate and surfactant applied to the plant. Various environmental factors including air temperature, humidity, and wind speed, can affect how quickly liquid crystals form in and on the plant. In some situations, liquid crystals can, in fact, be formed by phase separation of the main droplet. Although the surfactants listed herein form liquid crystals in the presence of glyphosate, it is believed that it is preferred that the surfactant molecules have a molecular weight of less than about 2,500. When the molecular weight of the surfactant is greater than about 2500, liquid crystals can still form in and on the plant, but they may not be as effective and efficient in glyphosate translocation as lower molecular weight surfactants.

Liquid crystals comprising a surfactant in the presence of epicuticular and intracuticular glyphosate are typically lyotropic liquid crystals; that is, the formation of liquid crystals is typically induced by the

ES 2 269 409 T3 presence of a solvent, such as water. The mesophases of liquid crystals depend not only on the solvent, but they can also depend on the temperature. Lyotropic liquid crystals comprising a surfactant in the presence of epicuticular and intracuticular glyphosates have been observed in cubic formation, hexagonal formation, reverse hexagonal formation, and lamellar and multilamellar formations having at least about 20 to about 30 or more separate layers. Both semetic and nemetic forms of liquid crystals comprising a surfactant have also been observed in the presence of glyphosate, both epicuticular and intracuticular. In the herbicidal formulations of the present invention, both epicuticular and intracuticular liquid crystals are formed in the presence of glyphosate, regardless of the presence or absence of a second surfactant.

In some formulations of the present invention comprising glyphosate and a surfactant that forms epicuticular and intracuticular liquid crystals, the liquid crystal comprises a layered matrix of surfactant molecules such that the hydrophilic moieties of the surfactant molecules in a layer of the layered matrix they are oriented towards the hydrophilic moieties of the surfactant molecules in a second layer of the layered matrix. The liquid crystals of the present invention, both epicuticular and intracuticular, can form this type of layered matrix and can have numerous layers as discussed above.

In some formulations of the present invention comprising glyphosate and a surfactant that forms epicuticular and intracuticular liquid crystals, the liquid crystals can be oriented in a layered matrix so that the lipophilic moieties of the surfactant molecules in a layer of the layered matrix are in contact with a hydrophobic surface on the foliage of a plant to which the formulation is applied. In addition, surfactant molecules in a layer of the layered matrix may be in contact with a hydrophobic surface located within a cuticle of a plant to which the formulation is applied.

In addition, some surfactants in the presence of glyphosate can form worm-like micelles, another class of structures organized in liquid form that can facilitate translocation of glyphosate through the waxy cuticle and into and through the plant, both epicuticularly and intracuticularly. . Worm-like micelles are typically less organized than liquid crystals but may still have sufficient organization to form hydrophilic channels on and in the plant to facilitate the introduction and translocation of glyphosate in and throughout the plant. Typically, surfactants that are sufficiently "flexible" will form these types of worm-like micelles.

Although the present invention is primarily directed to concentrated aqueous formulations of the potassium salt of glyphosate, said concentrated aqueous formulations may optionally further comprise one or more additional pesticides such as for example, water-soluble herbicidal actives, including without restriction water-soluble forms of acifluorfen, asulam, benazolin, bentazone, bialaphos, bispyribac, bromacil, bromoxynil, carfentrazone, chloramben, clopyralide, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, difenzoquat, dicuat, endothal, fenaco, fenoxaprop, flamprop, fiuazifop, fluoroglyphen, fluroxypyr, fomesafen, fosamine, glufosinate, haloxyfop, imazamet, imazametabenz, imazapyr, imazametabenz, imazapyr. imazaquln, imazethapyr, ioxynyl, MCPA, MCPB, mecoprop, methylassonic acid, naptalam, nonanoic acid, paraquat, piclorarn, sulfamic acid, 2,3,6-TBA, TCA and triclopyr.

Therefore, one embodiment of the invention is a concentrated aqueous composition comprising glyphosate predominantly in the form of its potassium salt, and a second anionic herbicide predominantly in the form of a potassium salt or other agriculturally acceptable salt or acid thereof, the total concentration of the glyphosate and the second anionic herbicide together being from about 360 to about 570 g ae / l, the composition further comprising a surfactant component, selected according to the invention, with a concentration of about 20 to about 300 g / l.

In this embodiment, it is preferred that the weight / weight ratio of glyphosate ae to the second anionic herbicide is not less than about 1: 1, for example from about 1: 1 to about 200: 1, preferably between 1: 1 and about 30: 1. The second anionic herbicide is preferably selected from the group consisting of acifluorophen, bialaphos, carfentrazone, clopyralid, 2,4-D, 2,4-DB, dicamba, dichlorprop, glufosinate, MCPA, MCPB, mecoprop, methylarsonic acid, nonanoic acid, picloram , triclopyr, and herbicides from the imidazolinone class, including imazamet, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, and imazethapyr.

The present invention also encompasses concentrated liquid formulations having an aqueous phase in which glyphosate is predominantly present in the form of the potassium salt thereof, and a non-aqueous phase that optionally contains a second herbicidal active ingredient that is relatively insoluble in water. . Such formulations illustratively include emulsions (including macro- and microemulsions, water-in-oil, oil-in-water, and water-in-oil-in-water), suspensions, and suspoemulsions. The non-aqueous phase may optionally comprise a microencapsulated component, for example a microencapsulated herbicide. In formulations of the invention having a nonaqueous phase, the concentration of ea of glyphosate in the composition as a whole is, however, within the ranges cited herein for concentrated aqueous formulations.

Exemplary water-insoluble herbicides that can be used in such formulations include acetochlor, aclonifen, alachlor, amethrin, amidosulfuron, anilofos, atrazine, azaphenidine, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulids, benzophenomobifeno, benzophenomobifeno butachlor, butamiphos, butralin, butroxydim, butylate, cafenstrol, carbetamide, carfentrazone-ethyl, clomethoxyphen, chlorbromuron, chloridazon, chlorimuron-ethyl,

ES 2 269 409 T3 clomitrophen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinmethyline, cinosulfuron, clethodim, clodinafop-propargyl, clomazone, clomeprop, chloravascular-methyl, cyanazine, cyclophuronyl, cyclohalofulfuron-cyclophuron , desmedipham, desmethrin, dichlobenyl, diclofop-methyl, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dinitramine, dinoterb, diphenamid, drthiopyr, diuron, EPTC, esprocarb, etalfluralin, Ethamethsulfuron-methyl, etofumesate, ethoxysulfuron, ethobenzanid, fenoxaprop-ethyl, fenuron, flamprop-methyl, flazasulfuron, fluazifop-butyl, fluchloralin, flumetsulam, fiumyclorac-pentyl, flumioxazin, fluometuron-fluorochloride, fluorochloride, fluorochloropoxyl fluroxypyr-1-methylheptyl, flurtamone, flutiacetyl, fomesafen, halosulfuron, haloxyfop-methyl, hexazinone, imazosulfuron, indanofan, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactocylofen, lena linuron, mefenacet, metamitron, metazachlor, metabenzthiazuron, methyldimron, metobenzuron, methobromuron, metolachlor, metosulam, methoxuron, metribuzin, metsulfuron, molinate, monolinuron, naproanilide, napropamide, oxeninadzuron, nephropamide, norobeninadulin, nephrozine, nephrozine, nephrozine oxasulfuron, oxifiuorfen, pebulate, pendimethalin, pentanochlor, pentoxazone, phenmedipham, piperofos, pretylachlor, primisulfuron, prodiamine, prometon, promethrin, propachlor, propanil, propaquizafop, propazine, profam, propisochlor, propizamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazolinate, pyrazosulfuron-ethyl, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac, quinmeracuranyl, perhaps, rhystomid-ethyl simethrin, sulcotrion, sulfentrazone, sulfometuron, sulfosulfuron, tebutam, tebutiuron, terbacil, terbumeton, terbutylazine, terbutryn, tenylchlor, thiazopyr, thifensulfuron, thiobencarb, thiocarbazyl, tralkoxydim trialate, triasulfuron, tribenuron, trietazine, trifiuralin, triflusulfuron and vernolate. It is preferred that the weight / weight ratio of glyphosate ae to said water-insoluble herbicide is not less than 1: 1, for example from about 1: 1 to about 200: 1, preferably between 1: 1 and about 30: 1.

Optionally, excipient ingredients other than the surfactant component defined above may be present in a composition of the invention, provided that the cloud point and non-crystallization properties of the composition remain in accordance with the invention. Such additional excipient ingredients include additional formulation additives such as colorants, thickeners, crystallization inhibitors, antifreeze agents including glycols, foam moderating agents, anti-drift agents, compatibilizing agents, etc.

One type of excipient ingredient often used in glyphosate formulations is an inorganic salt such as ammonium sulfate, included to enhance herbicidal activity or uniformity of herbicidal activity, of glyphosate. Since the content of inorganic salt in the formulation necessary to provide such enhancement is typically relatively high, often greater than the amount of glyphosate present, it will seldom be useful to add such a salt to a composition of the invention. The amount of ammonium sulfate, for example, that could be accommodated in a storage-stable aqueous composition containing the glyphosate potassium salt with a concentration of at least 360 g ea / l, would be so small that it would not bring a benefit. substantial. Therefore, an alternative is to include a small amount of a synergistic agent such as an anthraquinone compound or a phenyl substituted olefin compound as described in International Publication Nos. WO 98/33384 and WO 98/33385 respectively.

To determine whether a herbicidal formulation comprising glyphosate or a salt or ester thereof and a surfactant forms liquid crystals comprising a surfactant on the foliage of a plant or on the foliage of a plant, the following procedures are used. First, the surfactant / glyphosate formulation is tested as described above to determine if liquid crystals form epicuticularly on plant foliage. If it is determined that epicuticular liquid crystals form on the plant foliage, the following test procedure using high resolution polarized light microscopy is used to determine if the liquid crystals also form intracuticularly.

To determine if intracuticular liquid crystals form, typically fruit cuticles such as pear cuticles or tomato cuticles are used because they are very robust. The isolation of the fruit cuticle is carried out in a similar way to that of a broad leaf cuticle described above with some modifications. Typically, the enzyme used to separate the cuticle of the fruit is pectinase (10,000 units of activity per 100 ml). The concentration of the enzyme solution typically is from about 10% to about 30% w / w and the final enzyme solution typically contains an activity of from about 50 to about 200 units / ml. The fruit cuticle is incubated with the enzyme at room temperature for a period of approximately 1 hour or more to loosen the fruit cuticle. After detaching the cuticle, rinse well and wash before use.

To determine if intracuticular liquid crystals are formed with a surfactant / glyphosate formulation, a fruit cuticle is used as described above in conjunction with a monitoring system in which the substrate is a non-porous hydrophobic material, such as Parafilm. The fruit cuticle is placed on a support agar gel that rests on a support mesh, typically composed of carbon fibers. The cuticle / agar / mesh composition is then placed on a glass slide. The Parafilm is also mounted on the glass slide in this way.

Herbicidal formulations of interest containing a surfactant and glyphosate deposit on the cuticle or on the Parafilm. When the appearance of the liquid crystal of the formulation is observed with a polarized light at 100x magnification as described above, both the cuticle and the Parafilm control are removed by hand or mechanically with a foam tip at room temperature. Typically, the liquid crystals formed on the Parafilm wash away easily. Both the Parafilm control and the fruit cuticle, after washing, is left

ES 2 269 409 T3 that reach equilibrium for between about 24 and about 48 hours in a controlled environment (temperature between 20 and about 25 ° C, humidity from 50% to 75%).

After reaching equilibrium with the Parafilm control and the fruit cuticle, the areas where the formulation deposits were made are again rigorously washed by hand or mechanically with a foam tip. After cleaning, the cuticle and Parafilm are again examined for liquid crystal formation under polarized light at 100x magnification. If the microfine texture is observed after the second cleaning procedure, this is an indication of intracuticular liquid crystal formation, as these liquid crystals have not been removed after two wash cycles. In addition, an additional wash can be carried out on the cuticles of fruits that show liquid crystal formation to further show that liquid crystals cannot be washed when they are intracuticular. After the second wash we have not seen any liquid crystal formation in any of the observed Parafilm controls.

Typically, only a very small amount of solubilizer will be needed to impart the best formulation characteristics. In general, only a ratio of about 50: 1 (by weight), more preferably about 25: 1, still more preferably about 10: 1, and most preferably about 8: 1 of ethoxylated ethoxylated surfactant to solubilizer is needed. One skilled in the art will recognize that different factors can influence the amount of solubilizer necessary to impart the desired characteristics. The solubilizer can also be included in the formulation in a lower ratio that it may not function as a solubilizer, but will enhance efficacy, such as a surfactant to solubilizer ratio of about 5: 1, about 4: 1, about 3: 1 , about 2: 1 or about 1: 1.

Furthermore, the addition of a solubilizer imparts better viscosity characteristics to the concentrated formulations of the present invention. It is preferred to add sufficient solubilizer to the formulation to produce a formulation having a viscosity of less than 1000 cp at 6 ° C at a shear rate of 45 / s, even more preferably less than about 500 cp at 0 ° C at a rate of 45 / s shear and most preferably less than about 300 cp at 0 ° C at a shear rate of 45 / s. In a preferred embodiment, the herbicidal formulations of the present invention have a viscosity of about 1100 cp at 0 ° C at a shear rate of 45 / s to about 500 cp at 0 ° C at a shear rate of 45 / s. The new formulations of the present invention require only a small amount of solubilizer to produce the desired viscosities.

Another ingredient that can be optionally added to the glyphosate herbicidal formulations of the present invention to further improve herbicidal efficacy and related herbicidal properties is a dicarboxylic acid or salt of a dicarboxylic acid. Suitable dicarboxylic acids that can be added to herbicidal formulations comprising glyphosate or a salt or ester thereof and a surfactant as described herein include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, acid maleic, adipic acid, and fumaric acid, and combinations or mixtures thereof, with oxalic acid being preferred. Also in addition to or instead of the dicarboxylic acid, salts of the mentioned dicarboxylic acids can be incorporated into the herbicidal formulations of the present invention to improve herbicidal performance. Suitable salts include, for example, potassium oxalate, dipotassium oxalate, sodium oxalate, disodium oxalate, ammonium oxalate, diethanolamine oxalate, dimethylamine oxalate, alkanolamine salts of oxalic acid, and lower alkylamine salts of oxalic acid.

Formulations containing a dicarboxylic acid such as oxalic acid or a dicarboxylic acid such as potassium oxalate typically contain a sufficient amount of dicarboxylic acid / dicarboxylic acid salt to enhance the resulting efficacy of the herbicidal formulation. Typically, the weight ratio of total surfactant to carboxylic acid / carboxylic acid salt may be from about 1: 1 to about 50: 1, more preferably from 5: 1 to 40: 1, and most preferably from about 5: 1 to about 20: 1. This ratio of total surfactant to carboxylic acid / carboxylic acid salt significantly enhances the herbicidal performance of the resulting herbicidal formulation.

The dicarboxylic acid or salt thereof that can be added to the herbicidal formulations of the present invention to improve efficacy are suitably for use with glyphosate, or salts or esters thereof. Suitable glyphosate salts include those listed above, specifically isopropylamine salt, potassium salt, and trimethylammonium salt.

The present invention also includes a method of killing or controlling unwanted weeds or vegetation comprising the steps of diluting a liquid concentrate in a suitable amount of water to form a mixture in a tank and applying a herbicidally effective amount of the mixture. from reservoir to weed foliage or unwanted vegetation. In the same way, the method of killing or controlling weeds or unwanted vegetation is included in the invention, which comprises the steps of diluting a concentrate in solid particles in a suitable amount of water to form a mixture in a tank and applying an effective amount. As a herbicide from tank mix to weed foliage or unwanted vegetation.

In a herbicidal process of a composition of the invention, the composition is diluted in a suitable volume of water to provide an application solution which is then applied to the foliage of a plant or plants at an application rate sufficient to give a desired herbicidal effect. . This application rate is normally

ES 2 269 409 T3 expresses as the amount of glyphosate per unit area treated, p. eg, grams of acid equivalent per hectare (g ae / ha). Typically and illustratively, a "desired herbicidal effect" is constituted by at least 85% control of a plant species as measured by reduced growth or mortality after a period of time during which glyphosate exerts its herbicidal or phytotoxic effects. complete in treated plants. Depending on the plant species and growing conditions, this period of time can be as short as one week, but normally a period of at least two weeks is necessary for glyphosate to exert its full effect.

