MX368779B

Polyanionic polymers.

Abstract

Novel polyanionic polymers that include families of repeating units, such as maleic, itaconic and sulphonate repeating units. The polymers are at least tetrapolymers and can be in the form of acid or as partial or complete salts. The polymers can be synthesized using free radical initiators in the presence of vanadium compounds. Polymers have a variety of uses, particularly in agricultural contexts.

MX368779B, drawing sheet 1 — Sheet 1 of 22

Term

7.9 yearsleft in the term

Expires 27 August 2034.

33 claims: 4 independent, 29 dependent

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REIVINDICACIONES Habiéndose descrito la invención como antecede, se reclama como propiedad lo contenido en las siguientes reivindicaciones:1. Un producto agrícola caracterizado porque comprende fertilizante y un polímero mezclado con el fertilizante, el polímero es un polímero aniónico que comprende al menos cuatro unidades de repetición distribuidas a lo largo de la longitud de una cadena del polímero, las al menos cuatro unidades de repetición incluyen al menos una de cada una de una unidad maleica e itacónica, y dos diferentes unidades de repetición de sulfonato.
2
El producto agrícola de conformidad con la reivindicación 1, caracterizado porque el polímero es un tetrapolímero.
3
El producto agrícola de conformidad con la reivindicación 1, caracterizado porque el fertilizante es fertilizante sólido, y el polímero es aplicado al fertilizante como una dispersión líquida.
4
El producto agrícola de conformidad con la reivindicación 1, caracterizado porque el fertilizante está en forma líquida, y el polímero se mezcla con el fertilizante 1íquido. 165 +ΧΧΧΧΧ' S*·
5
El producto agrícola de conformidad con la reivindicación 1, caracterizado porque el fertilizante se selecciona del grupo que consiste en fertilizantes de arranque, fertilizantes a base de fosfatos, fertilizantes que contienen materiales de nitrógeno, fósforo, potasio, calcio, magnesio, boro, zinc, manganeso, cobre o molibdeno, y compuestos seleccionados del grupo que consiste en yeso, uno o mas miembros del grupo de Kieserita, sulfato de magnesio y potasio, azufre elemental, y sus mezclas.
6
El producto agrícola de conformidad con la reivindicación 1, caracterizado porque el polímero está presente a un nivel de alrededor de 0.001 a 20 g por 100 g del fertilizante.
7
El producto agrícola de conformidad con la reivindicación 1, caracterizado porque el polímero está en combinación con otro polímero aniónico que incluye unidades de repetición de maleicas e itacónicas.
8
Un método para fertilizar suelo, caracterizado porque comprende la etapa de aplicar el producto agrícola de conformidad con la reivindicación 1 al suelo.
9
Un producto agrícola caracterizado porque incluye un polímero en combinación con un fertilizante, el polímero es un polímero aniónico que comprende al menos cuatro unidades de repetición distribuidas a lo largo de la longitud de una cadena del polímero, las al menos cuatro 166 unidades de repetición incluyen al menos una cada una de unidades de repetición tipo B y tipo C, y dos diferentes unidades de repetición tipo G, las unidades de repetición tipo B seleccionadas del grupo que consiste en unidades de repetición, de monómeros sustituidos y no sustituidos de ácido y/o anhídrido maleico, ácido y/o anhídrido fumárico, acido y/o anhídrido mesacónico, mezclas de los anteriores, y cualesquiera isómeros, esteres, cloruros de ácido, y sales parciales o completas de cualquiera de los anteriores, en donde las unidades de repetición tipo B de monómeros sustituidos son sustituidas con uno o más grupos alquilo de C1-C6 de cadena lineal o ramificada sustancialmente libres de estructuras de anillo y átomos de halógeno, y en. donde las sales tienen cationes formadores de sales seleccionados del grupo que consiste en metales, aminas, y mezclas de los mismos, las unidades de repetición tipo C seleccionadas del grupo que consiste en unidades de repetición de monómeros sustituidos o no sustituidos de ácido itacónico, anhídrido itacónico, y cualesquiera isómeros, esteres y las sales parciales o completas de cualquiera de los anteriores, y mezclas de cualquiera de los anteriores, en donde las unidades de repetición tipo C de monómeros sustituidos son sustituidas con uno o más grupos alquilo de C1-C6 de cadena lineal o ramificada sustancialmente libres de estructuras de 167 anillo y átomos de halógeno, y en donde las sales tienen cationes formadores de sales seleccionados del grupo que consiste en metales, aminas, y sus mezclas, las unidades de repetición tipo G seleccionadas del grupo que consiste en unidades de repetición de monómeros sulfonados sustituidos o no sustituidos que poseen al menos un doble enlace carbono-carbono y al menos un grupo sulfonato y que están sustancialmente libres de anillos aromáticos y grupos amida, y cualesquiera isómeros, y las sales parciales o completas de cualquiera de los anteriores, y mezclas de cualquiera de los anteriores, en donde las unidades de repetición tipo G de monómeros sustituidos son sustituidas con uno o más grupos alquilo de C1-C6 de cadena lineal o ramificada sustancialmente libres de estructuras de anillo y átomos de halógeno, y en donde las sales de las unidades de repetición tipo G tienen cationes formadores de sales seleccionados del grupo que consiste en metales, aminas, y mezclas de los mismos, y el polímero aniónico contiene no mas de aproximadamente 10 por ciento en mol de olefinas y/o éteres no de carboxilato. 10. El producto agrícola de conformidad con la reivindicación 5, carácterizado porque el polímero es un tetrapolímero y tiene unidades de repetición maleicas e itacóriicas, y dos unidades de repetición de sulfonato 168 diferentes . 11. El producto agrícola de conformidad con la reivindicación 9, caracterizado porque el fertilizante es fertilizante sólido, y el polímero es aplicado al 5 fertilizante como una dispersión líquida. 12. El producto agrícola de conformidad con la reivindicación 9, caracterizado porque el fertilizante está en forma líquida, y el polímero se mezcla con el fertilizante líquido.
10
10 13. El producto agrícola de conformidad con la reivindicación 9, caracterizado porque el fertilizante se selecciona del grupo que consiste en fertilizantes de arranque, fertilizantes a base de fosfatos, fertilizantes que contienen materiales de nitrógeno, fósforo, potasio, calcio, 15 magnesio, boro, zinc, manganeso, cobre o molibdeno, y compuestos seleccionados del grupo que consiste en yeso, uno o más miembros del grupo de Kieserita, sulfato de magnesio y potasio, azufre elemental, y sus mezclas.
11
14. El producto agrícola de conformidad con la 20 reivindicación 9, caracterizado porque el polímero está presente a un nivel de alrededor de 0.001 a 20 g por 100 g del fertilizante.
12
15. El producto agrícola de conformidad con la reivindicación 9, caracterizado porque el polímero está en 25 combinación con otro polímero aniónico que incluye unidades 169 de repetición de maleicas e itacónícas.
13
16. Un método para fertilizar suelo, caracterizado porque comprende la etapa de aplicar el producto agrícola de conformidad con la reivindicación 9 al suelo.
14
17. Un método caracterizado porque comprende la etapa de aplicar a una planta, hojas de. una planta, una semilla de una planta o una planta terrestre adyacente, una cantidad efectiva de un polímero y un fertilizante, el polímero es un polímero aniónico que comprende al menos cuatro unidades de repetición distribuidas a lo largo de la longitud de una cadena del polímero, las al menos cuatro unidades de repetición incluyen al menos una de cada una de una unidad de repetición maleica e itacónica, y dos diferentes unidades de repetición de sulfonato.
15
18. El método de conformidad con la reivindicación 17, caracterizado porque el polímero es un tetrapolímero.
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19. El método de conformidad con la reivindicación 17, caracterizado parque el fertilizante está en forma líquida, y el polímero se. mezcla con el fertilizante líquido.
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20. El método de conformidad con la reivindicación 17, caracterizado porque el fertilizante está en forma sólida, y el polímero es aplicado a la superficie del fertilizante sólido.
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21. El método de conformidad con la reivindicación 17, caracterizado porque el fertilizante se selecciona del 170 grupo que consiste en fertilizantes a base de fosfatos, fertilizantes que contienen materiales de nitrógeno, fósforo, potasio, calcio, magnesio, boro, zinc, manganeso, cobre o molibdeno, y compuestos seleccionados del grupo que consiste en yeso, uno o más miembros del grupo de Kieserita, sulfato de magnesio y potasio, azufre elemental, y sus mezclas.
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22. El método de conformidad con la reivindicación 17, caracterizado porque el polímero está presente a un nivel de alrededor de 0.001 a 20 g por 100 g del fertilizante.
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23. Un método caracterizado porque comprende la etapa de aplicar a una planta, hojas de una planta, una semilla de una planta o una planta terrestre adyacente, una cantidad efectiva de un polímero y un fertilizante, el polímero es un polímero aniónico que comprende al menos cuatro unidades de repetición distribuidas a lo largo de la longitud de una cadena del polímero, las al menos cuatro unidades de repetición incluyen al menos una de cada una de unidades de repetición tipo B y tipo C, y dos diferentes unidades de repetición tipo Q, las unidades de repetición tipo B seleccionadas del grupo que consiste en unidades de repetición de monómeros sustituidos y no sustituidos de ácido y/o anhídrido maleico, ácido y/o anhídrido fumárico, ácido y/o anhídrido mesacónico, mezclas de los anteriores, y cualesquiera isómeros, esteres, cloruros de ácido, y sales parciales o completas de 171 cualquiera de los anteriores, en donde las unidades de repetición tipo B de monómeros sustituidos son sustituidas con uno o más grupos alquilo de C1-C6 de cadena lineal o ramificada sustancialmente libres de estructuras de anillo y átomos de halógeno, y en donde las sales tienen cationes formadores de sales seleccionados del grupo que consiste en metales, aminas, y mezclas de los mismos, las unidades de repetición tipo C seleccionadas del grupo que consiste en unidades de repetición de monómeros sustituidos o no sustituidos de ácido itacónico, anhídrido itacónico, y cualesquiera isómeros, ésteres y las sales parciales o completas de cualquiera de los anteriores, y mezclas de cualquiera de los anteriores, en donde las unidades de repetición tipo C de monómeros sustituidos son sustituidas con uno o más grupos alquilo de C1-C6 de cadena lineal o ramificada sustancialmente libres de estructuras de anillo y átomos de halógeno, y en donde las sales tienen cationes formadores de sales seleccionados del grupo que consiste en metales, aminas, y sus mezclas, las unidades de repetición tipo G seleccionadas del grupo que consiste en unidades de repetición de monómeros sulfonados sustituidos o no sustituidas que poseen al menos un doble enlace carbono-carbono y al menos un grupo sulfonato y que están sustancialmente libres de anillos aromáticos y grupos amida, y cualesquiera isómeros, y las sales parciales 172 o completas de cualquiera de los anteriores, y mezclas de cualquiera de los anteriores, en donde las unidades de repetición tipo G de monómeros sustituidos son sustituidas con uno o más grupos alquilo de C1-C6 de cadena lineal o ramificada sustancialmente libres de estructuras de anillo y átomos de halógeno, y en donde las sales de las unidades de repetición tipo G tienen cationes formadores de sales seleccionados del grupo que consiste en metales, aminas, y mezclas de los mismos, y el polímero aniónico contiene no más de aproximadamente 10 por ciento en mol de olefinas y/o éteres no de carboxilato.
21
24. El método de conformidad con la reivindicación 23, caracterizado porque el polímero es un tetrapolímero.
22
25. El método de conformidad con la reivindicación 23, caracterizado porque el fertilizante está en forma líquida, y el polímero se mezcla con el fertilizante líquido.
23
26. El método de conformidad con la reivindicación 23, caracterizado porque el fertilizante está en forma sólida, y el polímero es aplicado a la superficie del fertilizante sólido.
24
27. El método de conformidad con la reivindicación 23, caracterizado porque el fertilizante se selecciona del grupo que consiste en fertilizantes a base de fosfatos, fertilizantes que contienen materiales de nitrógeno, fósforo, 173 potasio, calcio, magnesio, boro, zinc, manganeso, cobre o raolibdeno, y compuestos seleccionados del grupo que consiste en yeso, uno o más miembros del grupo de Kíeserita, sulfato de magnesio y potasio, azufre elemental, y sus mezclas.
25
28. El método de conformidad con la reivindicación 23, caracterizado porque el polímero está presente a un nivel de alrededor de 0.001 a 20 g por 100 g del fertilizante.
26
29. El producto agrícola de conformidad con la reivindicación 10, caracterizado porque el tetrapolímero comprende aproximadamente 25-50 por ciento en mol de unidades de repetición maleicas, aproximadamente 40-60 por ciento en mol de unidades de repetición itacónicas, aproximadamente 315 por ciento en mol de unidades de repetición metialilsulfónicas, y aproximadamente 0.5-8 por ciento en mol de unidades de repetición alilsulfónicas, en donde la cantidad total de todas las unidades de repetición en el polímero se toma como 100 por ciento en mol.
27
30. El producto agrícola de conformidad con la reivindicación 29, caracterizado porque el tetrapolímero comprende aproximadamente 30-45 por ciento en mol de unidades de repetición maleicas, aproximadamente 40-55 por ciento en mol de unidades de repetición itacónicas, aproximadamente 4-6 por ciento en mol de unidades de repetición metialilsulfónicas, y aproximadamente 1-5 por ciento en mol de unidades de repetición alilsulfónica en donde la 174 cantidad total de todas las unidades de repetición en el polímero se toma como 100 por ciento en mol.
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31. El producto agrícola de conformidad con la reivindicación 30, caracterizado porgue el tetrapolímero comprende 4 5 por ciento en mol de unidades de repetición, maleicas, 50 por ciento en mol de unidades de repetición itacónicas, 4 por ciento en mol de unidades de repetición metialilsulfónicas, y 1 por ciento en mol de unidades de repetición alilsulfónicas, en donde la cantidad total de todas las unidades de repetición en el polímero se toma como 100 por ciento en mol.
29
32. El producto agrícola de conformidad con la reivindicación 29, caracterizado porque el tetrapolímero comprende aproximadamente 30 por ciento en mol de unidades de repetición maleicas, aproximadamente 50 por ciento en mol de unidades de repetición itacónicas, aproximadamente 15 por ciento en mol de unidades de repetición metialilsulfónicas, y aproximadamente 5 por ciento en mol de unidades de repetición alilsulfónicas, en donde la cantidad total de todas las unidades de repetición en el polímero se toma como 100 por ciento en mol.
30
33. El método de conformidad con la reivindicación 22, caracterizado porque el tetrapolímero comprende aproximadamente 25-50 por ciento en mol de unidades de repetición maleicas, aproximadamente 4 0-60 por ciento en mol .175 de unidades de repetición itacónicas, aproximadamente 3-15 por ciento en mol de unidades de repetición metialilsulfónicas, y aproximadamente 0,5-8 por ciento en mol de unidades de repetición alilsulfónicas, en donde la cantidad total de todas las unidades de repetición en el polímero se toma como 100 por ciento en mol.
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34. El método de conformidad con la reivindicación 33, caracterizado porque el tetrapolímero comprende aproximadamente 30-45 por ciento en mol de unidades de repetición maleicas, aproximadamente 40-55 por ciento en mol de unidades de repetición itacónicas, aproximadamente 4-6 por ciento en mol de unidades de repetición metialilsulfónicas, y aproximadamente 1-5 por ciento en mol de unidades de repetición alilsulfónicas, en donde la cantidad total de todas las unidades de repetición en el polímero se toma como 100 por ciento en mol.
32
35. El método de conformidad con la reivindicación 34, caracterizado porque el tetrapolímero comprende 45 por ciento en mol de unidades de repetición maleicas, 50 por ciento en mol de unidades de repetición itacónicas, 4 por ciento en mol de unidades de repetición metialilsulfónicas, y 1 por ciento en mol de unidades de repetición alilsulfónicas, en donde la cantidad total de todas las unidades de repetición en el polímero se toma como 100 por ciento en mol.
33
36. El método de conformidad con la reivindicación 33, caracterizado porque el tetrapolímero comprende aproximadamente 30 par ciento en mal de unidades de repetición maleicas, aproximadamente 50 por ciento en mol de unidades de repetición itacónicas, aproximadamente 15 por 5 ciento en mol de unidades de repetición metialilsulfónicas, y aproximadamente 5 por ciento en mol de unidades de repetición alilsulfónicas, en donde la cantidad total de todas las unidades de repetición en el polímero se toma como 100 pox' ciento en mol.