The selection of application rates that are effective as a herbicide for a composition of the invention is at the discretion of the person skilled in the agricultural art. In the same way, those skilled in the art will recognize that the individual conditions of the plant, the time and the growth conditions, as well as the specific active principles and their weight ratios in the composition, will influence the degree of herbicidal efficacy achieved. in the practice of this invention. Regarding the use of glyphosate compositions, there is much information on proper application rates. The use of glyphosate for two decades and the published studies related to such use have provided a wealth of information from which the weed control technician can select glyphosate application rates that are effective as a herbicide in particular species in stages. of particular growth, under particular environmental conditions.

Herbicidal compositions of glyphosate salts are used to control a wide variety of plants around the world, and in this connection it is believed that the potassium salt will not show to be different from other glyphosate salts.

Particularly important annual dicot plant species for whose control a composition of the invention can be used are without limitation marshmallow (Abutilon theophrasti), milkweed (Amaranthus spp.), Tobacco (Borreria spp.), Rapeseed, canola, Indian mustard, etc. . (Brassica spp.), Carnation (Commelina spp.), Shepherd's pins (Erodium spp.), Sunflower (Helianthus spp.), Morning glory (Ipomoea spp.), Kochia (Kochia scoparia), mallow (Malva spp.) , buckwheat, amphibian polygon, etc. (Polygonum spp.), Purslane (Portulaca spp.), Russian thistle (Salsota spp.), AIDS (Sida spp.), Wild mustard (Sinapis arvensis) and cadillo (Xanthium spp.).

Particularly important annual monocotyledonous plant species for whose control a composition of the invention can be used are, without limitation, wild oats (Avena fatua), grass (Axonopus spp.), Grass (Bromus tectorum), lent grass (Digitaria spp.) , paddy millet (Echinochloa crus-galli), crow's foot (Eleusine indica), annual ryegrass (Lolium multiflorum), rice, (Oryza sativa), ottochloa (Ottochloa nodosa), bay grass (Paspalum notatum), birdseed (Phalaris spp.), foxtail (Setaria spp.), wheat (Triticum aestivum) and corn (Zea mays).

Particularly important perennial dicot plant species for whose control a composition of the invention can be used are illustrated without limitation with mugwort (Artemisia spp.), Milkweed (Asclepias spp.), Sunder thistle (Cirsium arvense), lesser bindweed (Convolvulus arvensis ) and kudzu (Pueraria spp.).

Perennial monocotyledonous plant species particularly important for whose control a composition of the invention can be used are illustrated without limitation with brachiaria (Brachiara spp), common grass (Cynodon dactylon), tigernut (Cyperus esculentus), castanet (C. rotundus), pharmacy grass (Elymus repens), reed (Imperata cylindrica), perennial ryegrass (Lolium perenne), Tanzanian grass (Panicum maximum), cost (Paspalum dilatatum), cane (Phragmites spp.), sorghum (Sorghum halepense ) and reeds (Typha spp.).

Other particularly important perineal plant species for whose control a composition of the invention can be used are illustrated without limitation with horsetail (Equisetum spp.), Common fern (Pteridium aquilinum), blackberry (Rubus spp.) And gorse (Ulex europaeus ).

If desired, the user can mix one or more adjuvants with a composition of the invention and with the dilution water when preparing the application composition. Such adjuvants may include additional surfactants and / or an inorganic salt such as ammonium sulfate, in order to further enhance herbicidal efficacy. However, under most conditions a herbicidal method of use of the present invention gives acceptable efficacy in the absence of such adjuvants.

In a particular method contemplated for the use of a composition of the invention, the composition, after dilution with water, is applied to the foliage of the plants of a genetically transformed or selected crop to tolerate glyphosate and simultaneously to the foliage of the weeds of the unwanted plants growing near said crop plants. This method of use results in the control of unwanted weeds or plants while leaving the crop plants substantially undamaged. Crop plants that are genetically transformed or selected to tolerate glyphosate include those whose seeds are sold by the Monsanto company or with the permission of the Monsanto company, which carry the Roundup Ready trademark.®. These include, without restriction, varieties of cotton, soybeans, canola, cane sugar, wheat, and corn.

Compositions for treating plants can be prepared simply by diluting a concentrated composition of the invention in water. The application of the plant treatment compositions to the foliage is preferably carried out by spraying, using any conventional means for spraying liquids, such as spray nozzles, atomisers or the like. The compositions of the invention can be used in precision agricultural techniques in which apparatus are used to vary the amount of pesticide applied to different

ES 2 269 409 T3 parts of a field, depending on variables such as the particular plant species present, soil composition, etc. In one embodiment of such techniques, a global positioning system operating with the spray apparatus can be used to apply the desired amount of the composition to different parts of a field.

A plant treatment composition is preferably diluted sufficient to be ready to spray using conventional agricultural spray equipment. Spray volumes useful for the present invention may range from about 10 to about 1000 liters per hectare (l / ha) or greater, per spray application.

Examples

The following examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention. The examples will make it possible to better understand the invention and to perceive its advantages and some variations of the execution.

Example A

Preparation of the potassium glyphosate salt

In a glass container of approximately 4 liters capacity, 1264.1 grams of glyphosate acid were added with a test of 95.7%. The container was placed in an ice / water bath to provide cooling. The vessel was fitted with an overhead stirrer with a propeller blade approximately half the diameter of the vessel. A commercial 45% potassium hydroxide solution (VWR Scientific Products) was added. The rate of addition was controlled to prevent the resulting solution from boiling conspicuously. The height of the stirrer was adjusted as the volume of liquid changed to ensure good mixing. A total of 966.2 grams of potassium hydroxide was added. The concentration was adjusted by adding 195.3 grams of deionized water. Stirring was continued for about 1 hour. The final yield was 2418.4 grams which represents a weight loss of 7.2 grams. The calculated assay was glyphosate acid 50.0% or glyphosate potassium 61% and the calculated neutralization was 108%. The pH of a 10% dilution in deionized water was 4.76. The density of the resulting solution at 20 ° C was approximately 1.4661 grams / milliliter and the volume of 1000 grams at 20 ° C was then approximately 682 ml. This corresponds to a weight / volume concentration of approximately 730 grams / liter.

Example B

Preparation of comparative formulations and formulations of the present invention

Surfactant-containing compositions 2-01 through 2-13 are prepared as described below. Each contains glyphosate potassium salt, and were prepared using the glyphosate potassium 50% ae solution of Example A, above. Comparative compositions containing glyphosate potassium salt, an alkylpolyglucoside, and alkoxylated alkylamine surfactants (Compositions 2.01-2.05) were prepared to duplicate the compositions set forth in Examples 1, 2, 3, 7 and 15 of PCT Publication No. WO 00 / 15037, respectively.

Sample preparation: To a 117 ml jar, add approximately 80 grams of the potassium glyphosate solution from Example A. To this is added the appropriate ratio of adjuvant and water. A small amount of phosphoric acid was added to some samples to adjust the pH between 4.9 and 5.1. The resulting mixture is stirred with a magnetic stirrer (Cole-Parmer, Chicago, IL) until a single phase is obtained. In the case of materials that were viscous and therefore could not be mixed with the magnetic stirrer, the material was rolled with a roll laminator (US Stoneware, Manwah, NJ) until the surfactant dissolved. This material was allowed to stand overnight and was observed to ensure that it was single phase and had no air bubbles.

The density was then determined using a Mettler DA-300 density meter and the concentrations were calculated in grams per liter.

Cloud points were measured by heating a small amount of the material in a test tube until the solution became unclear or cloudy, then the test tube was removed from the heat and the temperature at which the solution became clear was observed. on cooling.

Viscosities were measured using a Haake Model VT500 (Haake, Inc., Karlsruhe Germany) equipped with the appropriate MV series cone and disk sensor system at a 45 s shear rate.-1. The temperature was varied with the attached water bath. For some samples for which insufficient sample was available, the viscosities were measured with a Brookfield Model DV-II equipped with a small sample adapter (Brookfield Laboratories, Inc., Stoughton, Mass).

ES 2 269 409 T3

ES 2 269 409 T3

<td rowspan="19">Table 3. Composition of formulations of Example B (2.06 to 2.13)</td><td rowspan="2">CO T ~ cn</td><td>active ^</td><td> 37,00%</td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">1100.00 I</td><td rowspan="19"></td><td></td><td> 494</td><td> 167</td><td></td><td rowspan="19"></td><td>cPs</td><td>Ν ' cn</td><td>CN</td><td>co CN</td><td>OR CD</td>

<td rowspan="2">CN cn</td><td>% active]</td><td> 37,29%</td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2"> 1100,00 |</td><td></td><td> 493</td><td> 165</td><td></td><td>cPs</td><td>CN co</td><td> (0</td><td> [109 |</td><td>co</td>

<td rowspan="3">CN</td><td rowspan="2">% active]</td><td rowspan="2"> 36,40%</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="3"> [100,00 |</td><td></td><td> 476</td><td>CD</td><td></td><td>cPs</td><td></td><td>co co</td><td>CD CO</td><td>CD</td>

<td rowspan="2">OR CN</td><td>% active |</td><td> 39,18%</td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">| OO'OOI-I</td><td></td><td> 529</td><td> 196</td><td></td><td>cPs</td><td></td><td>Ν ' cn</td><td>co cn</td><td>co to</td>

<td rowspan="2">CD OR CN</td><td>% active |</td><td> 34,70%</td><td></td><td></td><td>116.20% I</td><td></td><td></td><td></td><td rowspan="2">| oo'ooq</td><td></td><td> 449</td><td> 209 _</td><td></td><td>CPs</td><td>CO</td><td>cn</td><td>CD CN</td><td>co co</td>

<td rowspan="2">CO or_ CN</td><td>% active |</td><td> 36,70%</td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2"> 1100,00 |</td><td></td><td> 487</td><td>CN oo - · <- CD</td><td></td><td>cPs</td><td>or r *.</td><td>CN 00</td><td>CO</td><td></td>

<td rowspan="2">Γ- OR CN</td><td>% active |</td><td>34.53% i i</td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2">l ooooul</td><td></td><td> 449</td><td>209 J / I</td><td></td><td>w CL OR</td><td>co r-</td><td>CN OR</td><td>CN CN T "</td><td>lt * c |</td>

<td>> 5 or ^</td><td> 69,06</td><td> 16,07</td><td>or or or</td><td>10.00 I</td><td>OR or or'</td><td>00 TT or</td><td>CD CO Nt</td><td> 1,3019</td><td></td><td><d</td><td>or 0 cn cn</td><td>former EO Q) O H</td><td>cn CN</td><td>cn</td><td>OR</td><td>cn</td>

<td rowspan="2">CD OR CN</td><td>% active |</td><td> 37,28%</td><td></td><td></td><td></td><td></td><td></td><td></td><td rowspan="2"> |100,00 |</td><td></td><td> 494</td><td>165 g / l</td><td></td><td>ω CL or</td><td>co</td><td>cn cn</td><td>CD</td><td>cn CN</td>

<td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">50% potassium glyphosate</td><td rowspan="2">Huntsman Surfonic AGM 550</td><td rowspan="2">IT OR c 0) 0) AND or x: LLJ</td><td rowspan="2">| Ethoquad C / 12]</td><td rowspan="2">(Tomah ED-17-5 |</td><td rowspan="2">| Phosphoric acid]</td><td rowspan="2">CD CD <</td><td rowspan="2"></td>

<td>Density (g / cc) 20 ° C</td><td>g / l ea of glyphosate</td><td>Total surfactant solids</td><td>Cloud point</td><td>Viscosity Haake</td><td></td><td></td><td></td><td></td>

ES 2 269 409 T3

TABLE 4

Surfactants used in Example C

<td>Tension- active</td><td>Chemical structure</td><td>Trade name and supplier</td>

<td>TO</td><td></td><td>104-75-6 (Aldrich)</td>

<td>B</td><td>CifiHar "</td><td>Pfaftz & Bauer (www.pfaltzandb auer.com)</td>

<td>C</td><td>C18H37 N (CH2CH2O) 7CH3</td><td>not commercially available (prepared according to Example D above)</td>

<td>D</td><td>N- (EO)mH</td><td>not commercially available (prepared by ethoxylation of N-methyloctadecylamine)</td>

<td>AND</td><td>CieH37—~ N (ΕΟ) 5 · 3Η</td><td>not commercially available (prepared by ethoxylation of N-methyloctadecylamine)</td>

ES 2 269 409 T3

<td></td><td></td><td>.nh2</td><td>102-83-0 (Aldrich)</td>

<td>G</td><td>C * H9v</td><td>z .N \</td><td>CAS 62478-76-6 (not available in commerce)</td>

<td>Η</td><td>c8h17xCeH, /</td><td>nh2</td><td>(not commercially available)</td>

<td></td><td>7ΊΜ · ι</td><td></td><td>(not commercially available)</td>

<td></td><td>(Cg-Cj o)—</td><td>^ nh2</td><td>(Tomah)</td>

<td>Κ</td><td>Á / Vv</td><td></td><td>PA 10 (Tomah)</td>

ES 2 269 409 T3

<td>L</td><td></td><td>PA-12EH (Tomah)</td>

<td>Μ</td><td>111 JL xh 'z, b) w*</td><td>E-17-5 (Tomah)</td>

<td>N</td><td>1 / ΕΟΧπΗ fciru ^>>^*χΖ^0χΧΧ^ γζ'ΝΝ (Εθ)ηΗ m + n-5 J</td><td>Surfbníc AGM - 550 (Huntsman Petrochemical Corp.)</td>

<td> 0</td><td>(CrCi ·) -</td><td>DA-1214 (Tomah)</td>

<td>P</td><td>(Cu * C <d- or> Xs ^ x ^^ xZ,N>> szx ^ xs> <^NHe has</td><td>DA-1618 (Tomah)</td>

<td>Q</td><td>(C 5H ^) 0<wxz\ ix '' *</td><td>DA-18 (Tomah)</td>

<td>R</td><td></td><td>DA-14 (Tomah)</td>

<td>S</td><td>ΑΛΑΑ ^ -</td><td>DA-17 (Tomah)</td>

<td>T</td><td>/ K / V / 'k / K / OWW »CuHm-O ^ 7 7ílttl_j orov »iwu ·</td><td>B191O-5 (Witco)</td>

ES 2 269 409 T3

<td>υ</td><td>TeMSO-í AND’Q</td><td>/ EO EO</td><td>B1910-6 (Witco)</td>

<td>V</td><td></td><td>v / V.xW</td><td>B1910-9 (Witco)</td>

<td>w</td><td>I</td><td></td><td>Macklne 101</td>

<td>X</td><td></td><td></td><td>Fluorad FC-754</td>

<td></td><td>CaFir-J nXs / ''</td><td>\ Z \</td><td></td>

<td>Y</td><td></td><td></td><td>Chemoxide L70</td>

<td></td><td>{cocoy-Ν-σ</td><td></td><td></td>

<td>z</td><td>CiiCio + C &> - O—</td><td>[glycoside)</td><td>Agrímul APG</td>

<td></td><td></td><td>s</td><td>(Aldrich)</td>

<td>DC</td><td> _/*·*</td><td colspan="2">Genamln</td>

<td></td><td>(sMm) «» || w «Z Y</td><td colspan="2">3119 (Claríant)</td>

ES 2 269 409 T3

<td>DD</td><td colspan="2"></td><td>Jeffamlne EDR-148</td>

<td>EE</td><td colspan="2">ισ(sebum) - hi— (EOJmH (BO) nH fHwMI</td><td>Custom B-1965-F (Witao)</td>

ES 2 269 409 T3

<td>NN</td><td>^ z-tEOJa CbHu ^ \ Χ \ ΧΝ'Χ'(ΕΟ></td><td>Witco Exp-5388-48 (MON 59124)</td>

<td> 00</td><td>0 1 II Η 1ctoFi7 "^_N> / \ »XN\</td><td>S. Aulnbauh ckCAS</td>

<td>PP</td><td>0 ' 1 (coconut) - N+- (BO)toH (EO) .H n + m ”5</td><td>Witco custom B- 1965-F</td>

ES 2 269 409 T3

ES 2 269 409 T3

ES 2 269 409 T3

ES 2 269 409 T3

<td>GGG</td><td>CjíHu - (OCH2CH2)4NHCH3</td><td> 6566722</td>

<td>JJJ</td><td>(tallow) - (PO> 2 (EO)9N (CH3)2</td><td> 6866733</td>

ES 2 269 409 T3

<td>LLL</td><td>H (Wedge) - ¢ 3¼-</td><td> 6866759</td>

ES 2 269 409 T3

<td></td><td>C</td><td>'(EOJmiI</td><td></td><td></td>

<td></td><td>Cuffe— | X</td><td colspan="2"> ' XO— (BCJnH</td><td></td>

<td></td><td></td><td>'(ECJnH</td><td></td><td></td>

ES 2 269 409 T3

<td>uuu</td><td>QAi-</td><td>0- (BCtynH</td><td> 6801388</td>

<td></td><td>mkriQ</td><td></td><td></td>

<td>vw</td><td>CnHis · -</td><td>to*</td><td></td>

The following compounds were not compatible with glyphosate potassium 31% ae and surfactant 10%, but were compatible with glyphosate diammonium 31% ae and surfactant 10%.

Example C

Preparation of representative sample compositions of the invention

For the compositions of glyphosate potassium 31% by weight of ae / surfactant at 10% by weight: 1,550 g of aqueous solution of glyphosate potassium salt of 40% by weight of ae were weighed into a vial. 0.200 g of surfactant was added to the same vial. Enough deionized water was then added to the content to bring the total content to 2,000 g. The mixture was stirred for 2 hours at room temperature and inspected to see if a solution had formed. If solution was present, the test vial was allowed to stand at room temperature overnight. If solution was still present, the test vial was placed in an oven at 50 ° C for 1 week. If no phase separation had occurred within a week, the surfactant being tested was considered "compatible". All surfactants identified in Table 4 were compatible with the loading of potassium glyphosate 31% ae / 10% surfactant by weight.

For the compositions of glyphosate potassium 37% by weight of ae / surfactant at 12% by weight: 41.1 g of aqueous solution of glyphosate potassium salt of 45% by weight of ae was weighed into a container. To the same container 6.0 g of surfactant and 2.9 g of deionized water were added for a total weight of 50.0 g. The rest of the protocol is the same as that described for the samples at 31% by weight. The surfactants identified in Table 4 that were compatible with the 37 wt% ae / 12 wt% potassium glyphosate loading are listed in Table 5 below.

For glyphosate potassium 40 wt% ae / 10 wt% surfactant compositions: 1.79 g of glyphosate potassium salt aqueous solution 45 wt% ae was weighed into a vial. 0.2 g was added to the same vial

ES 2 269 409 T3 of surfactant. The rest of the protocol is the same as that described for the samples at 31% by weight. The surfactants identified in Table 4 that were compatible with the 40 wt% ae / 10 wt% potassium glyphosate loading are listed in Table 5 below.

For the 45 wt% ae / 15 wt surfactant potassium glyphosate compositions: 1,100 g of solid monopotassium glyphosate were weighed into a vial. 0.300 g of surfactant was added to the same vial. Enough deionized water was added to the vial to bring the final weight to 2,000 g. The rest of the protocol is the same as that described for the samples at 31% by weight. The surfactants identified in Table 4 that were compatible with the 45 wt% ae / 10 wt% potassium glyphosate loading are listed in Table 5 below.

For NH glyphosate compositions4+ at 31% by weight of ea / surfactant at 10% by weight:

1.48 g of aqueous diammonium glyphosate salt solution (1.7 eq) at 41.9% by weight was weighed into a vial. 0.2 g of surfactant and 0.32 g of deionized water were added to the same vial. The rest of the protocol is the same as that described for the 31% by weight potassium glyphosate samples. The surfactants identified in Table 4 that were compatible with the ammonium glyphosate loading at 31% ae / surfactant at 10% by weight are listed in Table 5 below.

For NH glyphosate compositions4+ at 37% by weight of ea / surfactant at 12% by weight:

1.76 g of aqueous diammonium glyphosate salt solution (1.7 eq) at 41.9% by weight was weighed into a vial. 0.2 g of surfactant was added to the same vial. The rest of the protocol is the same as that described for the 31% by weight potassium glyphosate samples. The surfactants identified in Table 4 that were compatible with the ammonium glyphosate loading at 37% ae / surfactant at 12% by weight are listed in Table 5 below.

Viscosity and compatibility data for selected compositions of Example C are listed in Table 5. It is understood that not all results of all compatibility tests are described herein. Some of the surfactants tested (but not described herein) were not compatible even with the 31 wt% loading of ea

Example D

Preparation of α-methyl-α> - (N-methyloctadecylammonium) poly (oxy-1,2-ethanediyl)

Hepta (oxyethylene) glycol (I) methyl ether tosylate

Hepta (oxyethylene) glycol methyl ether (mean MW 350, 47 g, 1 eq., Aldrich) and triethylamine (17.59 g, 1.3 eq.) Were dissolved in anhydrous methylene chloride (20 ml) and put in a nitrogen atmosphere. P-Toluenesulfonyl chloride (28.16 g, 1.1 eq.) Dissolved in anhydrous methylene chloride (20 ml) was added slowly, keeping the temperature below 10 ° C. After stirring for 4 hours at room temperature, the reaction mixture was filtered, and the solvent was removed from the filtrate under reduced pressure to give 64 g of an orange oil, 95% yield. NMR1H d 7.8 (d, 2H), 7.s (d, 2H), 4.1 (t, 2H), 3.6-3.4 (m, 26H), 3.2 (s, 3H) , 2.4 (s, 3H).

Preparation of Compound C of Table 4

N-methyloctadecyl amine (MW 283, 18.49 g, 2.2 eq.) Was dissolved in 200 ml of toluene and then potassium carbonate (4.1 g, 1 eq.) Was added. Tosylate (I) (15 g, 1 eq.) Was slowly added to the mixture and then the reaction was placed under a nitrogen atmosphere and heated overnight at 80 ° C. Solids from the completed reaction were separated by filtration over Celite. Toluene was removed from the filtrate under reduced pressure. The crude product was chromatographed using methylene chloride / methanol / ammonium hydroxide in a ratio 80: 5: 1. 16 g of the yellow semi-solid (II) were obtained, yield 85%. NMR1H, 3.6-3.4p (m, 26H), 3.3p (s, 3H), 2.6p (t, 2H), 2.4p (t, 2H), 2.2p (s, 3H) , 1.4p (m, 2H), 1.2p (s, 30H), 0.8p (t, 3H).

ES 2 269 409 T3

ES 2 269 409 T3

<td>Vise. Haake 25 ° C 101.82 cPs 15 ° C 118.51 cPs 1G ° C 198.34 cPs 5 ° C 221.90cPs 0 ° C 467.60 cPs</td><td>Vise. Haake 25 ° C 1077 cPs 15 ° C 1420 cPs 10 ° C 1963cPs 5 ° C 2269 cPs 0 ° C 2517 cPs -5 ° C, too thick</td><td>Vise. Haake 25 ° C 31.49cPs 15 ° C 64.15 cPs 10 ° C 76cPs i 5 ° C 96.58 cPs 0 ° C 146.77 cPs -5 ° C 164.23 cPs</td>

ES 2 269 409 T3

<td>Viscosity Brookfieid, 10 ° C, Nozzle 31 60 rpm, 60.1 cPs 12 rpm, 52.6 cPs</td><td>ü cu% S%% o 2 ¿g £ 8 o $ O- 2 * S ^ · '<o i S n S ® 3 1 S 8, 8 P? g > CM τ- t— iO oi</td><td>W g <n £ g Or go% £ 2 Φ Nú O CO <O ° CO ff? 0> § ro mn ro ma or or ro Or or «Ioooooy Do 2 © rr fts</td>

ES 2 269 409 T3

ES 2 269 409 T3

<td>Viscosity Brookfield, 10 ° C, Nozzle 31 60 rpm, 113 cPs 12 rpm, 114 cPs</td><td>Viscosity Brookfield, 10 ° C, Nozzle 31 60 rpm, 103 cPs 12 rpm, 107 cPs</td><td></td><td></td><td></td><td>Viscosity Brookfield, 10 ° C, Nozzle 31 60 rpm, 78.2 cPs 12 rpm, 76.5 cPs</td><td></td><td></td><td></td>

ES 2 269 409 T3

<td>No (gel)</td><td>No (gel)</td><td></td><td>Yes (very thick)</td><td>No (gel)</td><td></td><td></td><td>w</td>

<td></td><td></td><td>Yes but amount minority of solid present, initially a gel I know makes fluid</td><td></td><td></td><td></td><td></td><td>Do not</td>

<td></td><td></td><td>Probably yes, but ambiguous due to the amount minority of solid</td><td>w</td><td>Probably yes, but ambiguous due to the amount minority of solid</td><td>, -— | Do not</td><td>Do not</td><td>w</td>

ES 2 269 409 T3

ES 2 269 409 T3

It will be appreciated that compositions of the invention containing non-alkylpolyglucoside potassium glyphosate salt as a component of the surfactant system generally have a lower viscosity than similarly charged APG-containing potassium glyphosate salt compositions. The magnitude of this viscosity advantage depends to some extent on the choice and concentration of the particular surfactant (s) used. For example, the preceding description of specific embodiments of the present invention is not intended to be a complete list of each of the possible embodiments of the invention. Those skilled in this art will recognize that modifications can be made to the specific embodiments described herein that remain within the scope of the invention. Example E

Preparation of RRR-UUU surfactants

Compounds of formulas (36) or (37) were prepared

in which R1 and R9 are independently hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (R2O) pR13; R2 in each of the groups m (R2O), n (R2O), p (R2O) and q (R2O) is independently C2-C alkylene4; R3, R8, R13 and R15 they are independently hydrogen, or a hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R4 is - (CH2) yOR13 or - (CH2)YO (R2O) qR3; R5, R6, and R7 are independently hydrogen, or a hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or R4; R14 is hydrocarbyl or substituted hydrocarbyl having 1 to about 30 carbon atoms, or - (CH2)zO (R2O) pR3; m, n, p and q are independently an average number from 1 to about 50; X is -O-, -N (R14) -, -C (O) -, -C (O) O-, -OC (O) -, -N (R15) C (O) -, -C (O) N (R15) -, -S-, -SO-, or -SO2-; t is 0 or 1; A- is an agriculturally acceptable anion; e and z are independently an integer from 0 to about 30.

The compound was prepared by adding a compound R1-XH to an epoxide in a 1: 1 molar ratio in the presence of a base such as diisobutylaluminum hydride (DIBAL), NaH or a Lewis acid, such as BF3Et2Or, to form intermediate (91) as depicted in the reaction scheme shown below:

ES 2 269 409 T3

Compound (91) is then alkoxylated by conventional means to form a compound of formula (36). When X is -N + R8R9- in the above reaction scheme, compound (37) is formed.

The alkylaminopropanediol compounds having the formula (36), where X is -N (R14) -. R3, R5, R6 and R7 are hydrogen, R2O is ethylene, and R4 is -CH2O (R2O) qR3. Ethylene oxide was used for alkoxylation.

TABLE 6

<td>Compound</td><td>Ri</td><td>R14</td><td>n + q</td><td>Formulation</td>

<td>1 hour</td><td>tallow</td><td>H</td><td> 15</td><td> 421</td>

<td>1i</td><td>tallow</td><td>H</td><td> 23</td><td> 423</td>

<td>1j</td><td>tallow</td><td>H</td><td> 27</td><td> 427</td>

<td>1k</td><td>coconut</td><td>H</td><td> 23</td><td> 425</td>

<td> 11</td><td>coconut</td><td>H</td><td> 30</td><td> 427</td>

Alkylaminopropanol compounds 2a-c having the formula (36), where X is -N (R14) -, R3, R5, R6 and R7 are hydrogen, R2O is ethylene, and R4 is -CH2OCH2C6H5, by reaction of an amine with benzyl-glycidol, followed by alkoxylation and deprotection of the benzyl group by conventional catalytic hydrogenation, so that after R4 is -CH2OR3. Ethylene oxide was used for alkoxylation.

The 2d-j alkyl-aminopropanol compounds having the formula (36), where X is -N (R14) -, R3, R5, R6 and R7 are hydrogen, R2O is ethylene, and R4 is -CH2OR3, by reacting an amine with a corresponding glycidyl ether, followed by alkoxylation. Ethylene oxide was used for alkoxylation.

ES 2 269 409 T3

TABLE 7

<td>Compound</td><td>Ri</td><td>Rl4</td><td>r3</td><td>n</td><td>Formulation</td>

<td>2j</td><td>Ci8H37</td><td>ch3</td><td>Isopropyl</td><td> 5</td><td></td>

<td>2k</td><td>Ci8H37</td><td>ch3</td><td>isopropyl</td><td> 10</td><td></td>

<td> 21</td><td>C12H25</td><td>ch3</td><td>isopropyl</td><td> 5</td><td></td>

<td>2m</td><td>C12H25</td><td>ch3</td><td>isopropyl</td><td> 10</td><td></td>

Compounds (38) and (39) were prepared:

ES 2 269 409 T3 carbon, or - (CH2)zO (R2OR)pR3; m, n, p and q are independently an average number from 1 to about 50; X is -O-, -N (R14) -, -C (O) -, -C (O) O-, -OC (O) -, -N (R15) C (O) -, -C (O) N (R15) -, -S-, -SO-, or -SO2-; t is 0 or 1; A- is an agriculturally acceptable anion; e and z are independently an integer from 0 to about 30.

The compound was prepared by adding a compound R1 -XH to an epoxide in a 1: 2 molar ratio in the presence of a base such as diisobutylaluminum hydride (DIBAL), NaH or a Lewis acid, to form intermediate (92) as represented in the reaction scheme shown then:

Compound (92) is then alkoxylated by conventional means to form a compound of formula (38). When X is -N + R8R9- compound (39) is formed.

The number of alkylene oxide groups formed in the main chain of compound (92) depends on the molar ratio of compound R1 -XH to epoxide present during reaction. If the molar ratio of compound R1 -XH to epoxy is 1: 3, for example R2 is -CH2Ch2- ym is 2 in formula (92). The compound can then be alkoxylated as described above.

Compounds (40), (41), (42) and (43) were prepared:

ES 2 269 409 T3

Compounds of formula (40), (41), (42) or (43) were prepared by adding a compound R1-X- (R2OR)n-XH to an epoxide in a 1: 1 molar ratio in the presence of a base such as diisobutylaluminum hydride (DIBAL) as represented below:

ES 2 269 409 T3

The compound (93) is then alkoxylated by conventional means to form a compound of formula (40). When the starting material includes a quaternary ammonium salt (i.e. one X is -N + R8R9-), the compound has the formula (41) or (42). When two quaternary ammonium salts are present in the starting material (i.e. one X is -N + R8R9- and the other is -N + R11R12-), a compound of formula (43) is formed.

Example F

Preparation of Gemini ZZ, AAA, BBB, CCC glycytoles of formula (28)

Composite ZZ

1,12-methylaminoglucitoldodecane were put: R = methyl, n = 12: 1-deoxy-1- (methylamino) -D-glucitol (MW 195.15 g, 2 eq.), 1.12 dibromododecane (MW 328, 12.6 g, 1 eq.), Sodium bicarbonate (7.1 g, 2.2 eq) and 120 ml of anhydrous dimethylformamide, under nitrogen atmosphere and heated for 17 hours at 70 ° C. After completion of the reaction, unreacted sodium bicarbonate was filtered off, and then DMF was removed from the reaction under reduced pressure. 400 ml of ethyl acetate was added to precipitate the crude product, and the mixture was stirred for several hours to separate the entrapped DMF from the precipitated product. The crude product was recrystallized twice from a 1: 1 methanol / water solution to give 6.68 g of white solid or 15% yield. 300 MHz H NMR, MeOD4: 1.25-1.4 (broad, 16H), 1.5p (quint., 4H), 2.45p (sept., 4H), 2.55p (d, 4H), 3.6-3.8p (complex, 12H). Analysis: C26H58N2O11: Theoretical: C, 54.3, H, 10.1, N, 4.8. Found: C, 54.2, H, 9.9, N, 4.5.

Composite AAA

1,6-hexylaminoglycitol-propane: R = hexyl, n = 3: 1-deoxy-1- (hexylamino) -D-glucitol (MW 265, 15.76 g, 2 eq.), 1,3-dibromopropane were put (MW 202, 6.0 g, 2 eq.), Sodium bicarbonate (5.49 g, 2.2 eq.) And 180 ml of anhydrous dimethylformamide, under nitrogen atmosphere and heated for 17 hours at 70 ° C. After completion of the reaction, unreacted sodium bicarbonate was filtered off, and then DMF was removed from the reaction under reduced pressure. 600 ml of ethyl acetate was added to precipitate the crude product, and the mixture was stirred for several hours to separate the entrapped DMF from the precipitated product. The solvents were decanted and the product was further dried in a vacuum oven overnight at 80 ° C. 12 g of yellow semisolid were obtained which was 90% pure. All attempts at recrystallization or chromatography for further purification were unsuccessful. Yield 71%. 500 MHz H NMR, MeOD4. 0.9p (t, 6H), 1.25-1.4p (broad, 12H), 1.55p (quint, 4H), 1.75p (quint, 2H), 2.55-2.75p (complex, 12H), 3.6-3.8 p (complex, 12H). 50 MHz C NMR, MeOD4: 13.8p, 22.8p, 25.8p, 26.5p, 26.2p, 32.0p, 53.0p, 54.5p, 56.8p, 63.8p, 70.0p, 71.2p, 72 .0p, 72.5p. 2D-NMR experiments provided conclusive structure confirmation.