Independent claims33

623 paragraphs in 4 sections, as filed

FERTILIZERS WITH POLYANIONIC POLYMERS AND METHOD FOR APPLYING POLYANIONIC POLYMERS TO PLANTS

Field of the Invention

The present invention broadly relates to a new class of substantially water-soluble biodegradable polyanionic polymers, and to syntheses thereof that find particular utility in agricultural uses, for example, applied directly to the soil, or in combination with fertilizers to increase absorption of nutrients; as seed coatings and pesticide adjuvants; to reduce atmospheric ammonia derived from animal manures; as animal feed and water modifications; and to inhibit nitrification, urease hydrolysis, and phosphate binding in soils. More particularly, the invention relates to novel polymers that are at least tetrapolymers and preferably contain specific types of sulfonate and carboxylic repeat units, as well as methods of synthesis of dicarboxylate / sulfonate polymers including the novel polymers herein. Other uses of polyanionic polymers, alone or in combination with other polyanionic polymers (eg, dicarboxylic) and / or other functional ingredients, are also described.

Ref. 264524

Background of the Invention

For several years, Specialty Fertilize Products, LLC of Leawood, Kansas, has marketed a series of aqueous dispersions of maleic-itaconic polymers in the form of a partial salt. These products include AVAIL® for use with granular and liquid fertilizers (respectively the partial sodium and ammonium salts), and NUTRISPHERE-N® for use with granular and liquid fertilizers (the partial calcium salt). For example, such products can be sprayed or otherwise applied to the surface of solid fertilizers, such as urea, ammonium salts, monoammonium phosphate (MAP), diammonium phosphate (DAP), potash, and gypsum, or mixed with liquid fertilizers. , such as UAN and ammonium polyphosphate.

These previous products have been shown to have a number of surprising agricultural properties, including the ability to enhance the absorption of fertilizer nutrients (eg, phosphates, nitrogen, potassium, and micronutrients), to act as adjuvants for pesticides such as glyphosate herbicides, and, when supplemented with an organic drying agent, to dry very quickly when applied to solid fertilizers, thus facilitating the production of final coated solid fertilizer products. Furthermore, preferred polymers have been shown to have improved activity when fertilizer formulations containing different types of partial polymer salts are employed (US Patent Publication No. 2009-0217723). This technology is also described in US Patent Nos. 6,515,090, 7,655,597, 5 7,736,412, and 8,043,995 and related patents.

Despite the success of the above maleicositaconic polymers, agriculturally useful polymers having even higher activities would be desirable.

Brief Description of the Invention

The present invention overcomes the problems outlined above and provides a new class of polymers preferably having a high carboxylate content and sulfonate repeating units, which are highly water soluble and biodegradable. Polymer is a broad term herein, encompassing homopolymers and copolymers, the latter containing any number of different repeating units or moieties, such as terpolymers or tetrapolymers. The new preferred polymers herein are at least tetrapolymers 20 having at least four different repeating units distributed along the lengths of the polymer chains, preferably with at least one repeating unit of each of maleic repeating units , itaconic and sulfonate. Repeat units are suitably derived from corresponding monomers used in the synthesis of polymers, and have at least one repeat unit from each of three categories of separately defined repeat units, referred to herein as repeat units type B, type C and type G, and are explained in detail below.

The invention has a number of aspects, relating to the new polymers, synthesis of polyanionic polymers, and various uses of the new polymers, alone or in combination with other anionic polymers.

one. The new polymers

The new anionic polymers comprise at least four repeating units distributed along the length of the polymer chain, the at least four repeating units include at least one of each of type B, type C and type repeating units. G, Type B repeat units are selected from the group consisting of repeat units derived from substituted and unsubstituted monomers of acid and / or maleic anhydride, acid and / or fumaric anhydride, mesaconic acid and / or anhydride, mixtures of the foregoing, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein type B repeating units may be substituted with one or more alkyl groups C1-C6 straight or branched chain substantially free of ring structures and halogen atoms, and wherein the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the above, and mixtures of any of the above, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, at least about 90 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units, and mixtures thereof, the repeat units are found randomly throughout of the polymer, the polymer contains no more than about 10 mole percent of any of (I) non-carboxylate olefin repeating units, (ii) ether repeat units and (iii) unsulfonated monocarboxylic repeat units.

Preferably, the polymers comprise at least about 96 mole percent of the repeat units therein selected from the group consisting of type B, C and G repeat units and mixtures thereof, and still more preferably consist essentially of units repeater units selected from the group consisting of type B, C, and G repeat units and mixtures thereof. The polymers are also substantially free of ester groups and non-carboxylate olefin groups.

Especially preferred polymers have a type B repeat unit, a type C repeat unit, and two different type G repeat units, especially when the type B repeat unit is derived from maleic acid, the type C repeat unit is derived of itaconic acid, and the two repeating units type G are derived, respectively, from metalylsulfonic acid and allylsulfonic acid. In these polymers, the type B repeating unit is present at a level of about 35 to 55 mole percent, the type C repeating unit is present at a level of about 20 to 55 mole percent, the repeating unit type G derived from metalylsulfonic acid is present at a level of about 1-25 mole percent, and the type G repeat unit derived from allylsulfonic acid is present at a level of about 1 to 25 mole percent, where the total amount of all repeating units in the polymer is taken as 100 percent by mole. Other useful polymers comprise two different type B repeat units, a type C repeat unit, and a type G repeat unit, and wherein the polymer has at least one repeat unit selected from the group consisting of type B repeat units , type C and type G.

Suitably, the total amount of type B repeating units in the polymer is about 1-70 mole percent, the total number of type C repeating units in the polymer is about 1-80 mole percent, and the total amount of type G repeating units in the polymer is about 0.1 to 65 mole percent, where the total amount of all repeating units in the polymer is taken as 100 mole percent. Even more preferably, the total amount of type B repeating units in the polymer is about 20-65 mole percent, the total amount of type C repeating units in the polymer is about 15-75 mole percent, and the total amount of type G repeating units in the polymer is from about 1 to 35 mole percent, where the total amount of all repeating units in the polymer is taken as 100 mole percent.

The new polymers generally have a molecular weight of about 800-50,000, and more preferably of about 1000-5000. The polymers of the invention may be in free acid form or in partial or complete salt form, including one or more salt forming cations attached to the polymer. Such salt-forming cations are generally selected from the group consisting of metal cations, amines, micronutrients, and mixtures thereof, and especially those selected from the group consisting of alkali, alkaline earth, and transition metal cations.

The polymers of the invention can be used alone or in combination with another anionic polymer that includes maleic and itaconic acid repeating units. Furthermore, formulations containing polymers comprising a polymer according to the invention can be prepared in combination with one or more other ingredients, selected from the group consisting of boric acid, boron-containing compounds, boric compound solvents, alcohols, diols , polyols, organic acids, polyvinyl alcohols, dyes and mixtures thereof.

2. Synthesis of the polymer

The invention also provides useful polymer synthesis methods for the production of a variety of polymers containing dicarboxylate and sulfonate repeat units, including the novel polymers of the invention. Such methods comprise the stages of:

form an aqueous dispersion containing dicarboxylate and sulfonate repeat unit monomers, the dicarboxylate repeat unit monomers selected from the group consisting of type B repeat unit monomers, type C repeat unit monomers, and mixtures thereof, type B repeat unit monomers are selected from the group consisting of substituted and unsubstituted monomers of maleic acid and / or anhydride, fumaric acid and / or anhydride, mesaconic acid and / or anhydride, mixtures of the foregoing, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein the monomers of type B repeat units can be substituted with one or more straight or branched chain C1-C6 alkyl groups substantially free of ring structures and halogen atoms, and wherein the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, monomers of type C repeating units selected from the group consisting of substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing , and mixtures of any of the above, wherein the C-type repeat unit monomers may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have selected salt-forming cations from the group consisting of metals, amines, and mixtures thereof, the sulfonate repeat unit monomers selected from the group consisting of type G repeat unit monomers, monomers of type G repeating units selected from the group consisting of substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups, and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof;

heat the dispersion to an elevated temperature of about 50 to 125 ° C and add a vanadium compound to the dispersion; and then adding a free radical initiator comprising at least about 95% by weight of hydrogen peroxide to the dispersion, and causing the monomers within the dispersion to polymerize in an oxygen-containing environment until at least about 90% in The weight of the monomers have been converted to the polymer.

In preferred forms, the vanadium compound is added to the dispersion after the heating step, and the free radical initiator is added over a period of about 30 minutes - 24 hours while maintaining the dispersion at elevated temperature. The free radical initiator also preferably consists essentially of hydrogen peroxide. The synthesis is best carried out with the exclusion of substantial amounts of dissolved iron species and sulfate salts, and in an ambient air environment. Polymerization is usually carried out until at least about 98% by weight of the monomers has been converted into the polymer.

In preferred forms, the monomers comprise maleic monomers, itaconic monomers, allylsulfonate monomers, and metalylsulfonate monomers, and the vanadium compound is vanadium oxysulfate. The polymers can be recovered in the acid form or can be converted into partial or complete salts.

For best results, Type B repeating units are present at a level of less than 5 0 mole percent, and repeating units are randomly dispersed throughout the polymer.

In another aspect of the synthesis method, a polymer containing dicarboxylate and sulfonate repeat units can be prepared by a method comprising the steps of:

form an aqueous dispersion containing dicarboxylate and sulfonate monomers;

In preferred forms of this method, the vanadium compound is added to the dispersion after the heating step, and the free radical initiator is added over a period of about 30 minutes - 24 hours while maintaining the dispersion at temperature elevated. The free radical initiator preferably consists essentially of hydrogen peroxide, and the dispersion is prepared to the exclusion of substantial amounts of dissolved iron species and sulfate salts.

Polymerization is best carried out in an ambient air environment, and until at least about 98% by weight of the monomers have been converted into the polymer. The monomers comprise maleic monomers, itaconic monomers, allylsulfonate monomers, and metalylsulfonate monomers, and the vanadium compound is vanadium oxysulfate. As before, the polymers can be recovered in acid form or as partial or complete salts.

3. Fertilizer products

The invention also provides agricultural products and uses thereof, wherein the products comprise fertilizer and a polymer mixed with the fertilizer, the polymer being an anionic polymer comprising at least four repeating units distributed along the length of the chain of the polymer, the at least four repeating units including at least one of each of type B, type C and type G repeating units, Type B repeating units are selected from the group consisting of repeating units derived from substituted and unsubstituted monomers of maleic acid and / or anhydride, fumaric acid and / or anhydride, mesaconic acid and / or anhydride, mixtures of the foregoing, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein the type B repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group Consisting of metals, amines, and mixtures thereof, the anionic polymer contains no more than about 10 mole percent olefins and / or non-carboxylate ethers.

The fertilizer can be a solid, and in particular granular, fertilizer, and the polymer is applied to the fertilizer as a liquid dispersion. Alternatively, the fertilizer can be in liquid form, and the polymer is mixed with the liquid fertilizer. Fertilizers are preferably selected from the group consisting of starter fertilizers, phosphate-based fertilizers, fertilizers containing nitrogen, phosphorous, potassium, calcium, magnesium, boron, zinc, manganese, copper or molybdenum materials. An especially preferred solid fertilizer is urea. When the fertilizers are solid, the polymer is preferably present at a level of about 0.001 to 20 g per 100 g of fertilizer. The tetrapolymers of the invention can be used alone or in combination with another anionic polymer that includes maleic and itaconic acid repeating units.

More generally, the invention provides agricultural products comprising fertilizer and a polymer mixed with the fertilizer, the polymer being an anionic polymer comprising at least four repeating units distributed along the length of the polymer chain, and the units of Repeats include at least one each of a maleic, itaconic, and sulfonate repeat unit. More preferably, the polymer is a tetrapolymer and have maleic and itaconic acid repeat units, and two different sulfonate repeat units. The polymers can be recovered as a free acid or as partial or complete salts, and preferred forms include an amount of a micronutrient that is preferably bound or complexed with the polymer.

All the fertilizer / polymer products of the invention can be used by applying these products to the soil.

Four. Pesticide products

The invention provides pesticide products comprising a pesticide and a polymer, the polymer being an anionic polymer comprising at least four repeating units distributed along the length of the polymer chain, the at least four repeating units including at least one of each type B, type C and type G repeat units, Type B repeating units are selected from the group consisting of repeating units derived from substituted and unsubstituted monomers of maleic acid and / or anhydride, fumaric acid and / or anhydride, mesaconic acid and / or anhydride, mixtures of the foregoing, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein the type B repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group Consisting of metals, amines, and mixtures thereof, the anionic polymer contains no more than about 10 mole percent olefins and / or non-carboxylate ethers.

A wide variety of pesticides can be used in these products, such as those selected from the group consisting of herbicides, insecticides, fungicides, and nematocides. The entire product may be in solid, liquid or aerosol form, and may also include another polymer that includes maleic and itaconic acid repeating units. The polymers can be in the acid form, or as partial or complete salts.

More generally, the invention provides pesticide products comprising a pesticide and a polymer, the polymer being an anionic polymer comprising at least four repeating units distributed along the length of the polymer chain, the repeating units include at least each one of a maleic, itaconic and sulfonate repeating unit.

Particularly preferred compositions comprise a polymer mixed with glyphosate and micronutrients, the polymer being an anionic polymer comprising at least four repeat units distributed along the length of the polymer chain, the repeat units include at least one each of a maleic, itaconic and sulfonate repeating unit. Again, the polymers in these compositions can be in combination with another anionic polymer that includes maleic and itaconic acid repeat units, and the micronutrients can be complexed with the polymer. The polymers can be in the acid form, or as partial or complete salts.

All of the pesticide products of the invention can be used in pesticide methods comprising the step of applying the products to the soil, hard surfaces, and leaves of plants.

5. Sulfur Products

The invention further provides products comprising a compound selected from the group consisting of gypsum, one or more members of the Kieserite Group, magnesium and potassium sulfate, elemental sulfur, and mixtures thereof, and a polymer, the polymer being an anionic polymer comprising at least four repeating units distributed along the length of the polymer chain, the at least four repeating units including at least one each of type B, type C and type G repeating units, type B repeating units are selected from the group consisting of repeating units derived from substituted and unsubstituted monomers of acid and / or maleic anhydride, acid and / or fumaric anhydride, acid and / or mesaconic anhydride, mixtures of the above, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein type B repeating units can be substituted with one or more straight-chain or branched C1-C6 alkyl groups substantially free of ring structures and halogen atoms, and in where the salts have salt forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group Consisting of metals, amines, and mixtures thereof, the anionic polymer contains no more than about 10 mole percent olefins and / or non-carboxylate ethers.

Preferably, the compound comprises gypsum, and the polymer is present at a level of from about 0.01 to 10% w / w (more preferably from about 0.05 to 2%> w / w), where the total weight of the polymer and compound is it takes about 100% by weight. At least about 80 mole percent of the polymer repeating units contain at least one anionic group. More preferably, the polymer has from about 1 to 70 mole percent of the Type B repeat units, from about 15 to 75 mole percent of the Type C repeat units, and from about 0.1 to 65 mole percent of type G repeat units, and the total abundance of type B, C and G repeat units being at least about 90 mole percent. The polymer can have a molecular weight of approximately 800-50,000.

More generally, the products of this aspect of the invention comprise a compound selected from the group consisting of gypsum, one or more members of the Kieserite Group, magnesium and potassium sulfate, elemental sulfur, and mixtures thereof, and a polymer, the polymer being an anionic polymer comprising at least four repeating units distributed along the length of the polymer chain, repeat units include at least one each of an itaconic and sulfonate maleic repeat unit.

The sulfur products of the invention are used to fertilize the soil by applying the products to the soil.

6. Liquid or solution fertilizer products

In another aspect of the invention, liquid or solution fertilizer products (eg, gypsum or UAN) are provided including an aqueous dispersion fertilizer, and a polyanionic polymer comprising at least four repeating units distributed along the length of the polymer chain, the repeating units including at least one each of a repeating unit of maleic, itaconic, and sulfonic acid, and an amount of an alpha-hydroxy acid formulation. The fertilizer product is normally an aqueous dispersion that has a pH of about 4-7, or about 0.5-3.

Preferably, the alpha-hydroxy acids are saturated and essentially free of double bonds and carbon ring structures, and are selected from the group consisting of lactic acid, glycolic acid, citric acid, tartaric acid, tartronic acid, glyceric acid and dihydroxypropanedioic acid, and mixtures thereof.

In general, the fertilizer products preferably contain from about 10 to 45% w / w of the polymer, from about 3 to 60% w / w of the alpha-hydroxy acid, the remainder being solvent. The polymer suitably has at least four repeating units distributed along the length of the polymer chain, the repeating units include at least one each of an itaconic, maleic and sulfonate repeating unit. In particularly preferred forms, the polymer comprises at least four repeating units including at least one each of type B, type C and type G repeating units, type B repeating units are selected from the group consisting of units of repeat derived from substituted and unsubstituted monomers of maleic acid and / or anhydride, fumaric acid and / or anhydride, mesaconic acid and / or anhydride, mixtures of the above, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein type B repeating units can be substituted with one or more straight-chain or branched C1-C6 alkyl groups substantially free of ring structures and atoms of halogen, and wherein the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, at least about 90 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units, and mixtures thereof, the repeat units are found randomly throughout of the polymer, the polymer contains no more than about 10 mole percent of any of (I) non-carboxylate olefin repeating units, (ii) ether repeating units, and (iii) unsulfonated monocarboxylic repeat units.

The fertilizer products of the invention can also be enhanced by the presence of an amount of a polyvinyl alcohol (PVA) inside, especially at a level of about 0.1 to 10% w / w. Furthermore, a plurality of different PVAs can be used. The PVA must have a hydrolysis level of at least about 97 mole percent. The products may also include another polymer having maleic and itaconic acid repeating units therein.

The liquid or solution products of the invention are used by applying these products to the soil.

7. Potassium products

The invention in another aspect provides potassium products comprising potassium-containing solids at least partially soluble in water, for example, potassium chloride, having thereon the dry residue of an aqueous additive comprising a polymer salt containing a plurality of anionic repeat units including maleic and itaconic acid repeat units, With substantially all of the salt-forming cations of the polymer salt being alkali metal cations, the aqueous additive has a pH of from about 0.1 to 4 (most preferably from about 0.5 to 3, and more preferably from about 1). The polymer is preferably present on the surface of the potassium-containing solids at a level of about 0.001-10% by weight, based on the total weight of the product taken as 100% by weight. The aqueous additive may also contain a carboxymethyl cellulose salt.

The polymer is suitably at least one tetrapolymer and comprises at least four repeating units distributed throughout the polymer chain, the repeating units include at least one of each of a itaconic, maleic and sulfonate repeating unit. More preferably, the polymer as at least one of each of Type B, Type C and Type G repeat units, Type B repeat units are selected from the group consisting of repeat units derived from substituted and unsubstituted acid monomers and / or maleic anhydride, acid and / or fumaric anhydride, acid and / or mesaconic anhydride, mixtures of the foregoing, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein the type B repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, at least about 90 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units, and mixtures thereof, the repeat units are found randomly throughout of the polymer, the polymer contains no more than about 10 mole percent of any of (I) non-carboxylate olefin repeating units, (ii) ether repeating units, and (iii) unsulfonated monocarboxylic repeat units.

Preferably, at least about 96 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units and mixtures thereof, and even more preferably the repeat units consist essentially repeating units selected from the group consisting of repeating units type B, C and G and mixtures thereof; For best results, the polymer is substantially free of ester and non-carboxylate groups.

In another aspect, the polymer has a type B repeat unit, a type C repeat unit, and two different type G repeat units, is at least a tetrapolymer, and the type B repeat unit is derived from maleic acid, the type C repeating unit is derived from itaconic acid, and the two type G repeating units are derived respectively from metalylsulfonic acid and allylsulfonic acid.

More generally, the invention provides potassium products comprising at least partially water-soluble potassium-containing solids having thereon the dry residue of an aqueous additive comprising a polymer including at least four repeating units distributed throughout the Polymer chain, the repeat units include at least one each of a itaconic, maleic and sulfonate repeat unit.

The polymers of the invention can be in the acid form or as partial or complete salts of alkali metals. The polymers are normally in the form of aqueous dispersions and are applied as is to the potassium solids, followed by drying thereof, so that the polymer is in the form of a dry residue. The potassium products of the invention can be used by applying the products to the soil.

8. Seed Products

Improved coated seed products are also a part of the invention and comprise an agricultural seed coated with a polymer composition, the polymer composition includes an anionic polymer comprising at least four repeating units distributed along the length of the chain of the polymer, the at least four repeating units include at least one of each of one type B, type C and type G repeating units, Type B repeating units are selected from the group consisting of repeating units derived from substituted and unsubstituted monomers of maleic acid and / or anhydride, fumaric acid and / or anhydride, mesaconic acid and / or anhydride, mixtures of the foregoing, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein the type B repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group Consisting of metals, amines, and mixtures thereof, the polymer contains no more than about 10 percent by mole of non-carboxylate olefins and / or ethers.

The polymer composition is present in the seed product at a level of about 0.001 to 10% by weight, based on the total weight of the coated seed product. Preferably, at least about 96 mole percent of the repeating units in the polymer are selected from the group consisting of type B, C and G repeating units, and mixtures thereof, and most preferably the repeating units consist essentially of units repeating units selected from the group consisting of repeating units type B, C and G and mixtures thereof; Also, it is preferred that the polymers be substantially free of ester groups and of non-carboxylate olefins. Particularly suitable polymers have a type B repeat unit, a type C repeat unit, and two different type G repeat units, and especially when the polymer is a tetrapolymer, the type B repeat unit is derived from maleic acid, the type C repeat unit is derived from itaconic acid, and the two type G repeat units are derived respectively from metalylsulfonic acid and allylsulfonic acid.

Certain preferred polymers have a type B repeat unit present at a level of about 35 to 50 mole percent, the type C repeat unit present at a level of about 20 to 55 mole percent, the type G repeat unit derived from metalylsulfonic acid being present at a level of about 1 to 25 mole percent, and the type G repeating unit derived from allylsulfonic acid being present at a level of about 1 to 20 mole percent, where the total amount of all repeating units in the polymer is taken as 100 mole percent.

The polymers useful in the invention can be in the form of an acid or as partial or complete salts, in particular of micronutrient metals (for example, Zn, Μη, B, Fe, Mo, Cu, and mixtures thereof).

More generally, the invention provides an agricultural seed coated with a polymer composition, the polymer composition includes an anionic polymer comprising at least four repeating units distributed along the length of the polymer chain, the repeating units including at least one of each from a maleic, itaconic, and sulfonate repeat unit.

In preparing the seed products of the invention, the polymer is initially applied to the seed as an aqueous composition, preferably having a pH of about 5-7.

9. Methods to reduce atmospheric ammonia

The invention further provides a method of reducing atmospheric ammonia by applying a polymer composition to an area subject to ammonia evolution, the polymer composition includes an anionic polymer comprising at least four repeating units distributed throughout the length of the polymer chain, the repeating units including at least one each of an itaconic, maleic and sulfonate repeating unit. The area may be a livestock or poultry confinement facility that includes a manure collection area, vertical walls that form an enclosure, and a roof that substantially covers the area, and in such cases, the polymer composition can be apply directly to manure within the collection area. The polymer composition is preferably applied at a level of about 0.0189-11.34 liters (0.005-3 gallons) per ton of manure, in the form of an aqueous dispersion having a pH of about 1-5. If desired, another polymer can be used in combination with the anionic polymer and that includes maleic and itaconic acid repeating units. The Po polymers of the invention may be in the form of a partial or total salt, in particular partial calcium and / or ammonium salt. In addition, certain preferred polymer compositions include a first polymer in the form of a partial calcium salt, and a second polymer in the form of a partial ammonium salt.

Most preferably, the polymer repeating units include at least one each of type B, type C and type G repeating units, type B repeating units are selected from the group consisting of repeating units derived from substituted monomers and are not substituted maleic acid and / or anhydride, fumaric acid and / or anhydride, mesaconic acid and / or anhydride, mixtures of the above, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein type B repeating units can be substituted with one or more straight-chain or branched C1-C6 alkyl groups substantially free of ring structures and halogen atoms, and in where the salts have salt forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, at least about 90 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units, and mixtures thereof, repeat units are found randomly throughout the polymer , the polymer containing not more than about 10 mole percent of any of (I) non-carboxylate olefin repeating units, (ii) ether repeat units and (iii) unsulfonated monocarboxylic repeat units.

This polymer preferably has at least about 96 mole percent of the repeat units therein selected from the group consisting of type B, C and G repeat units, and mixtures thereof, and more preferably consists essentially of selected repeat units from the group consisting of repeating units type B, C and G, and mixtures thereof. These polymers are preferably substantially free of ester groups and of non-carboxylate compounds. A preferred polymer has a type B repeat unit, a type C repeat unit, and two different type G repeat units. In this case, the polymer is preferably a tetrapolymer with the type B repeating unit derived from maleic acid, the type C repeating unit derived from itaconic acid, and the two type G repeating units derived respectively from methylsulfonic acid and allylsulfonic acid. Also, the type B repeat unit is present at a level of about 35 to 50 mole percent, the type C repeat unit is present at a level of about 20 to 55 mole percent, the type G repeat unit Methylsulfonic acid derived is present at a level of about 1 to 25 mole percent, and the allylsulfonic acid derived type G repeat unit is present at a level of about 1 to 2 0 mole percent, where the total amount of all repeating units in the polymer is taken as 100 percent by mole.

Additional preferred compositions are operable to reduce ammonia in the atmosphere by applying the composition to a zone undergoing evolution of ammonia, with such composition comprising a first polymer composition comprising a first anionic polymer having at least four units of repeats distributed along the length of the polymer chain, the repeating units include at least one each of an itachaonic repeating unit, maleic and sulfonate, the first anionic polymer being in the form of a partial or complete calcium salt; and a second polymer composition comprising a second anionic polymer having maleic and itaconic acid repeating units along the length of the polymer chain, the second anionic polymer being a partial or complete ammonium salt. Such polymers are preferably each in the form of an aqueous dispersion and have at least four repeating units distributed along the length of the polymer chain, the repeating units include at least one each of an itachaonic repeating unit, maleic and sulfonate.