CCC compound

1.8- hexylaminoglycitol-octane: R-hexyl, n = 8: 1-Dinoxy-1- (hexylamino) -D-glucitol (MW 265, 15.0 g, 2 eq.), 1,8-dibromooctane (MW 262, 7.68 g, 1 eq,), potassium carbonate (8.56 g, 2.2 eq.) And 180 ml of anhydrous dimethylformamide under nitrogen atmosphere and heated for 20 hours at 70 ° C. After completion of the reaction, unreacted sodium carbonate was filtered off, and then DMF was removed from the reaction under reduced pressure. 600 ml of ethyl acetate was added to precipitate the crude product, and the mixture was stirred for several hours to separate the entrapped DMF from the precipitated product. The solvents were decanted and the product was further dried in a vacuum oven overnight at 80 ° C. Further purification was achieved by dissolving the crude product in a minimal amount of methanol and discarding any precipitated solid. 13.6 g of yellow semi-solid were recovered which were 90% pure. Yield 38%. 300 MHz H NMR, MeOD4: 0.9p (t, 6H), 1.21.4p (broad, 18H), 1.4-1.6p (broad, 8H), 2.4-2.6p (complex, 12H), 3.55 -3.8 (complex, 12H).

BBB compound

1.8- octylaminoglucitolpropane: R = octyl, n = 3: 1-deoxy-1- (octylamino) -D-giucitol (MW 293, 6.45 g, 2 eq.), 1,3-dibromopropane (MW 202, 2.2 g, 1 eq.), Sodium bicarbonate (2.0 g, 2.2 eq.) And 60 ml of anhydrous dimethylformamide, under nitrogen atmosphere and heated for 17 hours at 70 ° C. After completion of the reaction, unreacted sodium bicarbonate was filtered off, and then DMF was removed from the reaction under reduced pressure. 200 ml of ethyl acetate was added to precipitate the crude product, and the mixture was stirred for several

ES 2 269 409 T3 hours to separate the entrapped DMF from the precipitated product. The solvents were decanted and the product was further dried in a vacuum oven overnight at 80 ° C. 8.8 g of white semisolid were recovered which were 90% pure. All attempts at recrystallization or chromatography for further purification were unsuccessful. Yield 64%. 600 MHz H NMR, MeOD4: 0.87p (t, 6H), 1.2-1 -35p (broad, 20H), 1.5p (quint, 4H), 1.7p (quint, 2H), 2.5-2.7p ( complex, 12H), 3.6-3.8p (complex, 12H). 600 MHz C NMR, MeOD4: 14.6p, 23.7p, 24.55p, 27.4p, 28.6p, 30.4p, 30.8p, 33.0p, 54.0p, 55.8p, 58.2p, 64.8p, 71 , 7p, 72.5p, 73.0p 73.8p. 2D-NMR experiments provided conclusive structure confirmation.

Example G

Preparation of the compound of formula (23)

An alkoxylated amine was prepared, in which the amine has the formula:

A commercially available ethoxylated alcohol (such as Brij® 58) was converted to the corresponding tosylate by treatment with tosyl chloride in the presence of potassium hydroxide. The resulting tosylate was then reacted with a suitable alkylamine (such as methylamine, benzylamine, dimethylamine, etc.) in anhydrous tetrahydrofuran (THF) at 80 ° C overnight to provide the desired product.

Example H

Preparation of the compound of formula (25)

An alkoxylated poly (hydroxyalkyl) amine is prepared having the following formula:

An appropriate commercially available ethoxylated alcohol (such as Brij® 58) was converted to the corresponding tosylate by treatment with tosyl chloride in the presence of potassium hydroxide. The resulting tosylate was then reacted with an amine derivative (such as n-alkyl glucamines, etc.) in the presence of anhydrous sodium bicarbonate powder in refluxing anhydrous ethanol for one to two days to give the desired product.

Example I

Preparation of the compound of formula (74)

An alkoxylated quaternary ammonium salt is prepared having the following formula:

R * cr ch,

An alkoxylated amine of formula (73) was treated with methylene chloride in anhydrous THF at 50 ° C overnight to provide the desired product.

ES 2 269 409 T3

Example J

Preparation of the compound of formula (32)

An amine oxide was prepared as follows:

I HAVand

CteHtf-tocHsCHWK --- C, 6 ^ 33- (0CKjCH ^ -N- o «· litho

An alkylalkoxy dimethylamine was oxidized with hydrogen peroxide in methanol at room temperature overnight to provide the desired product.

Example K

Preparation of the compound of formula (72)

A guanidine compound of formula (72) was prepared as follows:

An alkylalkoxyamine was converted to the desired product by treatment with formamidosulfonic acid in methanol at room temperature.

Another compound of formula (72) was prepared as follows:

1) OC ^ CBjCKjCI hhh

2) ΝπΜθ ^ / α

The product was synthesized by acylation of the corresponding amine with chloroethyl isocyanate, followed by substitution with dimethylamine.

Example L

Preparation of compounds of formula (78) and (79) | cr | cr q ^ OChiCHíkrOTs --- ► ^^ C ^^ CHzU- ^ CH ^ -lT-íCHíCHzOUC ^ & I i

Compound (79) was made by alkylating tetramethyl-propylenediamine with excess hexadecyl-poly (ethylene oxide) tosylate in ethanol at reflux for two days, and purified by DOWEX 50WX2400 ion exchange resin eluting with 50 concentrated HCl. % in ethanol.

Coco-Ng

TsO-CHz(CHiOChy.np ^ -OTs - ^^ * - Coco-NHCHí{CKiOC4) _fT, C ^ -NH-Coco

Compound (78) was prepared by alkylating cocoamine with polyethylene oxide ditosylate in the presence of powdered anhydrous sodium carbonate in refluxing ethanol for two days.

ES 2 269 409 T3

Example N

Preparation of the compound of formula (26)

A commercially available ethoxylated alcohol is converted to the corresponding tosylate by treatment with tosyl chloride in the presence of potassium hydroxide. The D-glucosamine hydrochloride is then reduced in the presence of sodium borohydride and water to give the ring-open glucosamine salt. In the presence of potassium carbonate, glucosamine is reacted with alkylethoxy tosylate to give the desired product shown below:

D-glucosamine hydrochloride is reduced in the presence of sodium borohydride and water to give the ring-open glucosamine salt. The glucosamine salt is neutralized with sodium hydroxide and reacted with an alkyl aldehyde of suitable chain length under reducing conditions, that is, in the presence of ethanol, 4% Pd / C hydrogen gas at 4.2 kg / cm2 and 40 ° C to give the desired product shown below:

The alkoxylated compounds of formulas (33), (35), (64), and (71) are prepared by selecting a commercially available starting material, such as a tertiary amine, and alkoxylating the starting material by methods known in the art. to form one of the alkoxylated compounds.

Example P

Test of the formation of anisotropic aggregates and / or liquid crystals

Using the different procedures described herein to determine whether a surfactant in the presence of glyphosate forms an anisotropic aggregate, an epicuticular liquid crystal, and / or an intracuticular liquid crystal, the inventors have tested the formation of aggregates on numerous surfactants. anisotropic and / or liquid crystals. A number of surfactants have been tested in the presence of glyphosate using glyphosate isopropylamine formulations while other surfactants have been tested in glyphosate potassium formulations. The following table below illustrates the results of the numerous tests.

ES 2 269 409 T3

<td colspan="6">Nonionic surfactants that have the Formula: CWO- (EO)XH</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>W</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td> 11</td><td> 9</td><td>Neodol 1-9</td><td>N</td><td>N</td><td>N</td>

<td> 12</td><td> 10</td><td>Procol LA-10</td><td>N</td><td>N</td><td>N</td>

<td> 12</td><td> 12</td><td>Procol LA-12</td><td>N</td><td>N</td><td>N</td>

<td> 12</td><td> 15</td><td>Procol l A-15</td><td>N</td><td>N</td><td>S</td>

<td>12 (lauryl)</td><td> 23</td><td>Brij 35</td><td>N</td><td>S</td><td>S</td>

<td> 11-15</td><td> 9</td><td>Tergitol 15-S-9</td><td>N</td><td>N</td><td>N</td>

<td> 11-15</td><td> 12</td><td>Tergitoll 5-S-12</td><td>N</td><td>N</td><td>NE</td>

<td> 11-15</td><td> 15</td><td>Tergitol 15-S-15</td><td>N</td><td>N</td><td>NE</td>

<td> 12-15</td><td> 12</td><td>Neodol 15-12</td><td>N</td><td>N</td><td>S</td>

<td> 16</td><td> 2</td><td>Hetoxol CA-2</td><td>N</td><td>N</td><td>N</td>

<td> 16</td><td> 10</td><td>Hetoxol CA-10</td><td>N</td><td>N</td><td>S</td>

<td> 16</td><td> 20</td><td>Hetoxol CA-20</td><td>S</td><td>S</td><td>S</td>

<td> 16-18</td><td> 9</td><td>Hetoxol CS-9</td><td>N</td><td>N</td><td>S</td>

<td> 16-18</td><td> 15</td><td>Hetoxol CS-15</td><td>N</td><td>N</td><td>S</td>

<td> 16-18</td><td> 20</td><td>Hetoxol CS-20</td><td>NE</td><td>S</td><td>S</td>

<td> 16-18</td><td> 25</td><td>Hetoxol CS-25</td><td>S</td><td>S</td><td>S</td>

<td> 16-18</td><td> 27</td><td>Plurafac A38</td><td>S</td><td>s</td><td>S</td>

<td> 16-18</td><td> 30</td><td>Hetoxol CS-30</td><td>NE</td><td>s</td><td>S</td>

<td>iso 18</td><td> 10</td><td>Arosurf 66 E10</td><td>N</td><td>N</td><td>N</td>

ES 2 269 409 T3

<td>iso18</td><td> 20</td><td colspan="2">Arosurf 66 E20</td><td>N</td><td>S</td><td>S</td>

<td>18 (oleath)</td><td> 10</td><td colspan="2">Brij 97</td><td>N</td><td>S</td><td>S</td>

<td>18 (oleath)</td><td> 20</td><td colspan="2">Brij 98</td><td>NT</td><td>S</td><td>S</td>

<td colspan="4">Other nonionic surfactants in the IPA glyphosate formulation:</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="4">Agrimul PG 2069 alkyl polyglucoside</td><td>N</td><td>N</td><td>N</td>

<td colspan="4">Surfonic DNP 80 (PEG 8-dinonyl-phenol)</td><td>N</td><td>N</td><td>N</td>

<td colspan="4">SurfonicDNP 100 (PEG 10-d¡non¡l-phenol)</td><td>NE</td><td>NE</td><td>S</td>

<td colspan="4">Surfonic DNP 140 (PEG 15-dinonyl-phenol)</td><td>NE</td><td>NE</td><td>S</td>

<td colspan="4">Surfonic DNP 240 (PEG 24-dinonyl-phenol)</td><td>NE</td><td>NE</td><td>S</td>

<td colspan="7">Cationic surfactant that has the Formula: _, (EO), H ''(Buoy</td>

<td colspan="7">In Glyphosate IPA Formulation:</td>

<td>w</td><td colspan="2">x + y</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>coconut (8-16)</td><td colspan="2"> 2</td><td>Ethomeen C / 12</td><td>N</td><td>N</td><td>N</td>

<td>coconut</td><td colspan="2"> 5</td><td>Ethomeen C / 15</td><td>N</td><td>N</td><td>N</td>

<td>coconut</td><td colspan="2"> 10</td><td>Ethomeen C / 20</td><td>N</td><td>N</td><td>N</td>

<td>coconut</td><td colspan="2"> 15</td><td>Ethomeen C / 25</td><td>N</td><td>N</td><td>N</td>

<td>tallow (16-18)</td><td colspan="2"> 2</td><td>Ethomeen T / 12</td><td>N</td><td>N</td><td>N</td>

<td>tallow</td><td colspan="2"> 2</td><td>Armeen T12</td><td>N</td><td>N</td><td>N</td>

<td>tallow</td><td colspan="2"> 5</td><td>Ethomeen T / 15</td><td>N</td><td>N</td><td>N</td>

<td>tallow</td><td colspan="2"> 10</td><td>Ethomeen T / 20</td><td>N</td><td>N</td><td>N</td>

ES 2 269 409 T3

<td>tallow</td><td> 15</td><td>Ethomeen T / 25</td><td>N</td><td>N</td><td>N</td>

<td>stearyl (18)</td><td> 50</td><td>Trymeen6617</td><td>N</td><td>S</td><td>S</td>

<td colspan="6">In Formulation of potassium glyphosate:</td>

<td>coconut (8-16)</td><td> 2</td><td>Ethomeen C / 12</td><td>NE</td><td>N</td><td>S</td>

<td>coconut</td><td> 5</td><td>Ethomeen C / 15</td><td>N</td><td>N</td><td>N</td>

<td>tallow (16-18)</td><td> 2</td><td>Armeen T12</td><td>N</td><td>N</td><td>S</td>

<td>tallow</td><td> 5</td><td>Ethomeen T / 15</td><td>NE</td><td>S</td><td>S</td>

<td colspan="6">Cationic surfactant that has the Formula: zHCrf-N H</td>

<td colspan="6">In Glyphosate IPA Formulation</td>

<td colspan="2">w</td><td>Tradename:</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="2">tallow (16-18)</td><td>Armeen T</td><td>N</td><td>N</td><td>N</td>

<td colspan="6">Cationic surfactant that has the Formula:zch3Cv-N ch3</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td colspan="2">w</td><td>Tradename:</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="2">coconut (8-16)</td><td>Armeen DMCD</td><td>N</td><td>N</td><td>N</td>

<td colspan="2">tallow (16-18)</td><td>Armeen TMCD</td><td>N</td><td>N</td><td>N</td>

<td colspan="2">tallow</td><td>Armeen DMTD</td><td>N</td><td>N</td><td>N</td>

ES 2 269 409 T3

In Formulation of potassium glyphosate

<td colspan="2">w</td><td>Tradename:</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="2">coconut (8-16)</td><td>Armeen DMCD</td><td>N</td><td>N</td><td>N</td>

<td colspan="2">tallow (16-18)</td><td>Armeen DMTD</td><td>N</td><td>S</td><td>S</td>

<td colspan="6">Cationic surfactant that has the Formula: / Cw C * -N H</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td colspan="2">w</td><td>Tradename:</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="2">coconut (8-16) 1</td><td>Armeen 2C</td><td>N</td><td>N</td><td>NE</td>

<td colspan="2">tallow (16-18)</td><td>Armeen 2T</td><td>N</td><td>N</td><td>S</td>

<td colspan="6">Cationic surfactant that has the Formula: / (E0)xh Cw— Ñ ' ch3</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>w</td><td>x + y</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>stearyl (18)</td><td> 7</td><td>NA</td><td>N</td><td>N</td><td>N</td>

<td></td><td> 22</td><td>Arosurf 66 E20</td><td>N</td><td>S</td><td>S</td>

ES 2 269 409 T3

<td colspan="6">Cationic surfactant that has the Formula: / (EO ^ H Cw-N. X</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>w</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>coconut (8-16)</td><td> 5</td><td>NA</td><td>N</td><td>N</td><td>N</td>

<td>coconut</td><td> 10</td><td>NA</td><td>N</td><td>N</td><td>N</td>

<td>coconut</td><td> 15</td><td>NA</td><td>N</td><td>N</td><td>S</td>

<td>coconut</td><td> 20</td><td>NA</td><td>N</td><td>N</td><td>S</td>

<td>tallow (16-18)</td><td> 5</td><td>NA</td><td>NE</td><td>S</td><td>S</td>

<td>tallow</td><td> 10</td><td>NA</td><td>NE</td><td>S</td><td>S</td>

<td>tallow</td><td> 15</td><td>NA</td><td>NE</td><td>S</td><td>S</td>

<td>tallow</td><td> 20</td><td>NA</td><td>NE</td><td>S</td><td>S</td>

<td colspan="6">Cationic surfactant that has the Formula:ZH c, -o— (EO) í— (CHjJa — NsH</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>w</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