10. Improved feed and water

Improved feed comprising amounts of feed ingredients normally fed to the animal, and an amount of a feed modification including a partial or complete polymer salt, are provided, the amount of the modification sufficient to reduce the volatilized ammonia derived from the feces of animals fed the improved feed compared to volatilized ammonia from an animal fed identical feed without modification. The polymeric salts of the invention are generally in the form of aqueous dispersions that have a pH of about 1-5 and comprise at least four repeating units distributed along the length of the polymer chain, the repeating units they include at least one each of a maleic, itaconic, and sulfonate repeat unit.

In preferred forms, the at least four repeat units include at least one each of type B, type C, and type G repeat units, type B repeat units are selected from the group consisting of repeat units derived from monomers substituted and unsubstituted maleic acid and / or anhydride, fumaric acid and / or anhydride, mesaconic acid and / or anhydride, mixtures of the above, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein type B repeating units can be substituted with one or more straight-chain or branched C1-C6 alkyl groups substantially free of ring structures and halogen atoms, and in where the salts have salt forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, at least about 9 0 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units, and their mixtures, repeat units are found randomly throughout the polymer, the polymer containing not more than about 10 mole percent of any of (I) non-carboxylate olefin repeating units, (ii) ether repeat units and (iii) unsulfonated monocarboxylic repeat units.

Suitably, at least about 96 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units and mixtures thereof, and even more preferably the repeat units consist essentially in repeat units selected from the group consisting of type B, C and G repeat units and mixtures thereof; Furthermore, the polymer is substantially free of ester groups and of non-carboxylate compounds.

Especially preferred polymers have a type B repeat unit, a type C repeat unit, and two different type G repeat units, and, when in the form of a tetrapolymer, the type B repeat unit is derived from maleic acid, the type C repeat unit is derived from itaconic acid, and the two type G repeat units are derived, respectively, from metalylsulfonic acid and allylsulfonic acid. These polymer salts preferably have the type B repeating unit being present at a level of from about 3 5 to 50 mole percent, the type C repeating unit is present at a level of about 20 to 55 mole percent, the type G repeat unit derived from metalylsulfonic acid is present at a level of about 1-25 mole percent, and the allylsulfonic acid derived type G repeat unit is present at a level of about 1 to 20 mole percent, where the total amount of all repeat units in the polymer is taken as 100 mole percent.

In many cases, two separate polymer salts are used, one being a partial calcium salt, and the other being a partial ammonium salt. On the other hand, other different polymers that include maleic and itaconic acid repeating units can be used in the modifications of the invention.

Feed or pet food of the invention can be used as a method of reducing volatilized ammonia derived from animal feces, comprising the step of administering (feeding) animals one or more of the feed described above.

Similarly, the invention also provides improved animal waters comprising a mixture of water and a partial or complete polymer salt, the polymer salt is in an amount sufficient to reduce the volatilized ammonia derived from the feces of the animal fed the for animals improved, compared to volatilized ammonia from an animal fed identical water, without modification. The polymeric salts are preferably in the form of aqueous dispersions having a pH of about 1-5, and comprise at least four repeating units distributed along the length of the polymer chain, the repeating units include at least one each one of a maleic, itaconic and sulfonate repeating unit.

The at least four repeating units preferably include at least one each of type B, type C and type G repeating units, type B repeating units are selected from the group consisting of repeating units derived from substituted and unsubstituted monomers of acid and / or maleic anhydride, acid and / or fumaric anhydride, acid and / or mesaconic anhydride, mixtures of the above, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein type B repeating units can be substituted with one or more straight-chain or branched C1-C6 alkyl groups substantially free of ring structures and halogen atoms, and in where the salts have salt forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, at least about 90 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units, and mixtures thereof, repeat units are found randomly throughout the polymer , the polymer salt contains no more than about 10 mole percent of any of (I) non-carboxylate olefin repeating units, (ii) ether repeat units and (iii) unsulfonated monocarboxylic repeat units.

In a preferred case, the polymer salt has a type B repeat unit, a type C repeat unit, and two different type G repeat units, and especially when the polymer salt is a tetrapolymer, the type B repeat unit is derived from maleic acid, the type C repeating unit is derived from itaconic acid, and the two type G repeating units are derived respectively from metalylsulfonic acid and allylsulfonic acid. The type B repeat unit is preferably present at a level of about 35 to 50 mole percent, the type C repeat unit is present at a level of about 20 to 55 mole percent, the derived type G repeat unit of metalylsulfonic acid is present at a level of about 1 to 25 mole percent, and the type G repeat unit derived from allylsulfonic acid is present at a level of about 1 to 20 mole percent, where the total amount of all repeating units in the polymer is taken as 100 percent by mole.

The polymers of the invention are preferably in the form of partial salts, and the overall compositions may comprise two separate polymer salts, one polymer salt being a partial calcium salt, and the other polymer salt being a partial ammonium salt.

eleven. Methods for Improving Soil Conditions The invention provides methods of inhibiting a soil condition selected from the group consisting of nitrification processes, phosphate binding processes, urease activities, and combinations thereof, comprising the step of applying to the soil an effective amount of an anionic polymer that includes at least four repeating units distributed along the length of the polymer chain, repeat units include at least one each of one of maleic, itaconic, and sulfonate repeat units. The repeat units preferably include at least one each of type B, type C and type G repeat units, type B repeat units are selected from the group consisting of repeat units derived from substituted and unsubstituted acid monomers and / or maleic anhydride, acid and / or fumaric anhydride, acid and / or mesaconic anhydride, mixtures of the above, and any isomers, esters, acid chlorides, and partial or complete salts of any of the foregoing, wherein type B repeating units can be substituted with one or more straight-chain or branched C1-C6 alkyl groups substantially free of ring structures and halogen atoms, and in where the salts have salt forming cations selected from the group consisting of metals, amines, and mixtures thereof, type C repeating units selected from the group consisting of repeating units derived from substituted or unsubstituted monomers of itaconic acid, itaconic anhydride, and any isomers, esters, and partial or complete salts of any of the foregoing, and mixtures of any of the previous ones, wherein the C-type repeating units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and their mixtures, type G repeat units selected from the group consisting of repeat units derived from substituted or unsubstituted sulfonated monomers that possess at least one carbon-carbon double bond and at least one sulfonate group and that are substantially free of aromatic rings and amide groups , and any isomers, and the partial or complete salts of any of the foregoing, and mixtures of any of the foregoing, wherein the G-type repeat units may be substituted with one or more straight-chain or branched C 1 -C 6 -alkyl groups substantially free of ring structures and halogen atoms, and where the salts have salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof, at least about 90 mole percent of the repeat units therein are selected from the group consisting of type B, C and G repeat units, and mixtures thereof, repeat units are found randomly throughout the polymer , the polymer contains no more than about 10 mole percent of any of (I) non-carboxylate olefin repeating units, (ii) ether repeat units and (iii) unsulfonated monocarboxylic repeat units.

In a particular case, the polymer has a type B repeat unit, a type C repeat unit, and two different type G repeat units; especially when the polymer is a tetrapolymer, the type B repeating unit is derived from maleic acid, the type C repeating unit is derived from itaconic acid, and the two type G repeating units are derived respectively from methylsulfonic acid and allylsulfonic acid.

In preferred forms the repeating unit type

<td>B is</td><td>Present</td><td>preferably</td><td>yet</td><td>level</td><td>of</td>

<td colspan="2">about 35 to</td><td>50 percent in</td><td>mo1, the</td><td>Unit</td><td>of</td>

<td>repetition</td><td>type C</td><td>is present</td><td>in a</td><td>level</td><td>of</td>

about 2 0 to 55 mole percent, the G-type repeat unit derived from metalylsulfonic acid is present at a level of about 1 to 25 mole percent, and the Type G repeat unit derived from allylsulfonic acid is present in a level of about 1 to 20 mole percent, where the total amount of all repeating units in the polymer is taken as 100 mole percent.

In the embodiment of the invention, the anionic polymer is mixed with a solid, liquid or gaseous ammonia fertilizer, and especially solid fertilizers; in the latter case, the polymer is applied to the surface of the fertilizer as an aqueous dispersion followed by drying, so that the polymer is present in the solid fertilizer as a dry residue. The polymer is generally applied at a level of about 0.01 to 10% by weight, based on the total weight of the polymer / fertilizer product taken as 100% by weight. When the fertilizer is an aqueous liquid fertilizer, the polymer is added to it with mixing.

The polymers of the invention are preferably in aqueous dispersion and have a pH of up to about 3. These polymers can be used alone or in combination with another anionic polymer that includes maleic and itaconic acid repeating units.

Detailed description of the invention

The novel polymers of the invention

The novel polyanionic polymers of the present invention (sometimes referred to herein as Class I polymers) are at least one tetrapolymers, i.e. they are composed of at least four different repeat units individually and independently selected from the group consisting of type B repeat units , type C and type G, and mixtures thereof, described in detail below. However, polymers comprise polymers that have more than four distinct repeat units, with excess repeat units being selected from the group consisting of type B, type C, and type G repeat units, and mixtures thereof, as well like other monomers or repeating units that are not B, C or G repeating units.

Preferred polymers contain at least one repeating unit of each of types B, C, and G, another repeating unit selected from the group consisting of type B, type C, and type G repeating units, and optionally other units of unselected repeats of type B, type C, and type G repeat units. Particularly preferred polymers comprise a single Type B repeat unit, a single Type C repeat unit, and two different Type G repeat units, or two different Type B repeat units, a single Type C repeat unit, and one or more different type G repeat units.

However constituted, the preferred polymers contain at least about 90 mole percent (more preferably at least about 96 mole percent) of repeating units selected from the group consisting of type B, C and G repeating units ( that is, the polymers should contain no more than about 10 mole percent (preferably no more than about 4 mole percent) of unselected repeating units of types B, C, and G). The most preferred final polymers should be substantially free of ester groups (ie, not more than about 5 mole percent of ester groups, more preferably not more than about 1 mole percent).

<td></td><td>Polymers</td><td>can be converted</td><td>in</td><td>a</td><td>wide</td>

<td>spectrum</td><td>of salts, either</td><td>fully saturated (</td><td>in</td><td>where</td><td>everybody</td>

<td>the</td><td>anionic groups</td><td colspan="2">are paired with</td><td>a</td><td>cation</td>

<td colspan="2">suitable for example</td><td>a metal or amine) or</td><td colspan="3">partial (in</td>

where not all anionic groups are so closely matched), and can be done using either a single cation (eg, sodium), or using any number of different cations at any level (eg, mixed sodium and ammonium cations). The metal cations can be simple cations such as sodium or calcium, but more complex cations can also be used, such as cations containing one metal atom and another atom), also, for example, vanadyl cations. Among the preferred metal cations (to be used alone or as mixed salts) are those derived from alkali, alkaline earth and transition metals. The polymers can also be in the form of partial or complete amine salts (as used herein, amines refers to primary, secondary or tertiary amines, monoamines, diamines and triamines, as well as ammonia, ammonium ions, amines quaternary, quaternary ammonium ions, alkanolamines (eg, ethanolamine, diethanolamine, and triethanolamine), and tetraalkylammonium species). The most preferred class of amines are alkyl amines, wherein the alkyl group or groups have or have 1-30 carbon atoms and are of straight or branched chain configuration. Such amines should be essentially free of aromatic rings (not more than about 5 mole percent aromatic rings, and more preferably not more than about 1 mole percent thereof). A particularly suitable alkyl amine is isopropylamine.

The degree of cation substitution and the identity of the cation or cations can be varied completely independently of each other. This flexibility allows the production of various polymers of total or partial salts with desirable properties. The solubility and other properties of polymers can be modified by judicious selection of the types and amounts of salt-forming cations. For example, by increasing the level of divalent cations (eg, Ca, Mg) and raising the pH of the aqueous dispersions of the above polymers to pH 1, the resulting polymer salts are especially useful as films and coatings.

one. Type B repeat units

The type B repeat units according to the invention are dicarboxylate repeat units derived from monomers of maleic acid and / or anhydride, acid and / or fumaric anhydride, mesaconic acid and / or anhydride, substituted maleic acid and / or anhydride, substituted fumaric acid and / or anhydride, substituted mesaconic acid and / or anhydride, mixtures of the foregoing, and any isomers, esters, acid chlorides, and the partial or complete salts of any of the foregoing. As used herein with respect to Type B repeating units, "substituted species" refers to alkyl substituents (preferably straight-chain or branched-chain alkyl groups substantially free of ring structures), and halo substituents (is ie, not more than about 5 mole percent of any of the halo ring structures or substituents, preferably not more than about 1 mole percent of either); the substituents are normally attached to one of the carbon-carbon double bond carbons of the monomer or monomers employed. Similarly, salts of type B repeating units refer to partial or complete salts prepared using salt-forming cations selected from the group consisting of metals, amines, and mixtures thereof. In preferred forms, the total amount of type B repeating units in the polymers of the invention should range from about 1 to 70 mole percent, most preferably from about 20 to 65 mole percent, and more preferably from about 35 to 55 mole percent, where the total amount of all repeating units in the polymer is taken as 100 mole percent.

Maleic acid, methylmaleic acid, maleic anhydride, methylmaleic anhydride, and mesaconic acid (either alone or as various mixtures) are the most preferred monomers for generating type B repeat units. Those skilled in the art will appreciate the utility of in-conversion. Place acid anhydrides into acids in a reaction vessel just before or even during a reaction. However, it is also understood that when corresponding esters (eg, maleic or citraconic acid esters) are used as monomers during the initial polymerization, this must be followed by hydrolysis (acid or base) of pendant ester groups to generate a polymer definitive carboxylate substantially free of ester groups.

2. Type C repeater units

Type C repeat units according to the invention are derived from itaconic acid and / or anhydride monomers, substituted itaconic acid and / or anhydride, as well as isomers, esters, acid chlorides, and the partial or complete salts of any of the previous ones. Type C repeating units are present in the preferred polymers of the invention at a level of from about 1 to 80 mole percent, most preferably from about 15 to 75 mole percent, and more preferably from about 20 to 55 percent in mol, where the total amount of all repeating units in the polymer is taken as 100 percent in mol.

The itaconic acid monomer used to form the type C repeating unit has a carboxyl group, which is not directly attached to the unsaturated carbon-carbon double bond used in the polymerization of the monomer. Therefore, the preferred type C repeating unit has a carboxyl group attached directly to the polymer backbone, and another carboxyl group separated by a carbon atom from the polymer backbone. The definitions and discussion regarding substituted, salt, and useful salt-forming cations (metals, amines, and mixtures thereof) with respect to type C repeat units, are the same as those established for type B repeat units .

Itaconic acid and unsubstituted itaconic anhydride, either alone or in various mixtures, are the most preferred monomers for the generation of type C repeating units. Again, if itaconic anhydride is used as a starting monomer, it is normally useful for converting the Itaconic anhydride monomer to the acid form in a reaction vessel just before or even during the polymerization reaction. Any of the remaining ester groups in the polymer are normally hydrolyzed, so that the final carboxylated polymer is substantially free of ester groups.

3. Type G repeat units

Type G repeat units according to the invention are derived from substituted or unsubstituted sulfonate-bearing monomers having at least one carbon-carbon double bond and at least one sulfonate group, in the form of an acid, partial or complete salt, or other, and that they are substantially free of aromatic rings and amide groups (i.e., not more than about 5 mole percent of any of the aromatic rings or amide groups, preferably not more than about 1 mole percent of either). Type G repeat units are preferably selected from the group consisting of straight or branched chain C1-C8 alkenylene sulfonates, substituted forms thereof, and any isomers or salts of any of the foregoing; Particularly preferred are the alkenylene sulfonates selected from the group consisting of vinyl, allyl, and metalylsulfonic acids or salts. The total amount of type G repeating units in the polymers of the invention should range from about 0.1 to 6 5 mole percent, most preferably from about 1 to 35 mole percent, and more preferably from about 1 to 25 percent in mol, when the total amount of all repeating units in the polymer is taken as 100 percent in mol. The definitions and discussion regarding substituted, salt, and useful salt-forming cations (metals, amines, and mixtures thereof) with respect to type G repeat units, are the same as those established for type B repeat units .

Vinylsulfonic Acid, Allylsulfonic Acid and Methylsilylsulfonic Acid, either alone or in various mixtures, are considered the most preferred monomers for the generation of Type G repeat units. The alkali metal salts of these acids have also been found to be very useful as well as monomers. In this regard, it was unexpectedly discovered that during the polymerization reactions produced by the novel polymers of the invention, the presence of mixtures of alkali metal salts of these monomers with acidic forms thereof does not inhibit the termination of the polymerization reaction. For the same reason, mixtures of monomers of maleic acid, itaconic acid, sodium allylsulfonate, and sodium metalylsulfonate do not inhibit the polymerization reaction.

Other preferred characteristics of the novel polymers

As noted above, the total abundance of type B, C, and G repeat units in the polymers of the invention is preferably at least about 90 mole percent, most preferably at least about 96 mole percent, and more preferably the Polymers consist essentially of or are 100 percent by mole of repeating units type B, C and G. It will be understood that the relative amounts and identities of polymer repeating units can be varied, depending on the specific properties desired in the resulting polymers. Furthermore, it is preferred that the polymers of the invention contain not more than about 10 mole percent (most preferably not more than about 5 mole percent) of any of (I) non-carboxylate olefin repeating units , (ii) ether repeat units, (iii) ester repeat units, (iv) unsulfonated monocarboxylic repeat units and (v) amide-containing repeat units. "No carboxylate and no sulfonated" refers to repeating units that have essentially no carboxylate or sulfonate groups in the corresponding repeating units. Suitably, the molar ratio of type B and type C repeating units in combination with type G repeating units (i.e. the (B + C) / G molar ratio) should be approximately 0.5 to 20: 1, most preferably from about 2: 1 to 20: 1, and more preferably from about 2.5: 1 to 10: 1. Still further, the polymers should be essentially free (eg, less than about 1 mole percent) of repeating units containing alkyloxylates or alkylene oxide (eg, ethylene oxide), and more desirably entirely free of the themselves.

Preferred polymers of the invention have repeat units thereof randomly located along the polymer chain without any ordered sequence of repeat units. Therefore, the polymers herein are not, for example, alternating with different repeating units in a defined sequence along the polymer chain.

It has also been determined that the preferred polymers of the invention should have a very high percentage of the repeating units thereof with at least one anionic group, for example, at least about 80 mole percent, most preferably at least about 90 mole percent, more preferably at least about 95 mole percent, and most preferably essentially all repeating units contain at least one anionic group. It will be appreciated that repeat units B and C have two anionic groups per repeat unit, while preferred sulfonate repeat units have one anion group per repeat unit.

For a variety of applications, certain tetrapolymer compositions are preferred, i.e., a preferred range of polymer backbone composition (in mole percent, using the parent monomer names of the corresponding repeat units) is: maleic acid 35-50%; itaconic acid 20-55%>; 1-25% metalylsulfonic acid; and 1-20% allylsulfonic sulfonic acid, when the total amount of all repeat units in the polymer is taken as 100 mole percent. It has also been found that even small amounts of repeating units, which are neither B nor C repeating units, can significantly affect the properties of the final polymers, compared to previous BC polymers. Therefore, even 1 mole percent of each of 2 different G repeat units can result in a tetrapolymer exhibiting drastically different behaviors, compared to BC polymers.

The molecular weight of the polymers is also highly variable, again depending mainly on the desired properties. Generally, the molecular weight distribution of the polymers according to the invention is conveniently measured by size exclusion chromatography. Generally speaking, the molecular weight of the polymers varies from about 800-50,000, and more preferably from about 1000-5000. For some applications, it is appropriate that at least 90% of the finished polymer be at or above a molecular weight of about 1,000 as measured by size exclusion chromatography in 0.1M sodium nitrate solution through index detection. refraction at 35 ° C using polyethylene glycol standards. Of course, other techniques for such measurement can be employed as well.

The polymers of the invention can be mixed with or complexed with metallic or non-metallic ions, and especially those selected from the group of simple cations, such as amines, alkali metals, Fe, Mn,

Mg, Zn, Cu, Ni, Co, Mo, V, Cr, Si, B, Ca, and compounds containing these cations, for example boric acid, borates, molybdates, more complex cations such as vanadyl ions [V0 ]2+, and other complex ions containing vanadium, and mixtures of any of the above.

The polymers of the invention can also be used in formulations containing a wide variety of other ingredients, including, but not limited to alcohols, diols, polyols, organic acids, polyvinyl alcohols, dyes, plastics, and mixtures thereof.

Synthesis of the polymers of the invention

Virtually any conventional free radical polymerization method may be suitable for the synthesis of the polymers of the invention. However, a preferred and novel synthesis can be used, which is applicable not only for the production of the polymers of the invention, but also for the synthesis of polymers containing dicarboxylate repeat units and sulfonate repeat units and containing preferably at least one carbon-carbon double bond. Such types of polymers are described in US Patent Nos. 5,536,311 and 5,210,163.

Generally speaking, the new synthesis methods comprise carrying out a free radical polymerization reaction between the dicarboxylate and sulfonate repeat units in the presence of hydrogen peroxide and vanadium-containing species to achieve a conversion to polymer in excess of 90 %, and more preferably in excess of 98%, in mol. That is, a dispersion of the sulfonated and dicarboxylate monomers is created and free radical initiators are added followed by allowing the monomers to polymerize.

Of course, the preferred dicarboxylate and sulfonate repeat units are those described above as repeat units B, C, and G. Furthermore, it has been found that acceptable polymers can be synthesized with relatively low amounts of type B repeat units maleic, without creating monomers without overreacting. US Patent No. 5,135,677 describes the synthesis of polymers containing maleic acid and other water soluble repeat units. The '677 patent teaches that the amount of maleic acid repeat units is at least 50 percent by weight, more preferably at least 75 percent by weight, and that if smaller amounts of maleic acid repeat units are used , large amounts of residual monomers are created and the resulting polymers are poor in biodegradability. However, it has been found that by judicious selection of repeating units

B, C, and G of the invention, essentially complete polymerization is achieved even with the maleic acid type B repeat units below 50 mole percent of the reaction mixture, as noted above.

Preferably, hydrogen peroxide is the only initiator used in the reaction, but in any case, it is appropriate to carry out the reaction in the absence of any substantial amounts of other initiators (i.e., the total weight of the initiator molecules used should be about 95% by weight hydrogen peroxide, most preferably about 98%> by weight, and more preferably 100% by weight thereof). Various sources of vanadium can be employed, with vanadium oxosulfates being preferred.

These polymerization reactions have been found to be more suitable to perform in substantially aqueous dispersions (eg, dispersants are at least about 95% by weight water, most preferably at least about 98% by weight water, and more preferably 100% by weight Water). Aqueous dispersions may also contain additional monomers, but only to the lesser degree observed.

It has also been found that preferred polymerization reactions can be carried out without the use of inert atmospheres, for example, in an ambient air environment. As is well known in the art, free radical polymerization reactions in dispersions are normally carried out in a manner that excludes the significant presence of oxygen. As a result, these prior techniques involve necessary and laborious measures such as degassing, inert gas coating of the reactor contents, monomer treatments to prevent air from being present, and the like. These past records increase the cost and complexity of polymerizations, and can present safety hazards. However, in the polymerizations of the polymers of the present invention, inert gas or other related steps are not required, although they may be employed if desired.

A preferred embodiment comprises the creation of highly concentrated aqueous dispersions of solid monomer particles (including saturated dispersions containing undissolved monomers) at a temperature of from about 50 to 125 ° C, more preferably from about 75 to 110 ° C, and the addition of vanadium oxysulfate to give a concentration of vanadium in the dispersion of from about 1 to 1000 ppm, and more preferably from about 5 to 500 ppm (metal-based). This is followed by the addition of hydrogen peroxide over a period of from about 30 minutes - 24 hours (more preferably from about 1 to 5 hours) in an amount effective to achieve polymerization. This process is commonly performed in a stirred tank reactor equipped with facilities for temperature and composition control, but any suitable equipment used for polymerization can be employed.

Another highly preferred and efficient embodiment involves charging a stirred tank reactor with water, followed by heating and the addition of monomers to give a dispersion having about 40 to 75% w / w solids concentration. When maleic and / or itaconic monomers are used, they can be derived either from the corresponding acid monomers, or from an in si tu conversion of the anhydrides to acid in the water. Sulfonated and carboxylate monomers in their acid and / or anhydride form are preferred, although salts can also be used. Surprisingly, incomplete dissolution of the monomer has been found not to be very detrimental to polymerization; in fact, the initially undissolved fraction of monomers dissolves sometime after the polymerization has started.

After the initial heating and the introduction of the monomers, the contents of the reactor are kept at a temperature of between approximately 80 to 125 ° C, with the subsequent addition of vanadium oxysulfate. Up to this point in the reaction protocol, the order of addition of the materials is not critical. After the introduction of vanadium oxysulfate, a solution of hydrogen peroxide is added over time until substantially all of the monomers convert to polymer. The peroxide addition can be done at a constant rate, a variable rate, and with or without pauses, at a fixed or variable temperature. The concentration of peroxide solution used is not very critical, although the concentration at the lower end should not dilute the contents of the reactor to the point where the reaction becomes excessively slow or impractically diluted. At the high end, the concentration should not cause difficulties in performing the polymerization safely on the equipment being used.

After the polymerization is complete, the cations present can be left as is, or additional cations can be added. For example, the reactor contents can be neutralized to a higher pH by the addition of various alkali metals or alkaline earth metal cations, ammonia, amines, or any other suitable cation source, thereby providing various mixed polymer salts, if desired.

Preferably, the polymerization reactions of the invention are carried out to exclude substantial amounts of dissolved iron species (i.e., more than about 5% by weight of such species, and more preferably substantially less, in the order of below about 5 ppm, and more suitably below about 1 ppm). This is distinct from certain prior techniques that require the presence of iron-containing materials. However, it is acceptable to carry out the polymerization of the invention in 304 or 316 stainless steel reactors. It is also preferred to exclude from the polymerization reaction significant amounts (not more than about 5% by weight) of the ammonium sulfate salts, amine, alkali and alkaline earth metals, as well as their related sulfur-containing precursors and salts, such as bisulfites, sulfites and metabisulfites. The use of these sulfate-related compounds has been found to leave a relatively high amount of sulphates and the like in the final polymers, which should also not be separated or left as a product contaminant.

The high polymerization efficiencies of the preferred synthesis are the result of the use of water as a solvent and without the need for other solvents, the removal of other initiators (eg azo, hydroperoxide, persulfate, organic peroxides) ingredients of iron and sulfate , the lack of recycling circuits, so that substantially all monomers are converted into finished polymers in a single reactor. This is further enhanced by the fact that the polymers are formed first, and subsequently, if desired, partial or complete salts can be created. Important factors are the simultaneous presence of water solvent, peroxide initiator, vanadium compound, and monomers provided at the appropriate times and at useful temperatures. This may be arranged in any equipment and in any manner known in the art, ie, the manner in which this is arranged is not critical. For example, a certain proportion of the monomers may be in water solution in a reaction vessel, while additional monomers and peroxide are added to the vessel while the reaction proceeds in the presence of adequate levels of vanadium compound.

Examples

The following Examples 1-4 describe preferred synthesis techniques for the preparation of polymers; It should be understood, however, that these examples are provided by way of illustration only and nothing in them should be taken as a limitation on the overall scope of the invention.

Example 1 - Exemplary Synthesis

Apparatus:

A cylindrical reactor, capable of being heated and cooled, and equipped with an efficient mechanical stirrer, condenser, gas outlet (open to the atmosphere), solid loading port, liquid charging port, thermometer and feed tube was used. peroxide.

Procedure: Water was charged into the reactor, stirring was started along with heating to a target temperature of 95 ° C. During this phase, itaconic acid, sodium methylsulfonate, sodium allylsulfonate and maleic anhydride were added in order to make a 50% w / w dispersion in solids with the following monomer mole fractions: maleic: 45% itaconic: 35% metalylsulfonate : 15% allylsulfonate: 5% When the reactor temperature reached 95 ° C, vanadium oxysulfate was added to give a vanadium metal concentration of 25 ppm by weight. After the vanadium salt was completely dissolved, hydrogen peroxide (50% w / w dispersion) was added continuously over 3 hours, using the feed tube. The total amount of hydrogen peroxide added was 5% by weight of the dispersion in the reactor before the peroxide addition. After completing the peroxide addition, the reactor was held at 95 ° C for two hours, followed by cooling to room temperature.

The resulting polymer dispersion was found to have less than 2% w / w total residual monomers as determined by chromatographic analysis.