ES 2 269 409 T3

<td colspan="6">In Formulation of potassium glyphosate:</td>

<td>w</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>isotridecyloxy</td><td> 5</td><td>Tomah E-17-5</td><td>N</td><td>N</td><td>N</td>

<td colspan="6">Cationic surfactant that has the Formula: C - 0- (EO), - (OHj), -</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>w</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

ES 2 269 409 T3

<td>In Formulation</td><td colspan="5">potassium glyphosate:</td>

<td>w</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="3">Cationic surfactant that has the Formula:</td><td></td><td></td><td></td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>w</td><td>x + y</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>coconut (8-16)</td><td> 2</td><td>Ethoquad C / 12</td><td>N</td><td>N</td><td>NE</td>

<td>coconut</td><td> 5</td><td>NA</td><td>N</td><td>N</td><td>NE</td>

<td>coconut</td><td> 5</td><td>Rewoquat CPEM</td><td>N</td><td>N</td><td>NE</td>

<td>tallow (16-18)</td><td> 2</td><td>Ethoquad T / 12</td><td>N</td><td>N</td><td>N</td>

<td>tallow</td><td> 5</td><td>NA</td><td>N</td><td>N</td><td>NE</td>

<td>tallow</td><td> 10</td><td>Ethoquad T / 20</td><td>N</td><td>N</td><td>NE</td>

<td>tallow</td><td> 15</td><td>Ethoquad 5/25</td><td>N</td><td>N</td><td>NE</td>

<td colspan="6">In Formulation of potassium glyphosate:</td>

<td>w</td><td>x + y</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>coconut (8-16)</td><td> 2</td><td>Ethoquad C12</td><td>NE</td><td>S</td><td>S</td>

<td>coconut</td><td> 5</td><td>NA</td><td>NE</td><td>S</td><td>S</td>

ES 2 269 409 T3

<td>tallow (6-18)</td><td> 5</td><td>Ethoquad T12</td><td>NE</td><td>S</td><td>S</td>

<td colspan="6">Cationic surfactant that has the Formula: (? θ) χΗ X * -y * - (EO) yH Cw</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>w</td><td>x + y</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>tallow (6-18)</td><td> 5</td><td>NA</td><td>NE</td><td>S</td><td>S</td>

<td>tallow</td><td> 10</td><td>NA</td><td>NE</td><td>S</td><td>S</td>

<td>tallow</td><td> 30</td><td>NA</td><td>N</td><td>N</td><td>N</td>

<td colspan="6">Cationic surfactant that has the Formula: ch3r Cw — γ- (B% H (3¾</td>

<td>w</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

ES 2 269 409 T3

Cationic surfactant that has the Formula:

CH3

X-

Cw-N+-CH3 ch3

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td colspan="2">w</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="2">dodecyl (12)</td><td>Arquad C-50</td><td>N</td><td>N</td><td>N</td>

<td colspan="2">tallow (16-18)</td><td>Arquad T-50</td><td>N</td><td>N</td><td>NE</td>

<td colspan="6">In Formulation of potassium glyphosate:</td>

<td colspan="2">w</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td colspan="2">dodecyl (12)</td><td>Arquad C-50</td><td>NE</td><td>S</td><td>S</td>

<td colspan="2">tallow (16-18)</td><td>Arquad T-50</td><td>NE</td><td>S</td><td>S</td>

<td colspan="6">Cationic surfactant that has the Formula: ch3 ch3I í . N__ (CH ^ - N —cw</td>

<td colspan="6">In Glyphosate IPA Formulation:</td>

<td>w</td><td>X</td><td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td> 10</td><td> 2</td><td>Gemini 10-2-10</td><td>NE</td><td>NE</td><td>S</td>

<td> 10</td><td> 3</td><td>Gemini 10-3-10</td><td>NE</td><td>NE</td><td>S</td>

<td> 10</td><td> 4</td><td>Gemini 10-4-10</td><td>NE</td><td>NE</td><td>S</td>

<td> 14</td><td> 2</td><td>Gemini 14-2-14</td><td>NE</td><td>NE</td><td>S</td>

<td> 14</td><td> 3</td><td>Gemini 14-3-14</td><td>NE</td><td>NE</td><td>S</td>

ES 2 269 409 T3

<td colspan="2">16 2 Gemini 16-2-16 NE</td><td>NE</td><td>S</td>

<td colspan="4">Anionic surfactant in glyphosate IPA formulation:</td>

<td>Name</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>oleth-10-phosphate</td><td>N</td><td>N</td><td>S</td>

<td>oleth-20-phosphate</td><td>N</td><td>N</td><td>S</td>

<td>oleth-25-phosphate</td><td>N</td><td>N</td><td>S</td>

<td>2-ethylhexyl-phosphate</td><td>N</td><td>N</td><td>N</td>

<td>laureth-3-phosphate</td><td>N</td><td>N</td><td>N</td>

<td>palmitic acid</td><td>N</td><td>N</td><td>S</td>

<td>oleic acid</td><td>N</td><td>N</td><td>S</td>

<td>stearic acid</td><td>N</td><td>N</td><td>S</td>

<td>caprylic acid</td><td>NE</td><td>NE</td><td>N</td>

<td>sodium alkylbenzenesulfonate</td><td>N</td><td>N</td><td>NE</td>

<td>sodium lauryl sulfate</td><td>N</td><td>N</td><td>S</td>

<td>ethoxylated aryl phosphated</td><td>N</td><td>N</td><td>N</td>

<td>phosphate ester, free acid</td><td>N</td><td>N</td><td>N</td>

<td>nonyl-phenyl ethoxylated phosphated, free acid</td><td>N</td><td>N</td><td>N</td>

<td colspan="4">Amphoteric surfactant in an IPA glyphosate formulation:</td>

<td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>Lecithin</td><td>N</td><td>S</td><td>S</td>

<td>Velvetex® BC coco-betaine</td><td>N</td><td>N</td><td>N</td>

ES 2 269 409 T3

<td colspan="4">Fluorinated surfactant in an IPA glyphosate formulation:</td>

<td>Tradename</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>Fluorad® 135 Alkyl Quaternary Ammonium Iodides</td><td>N</td><td>N</td><td>N</td>

<td>Fluorad® 754 Alkyl Quaternary Ammonium Chlorides</td><td>N</td><td>N</td><td>N</td>

<td>Fluorad® FC129 fluorinated potassium alkyl carboxylate</td><td>N</td><td>N</td><td>N</td>

<td>Fluorad® FC-171 fluorinated alkyl alkoxylate</td><td>N</td><td>N</td><td>N</td>

<td>Fluorad® FC121 ammonium perfluoroalkyl sulfonates</td><td>N</td><td>N</td><td>N</td>

<td>Fluowet PL SO fluorinated / phosphinic phosphinic acid</td><td>N</td><td>N</td><td>N</td>

<td>Surfactant mixtures in IPA glyphosate formulation:</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>Hetoxol CA2 / Ethomeen T / 25</td><td>N</td><td>N</td><td>N</td>

<td>ST 8302 / Ethoquad T / 25</td><td>N</td><td>N</td><td>N</td>

<td>ST 8303 / Ethoquad T / 25</td><td>NE</td><td>S</td><td>S</td>

<td>Arosurf 66 E / 10 / Ethoquad T / 25</td><td>NE</td><td>S</td><td>S</td>

<td>Arosurf 66 E20 / Ethoquad T / 25</td><td>NE</td><td>S</td><td>S</td>

<td>Arosurf 66 E20 / Ethomeen T / 25</td><td>NE</td><td>S</td><td>S</td>

<td>Hetoxol CS20 / Ethomeen T / 15</td><td>NE</td><td>S</td><td>S</td>

<td>Hetoxol CS20 / Ethomeen T / 20</td><td>S</td><td>S</td><td>S</td>

<td>Hetoxol CS20 / Ethomeen T / 25</td><td>S</td><td>S</td><td>S</td>

<td>Hetoxol CS20 / Ethomeen T / 30</td><td>NE</td><td>S</td><td>S</td>

<td>Hetoxol CS20 / Ethomeen T / 35</td><td>NE</td><td>S</td><td>S</td>

<td>Hetoxol CS20 / Ethomeen T / 40</td><td>NE</td><td>S</td><td>S</td>

ES 2 269 409 T3

<td>Hetoxol CS20 / T rymeen 6617</td><td>N</td><td>S</td><td>S</td>

<td>Hetoxol CS20 + Duoquat T-50</td><td>NE</td><td>NE</td><td>N</td>

<td>Hetoxol CS20 + Arquad C-50</td><td>NE</td><td>NE</td><td>S</td>

<td>Hetoxol CS20 + lauryl-choline chloride</td><td>NE</td><td>NE</td><td>S</td>

<td>Hetoxol CS25 + Ethomeen T25</td><td>S</td><td>S</td><td>S</td>

<td>Hetoxol CS15 + Ethomeen T25</td><td>NE</td><td>S</td><td>S</td>

<td>Hetoxol CS20 + Ethomeen T20</td><td>S</td><td>S</td><td>S</td>

<td>Hetoxol CS25 + Ethomeen T20</td><td>S</td><td>S</td><td>S</td>

<td>Hetoxol CS15 + lauryl choline chloride</td><td>NE</td><td>NE</td><td>S</td>

<td>Brij 78 + Ethomeen T20</td><td>S</td><td>S</td><td>S</td>

<td>Brij 78 + Ethomeen T25</td><td>S</td><td>S</td><td>S</td>

<td>Brij 78 + Ethoquad T20</td><td>S</td><td>S</td><td>S</td>

<td>Brij 78 + Ethoquad T25</td><td>S</td><td>S</td><td>S</td>

<td>Neodol 1- 9 / Ethomeen T / 25</td><td>N</td><td>N</td><td>N</td>

<td>Agrimul PG 2069 / Ethomeen T / 25</td><td>N</td><td>N</td><td>N</td>

<td>Tergitol 15-S-9 / Ethomeen T / 25</td><td>N</td><td>N</td><td>N</td>

<td>Tergitol 15-S-12 / Ethomeen T / 25</td><td>N</td><td>N</td><td>N</td>

<td>Tergitol 15-S-15 / Ethomeen T / 25</td><td>N</td><td>N</td><td>N</td>

<td>Procol LA 10 + Ethoquad T25</td><td>NE</td><td>NE</td><td>N</td>

<td>Procol LA 12 + Ethoquad T25</td><td>NE</td><td>NE</td><td>N</td>

<td>Procol La 15 + Ethoquad T25</td><td>NE</td><td>NE</td><td>S</td>

<td>Hetoxol C 520 + PEG 7 dimethylammonium chloride</td><td>NE</td><td>NE</td><td>S</td>

<td>Hetoxol CS20 + PEG 22 dimethylammonium chloride</td><td>NE</td><td>S</td><td>S</td>

<td>Plurafac A 38 + Ethomeen T25</td><td>S</td><td>S</td><td>S</td>

<td>Plurafac A 38 + Ethoquad T25</td><td>S</td><td>S</td><td>S</td>

<td>Plurafac A38 + Ethomeen T20</td><td>S</td><td>S</td><td>S</td>

<td>Plurafac A 38 + Ethoquad T20</td><td>S</td><td>S</td><td>S</td>

<td>Hetoxol CS20 + Gemini 10-2-10</td><td>NE</td><td>NE</td><td>S</td>

<td>Hetoxol CS20 + Gemini 10-3-10</td><td>NE</td><td>NE</td><td>S</td>

<td>Hetoxol CS20 + Gemin¡ 10-4-10</td><td>NE</td><td>NE</td><td>S</td>

100

ES 2 269 409 T3

<td>Hetoxol CS 20 + Gemin¡ 14-2-14</td><td>NE</td><td>NE</td><td>S</td>

<td>Hetoxol CS 20 + Gem¡n¡ 14-3-14</td><td>NE</td><td>NE</td><td>S</td>

<td>Caprylic Acid + Ethomeen T25</td><td>NE</td><td>NE</td><td>N</td>

<td>Capric acid + Ethomeen T25</td><td>NE</td><td>NE</td><td>N</td>

<td>Lauric acid + Ethomeen T25</td><td>NE</td><td>NE</td><td>N</td>

<td>Myristic acid + Ethomeen T25</td><td>NE</td><td>NE</td><td>N</td>

<td>Palmitic acid + Ethomeen T25</td><td>NE</td><td>NE</td><td>S</td>

<td>Oleic acid + Ethomeen T25</td><td>NE</td><td>NE</td><td>N</td>

<td>Lecithin + Ethomeen T25</td><td>N</td><td>N</td><td>S</td>

<td>Lecithin + Ethoquad T25</td><td>N</td><td>N</td><td>S</td>

<td>Lecithin + Ethomeen T20</td><td>N</td><td>N</td><td>S</td>

<td>Lecithin + Ethoquad T20</td><td>N</td><td>N</td><td>S</td>

<td>Lecithin + Fluorad FC 754</td><td>N</td><td>N</td><td>S</td>

<td>Lecithin + Hetoxol CS20</td><td>NE</td><td>S</td><td>S</td>

<td>Lecithin + Hetoxol CS25</td><td>NE</td><td>S</td><td>S</td>

<td>Fluowet PL 80 + Ethomeen T25</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad C12 + Tergitol 15-S-7</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad T12 + Tergitol 15-S-7</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad C12 + Tergitol 15-S-9</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad T12 + Tergitol 15-S-9</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad C12 + Tergitol 15-S-12</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad T12 + Tergitol 15-S-12</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad C12 + Tergitol 15-S-15</td><td>N</td><td>N</td><td>N</td>

<td>Ethoquad C12 + Arosurf66 E10</td><td>NE</td><td>N</td><td>N</td>

<td>Ethoquad T12 + Arosurf 66 E10</td><td>NE</td><td>N</td><td></td>

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<td>Mixtures of surfactants in potassium glyphosate formulation</td><td>CL intra</td><td>CL epi</td><td>AA</td>

<td>Ethoquad C12 + Tergitol 15-S-7</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad T12 + Tergitol 15-S-7</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad C12 + Tergitol 15-S-9</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad T12 + Tergitol 15-S-9</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad C12 + Tergitol 15-S-12</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad T12 + Tergitol 15-S-12</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad C12 + Tergitol 15-S-15</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad T12 + Tergitol 15-S-15</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad C12 + Arosurf 66 E10</td><td>NE</td><td>S</td><td>S</td>

<td>Ethoquad T12 + Arosurf 66 E10</td><td>NE</td><td>S</td><td>S</td>

Cw is an alkyl group that has w carbon atoms

X is a chloride anion

EO is ethylene oxide

AA is an anisotropic aggregate CL intra is intracuticular liquid crystal CL epi is epicuticular liquid crystal

Yes is yes

N is no

NE is untested

NA is not applicable (ie no trade name).

An especially preferred herbicide is N-phosphonomethylglycine (glyphosate), a salt, adduct or ester thereof, or a compound that is converted to glyphosate in plant tissues or that provides the glyphosate ion in another form. Glyphosate salts that can be used in accordance with this invention are summarized in US Patent No. 4,405,531, which is incorporated by reference herein. Glyphosate salts in general are composed of alkali metals, halogens, organic amines, or ammonium, and include, but are not limited to, the following. The mono, di or tri alkali metal salts of potassium, lithium and sodium. The alkaline earth metal salts of calcium, magnesium and barium. Salts of other metals including copper, manganese, nickel and zinc. The mono, di and trihalide salts of fluorine, chlorine, bromine and iodine. Monoammonium, alkyl and phenylammonium salts, including the mono, di and tri forms, comprising ammonium, methylammonium, ethylammonium, propylammonium, butylammonium and aniline. Alkylamine salts, including the mono-, di- and tri- forms, comprising methylamine, ethylamine, propylamine, butylamine, methylbutylamine, stearylamine and tallowamine. Alkenylamine salts based on ethylene, propylene or butylene. Cyclic organic amine salts including pyridine, piperidine, morpholone, pyrrolidone, and picolene. Alkylsulfonium salts of methylsulfonium, ethylsulfonium, propylsulfonium, and butylsulfonium. Other salts include sulfoxonium, methoxymethylamine, and phenoxyethylamine. Preferred glyphosate salts include potassium (mono-, di-, and tri- forms), sodium (mono-, di-, and tri- forms), ammonium, trimethylammonium, isopropylamine, monoethanolamine, and trimethylsulfonium.