Example 2 - Exemplary Synthesis

Apparatus:

Same as Example 1

Procedure: Water was charged into the reactor, stirring was started along with heating to a target temperature of 100 ° C. During this phase, itaconic acid, sodium methylsulfonate, sodium allylsulfonate and maleic anhydride were added in order to make a 70% w / w dispersion in solids with the following monomer mole fractions: maleic: 45% itaconic: 50% metalylsulfonate : 4% allylsulfonate: 1%

When the reactor temperature reached 100 ° C, vanadium oxysulfate was added to give a vanadium metal concentration of 25 ppm by weight. After the vanadium salt was completely dissolved, hydrogen peroxide (as a 50% dispersion> w / w) was added continuously over 3 hours, using the feed tube. The total amount of hydrogen peroxide added was 7.5% by weight of the dispersion in the reactor before the peroxide addition. After completing the peroxide addition, the reactor was held at 100 ° C for two hours, followed by cooling to room temperature.

<td>It was found</td><td>than</td><td>the</td><td>dispersion</td><td>of</td><td>polymer</td>

<td>resulting had less</td><td>of</td><td> 1%</td><td>total p / p</td><td>of</td><td>monomers</td>

residuals as determined by chromatographic analysis.

Example 3- Exemplary Synthesis

A terpolymer salt dispersion containing 70% by weight of polymer solids in water was prepared using a cylindrical reactor capable of being heated and cooled, and equipped with an efficient mechanical stirrer, a condenser, an open gas outlet to the atmosphere, the respective ports for charging liquids and solids to the reactor, a thermometer, and a peroxide feed tube.

Water (300 g) was charged into the reactor with stirring and heating to a target temperature of 95 ° C. During heating, itaconic acid, sodium methylsulfonate and maleic anhydride were added in order to make a 75% w / w solid dispersion with the following monomer mole fractions: maleic anhydride - 20%; itaconic acid - 60%; Sodium Methylsulfonate Salt - 20%. When the monomers were initially added, they were in suspension in the water. As the temperature rose, the monomers dissolved more completely before the polymerization started, and the maleic anhydride was hydrolyzed to maleic acid. When the reactor temperature reached 95 ° C, vanadium oxysulfate was added to obtain a vanadium metal concentration of 50 ppm by weight of the reactor contents at the time of the addition of the vanadium salt. After the vanadium salt completely dissolved, hydrogen peroxide as a 50%> w / w dispersion in water was added continuously for two hours. At the time of the addition of hydrogen peroxide, not all monomers were completely dissolved, achieving what is sometimes known as sludge polymerization; the initially undissolved monomers dissolved later in the course of the reaction. The total amount of hydrogen peroxide added equaled 5% by weight of the dispersion in the reactor before the peroxide addition.

After the peroxide addition was complete, the reaction mixture was held at 95 ° C for two hours, and then allowed to cool to room temperature. The resulting polymer dispersion had a pH slightly below 1.0 and was a partial sodium salt due to the sodium cation in the sulfonate monomers. The dispersion was found to have a monomer content of less than 2% w / w, calculated as a fraction of the total solids in the reaction mixture, determined by chromatographic analysis. Consequently, more than 98% w / w of the monomers added initially were converted to polymer.

Example 4 - Preparation of partial tetrapolymer salts

A tetrapolymer partial sodium salt dispersion containing 40% by weight of polymer solids in water was prepared by the preferred free radical polymerization synthesis of the invention, using an aqueous monomer reaction mixture having 45 mole percent of maleic anhydride, 35 percent by mole of itaconic acid, 15 percent by mole of sodium metallsulfonate salt, and 5 percent by mole of allylsulfonate. The final tetrapolymer dispersion had a pH slightly below 1.0 and was a partial sodium salt due to the sodium cation in the sulfonate monomers. At least about 90% of the monomers were polymerized in the reaction.

This partial sodium salt tetrapolymer is used to create a series of 40% solids in partial water salts. In each case, apart from the sodium present in the tetrapolymer mixture, appropriate bases or base precursors (eg carbonates), or mixtures thereof, were added to the aqueous tetrapolymer at room temperature to generate the corresponding salts. In all cases except for Salt A below, sodium in situ resulting from synthesis was the main source of sodium used in conversions; In Salt A, most of the sodium came from the use of NaOH. Specifically, the following basic reagents with amounts of the tetrapolymer were employed to give the following salts:

Salt A - sodium hydroxide, pH 7.

Salt B - ammonium hydroxide and a smaller amount of sodium hydroxide, pH 2.

Salt C - calcium carbonate and a smaller amount of sodium hydroxide, pH 1.5.

Salt D - calcium carbonate and a minor amount of sodium hydroxide, pH 3.5.

E-isopropylamine salt, pH 4.8.

Salt F - triethanolamine, pH 7.

Salt G - zinc carbonate, manganese carbonate, basic copper carbonate and sodium hydroxide, pH 6 (Zn content of 2% by weight, Mn content of% by weight, Cu content of 250 ppm).

Salt H - zinc carbonate, pH 3 (Zn content of 5% by weight).

Salt I - manganese carbonate, pH 4 (Mn content of 5% by weight).

Mixtures of the novel polymers of the invention with other polymers

The novel polymers herein can be a part of polymer blends or fractions, including other types of polymers, especially dicarboxylate polymers, and particularly those containing maleic and itaconic acid repeat units. These mixed polymer formulations can be used in all of the contexts described below.

The preferred types of different polymers useful in mixed polymer products are called Class IA and Class II polymers.

Class IA polymers

Class IA polymers contain both carboxylate and sulfonate sulfate functional groups, but are not Class I higher-order tetrapolymers. For example, maleic, itaconic, and allylsulfonic repeat unit terpolymers, which are known per se in The prior art will function as the polyanionic polymer component of the compositions of the invention. Thus, Class IA polymers are typically homopolymers, copolymers, and terpolymers, suitably including individually repeating units and independently selected from the group consisting of type B, type C, and type G repeating units, without the need for any additional repeating units. Such polymers can be synthesized in any known way, and can also be produced using polymer synthesis.

Class I previously described.

Class IA polymers preferably have the same molecular weight ranges and other specific parameters (eg, pH and polymer solids loading) described above in relation to Class I polymers, and can be converted to partial or complete salts using the same techniques described with reference to Class I polymers. Class IA polymers are most suitably synthesized using the techniques described above in connection with Class I polymers. Class II polymers Generally speaking, polyanionic polymers in this class are of the type described in US Patent No. 8,043,995, which it is incorporated herein by reference in its entirety. The polymers include repeating units derived from at least two different monomers individually and respectively taken from the group consisting of what has been referred to for ease of reference as B 'and C monomers; alternatively, the polymers can be formed as homopolymers or copolymers of recurring C monomers. The repeating units can be randomly distributed along the polymer chains.

In detail, the repeating unit B 'has the general formula

general and the repeating unit C 'has the formula

OR

where each R7 is individually and respectively selected from the group consisting of H, OH, linear, branched chain, and cyclic C1-C30 alkyl or aryl groups, formate (Co), acetate (Ci), propionate (C2), butyrate (C3 ) linear, branched-chain and cyclic C1-C30 alkyl or aryl, etc. to C30-based ester groups, R'CO2 groups, OR 'groups and COOX groups, where R is selected from the group consisting of linear, branched chain and cyclic C1-C30 alkyl or aryl groups and X is selected from group consisting of H, alkali metals, NH4 and C1-C4, R3 and R4 alkyl ammonium groups are selected individually and respectively from the group consisting of H, linear, branched chain and cyclic C1-C30 alkyl or aryl groups, Rs, Re, Rio and Rn are individually and respectively selected from the group consisting of H, alkali metals, NH4 and the Ci-C alkyl ammonium groups4, Y is selected from the group consisting of Fe, Mn, mg, Zn, Cu, Ni, Co, Mo, V, W, the alkali metals, the alkaline earth metals, polyatomic cations containing any of the above (for example , V0+2), amines, and mixtures thereof; and Rb and Rg are individually and respectively selected from the group consisting of nothing (ie, groups do not exist), CH2, C2H4 and C3H6.

As can be appreciated, Class II polymers typically have different types and sequences of repeating units. For example, a Class II polymer comprising repeating units B1 and C 'can include all three forms of repeat units B' and all three forms of repeat units C '. However, for reasons of cost and ease of synthesis, the most useful Class II polymers are composed of repeating units B 'and C. In the case of Class II polymers consisting mainly of repeating units B' and C, R5, Re, Rio, and R11 are individually and respectively selected from the group consisting of H, the alkali metals, NH4, and C1-C4 alkyl ammonium groups. This particular Class II polymer is sometimes called a butanedioic methylene succinic copolymer and can include various salts and derivatives thereof.

Class II polymers can have a wide range of repeating unit concentrations in the polymer. For example, Class II polymers having variable B ': C ratios (eg, 10:90, 60:40, 50:50, and up to 0: 100) are contemplated and encompassed by the present invention. Such polymers would be produced by various amounts of monomers in the reaction mixture from which the end product is produced over time and type B 'and C repeat units may be arranged in the polymer backbone in a random order or in an alternative pattern.

Class II polymers can have a wide variety of molecular weights, ranging for example from 5005,000,000, depending mainly on the desired end use. Additionally, n can range from about 1-10,000 and more preferably from about 1-5,000.

Preferred Class II polymers are generally synthesized using dicarboxylic acid monomers, as well as precursors and derivatives thereof. For example, polymers containing mono and dicarboxylic acid repeat units are contemplated with vinyl ester repeat units and vinyl alcohol repeat units; however, polymers comprising primarily dicarboxylic acid repeat units are preferred (eg, at least about 85%, and more preferably at least about 93%, of the repeat units are of this character). Class II polymers can easily complex with salt-forming cations using conventional methods and reagents.

Synthesis of Class II Polymers

In general, Class II polymers are made by free radical polymerization that serves to convert selected monomers into desired polymers with repeating units. Such polymers can be further modified to impart particular structures and / or properties. A variety of techniques can be used for the generation of free radicals, such as the addition of peroxides, hydroperoxides, azo initiators, persulfates, percarbonates, per-acid, charge transfer complexes, irradiation (eg UV, electron beam , X-rays, gamma radiation, and other types of ionizing radiation) and combinations of these techniques. Of course, a wide variety of methods and techniques are well known in the art of polymer chemistry for initiating free radical polymerizations. The ones mentioned in this document are just some of the most frequent methods and techniques of use. Any suitable technique for performing free radical polymerization is likely to be useful for the purposes of practicing the present invention.

The polymerization reactions are carried out in a compatible solvent system, namely a system that does not unduly interfere with the desired polymerization, using essentially any desired concentration of monomers. A number of suitable aqueous or non-aqueous solvent systems can be employed, such as ketones, alcohols, esters, ethers, aromatic solvents, water, and mixtures thereof. Water alone and ketones and lower alcohols (C1-C4) are especially preferred, and these can be mixed with water if desired. In some cases, the polymerization reactions are carried out with the substantial exclusion of oxygen, and more generally under an inert gas such as nitrogen or argon. There is no particular criticality in the type of equipment used in the synthesis of the polymers, i.e. stirred tank reactors, continuous stirred tank reactors, piston flow reactors, tube reactors and any combination of the above arranged in series can be employed. A wide range of suitable reaction arrangements are well known in the polymerization art.

In general, the initial polymerization step is carried out at a temperature of from about 0 ° C to about 120 ° C (more preferably from about 30 ° C to about 95 ° C for a period of from about 0.25 hours to about 24 hours and even more preferably from about 0.25 hours to about 5 hours). Generally, the reaction is carried out with continuous stirring.

After the polymerization reaction is complete, Class II polymers can be converted to partial or saturated salts using conventional techniques and reagents.

Preferred Class II maleic-itaconic polymers

The most preferred Class II polymers are composed of maleic and itaconic B 'and C repeat units and have the generalized formula

where X is either H or another salt-forming cation, depending on the level of salt formation.

In a specific example of the synthesis of maleic-itaconic Class II polymer, acetone (803 g), maleic anhydride (140 g), itaconic acid (185 g) and benzoyl peroxide (11 g) were stirred together under inert gas in a reactor. The supplied reactor included a suitable sized jacketed glass cylinder reactor with mechanical stirrer, a temperature measurement device for the content in contact with the contents of the reactor, an inert gas inlet, and a removable reflux condenser. This mixture was heated by circulating hot oil in the reactor jacket and stirred vigorously at an internal temperature of about 65 to 70 ° C. This reaction was carried out over a period of approximately 5 hours. At this point, the contents of the reaction vessel were poured into 300 g of water with vigorous mixing. A clear solution was obtained. The solution was subjected to distillation under reduced pressure to remove excess solvent and water. After sufficient solvent and water have been removed, the solid reaction product is precipitated from the concentrated solution, and recovered. The solids were subsequently dried under vacuum. A schematic representation of this reaction is shown below.

Stage 1

COOH

OOH

Itaconic acid

Acetone solution

acetone solvent

Benzoyl peroxide initiator hours

T = 55 - 7C ° C

Polymer (with partial anhydride content)

Stage 2

H;OR

COOH

--k ^ '- COOH

Fully hydrolyzed acid polymer, aqueous solution

Preferred Uses of the Novel Polymers of the Invention

The novel (Class I) polymers of the invention, either alone, as a part of a mixed polymer product, and / or with other ingredients, can be used in a variety of contexts, some of which are described below. All of the foregoing descriptions regarding Class I, IA, and II polymers are applicable to each of the uses described below, i.e., all of the foregoing polymer descriptions are to be considered as incorporated by reference in each of the following usage categories. Likewise, the definitions established in the use categories are to be considered as applicable to all those categories.

one. Agricultural assets

The Class I polymers herein (with or without complex ions) can be used directly as agricultural active compounds. For example, such polymers can be dispersed in an aqueous liquid medium and applied to the foliage of plant leaves or applied to plants growing adjacent to the soil. Polymers have been found to increase plant uptake of both polymer-borne metallic nutrients and environmental non-polymeric nutrients found in adjacent soil. In such uses, effective amounts of the compositions comprising the above defined polymers are employed, either in liquid dispersions or in dry, granular form. Therefore, the application of the polymer only results in the improvement of the growth characteristics of the plants, presumably by increasing the availability of naturally occurring environmental nutrients. Typically, the polymers are applied at a level of about 0.000453 to about 45.3 kilos (about 0.001 to about 100 pounds) of polymer per acre of growing soil or plants, most preferably from about 0.002265 to about 22.65 kilos (about 0.005 at about 50 pounds of polymer per acre, and more preferably from about 0.00453 to about 0.906 kilos (about 0.01 to about 2 pounds).

2. Uses of fertilizers

In other preferred uses, Class I polymers can be used to form composite products where the polymers are in close contact with fertilizer products including but not limited to phosphate-based fertilizers, such as MAP, DAP, triple superphosphate, ordinary superphosphate, any from a number of well-known NPK fertilizer products, and / or fertilizers containing nitrogen materials such as ammonia (anhydrous or aqueous), ammonium nitrate, ammonium sulfate, urea, ammonium phosphates, sodium nitrate, calcium nitrate, potassium nitrate, soda nitrate, urea formaldehyde, metal ammonium phosphates (eg zinc, iron); phosphorous materials such as calcium phosphates (normal and superphosphate phosphate), ammonium phosphate, ammonium superphosphate, phosphoric acid, superphosphoric acid, basic slag, rock phosphate, colloidal phosphate, bone phosphate; potassium materials such as potassium chloride, potassium sulfate, potassium nitrate, potassium phosphate, potassium hydroxide, potassium carbonate; calcium materials, such as calcium sulfate, calcium carbonate, calcium nitrate; magnesium materials, such as magnesium carbonate, magnesium oxide, magnesium sulfate, magnesium hydroxide; sulfur materials such as ammonium sulfate, sulfates from other fertilizers discussed here, ammonium thiosulfate, elemental sulfur (either alone or included with or coated on other fertilizers), · micronutrients such as Zn, Mn, Cu, Fe, B, Mo, and other micronutrients discussed here; oxides, sulfates, chlorides, and chelates of such micronutrients (eg, zinc oxide, zinc sulfate, and zinc chloride); such chelates sequestered in other carriers such as EDTA; boron materials such as boric acid, sodium borate, or calcium borate; organic waste and wastewater such as manure, wastewater, by-products from the food processing industry, and pulp and by-products from paper mills; and molybdenum materials such as sodium molybdate. As known in the art, these fertilizer products can exist as dry powders / granules or as dispersions in water. Fertilizers can be of the conventional variety, or they can be starter fertilizers.

In such contexts, Class I polymers can be mixed with the fertilizer products, applied as a surface coating to the fertilizer products, or otherwise thoroughly mixed with the fertilizer products. Preferably, in such combined fertilizer / polymer compositions, the fertilizer is in the form of particles having an average diameter of about the powder size (less than about

0.001 cm) to about 10 mm, most preferably from about 0.1 mm to about 5 mm, and more preferably from about 0.15 mm to about 3 mm. The polymer is present in such combined products at a level of from about 0.01 g to about 7 g of polymer per 100 g of fertilizer (eg, phosphate-based fertilizers), most preferably from about 0.08 g to about 5 g of polymer per 100 g of fertilizer, and more preferably from about 0.09 g to about 2 g of polymer per 100 g of fertilizer. Again, the polymer fraction of such combined products can include the polymers defined above, or such polymers complexed with the aforementioned ions. In the case of the combined fertilizer / polymer products, the combined product is applied at one level such that the amount of polymer applied is about 10 to 150 g of polymer per acre of soil, most preferably about 30 to 125 g of polymer per acre, and more preferably about 4 0 to 12 0 g of polymer per acre of soil. Products combined in the same way can be applied as liquid dispersions or as dry granulated products, at the discretion of the user. When polymers according to the present invention are used as a coating, the polymer comprises between about 0.005% and about 15% by weight of the coated fertilizer product, most preferably the polymer comprises between about 0.01% and about 10%> by weight of the product coated fertilizer, and more preferably between 0.5%> and about 1% by weight of the coated fertilizer product. Polymer-coated fertilizer products have been found to obtain highly desirable characteristics due to alteration of the mechanical and physical properties of the fertilizer.

Especially preferred Class I polymers for use in agricultural settings are synthesized as partial sodium salts and include the following repeating units: maleic - from about 20 to 55 mole percent, most preferably from about 25 to 50 mole percent , and more preferably from about 30 to 45 mole percent; itaconic - from about 35 to 65 mole percent, most preferably from about 40 to 60 mole percent, and more preferably about 50 mole percent; total sulfonated - from about 2 to 40 mole percent, most preferably from about 3 to 25 mole percent, and more preferably from about 5 to 20 mole percent. The total sulphonated fraction is preferably made from a combination of alkylsulfonic and methylsulfonic repeat units, viz. Metalsulfonic - from about 1 to 20 mole percent, most preferably from about 3 to 15 mole percent, and more preferably from about 4 to 6 mole percent and allylsulfonic - from about 0.1 to 10 mole percent, most preferably from about 0.5 to 8 mole percent, and more preferably from about 1 to 5 mole percent. These types of polymers are typically converted to partial or complete salts (preferably using cations such as alkali metal, ammonium, zinc, and mixtures thereof) at a pH of about 0.2 to 4, more preferably of about 0.3 to 3, and more preferably from about 1 to 2.5.

As mentioned, these preferred Agricultural Class I polymers are suitably initially synthesized as partial sodium salts. This is due to the fact that the most preferred sulfonated repeat units are derived from sodium salts, for reasons of cost and availability.

A preferred polymer of this type is a partial sodium salt having a pH of about 1, with a molar composition of repeating units of maleic of 45 mole percent, itaconic of 50 mole percent, 4 percent methylsulfonic in mol and allylsulfonic 1 percent in mol. This specific polymer is referred to herein as the T5 polymer.

Useful variants of the T5 polymer include mixed partial sodium and zinc salts having about 5% w / w Zn on a metal basis and with a pH of about 3. It is made by reacting the T5 tetrapolymer with basic zinc carbonate in water . Alternatively, the product can be made by reaction with zinc metal.

Another preferred type of polymer is a T-20 tetrapolymer containing about 30 mole percent maleic repeat units, about 50 mole percent itaconic repeat units, and a total of about 2 0 mole percent mol sulfonated repeating units, consisting of about 15 percent by mole of methylsulfonate repeating units and about 5 percent by mole of allylsulfonate repeating units. T-20 tetrapolymer variants include partial salts (preferably alkali metal, ammonium, zinc, and mixtures thereof) having a pH of about 1-3. Such a variant is a partial mixture of sodium and partial ammonium salt at a pH of about 2.5, made by adding ammonia to the aqueous solution of T-20 partial sodium salt until the target pH is reached. This polymer has a significant lipophilic character and is useful in formulations containing pesticides.

Preferred formulations for coating granular nitrogenous fertilizers (eg, urea) include a novel tetrapolymer of the invention (preferably T5 polymer), boric acid, low molecular weight polyvinyl alcohol, and water. For example, such coating formulations may have from about 20 to 50% w / w (more preferably about 34% w / w) of tetrapolymer, from about 0.1 to 5% w / w (most preferably about 1.5% w / w ) of low molecular weight polyvinyl alcohol, and from about 25 to 60% w / w (more preferably about 57.5% w / w) of water. Such formulations are compatible with colorant dyes and provide superior coating performance.

Preferred formulations for the addition of liquid nitrogen fertilizers include a novel tetrapolymer of the invention in the form of a mixed calcium / sodium salt (preferably T5 polymer), lactic acid, boric acid, and water at a pH of about 0.5-3. For example, such formulations may have from about 20 to 50% w / w (more preferably about 35.5% w / w) of tetrapolymer, from about 20 to 40% w / w (more preferably from about 30%> w / w lactic acid), from about 2-10% w / w (more preferably from about 4.5% w / w) and from about 20 to 45% w / w (more preferably from about 30% w / w) of water .

Example 5 - Evaluation of partial tetrapolymer salt as a phosphorus fertilizer enhancer

The above described ammonium / sodium tetrapolymer salt B was tested for its ability to prevent phosphorous binding in dispersions. In soils, the fixation of phosphorus (phosphates) with cations, such as Ca, Mn, Mg, Al and Fe, limits the absorption of phosphorus by plants, which in turn depresses yields. This interaction with the soil can be simulated in water using dispersible water soluble phosphates (P205). These dispersions create an ideal environment for fixation tests, with visible phosphate precipitation being determined.

A first 1000 ppm stock dispersion of free calcium ions from calcium chloride was prepared and aliquots thereof were pipetted into eight separate 50 mL Erlenmeyer flasks, followed by dilution with deionized water to 50 mL total volume. This produced two sets of flasks for us. 1 and 2, each set having four individual flasks containing, respectively, 10, 100, 500 and 1000 ppm of free calcium ions in water.

A second 1000 ppm free iron ion stock dispersion made from ferrous sulfate was also created and pipetted into eight additional Erlenmeyer flasks for

100 create two sets of jars us. 3 and 4, each set having four individual flasks containing, respectively, 10, 100, 500 and 1000 ppm of free iron ions in water.

Partial t-tetrapolymer salt B (a sodium / ammonium salt, pH approximately 2.5) was added to flasks of Sets 1 and 3 in an amount of 0.50% (v / v) to represent a usage amount of fertilizer typical liquid. Sets 2 and 4 were left untreated as controls. A 1% by weight phosphate dispersion was made using standard 10-34-0 liquid phosphate fertilizer, and this was pipetted into all 16 Erlenmeyer flasks in a staged fraction, using 0.5 mL aliquots, for a total of 5.0 mL of phosphate dispersion. The degree of phosphate precipitation was recorded after each aliquot was added to the flasks, using a percentage scale, where 0%> was clear and colorless, and 100%) was a solid opaque precipitate (lower concentrations of non-cations). reached 100% and were fully bonded at a level of about 75% precipitate). The results of these tests are indicated in the following Tables 1 and 2.

101

Example 5, Table 1 - Ca flasks, Sets 1 and 2

<td rowspan="2">Ca Reaction Flasks</td><td colspan="10">Phosphate addition - mL</td>

<td>10 ppm w / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td>

<td>100 ppm w / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td>

<td>500 ppm w / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 20%</td><td> 30%</td><td> 50%</td><td> 100%</td><td> 100%</td>

<td>1000 ppmc / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 20%</td><td> 40%</td><td> 70%</td><td> 100%</td><td> 100%</td><td> 100%</td>

Example 5, Table 2 - Flasks of Faith, Sets 3

And 4

<td rowspan="2">Faith Reaction Flasks</td><td colspan="10">Phosphate addition - mL</td>

<td>10 ppm w / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td>

<td>100 ppm w / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td>

<td>500 ppm w / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 25%</td><td> 50%</td><td> 100%</td><td> 100%</td>

<td>1000 ppmc / Polymer</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 0%</td><td> 20%</td><td> 40%</td><td> 80%</td><td> 100%</td><td> 100%</td>

As is evident from the above data, the polymers of the invention significantly reduce the

102 precipitation in all Ca and Fe reaction flasks, except for the 10 ppm dispersions, which had no precipitation at any level of phosphate addition. In the 100 ppm Ca reaction flasks, the polymer supplemented flasks did not exhibit precipitation at any level of phosphate addition, while the 100 ppm flask without polymer exhibited significant precipitation (corresponding to the prevention of phosphorous fixation) starting at the 1.5 mL level. Similarly, in Fe reaction flasks at phosphate addition levels of 500 and 1000 ppm, the performance of the supplemented polymer flasks was significantly better than in the non-polymer flasks.

3. Uses with sulfur-containing compounds

A particularly important agricultural utility of the novel Class I polymers of the invention is the ability of the polymers to improve the agricultural efficacy of sulfur-containing compounds, such as gypsum, one or more members of the Kieserite Group, magnesium and potassium sulfate, elemental sulfur, and mixtures thereof. Polymers can be applied as surface coatings, as solid fertilizers, or can be added to liquid fertilizers in solution as a liquid; This combined liquid material can then be sprinkled on the soil prior to planting. Furthermore, polymers release calcium

103 soluble and species containing soluble gypsum sulfur and other minerals in compositions containing significant amounts of calcium sulfate. Calcium sulfate exists in a wide range of forms, crystal structures, hydration levels, and particle morphologies, but its calcium sulfate content has been difficult to exploit for plant nutrition purposes due to poor solubility of the species that contain calcium and sulfur in them.

It has been found that the addition of relatively small levels of the novel polymers of the invention applied to solid calcium sulfate or calcium sulfate containing materials serves to increase the release of soluble calcium and sulfur species from calcium sulfate or materials. Similar. In general, the polymers are used at a level of from about 0.01 to 10% w / w, more preferably from about 0.05 to 2% w / w, where the total weight of the products containing polymer / calcium sulfate or sulfate of Calcium is taken as 100% by weight.

Example 6 - Gypsum treatment with Class I tetrapolymer

In this test, granulated gypsum was coated with polymer T5, which was diluted with water to give a polymer content of approximately 40% w / w. This polymeric material was applied to gypsum in a proportion of 0.50%> w / w.

104

Three polymer-free gypsum controls were performed for each test, along with three replications of added gypsum polymer. In each test, a 1 g sample of the uncoated or coated gypsum was placed in a 50 mL Erlenmeyer flask, followed by the addition of 10 mL of water and stirring on a reciprocating shaker at low setting for a period of selected time. After the selected shaking period, the contents of each flask were filtered into a 50 mL centrifuge tube through Whatman 1 filter paper. The pH of the filtered solution was then measured, and then the solution was diluted 10-fold with 2.0% nitric acid and analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES) for sulfur and calcium content. The pH of the filtered solution was also recorded. The results are set out in the following tables.