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Since the most important herbicidal derivatives of N-phosphonomethylglycine are some of its salts, glyphosate compositions useful in the present invention will be described in more detail with respect to such salts. These salts are known and include ammonium, IPA, alkali metal salts (such as the mono, di, and tripotassium salts), and trimethylsulfonium. The N-phosphonomethylglycine salts are commercially important in part because they are soluble in water. The salts listed immediately above are very soluble in water, and therefore allow highly concentrated solutions that can be diluted at the site of use. According to the method of this invention related to the herbicide glyphosate, an aqueous solution containing a herbicidally effective amount of glyphosate and other components according to the invention is applied to the foliage of plants. Such an aqueous solution can be obtained by diluting a concentrated glyphosate salt solution with water or dispersing solution in water of a dry glyphosate formulation (ie, granular, powder, tablet or briquette).

Exogenous chemicals must be applied to plants at a rate sufficient to give the desired biological effect. Typically application rates are expressed as the amount of exogenous chemical per unit area treated, eg grams per hectare (g / ha). What constitutes a "desired effect" varies according to the patterns and practice of those who research, develop, market, and use a specific class of exogenous chemicals. For example, in the case of a herbicide, the amount applied per unit area to give 85% control of a plant species as measured by reduced growth or mortality is often used to define a commercially effective rate.

Herbicidal efficacy is one of the biological effects that can be enhanced by this invention. "Herbicidal efficacy" as used herein refers to any observable measure of plant growth suppression, which may include one or more of the actions (1) kill), (2) inhibit growth , reproduction or proliferation, and (3) eliminate, destroy, or otherwise diminish the appearance and activity of plants.

The herbicidal efficacy data set forth herein describes "inhibition" as a percentage following a standard procedure in the art that reflects a visual assessment of plant mortality and growth reduction compared to untreated plants, done by specially trained technicians. trained to make and record such observations. In all cases, a single technician makes all evaluations of percent inhibition in any of the experiments or assays. These measurements are based on and regularly published by the Monsanto company in its herbicide trade.

The selection of application rates that are biologically effective for a specific exogenous chemical depends on the skill of the normal agricultural scientist. Those skilled in the art will also recognize that individual plant conditions, time and growth conditions, as well as the specific exogenous chemical and formulation thereof selected, will affect the efficacy achieved when practicing this invention. Useful application rates for exogenous chemicals used may depend on all of the above conditions. Regarding the use of the process of this invention for the herbicide glyphosate, much information is known about proper application rates. Two decades of glyphosate use and published studies related to such use have provided a wealth of information from which a weed control technician can select the glyphosate application rates that are effective as a herbicide in the particular species in which plants are used. particular growth stages, under particular environmental conditions.

Herbicidal compositions of glyphosate or derivatives thereof are used to control a very wide variety of plants around the world. Such compositions can be applied to a plant in a herbicidally effective amount and can effectively control one or more plant species of one or more of the following genera without restriction: Abutilon, Amaranthus, Artemisia, Asclepias, Avena, Axonopus, Borreria, Brachiaria, Brassica, Bromus, Chenopodium, Cirsium, Commelina, Convolvulus, Cynodon, Cyperus, Digitaria, Echinochloa, Eleusine, Elymus, Equisetum, Ipomoeadium, Helianthus Kochia, Lolium, Malva, Oryza, Ottochloa, Panicum, Paspalum, Phalaris, Phragmites, Polygonum, Portulaca, Pteridium, Pueraria, Rubus, Salsola, Setaria, Sida, Sinapis, Sorghum, Triticum, Typha, Ulex, Xanthium, and Zea.

Particularly important species for which glyphosate compositions are used are exemplified without limitation by the following:

Annuals broadleaf:

marshmallow (Abutilon teophrasti), pigweed (Amaranthus spp.) tobacco (Borreria spp.) rapeseed, canola, Indian mustard, etc. (Brassica spp.) Carnation (Commelina spp.)

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ES 2 269 409 T3 Shepherd's pins (Erodium spp.) Sunflower (Helianthus spp.) Morning glory (Ipomoea spp.) Kochia (Kochia scoparia) mallow (Malva spp.) Buckwheat, amphibian polygon, etc. (Polygonum spp.) Purslane (Portulaca spp.) Russian thistle (Salsota spp.) AIDS (Sida spp.) Wild mustard (Sinapis arvensis) cadillo (Xanthium spp.).

Narrow Leaf Annuals:

wild oats (Avena fatua) grass (Axonopus spp.) grass (Bromus tectowm) lent grass (Digitaria spp.) rice millet (Echinochloa crus-galli) houndstooth (Eleusine indica) annual ryegrass (Lolium multiflorum) rice, (Oryza sativa) ottochloa (Ottochloa nodosa) bay grass (Paspalum notatum) canary seed (Phalaris spp.) Foxtail (Setaria spp.) Wheat (Triticum aestivum) corn (Zea mais)

Broadleaf perennials:

sagebrush (Artemisia spp.) milkweed (Asclepias spp.) common thistle (Cirsium arvense) lesser bindweed (Convolvulus arvensis) kudzu (Pueraria spp.)

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Narrow-leaved perennials:

brachiaria (Brachiara spp) common grass (Cynodon dactylon) tigernut (Cyperus esculentus) castanet (C. rotundus) apothecary grass (Elymus repens) reed (Imperata cylindrica) perennial ryegrass (Lolium perenne) Tanzania grass (Panicum maximum) cost ( Paspalum dilatatum) cane (Phragmites spp.) Sorghum (Sorghum halepense) reeds (Typha spp.)

Other perennials:

horsetail (Equisetum spp.) common fern (Pteridium aquilinum) blackberry (Rubus spp.) gorse (Ulex europaeus).

Therefore, the process of the present invention, related to the herbicide glyphosate, can be useful in any of the above species.

Efficacy in greenhouse trials, typically at rates of exogenous chemical lower than those typically effective in this field, is an indicator that tests consistency of performance in the field at normal use rates. However, even the most promising composition sometimes does not show enhanced performance in individual greenhouse trials. As illustrated in the examples herein, a pattern of enhancement emerges from a series of greenhouse trials; When this pattern is identified, it is strong evidence of biological enhancement that will be useful in the field.

The compositions of the present invention can be applied to plants by spraying using any conventional means for spraying liquids, such as spray nozzles, atomizers or the like. The compositions of the present invention can be used in precision agricultural techniques, in which an apparatus is used to vary the amount of exogenous chemical applied to different parts of a field, depending on variables such as the particular plant species present, soil composition, and the like. In one embodiment of such techniques, a global positioning system can be used with the spray apparatus to apply the desired amount of the composition to different parts of a field.

At the time of application to plants the composition is preferably diluted sufficient to easily spray using conventional agricultural spray equipment. Preferred application rates for the present invention vary depending on a number of factors, including the type and concentration of active ingredient and the plant species involved. Useful rates for applying an aqueous composition to the foliage of a field range from about 25 to about 1,000 liters per hectare (l / ha) by spray application. Preferred application rates for aqueous solutions are in the range of about 50 to about 300 l / ha.

Living plant tissues must absorb many exogenous chemicals (including the herbicide glyphosate) and translocate them within the plant in order to produce the desired biological effect (eg, herbicide). Therefore, it is important that the herbicidal composition is not applied in a way that excessively damages and disrupts the normal functioning of the local plant tissue too quickly so that translocation is reduced.

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However, such a limited degree of local damage may be negligible, or even beneficial in its impact on the biological efficacy of some exogenous chemicals.

A large number of compositions are illustrated in the following Examples. Many concentrated glyphosate compositions have provided sufficient herbicidal efficacy in greenhouse trials to warrant field testing on a wide variety of weed species under a variety of application conditions.

The spray compositions of Examples 1-70 contained an exogenous chemical, such as glyphosate potassium salt, in addition to the listed excipient ingredients. The amount of exogenous chemical was selected to provide the desired rate in grams per hectare (g / ha) when applied in a spray volume of 93 l / ha. Different rates of exogenous chemical were applied for each composition. Therefore, except where otherwise noted, when the spray compositions were tested, the concentration of exogenous chemical varied in direct proportion to the rate of exogenous chemical, but the concentration of excipient ingredients remained constant throughout. of the different rates of exogenous chemical.

The concentrated compositions were tested by dilution, dissolution or dispersion in water to form spray compositions. In these spray compositions prepared from concentrates, the concentration of the excipient ingredients varied with that of the exogenous chemical.

In the following illustrative Examples of the invention, greenhouse and field trials were conducted to evaluate the relative herbicidal efficacy of glyphosate compositions. Compositions included for comparative purposes included the following:

Composition 139: consisting of glyphosate salt of IPA 570 g / l in aqueous solution without added surfactant.

Composition 554: consisting of 725 g / l potassium glyphosate salt in aqueous solution without added surfactant.

Composition 754: consisting of glyphosate IPA salt at 50% by weight in aqueous solution, together with surfactant. This formulation is sold by the Monsanto company under the trademark ROUNDUP ULTRAMAX®.

Composition 360: consisting of glyphosate IPA salt at 41% by weight in aqueous solution, together with surfactant. This formulation is sold by the Monsanto company under the trademark ROUNDUP ULTRA®.

Composition 280: consisting of 480 g ea / l of glyphosate IPA salt in aqueous solution, together with ethoxylated ether amine surfactant 120 g / l (M121).

Composition 560: consisting of 540 g ea / l of glyphosate potassium salt in solution, together with ethoxylated ether amine surfactant 135 g / l (M121).

Composition 553: consisting of 360 g ea / l of glyphosate IPA salt in solution, together with ethoxylated quaternary surfactant based on tallowamine with EO-25 111 g / l, polyoxyethylene 10 EO-cetyl-ether 74 g / l and oxide of myristyldimethylamine 12 g / l.

Composition 318: consisting of 487 g of ea / l of potassium glyphosate salt in aqueous solution, together with alcohol ceteh (2PO) (9EO) alkoxylated 65 g / l, (10EO)-tallow-ethoxylated amine 97 g / l and n -octylamine 85 g / l.

Composition 765: consisting of 472 g of ea / l of potassium glyphosate salt in aqueous solution, together with cocoamine 5EO 117 g / l, iso-stearyl-10EO 52 g / l and cocoamine 13 g / l.

Different proprietary excipients were used in the compositions of the Examples. They can be identified as follows:

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<td>Ref.</td><td>Name commercial</td><td>Maker</td><td>Chemical description</td>

<td>AE10</td><td>Arosurf 66 E- 10</td><td>Witco</td><td>Branched alkyl-ethoxylate 10EO</td>

<td>AGN68</td><td>DF 68 (89)</td><td>Agnique</td><td>Silicone defoamer</td>

<td>APG67</td><td>APG 2067</td><td></td><td>Alkyl-polyglucoside C8-10 alkyl group and 1.7 glucose groups</td>

<td>APG69</td><td>APG 2069</td><td></td><td>Alkyl-polyglucoside C8-10 alkyl group and 1.6 glucose groups</td>

<td>AR41</td><td>Arphos HE- 6641</td><td>Witco</td><td>Phosphoric acid C4EO3</td>

<td>ARMC</td><td>Armeen C</td><td></td><td>Primary C8-16 alkyl- (coco) -amine mixture</td>

<td>ARO66</td><td>Arosurf 66 E10</td><td>Witco</td><td>PEG-20 isostearyl ether</td>

<td>ARQ27</td><td>Arquad T-27w</td><td></td><td>27% chloride solution tallow-trimethylammonium</td>

<td>ARQ37</td><td>Arquad 1237W</td><td></td><td>Cocotrimethylammonium chloride (37% in water)</td>

<td>ARQ50</td><td>Arquad C-50</td><td>Akzo</td><td>Coconut trimethylammonium chloride</td>

<td>B1A</td><td>B-2050-01A</td><td></td><td>C16-18 ethoxylated linear alcohol 9.4 EO</td>

<td>B1B</td><td>B-2050-01B</td><td></td><td>C16-18 alkyloxylated linear alcohol 9.4 EO + 2.2 PO</td>

<td>B1C</td><td>B2050-01C</td><td></td><td>C16-18 alkyloxylated linear alcohol 9.4 EO + 4.2 PO</td>

<td>B1F</td><td>B 2050-01F</td><td></td><td>C16-18 alkyloxylated linear alcohol 9.6 EO + 4.4 PO</td>

<td>BRI35</td><td>Brij 35</td><td></td><td>Ethoxylated lauryl ether (23EO)</td>

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<td>BR156</td><td>Brij 56</td><td></td><td>Polyoxyethiienated Cetyl Ether (10EO)</td>

<td>BRI58</td><td>Brij 58</td><td></td><td>Polyoxyethiienated Cetyl Ether (20EO)</td>

<td>BR178</td><td>Brij 78</td><td></td><td>Ethoxylated stearyl ether (20EO)</td>

<td>CETAC</td><td></td><td></td><td>Cetyl trimethylammonium chloride</td>

<td>DUO50</td><td>Duoquat T-50</td><td>Akzo</td><td>Quaternary Alkyldiamine Salt</td>

<td>EA175</td><td></td><td>Tomah</td><td>Eteramlna EO</td>

<td>ED175</td><td></td><td>Tomah</td><td>D¡-ether amine EO</td>

<td>EMC42</td><td>Emcol CC42</td><td>Witco</td><td>Pol¡prop¡lengl¡col-40 chloride diethylammonium</td>

<td>EMUL</td><td>Emulgin L</td><td>Cognis</td><td>Cetereth 2 propoxylate 9 ethoxylate</td>

<td>ΕΤΗ 12</td><td>Ethomeen C12</td><td>Akzo</td><td>Ethoxylated cocoamine 2EO</td>

<td>ΕΤΗ 15</td><td>Ethomeen T / 15</td><td>Akzo</td><td>Ethoxylated tallowamine 5EO</td>

<td>ETH25</td><td>Ethomeen T / 25</td><td>Akzo</td><td>Quaternary ammonium chloride ethoxylated tallow 15EO</td>

<td>ΕΧΡΟΑ</td><td>EXP Β 2030-A</td><td></td><td>Coco-15EO-benyl quaternary</td>

<td>ΕΧΡΟΒ</td><td>EXP Β 2030-B</td><td></td><td>Tallow-15EO-benny quaternary</td>

<td>EXPOC</td><td>EXP B 2030-C</td><td></td><td>N, N-C16-dimethyl-14EO-benyl quaternary</td>

<td>ΕΧΡ86</td><td>Experimental 5880-86B</td><td></td><td>C16-18 alcohol propoxylated 10.4 PO</td>

<td>GEN2</td><td>Genamin T200NF AV 01 / 37-2</td><td>Clariant</td><td>Monoethoxylated alkylamine C18NMe (EO) 7H</td>

<td>GEN3</td><td>Genamin T200NF AV 01 / 37-3</td><td>Clarlant</td><td>Monoethoxylated alkylamine C18NMe (EO) 15H</td>

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<td>GEN4</td><td>Genamin T200NF AV 01 / 37-4</td><td>Clariant</td><td>Monoethoxylated alkylamine C18NMe (EO) 23H</td>

<td>ΗΕΤ20</td><td>Hetoxol CS20</td><td></td><td>Ethoxylated C16-C18 Ether (20EO)</td>

<td>INTOO</td><td>Intermediate 1 RF 8000</td><td>Witco</td><td>Tridecanol phosphate ester + 4 EO (C13) O (CH2CH2) 4 (PO (OH2))</td>

<td>L770</td><td>SilwetL-77</td><td>Witco</td><td>hepamethyl-trisiloxane 7EO-methyl- ether</td>

<td>LF700</td><td>Plurafac LF700</td><td>BASF</td><td>C16-C18 alkoxylated alkyl</td>

<td>Μ117</td><td>MON 59117</td><td></td><td>Ethoxylated ethermine</td>

<td>Μ121</td><td>MON 58121</td><td>Huntsman Surfonic AGM550</td><td>(C12-14) O (CHCH3CH2) O (CHCH3CH2) N (EO) x (EO) y x + y = 5</td>

<td>Μ128</td><td>MON78128</td><td></td><td>Formulation of glyphosate monoethanolamine 480 g ea / l and M121 120 g / l</td>

<td>Μ368</td><td>MON 78368</td><td></td><td>Formulation of glyphosate IPA 357 g ea / l with EMUL 57 g / l, ethoxylated tallowamine (10EO) 85 g / l and n-octylamine 57g / l.</td>

<td>619</td><td>MON68619</td><td></td><td>Glyphosate formulation of IPA 360 g ea / l with ETH25 70 g / l, BRI56 46 g / l and CETAC 23 g / l</td>

<td>Μ620</td><td>MON68620</td><td></td><td>- Glyphosate formulation of IPA 360 g ea / l with ETH25 83 g / l, BRI56 56 g / l and CETAC 27 g / l</td>

<td>ΜΡΕ01</td><td>MPEAE</td><td></td><td>EO-ethermine</td>

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<td>ΜΤ13</td><td>M-T4513-2</td><td>Tomah</td><td>C14-15 dimethylated ether amine 13EO</td>

<td>ΝΕΟ25</td><td>Neo 25-9</td><td></td><td>C12-15 ethoxylated alcohol hydrophobic and 9 EO</td>

<td>Ν013</td><td>Nopar13</td><td>Exxon</td><td>Normal paraffin</td>

<td>OA</td><td></td><td>Fluka</td><td>Octylamine</td>

<td>PG069</td><td>APG-2069</td><td>Agrimul APG</td><td>C9-C11 alkyl ether glucoside</td>

<td>S01</td><td></td><td></td><td>Hexadecyl-eincose (oxide ethylene) dimethylamine</td>

<td>S02</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) 3-amino-propyl-1-amine</td>

<td>S03</td><td></td><td></td><td>Hexadecyl / octadecyl (oxide propylene) -none (ethylene oxide) dimethylamine</td>

<td>S04</td><td></td><td>r</td><td>Tallow-di (propylene oxide) none (ethylene oxide) - dibutylamine</td>

<td>S05</td><td></td><td></td><td>Tallow-di (propylene oxide) none (ethylene oxide) -3'-aminopropylamine.</td>

<td>S06</td><td></td><td></td><td>Tallow-di (propylene oxide) none (ethylene oxide) -N-methylglucamine</td>

<td>S07</td><td></td><td></td><td>Hexadecyl-penta (oxide of propylene) -eicosa (oxide of ethylene) -dimethylamine</td>

<td>S08</td><td></td><td></td><td>Tridecyl-hexa (ethylene oxide) tri (propylene oxide) - dimethylamine</td>

<td>S09</td><td></td><td></td><td>N-methyloctadecylamino-glucitol</td>

<td>S10</td><td></td><td></td><td>Hexadecyl-eicosse (ethylene oxide) dimethylamine</td>

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<td>S11</td><td></td><td></td><td>Hexadecyl-eicosse (oxide ethylene) Tris</td>

<td>S12</td><td></td><td></td><td>Hexadecyl-elcosa (oxide of ethylene) methylamine</td>

<td>S13</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) N-methyl-glucamine</td>

<td>S14</td><td></td><td></td><td>1 -deoxy-1 - (octadecylamino) -Dgiucitol</td>

<td>S15</td><td></td><td></td><td>Tallow-di (propylene oxide) none (ethylene oxide) -N-methylglucamine</td>

<td>S16</td><td></td><td></td><td>N-dodecylglucamine</td>

<td>S17</td><td></td><td></td><td>N-methyloctadecylamine-glucitol</td>

<td>S18</td><td></td><td></td><td>N, N-dimethyloctadecyl-glucitol-chloro- amino quat.</td>

<td>S19</td><td></td><td></td><td>Cetyl alcohol ethoxylate</td>

<td>S20</td><td></td><td></td><td>N-methyldodecylamino-glucitol</td>

<td>S21</td><td></td><td></td><td>N, N-dimethyldodecyl-glucitol-chloro- amino quat.</td>

<td>S22</td><td></td><td></td><td>10 EO isotridecyl phosphate ester (60% monoester)</td>

<td>S23</td><td></td><td></td><td>n-hexyl-glucamine</td>

<td>S24</td><td></td><td></td><td>n-dodecll-glucamine</td>

<td>S39</td><td></td><td></td><td>Elcosano-1,20-bis (chloride of trimethylammonium)</td>

<td>S40</td><td></td><td></td><td>Dodecane-1,12-b¡s (chloride of trimethylammonium)</td>

<td>S41</td><td></td><td></td><td>Hexadecane-1,16-bis (trimethylammonium chloride)</td>

<td>S42</td><td></td><td></td><td>Ν, Ν-octylglucitol -1,3-propane</td>

<td>S43</td><td></td><td></td><td>N, N-dodecylglucitol-1,3-propane</td>

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<td>S44</td><td></td><td></td><td>Ν, N-hexylglucitol-1,3-propane</td>

<td>S45</td><td></td><td></td><td>N, N'-dioctyl-1,3-diamino-propane octa (ethylene oxide)</td>

<td>S46</td><td></td><td></td><td>N, N'-didodecyl-1,3-diaminopropane eicosse (ethylene oxide)</td>

<td>S47</td><td></td><td></td><td>N, N'-didecyl-1,3-diaminopropane deca (ethylene oxide)</td>

<td>S48</td><td></td><td></td><td>N, N'-didecyl-1,3-diaminopropane octadeca (ethylene oxide)</td>

<td>S49</td><td></td><td></td><td>N.N'-didodecyl-1,3-diaminopropane deca (ethylene oxide)</td>

<td>S50</td><td></td><td></td><td>N, N'-didodecyl-1,3-diaminopropane eicosse (ethylene oxide)</td>

<td>S51</td><td></td><td></td><td>Dodecyl-tetra (ethylene oxide) Tris</td>

<td>S52</td><td></td><td></td><td>Tris (hydroxymethyl), N- dodecylaminomethane</td>

<td>S53</td><td></td><td></td><td>Dodecyl-tetra (ethylene oxide) dimethyl amine</td>

<td>S54</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) dimethylamine</td>

<td>S55</td><td></td><td></td><td>Dodecyl-tetra (ethylene oxide) -trimethylammonium chloride</td>

<td>S56</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) -trimethylammonium chloride</td>

<td>S57</td><td></td><td></td><td>Hexadecyl-eicosse (ethylene oxide) -trimethylammonium chloride</td>

<td>S58</td><td></td><td></td><td>Monoethoxylated alkylamine C18NMe (EO) 7.5H</td>

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<td>S59</td><td></td><td></td><td>Monoethoxylated alkylamine C18NMe (EO) 11H</td>

<td>S60</td><td></td><td></td><td>N-methyldodecylamino-glucitol</td>

<td>S61</td><td></td><td></td><td>Ethoxylated cetyl alcohol (10EO)</td>

<td>S62</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) - tris</td>

<td>S65</td><td></td><td></td><td>Octylamino-glucitol</td>

<td>S66</td><td></td><td></td><td>Dodecyl-tetra (ethylene oxide) methyl amine</td>

<td>S67</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) methylamine</td>

<td>S68</td><td></td><td></td><td>Hexadecyl-eicosse (ethylene oxide) methylamine</td>

<td>S71</td><td></td><td></td><td>Bis- [N-hexadecyldeca (ethylene oxide) -propylene] diammonium chloride</td>

<td>S72</td><td></td><td></td><td>Bis- [N-hexadecyleicose (ethylene oxide) -propylene] chloride devil</td>

<td>S73</td><td></td><td></td><td>3- (N-dodecyl-methylamino) -1,2-propanediol-penta (oxide ethylene)</td>

<td>S74</td><td></td><td></td><td>3- (N-dodecyl-methylamino) -1,2 propanediol-deca (ethylene oxide)</td>

<td>S75</td><td></td><td></td><td>3- (N-methyl) -octadecylamino-1,2-propanediol-penta (oxide ethylene)</td>

<td>S76</td><td></td><td></td><td>3- (N-methyl-octadecylamine) -1,2 propanediol-deca (ethylene oxide)</td>

<td>S77</td><td></td><td></td><td>Hexadecyl / octadecyl-di (propylene oxide) -none (ethylene oxide) dimethylamine</td>

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<td>S78</td><td></td><td></td><td>1 -h id roxy-3- (N-methyloctadecylamino) -propan-2-olpenta (ethylene oxide)</td>

<td>S79</td><td></td><td></td><td>1-hydroxy-3- (N-methyloctadecylamino) -propan-2-olnone (ethylene oxide)</td>

<td>S80</td><td></td><td></td><td>1-hydroxy-3- (N-methyldodecylamino) -propan-2-olpenta (ethylene oxide)</td>

<td>S81</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) - hydroxyethylene amine</td>

<td>S82</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) 2'-methylamino-ethylene-N-methyl-amine</td>

<td>S83</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) - 2'-dimethylamino-ethylene-N- methylamine</td>

<td>S84</td><td></td><td></td><td>Hexadecyl-deca (ethylene oxide) 3'-amine-2'-hydroxypropylamine</td>

<td>S85</td><td></td><td></td><td>Ethoxylated methyl stearyl amine 7.5EO</td>

<td>S86</td><td></td><td></td><td>Ethoxylated methyl stearyl amine 5.9EO</td>

<td>S87</td><td></td><td></td><td>Ethoxylated methyl stearyl amine 11EO</td>

<td>S91</td><td></td><td></td><td>Eicosa (ethylene oxide) hexadecylΝ, Ν-dimethylamine</td>

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<td>S92</td><td></td><td></td><td>Tallow-eicosse (ethylene oxide) dimethylamine</td>

<td>S93</td><td></td><td></td><td>Tallow-pentacose (ethylene oxide) dimethylamine</td>

<td>S94</td><td></td><td></td><td>Sebum-eicosa (ethylene oxide) -Tris</td>

<td>S95</td><td></td><td></td><td>Tallow-pentacose (ethylene oxide) - Tris</td>

<td>S96</td><td></td><td></td><td>deca (ethylene oxide) hexadecylΝ, Ν-dimethylamine</td>

<td>S97</td><td></td><td></td><td>deca (ethylene oxide) eicosyl-N, N- dimethylamine</td>

<td>S98</td><td></td><td></td><td>hexadecyl-eicosse (oxide of ethylene) -N-methyl-dodecylamine</td>

<td>S99</td><td></td><td></td><td>Bis- (coco-amino) -eicosose (ethylene oxide)</td>

<td>S100</td><td></td><td></td><td>3-tallowamino-1,2-propanediolpentadeca (ethylene oxide)</td>

<td>S101</td><td></td><td></td><td>3-tallowamino-1,2-propanediol tetraecose (ethylene oxide)</td>

<td>S102</td><td></td><td></td><td>3-tallowamino-1,2-propanedolheptaeicosse (ethylene oxide)</td>

<td>S103</td><td></td><td></td><td>3-cocoamino-1,2-propanedioltrieicosse (ethylene oxide)</td>

<td>S104</td><td></td><td></td><td>3-cocoamino-1,2-propanedoltraconta (ethylene oxide)</td>

<td>SC85</td><td>SC1485</td><td>Albermarle</td><td>Myristyl dimethylamine oxide 8</td>

<td>SUR10</td><td>Surfonic L12- 10</td><td>Huntsman</td><td>Ethoxylated alcohol C10-12 10 EO</td>

<td>SUR12</td><td>Surfonic L12- 12</td><td>Huntsman</td><td>Ethoxylated alcohol C10-12 12 EO</td>

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<td>SUR50</td><td>Surfonic AGM- fifty</td><td>Huntsman</td><td>Alkyl ethermine</td>

<td>SUR6</td><td>Surfonic L12-6</td><td>Huntsman</td><td>Ethoxylated alcohol C10-12 6 EO</td>

<td>SUR9</td><td>Surfonic ADD-9</td><td>Huntsman</td><td>Tridecyl alcohol 9 EO</td>

<td>Τ003Α</td><td>B-1910-03A</td><td></td><td>Seboamine + 10EO</td>

<td>Τ003Β</td><td>B-1910-03B</td><td></td><td>Seboamine + 15EO</td>

<td>T003C</td><td>B-1910-03C</td><td></td><td>Seboamine + 20EO</td>

<td>T003D</td><td>B-1910-03D</td><td></td><td>Seboamine + 25EO</td>

<td>Τ003Ε</td><td>B-1910-03 E</td><td></td><td>Seboamine + 30EO</td>

<td>Τ23Ε2</td><td>T23E1PAE2</td><td>Tomah</td><td>Ethermine with a hydrophobic C12-13 linear alcohol with 1 EO and 2 EO in the C12-amine 13O (OCH2CH2) CH2CH2CH2N (EO) x (EO) yx = y = 2</td>

<td>Τ23Ε5</td><td>T23E1PAE5</td><td>Tomah</td><td>Ethermine with a hydrophobic C12-13 linear alcohol with 1 EO and 5 EO in amine C12- 13O (OCH2CH2) CH2CH2CH2N (EO) x (EO) yx = y = 5</td>

<td>ΤΑΜ 12</td><td>Take it 25-12</td><td></td><td>C12-C15 ethoxylated alcohol (11.9 EO)</td>

<td>TED5</td><td>ED-17-5</td><td>Tomah</td><td>C130 (CH2) 3N (EO) X (CH2) 3N (EO) y (EO) z x + y + z = 5</td>

<td>TER9</td><td>Tergitol 15 S-9</td><td></td><td>Secondary alcohol C11- 15 ethoxylate (9EO)</td>

<td>ΤΡΑΟΕ</td><td>DPA-400E</td><td>Tomah</td><td>Polyethylene Glycol 400 converted to a dieteramine (NH2) (CH2) 3O (CH2CH2) n (CH2) 3- (NH2)</td>

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<td>TPAE6</td><td>NDPA-14-E6</td><td>Tomah</td><td>hexamethylene diol converted to a symmetric ethoxylated di-ethermine with 6 EO (Tomah NDPA with 6 EO)</td>

<td>TQ14</td><td>Q14-M3</td><td>Tomah</td><td>chloride trimethylisodecyloxypropylamine (quaternary ethermine)</td>

<td>TQ17</td><td>Q17-M3</td><td>Tomah</td><td>chloride trimethylisotridecyloxypropylamine (quaternary ethermine)</td>

<td>VAR02</td><td>Varonic K-202</td><td>Witco</td><td>ethoxylated coco-amine 2EO</td>

<td>VAR05</td><td>Varom'c K-205</td><td>Witco</td><td>ethoxylated coco-amine 5EO</td>

<td>WEX5</td><td>Experimental B1910-5</td><td>Witco</td><td>N-dedecioxypropyl-1,3-diaminopropane 3,4 EO</td>

<td>WEX6</td><td>Experimental B1910-6</td><td>Witco</td><td>N-dedecioxypropyl-1,3-diaminopropane 6.1 EO</td>

<td>WEX7</td><td>Experimental B1910-7</td><td>Witco</td><td>N-dedecioxypropyl-1,3-diaminopropane 9.5 EO</td>

<td>WIT05</td><td>Witcamine SIZE 105</td><td>Witco</td><td>Ethoxylated tallow amine 10 EO</td>

<td>WIT305</td><td>Witcamine TAM 305</td><td>Witco</td><td>Coco-amine 5 EO</td>

<td>WIT60</td><td>Witcamine SIZE 60</td><td></td><td>Ethoxylated tallow amine 6 EO</td>

<td>WIT80</td><td>Witcamine SIZE 80</td><td>Witco</td><td>Ethoxylated tallow amine 8 EO</td>

Unless otherwise indicated, the aqueous spray compositions were prepared by mixing the surfactant with the appropriate amount of potassium glyphosate added as a 47.5% by weight solution of ea. The composition was placed in a 55% water bath. ° C to 60 ° C for about 30 minutes until a clear homogeneous solution was obtained. In some compositions the surfactant melted prior to mixing.

The following procedure was used to test the Example compositions for herbicidal efficacy, except where otherwise noted.

Seeds of the indicated plant species were planted in 88 mm pots2 in a soil mixture that was previously sterilized and previously fertilized with slow release fertilizer 14-14-14 NPK at a rate of 3.6 kg / m3. The pots were placed in a greenhouse with sub-irrigation. About a week after leaving, the seedlings were thinned as necessary, including the removal of any unhealthy or abnormal plants, to create a uniform series of test pots.

The plants were kept in the greenhouse for the duration of the test, where they received a minimum of 14 hours of light per day. If natural light was insufficient to meet the daily requirement, artificial light with an intensity of about 475 microeinsteins was used to make up the difference. Exposure temperatures were not controlled

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Different treatments were assigned to the pots in a totally randomized experiment design with 6 reproductions. A group of untreated pots was left as a reference against which the effects of the treatments could then be evaluated.

The application of the glyphosate compositions was done by spraying with a spray train equipped with a 9501 injector calibrated to deliver a spray volume of 93 liters per hectare (l / ha) at a pressure of 165 kilopascals (kPa). After treatment, the pots were returned to the greenhouse until ready for evaluation.

Treatments were done using dilute aqueous compositions. These could be prepared as spray compositions directly from their ingredients or by dilution with water or preformulated concentrated compositions.

To assess herbicidal efficacy, all plants in the test were examined by a single habituated technician, who recorded the percentage of control, a visual measure of the efficacy of each treatment compared to untreated plants. 0% of the control indicates no effect, and 100% of the control indicates that all plants died completely. The% control values recorded represent the mean of all replications of each treatment. Example 1

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 1a.

TABLE 1a

<td>Comp.</td><td>Salt</td><td></td><td>Component 1</td><td>g / i</td><td>Component 2</td><td>g / i</td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 1a and comparative compositions 139, 554, 754 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 1b and 1c.

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TABLE 1b% ABUTH control

<td>Composition</td><td>75 g of ea / ha</td><td>100 g ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td>

TABLE 1c% ECHCF control

<td>Composition</td><td>75 g of ea / ha</td><td>100 g ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td>

Example 2

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 2a.

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TABLE 2a

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 2a and comparative compositions 554, 754 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 2b and 2c.

TABLE 2b% of ABUTH control

<td>Composition</td><td>150 g of ea / ha</td><td>200 g ea / ha</td><td>300 g ea / ha</td><td>400 g of ea / ha</td>

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TABLE 2c% of ECHCF control

<td>Composition</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td><td>400 g of ea / ha</td>

Results for ABUTH and ECHCF: Overall, the formulations in this example were slightly less effective than the conventional 754 and 360.

Example 3

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 3a.

TABLE 3a

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Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 3a and comparative compositions 554, 139 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 3b and 3c.

TABLE 3b% of ABUTH control

<td>Composition n</td><td>100 g ea / ha</td><td>150 g ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td>

TABLE 3c% b of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td>

Results for ABUTH and ECHCF: Taken together, the formulations in this example were not as effective as the conventional 754 and 360. However, formulations 622 and 676 had a yield close to the conventional 360 and 754.

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Example 4

Aqueous concentrate compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 4a.

TABLE 4a

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 4a and comparative compositions 554, 139, 754 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 4b and 4c.

TABLE 4b% of ABUTH control

<td>Composition</td><td>150 g of ea / ha</td><td>200 g ea / ha</td><td>300 g ea / ha</td><td>400 g of ea / ha</td>

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TABLE 4c% of ECHCF control

<td>Composition</td><td>150 g of ea / ha</td><td>200 g ea / ha</td><td>300 g of ea / ha</td><td>400 g of ea / ha</td>

Results for ABUTH and ECHCF: All formulations in this example were determined to be similar to each other for overall efficacy. Neither formulation was as effective as the conventional 360 and 754. Formulations 476F1H and 476B6V were similar to the standard 360 and 754 for ECHCF.

Example 5

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 5a.

TABLE 5a

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 5a and comparative compositions 554, 360, 139, and 754 were applied. The results, average of all the reproductions of each treatment, are shown in Table 5b and 5c.

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TABLE 5b% of ABUTH control

<td>Composition</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td><td>400 g of ea / ha</td>

TABLE 5c% of ECHCF control

<td>Composition</td><td>150 g of ea / ha</td><td>200 g ea / ha</td><td>300 g of ea / ha</td><td>400 g of ea / ha</td>

Results for ABUTH and ECHCF: The 387-15G formulation was similar in efficacy to the conventional 360 and 754 for ABUTH and ECHCF. The 387-24N formulation was the next most effective formulation for ABUTH and ECHCF. Treatments were poorly applied for 387-98C with 300 and 400 g / ha, and therefore no data was collected.

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Example 6

Aqueous concentrate compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 6a.

TABLE 6a

<td>387-13M</td><td>K</td><td> 410</td><td>VAROS</td><td> 132,2</td><td></td><td></td><td></td><td></td>

<td>387-25F</td><td>K</td><td> 476</td><td>VAROS</td><td> 66,2</td><td> 117</td><td> 66,2</td><td></td><td></td>

<td>387-38C</td><td>K</td><td> 488</td><td>VAROS</td><td> 66,7</td><td>APG67</td><td> 66,7</td><td></td><td></td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 6a and comparative compositions 554, 139, 360, and 754 were applied. The results, average of all the reproductions of each treatment, are shown in Table 6b and 6c.

TABLE 6b% of ABUTH control

<td>Composition</td><td>150 g ea / ha</td><td>200 g ea / ha</td><td>300 g ea / ha</td><td>400 g ea / ha</td>

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TABLE 6c% of ECHCF control

<td>Composition</td><td>150 g ea / ha</td><td>200 g ea / ha</td><td>300 g of ea / ha</td><td>400 g of ea / ha</td>

Results for ABUTH and ECHCF: The 387-13M formulation was similar in efficacy to the conventional 360 and 754 for ECHCF. The 387-25F formulation was the next most effective. No formulation in this experiment was as effective as the standard 360 and 754 for ABUTH.

Example 7

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 7a.

TABLE 7a

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 6a and comparative compositions 360, 754, 139, and 554 were applied. The results, average of all the reproductions of each treatment, are shown in Table 7b and 7c.

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TABLE 7b% of ABUTH control

<td>Composition</td><td>75 g ea / ha</td><td>100 g of ea / ha</td><td>150 g ea / ha</td><td>200 g of ea / ha</td>

TABLE 7c% of ECHCF control

<td>Composition</td><td>75 g of ea / ha</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td>

Results for ABUTH and ECHCF: No formulation in this trial was as effective as the conventional 360 and 754. The 615C3M and 615D2M test formulations were the best for efficacy in ABUTH. Example 8

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 8a.

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TABLE 8a

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 8a and comparative compositions 360 and 754 were applied. The results, average of all the reproductions of each treatment, are shown in Table 8b and 8c.

TABLE 8b% of ABUTH control

<td>Composition</td><td>100 g ea / ha</td><td>200 g ea / ha</td><td>300 g ea / ha</td><td>400 g ea / ha</td>

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TABLE 8c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td><td>400 g of ea / ha</td>

Results for ABUTH and ECHCF: No formulation in this assay was as effective as the conventional 360 and 754 for ABUTH. However, most of the formulations were similar to the 754 standard for ECHCF. Example 9

Aqueous concentrate compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 9a.

TABLE 9a

<td>652A9K</td><td>K</td><td> 540</td><td>ETH12</td><td> 54,0</td><td>WIT60</td><td> 54,0</td><td>INTOO</td><td> 27,0</td>

<td>652B8S</td><td>K</td><td> 540</td><td>ETH12</td><td> 54,0</td><td>WIT80</td><td> 54,0</td><td>INTOO</td><td> 27,0</td>

<td>651E2D</td><td>K</td><td> 540</td><td>ETH12</td><td> 54,0</td><td>WIT60</td><td> 54,0</td><td>INTOO</td><td> 30,0</td>

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Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 9a and comparative compositions 139, 553, 360 and 754 were applied. The results, average of all the reproductions of each treatment, are shown in Table 9b and 9c.

TABLE 9b% of ABUTH control

<td>Composition</td><td>100 g ea / ha</td><td>150 g of ea / ha</td><td>200 g ea / ha</td><td>300 g ea / ha</td>

TABLE 9c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td>

Results for ABUTH and ECHCF: Compositions 652A9K, 652B8S, and 651E2D were slightly superior to compositions 650C7S, 651H9E, and 649G2S in ABUTH. The yield of the compositions was slightly less than the yield of the 360 composition.

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Example 10

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 10a.

TABLE 10a

<td>Comp.</td><td>Salt</td><td>g / i</td><td>Component 1</td><td>g / i</td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 10a and comparative compositions 560, 754 and 350 were applied. The results, average of all the reproductions of each treatment, are shown in Table 10b and 10c.

TABLE 10b% of ABUTH control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td>

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TABLE 10c% of ECHCF control

<td>Composition</td><td>100 g ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td>

Results for ABUTH and ECHCF: Composition 140C5L exhibited similar herbicidal efficacy versus comparative composition 560 on marshmallow (ABUTH) and demonstrated higher herbicidal efficacy versus comparative composition 560 on rice field millet (ECHCF). Composition 129D2D produced one of the weakest yields in marshmallow but was similar to Composition 560 in rice millet. Increasing the surfactant from 9.9% (composition 127A3K and 127B4S) to 13.2% (compositions 129A8D and 129B7W) did not substantially affect performance.

Example 11

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 11a.

TABLE 11a

<td>024E0P</td><td>K</td><td> 485</td><td>S87</td><td> 91</td><td>ETH12</td><td> 91</td><td>Oxalic acid</td><td> 13</td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 11a and comparative compositions 139, 554, 754 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 11b and 11c.

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TABLE 11b% of ABUTH control

<td>Composition</td><td>100 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td><td>400 g of ea / ha</td>

TABLE 11c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td><td>400 g of ea / ha</td>

Example 12

Aqueous concentrate compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 12a.

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TABLE 12a

<td>Comp.</td><td>Salt</td><td>g / i</td><td>Component 1</td><td>g / i</td><td>Component 2</td><td>g / i</td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 12a and comparative compositions 139, 554, 754 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 12b and 12c.

TABLE 12b% of ABUTH control

<td>Composition</td><td>100 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td><td>400 g ea / ha</td>

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TABLE 12c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td><td>400 g of ea / ha</td>

Results for ABUTH and ECHCF: All compositions exhibited enhanced herbicidal efficacy versus compositions 139 and 554.

Example 13

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 13a.

TABLE 13a

<td>765T5</td><td>K</td><td> 473</td><td>ARO66</td><td> 4%</td><td>VAROS</td><td> 9,0%</td><td>ARMC</td><td> 1,0%</td>

Compositions 677I9 and 563P5 additionally contain 102 g / l ethylene glycol.

The compositions in Table 13a and comparative composition 754 were sprayed in Fredericksburg, Texas on 5-7.5 cm tall tame nettle (LAMAM), a common winter annual plant treated with ROUNDUP ULTRA® in pre-burn applications. planted. The results, mean of all the reproductions of each treatment, are shown in Table 13b.

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TABLE 13b

Example 14

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 14a.

TABLE 14a

<td>959D4E</td><td>K</td><td> 480</td><td>ETH12</td><td> 48</td><td>WIT05</td><td> 48</td><td>INT00</td><td> 24</td><td>glycol</td><td> 33</td>

<td>478E2U</td><td>K</td><td> 480</td><td>ETH12</td><td> 48</td><td>WIT05</td><td> 48</td><td>INT00</td><td> 24</td><td>glycol</td><td> 120</td>

<td>960H3C</td><td>K</td><td> 540</td><td>ETH12</td><td> 61</td><td>WIT05</td><td> 74</td><td></td><td></td><td>glycol</td><td> 34</td>

<td>478F6K</td><td>K</td><td> 540</td><td>ETH12</td><td> 61</td><td>WIT05</td><td> 74</td><td></td><td></td><td>glycol</td><td> 102</td>

<td>960J8J</td><td>K</td><td> 540</td><td>ETH12</td><td> 68</td><td>WIT05</td><td> 68</td><td></td><td></td><td>glycol</td><td> 34</td>

<td>693N0L</td><td>K</td><td> 540</td><td>ETH12</td><td> 68</td><td>WIT05</td><td> 68</td><td></td><td></td><td>glycol</td><td> 102</td>

<td>164B1H</td><td>K</td><td> 540</td><td>SUR50</td><td> 100</td><td>Acid citric</td><td> 4</td><td></td><td></td><td></td><td></td>

<td>187A7Y</td><td>K</td><td> 484</td><td>SUR50</td><td> 91</td><td>Acid citric</td><td> 3</td><td></td><td></td><td></td><td></td>

137

ES 2 269 409 T3

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 14a and comparative compositions 554, 754 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 14b and 14c.

TABLE 14b% of ABUTH control

<td>Composition</td><td>100 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td><td>400 g of ea / ha</td>

138

ES 2 269 409 T3

TABLE 14c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td><td>400 g of ea / ha</td>

Conventional formulations 360 and 754 outperformed the formulations in this test. The addition of glycols and citric acid had little effect on efficacy.

Example 15

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 15a.

139

ES 2 269 409 T3

TABLE 15a

<td>Comp.</td><td>Salt</td><td>g / i</td><td>Component 1</td><td>g / i</td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 15a and comparative compositions 139 and 554 were applied. The results, average of all the reproductions of each treatment, are shown in Table 15b and 15c.

TABLE 15b% of ABUTH control

<td>Composition</td><td>75 g ea / ha</td><td>100 g ea / ha</td><td>150 g ea / ha</td>

140

ES 2 269 409 T3

TABLE 15c% of ECHCF control

<td>Composition</td><td>75 g ea / ha</td><td>100 g ea / ha</td><td>150 g ea / ha</td>

Example 16

Aqueous concentrate compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 16a.

TABLE 16a

<td>Comp.</td><td>Salt</td><td>g ea / l</td><td>Component 1</td><td>g / i</td><td>Component 2</td><td>g / i</td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 16a and comparative compositions 139, 554, 754 and 360 were applied. The results, average of all the reproductions of each treatment, are shown in Table 16b and 16c.

141

ES 2 269 409 T3

TABLE 16b% of ABUTH control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td>

TABLE 16c% of ECHCF control

<td>Composition</td><td>100 g ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td>

No K salt formulation outperformed Composition 360 or Composition 754 in controlling marshmallow. Example 17

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 17a and Table 17b.

142

ES 2 269 409 T3

TABLE 17a

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 17a and comparative compositions 139, 765 and 754 were applied. The results, average of all the reproductions of each treatment, are shown in Table 17b and 17c.

TABLE 17b% of ABUTH control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g ea / ha</td><td>200 g ea / ha</td><td>300 g of ea / ha</td>

143

ES 2 269 409 T3

TABLE 17c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td>

All potassium salt formulations were less effective in marshmallow versus composition 360 and 754. The efficacy of the amine and phosphate ester formulations in ECHCF was nearly equivalent to compositions 360 and 754.

Example 18

Aqueous concentrated compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 18a.

TABLE 18a

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 18a and comparative compositions 139, 360, 554 and 754 were applied. The results, average of all the reproductions of each treatment, are shown in Table 18b and 18c.

144

ES 2 269 409 T3

TABLE 18b% of ABUTH control

<td>Composition</td><td>100 g ea / ha</td><td>150 g ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td>

TABLE 18c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g ea / ha</td>

Example 19

Aqueous concentrate compositions containing glyphosate salt and excipient ingredients were prepared as shown in Table 19a.

145

ES 2 269 409 T3

TABLE 19a

<td>676Y5</td><td>K</td><td> 480</td><td>ETH12</td><td> 64</td><td>WIX80</td><td> 64</td><td>INTOO</td><td> 32</td>

<td>677W2</td><td>K</td><td> 480</td><td>ETH12</td><td> 40</td><td>WIT80</td><td> 48</td><td>INTOO</td><td> 24</td>

Marshmallow (ABUTH) and Japanese millet (ECHCF) plants were grown and treated by the above standard procedures. The compositions of Table 19a and comparative compositions 139, 360, 554 and 754 were applied. The results, average of all the reproductions of each treatment, are shown in Table 19b and Table 19c.

TABLE 19b% of ABUTH control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g ea / ha</td><td>300 g ea / ha</td>

146

ES 2 269 409 T3

TABLE 19c% of ECHCF control

<td>Composition</td><td>100 g of ea / ha</td><td>150 g of ea / ha</td><td>200 g of ea / ha</td><td>300 g of ea / ha</td>

Neither salt of glyphosate potassium was as effective as compositions 754 and 360. Two formulations of potassium salt, both with 3: 1 surfactant ratios, performed close to both standards.

Example 20

The surfactant used in Example 68 was Ethomeen C / 15 (ethoxylated cocoamine (15 EO)).

A concentrated aqueous composition containing 606 grams / l ae (29.0% ae) of potassium glyphosate salt and 5.05% surfactant was prepared by a procedure similar to that of Example 66. The relative density was determined of the composition at 20 / 15.6 ° C was 1.399. The cloud point of the composition was determined to be 72 ° C.

147

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Document	Office	Kind	Date
20000205524P	United States of America	–	2000-05-19
20552400	United States of America	P	2000-05-19
20552400	United States of America	P	2000-05-19
20000206628P	United States of America	–	2000-05-24
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20662800	United States of America	P	2000-05-24
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27323401	United States of America	P	2001-03-02
20010274368P	United States of America	–	2001-03-08
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205524P01937648	–	–	–
206628P	–	–	–
273234P	–	–	–
274368P	–	–	–
US20000205524P	–	–	–
US20000206628P	–	–	–
US20010273234P	–	–	–
US20010274368P	–	–	–

Members148

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UY26722A1	Uruguay	A1	2001-07-31
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