Example 6, Table 1

<td>20 min. agitation</td><td>%AC</td><td>% S</td><td>pH</td><td>% Ca average</td><td>% S average</td>

<td>Control samples</td><td> 1.55</td><td> 1.69</td><td> 6.96</td><td rowspan="3"> 1.81</td><td rowspan="3"> 2.04</td>

<td>T5 Polymer Samples</td><td> 1.41</td><td> 1.54</td><td> 5.99</td><td rowspan="3"> 1.86</td><td rowspan="3"> 2.11</td>

105

Example 6, Table 2

<td>60 min. agitation</td><td>%AC</td><td>% S</td><td>PH</td><td>% Ca average</td><td>% S average</td>

<td>Control samples</td><td> 1.71</td><td> 1.91</td><td> 7.08</td><td rowspan="3"> 1.74</td><td rowspan="3"> 1.98</td>

<td>T5 Polymer Samples</td><td> 1.46</td><td> 1.61</td><td> 6.00</td><td rowspan="3"> 1.87</td><td rowspan="3"> 2.12</td>

Example 6, Table 3

<td>240 min. agitation</td><td>% Ca</td><td>% S</td><td>pH</td><td>% Ca average</td><td>% S average</td>

<td>Control samples</td><td> 1.72</td><td> 1.93</td><td> 6.94</td><td rowspan="3"> 1.81</td><td rowspan="3"> 2.10</td>

<td>T5 Polymer Samples</td><td> 1.52</td><td> 1.69</td><td> 6.32</td><td rowspan="3"> 2.09</td><td rowspan="3"> 2.35</td>

Example 6, Table 4

<td>24 hr. agitation</td><td>% Ca</td><td>% S</td><td>pH</td><td>% Ca average</td><td>% S average</td>

<td>Control samples</td><td> 1.88</td><td> 2.14</td><td> 7.24</td><td rowspan="3"> 1.82</td><td rowspan="3"> 2.10</td>

<td>T5 Polymer Samples</td><td> 2.00</td><td> 2.19</td><td> 6.79</td><td rowspan="3"> 2.10</td><td rowspan="3"> 2.35</td>

106

As can be seen, with increasing agitation time, the amount of free sulfur and calcium increased significantly in the controls, confirming that the plaster coating with polymer T5 increased the amount of sulfur available for absorption by the plant.

Further increased sulfur and calcium availability can be obtained using a coating mixture comprising 35% w / w T5 tetrapolymer, about 2% w / w low molecular weight polyvinyl alcohol, and about

<td>40% w / w</td><td>of</td><td colspan="2">glycolic acid, with balance being</td><td>Water.</td>

<td>Through</td><td>the</td><td>removing the</td><td>most of the water</td><td>and the</td>

<td>addition</td><td>of</td><td>Glycolic Acid</td><td colspan="2">and PVA, were observed</td>

improved coating behaviors, allowing the use of smaller amounts of polymer.

Four. Uses with liquid or solution fertilizers

The use of alpha-hydroxy carboxylic acid compounds with the polymers of the invention in the context of liquid or solution fertilizers can produce better results. Alpha-hydroxy acids can be used alone or in mixtures of 2 or more acids. The most useful alpha-hydroxy acids are saturated and essentially free of carbon double bonds and ring structures, including both aliphatic and aromatic ring structures (i.e., not more than about 5 percent by mole of double bonds or carbon structures). ring). Such alpha acids

107 Hydroxy possess at least one carboxylic acid functional group and have at least one hydroxyl group on the carbon atom adjacent to the carboxylate group. Especially preferred acids of this character include lactic acid (D, L, or racemic mixtures are useful), glycolic acid, citric acid, tartaric acid, tartronic acid, glyceric acid, and dihydroxypropanedioic acid. Alpha hydroxy acids can have more than one carboxylic acid functional group per molecule, more than one alpha hydroxy group, or any combination thereof.

Preferred alpha-hydroxy acid / polymer formulations generally include from about 10 to 45% w / w, more preferably from about 15 to 35% w / w, of the polymers of the invention, preferably including at least one Class I polymer ; from about 3 to 60% w / w, more preferably from about 10 to 4 0% w / w, of alpha-hydroxy carboxylic acids; and the rest being an inert solvent, preferably water. The above ranges are based on the total weight of the formulations taken as 100% by weight. The following representative formulation has been found to be particularly useful for use with liquid or solution fertilizers, especially gypsum in solution: 35% w / w of the T5 polymer described above, 30% w / w of glycolic acid, and the remainder being Water.

108

Polymer / alpha-hydroxy carboxylic acid formulations can be further improved with the addition of polyvinyl alcohols (PVA's) to them. Although essentially all PVAs are useful, preferred PVAs are of relatively low average molecular weight, so that a 4% w / w solution in water of PVAs in water at 20 ° C ranges from about 1 to 1000 centipoise. Very small amounts of PVAs can be used in a range of about 0.1% w / w - 10% w / w of the total composition, and more preferably about 0.05% w / w - 2% w / w. It is also possible to use more than one molecular weight of PVA, but the combinations of PVA are suitably within the above viscosity ranges. Still further, preferred PVAs have high levels of hydrolysis, where at least 97 mole percent, and preferably at least about 98 mole percent, of the functional groups are hydrolyzed. A representative composition for use with gypsum includes 35% w / w of T5 polymer, 30% w / w of glycolic acid, 1.5% w / w of PVA (eg, DuPont Elvanol 70-03), and the remainder being water.

The pH levels of liquid or solution fertilizers that include alpha hydroxy acid formulations should be approximately 0.5 to 3, very

109 preferably about 1.

Example 7 - Addition of Class I Tripolymer to UAN

In this series of tests, standard UAN was supplemented with 0.50% by weight of a mixture containing 35.5% by weight of partial calcium salt of polymer T5 (pH of approximately 1.0), 4.5% by weight of boric acid, 30% in weight of lactic acid, the rest being water. This material was used at a level of 151.2 1 / acre corresponding to 54.4 kg of nitrogen / acre with different types of hybrid corn seeds planted. Comparative tests were also performed using UAN without polymer, and UAN supplemented with the recommended amount on the NutriSphere-N label available in the market for liquid fertilizers. All tests were carried out in 6 repetitions with the liquid fertilizers applied by emission before emergence, two days after planting. Corn yields were recorded for each test and averaged.

Example 7, Table 1

<td>UAN treatment</td><td>Hybrid</td><td>Yield (Bu / acre)</td>

<td>+ NutriSphere-N</td><td> 121.6</td>

<td>+ NutriSphere-N</td><td> 137.6</td>

110

<td>+ NutriSphere-N</td><td> 129</td>

<td>+ NutriSphere-N</td><td> 93.9</td>

5. Specific uses with granular fertilizers containing potassium

Another significant agricultural utility of the Class I polymers of the invention involves use with granular potassium-containing fertilizers in order to decrease fertilizer losses. That is, the polymers can be applied directly to granular potassium fertilizer at least partially soluble in water, and especially potassium chloride-based fertilizers, at a level of about 0.001 to 10% by weight, more preferably about 0.004 to 2% by weight, based on the total weight of the polymer / potassium fertilizer material taken as 100% by weight. In order to form suitable coatings on these fertilizers without generating significant amounts of hydrochloric acid, it is generally preferred that the polymers be neutralized with a suitable cation to a pH of about 0.1 to 4, and more preferably around 1. A preferred formulation involves creating a partial salt of the polymer

111

Τ5 (at a concentration of 50% w / w) in aqueous dispersion at 20 ° C, reacting the polymer with 45% w / w of potassium hydroxide to reach a pH of approximately 0.1-4. The resulting dispersion is adjusted by evaporation and addition of water to give a 40% solids dispersion> w / w at room temperature. This composition, which is called T5-K-Na, is coated on commercial potassium chloride granules at a level of about 0.001% w / w - 5% w / w.

It has been found that the use of the novel polymers of the invention is not essential in formulations that include soluble potassium-containing solids. Therefore, this aspect of the invention contemplates the provision of formulations comprising a mixture of a Class I and / or Class II polymer (having at least about 10%, more preferably at least about 25%, of the functional groups on the same being anionic) in partial or complete salt form, with substantially all of the cations therein being alkali metal and at a pH of between about 0.5 to 3, and more preferably about 1. Such formulations are applied to at least partially soluble potassium-containing solids and allowed to dry so that the dry residue thereof is applied to the surface of the solids. The same usage levels as described above with reference to the

112 Calcium sulfate products are applicable to these potassium products as well. The polymer is generally present at a level of from about 0.001 to 10% by weight, more preferably from about 0.004 to 2% by weight, based on the total weight of the polymer / potassium containing solids product taken as 100% by weight.

6. Uses as seed coatings

Another alternative use of Class I polymers in accordance with the present invention includes the use of the polymers as seed coatings. In such cases, the polymers comprise at least about 0.001 to 10% or by weight of the coated seed, more preferably from about 0.004 to 2%> by weight of the coated seed. Using the polymer as a seed coat offers polymer in close proximity to the seed when planted so that the polymer can exert its beneficial effects in the environment where it is most needed. That is, the novel polymers provide an environment conducive to growth of the improved plant in the area where the effects can be localized around the desired plant. In the case of seeds, the polymer coating provides a strengthened opportunity for seed germination, subsequent plant growth, and an increase in the availability of nutrients to plants, which is provided by the polymer salts.

113

In preferred practice, Class I polymers are in aqueous dispersion and have a relatively high metal content, and particularly micronutrient metals, such as Zn, Μη, B, Fe, Mo, and Cu, to provide sufficient micronutrients for optimal growth of the seeds. On the other hand, the polymers are desirably relatively free of suspended or settled solids for reasons of homogeneity and aesthetic appearance, and should have a pH in the range of about 2 to 8, and preferably of about

5-7. In practice, the polymers are applied to the seed surfaces in any convenient way, and allowed to dry thereon, so that the finished seeds have the dry residue of the original liquid polymer and nutrients on the seed surfaces.

7. Uses in the reduction of atmospheric ammonia

The novel Class I polymers herein can be used to treat livestock or poultry confinement facilities to reduce and mitigate the effects of gaseous ammonia within the facility. Generally, these types of facilities have a manure collection area, vertical walls that form an enclosure, and a roof that substantially covers the area. This utility consists in applying a treatment material to the manure inside the

114 collection area in an effective amount to decrease the concentration of gaseous ammonia within the installation. Said material comprises an aqueous mixture of a polymer according to the present invention, and in particular a partial or saturated amine, alkali or alkaline earth metal (for example, calcium or ammonium) salt of the polymer. Preferably, the treatment mixture is applied directly to the collection area (eg manure pit) below the enclosure. The treatment material that includes the polymer herein should be applied at a level of from about 0.0189-11.34 liters (0.005-3 gallons) per ton of manure, and more preferably from about 0.0378 to 9.45 liters (0.01 to 2.5 gallons) by Ton. The composition is preferably acidic having a pH of from about 1-5, and more preferably of about 2-4. The treatment material is capable of operating to reduce the amount of ammonia gas within the confinement zone within 24 hours after application of the materials.

US Patent Publication No. 2014/0041431 is incorporated herein by reference in its entirety. This publication describes techniques for the reduction of atmospheric ammonia by using Class II polymers. These same techniques without alteration can be used with the Class I polymers of this invention, and

115 also all the different Class I, Class IA and Class II polymer blends.

Sometimes it is useful to employ a plurality of different polymers in the treatment compositions. For example, useful compositions can include from about 40 to 80% (more preferably 55 to 75%) by weight of a partial calcium salt of a Class I polymer of the invention, and from about 20 to 60% (more preferably 25 to 45%) by weight of a partial ammonium salt of the same or different from the polymer according to the invention. Both of these polymers are in the form of 4 0% w / w aqueous dispersions, so that the total amount of polymer per se in each is 40%> of the above ranges.

The polymers of the invention (i.e., Class I polymers, or different mixtures of Class I, Class IA, and Class II polymers) can also be used, alone or in combination with other polymers, to treat areas subject to gas evolution. ammonia, for example, domestic pet beds, in order to reduce the ammonia odor emanating from them.

Complete treatment materials should preferably contain at least about 30 to 60% by weight (more preferably about 3 to 50% by weight) of polymer solids derived from all polymers.

116 present in the treatment materials, and from about 4 to 70% by weight (more preferably from about 50 to 65% by weight) of water. Other ingredients can be used in addition to polymers and water, such as pH adjusting agents, pH regulating agents, preservatives, and emulsifiers. Any of these other ingredients are preferably used at a lower level, for example, from about 1 to 10% by weight. The pH of the entire treatment materials should be acidic, preferably from about 1 to 5, more preferably from about 2-4.

When the preferred treatment materials comprise calcium and ammonium partial salts of the polymers, it is desirable that the amount of the polymer in the calcium partial salt be greater than the amount of the polymer in the ammonium partial salt, on a weight basis. That is, taking the total weight of both polymer salt solids as 100% by weight, the partial calcium salt copolymer solids should be present at a level of about 50 to 80% by weight (most preferably about 55 to 75% by weight, and more preferably from about 60 to 65% by weight), and the ammonium partial salt copolymer solids should be present at a level of from about 20 to 50% by weight (most preferably from about 25 to 45% by weight, and more preferably from about 35 to

117

40% by weight).

The application of the dual partial salt copolymer materials of the invention is very simple. In the case of manure collection pits, the material only needs to be poured over the top of the manure and will be fairly easily propagated and diffused in the manure mass to quickly reduce the amount of nitrogen gas generated and maintained within the lockdown. For dairy or poultry stables that have soil structures with dirt and manure mixed in with the dirt, the treatment material is suitably sprayed on top of the dirt-manure mix, with or without Mix. Here again, the action of the treatment material is quite fast and long-lasting.

In general, treatment mixes are used at a level of about 0.0189-11.34 liters (0.005-3 gallons) of material per ton of manure, preferably around 0.0378 to 9.45 liters (0.01 to 2.5 gallons) / ton, most preferably around 0.07563.78 liters (0.02 to 1 gallon) per ton, and more preferably around 0.1134 to 0.1323 liters (0.03 to 0.035 gallons) per ton.

Almost immediately after application of the treatment material to manure, the amount of ammonia

118 gaseous inside the confinement installation is significantly reduced, and said reduction persists for a considerable time. Generally, the predominant amount of ammonia gas should be reduced by at least about 50% (more preferably at least about 60%) within 24 hours after application. A single treatment also preferably serves to maintain a reduction in ammonia gas of at least about 30% (more preferably at least about 40%) for at least about 14 days (more preferably at least about 21 days).

8. Uses as animal feed and / or water modifications

US patent application SN 14/049887, filed on October 9, 2013, describes the use of Class I and / or Class II polymers as animal feed or water modifications that serve to decrease ammonia concentrations in excreta of the animal. That application is incorporated herein by reference in its entirety. The methods, animal feed and animal waters described herein can be directly duplicated, without any alternations, in the context of the present invention, except for the use of any mixture of Class I, Class IA and Class polymers. II of this document. Therefore, the types of polymer salts, the

119 range of polymer solids, and the amounts of water remain the same in the present invention. Similarly, the same specific methods of use can be employed in the context of the present invention, with the only difference being the particular polymers used.

For example, conventional poultry feeds comprising feed ingredients that include amounts of cornmeal and soy can be improved using modifications containing Class I polymers, alone or in combination with other polymers, such as Class la polymers. and Class II. In the same way, poultry water can be supplemented in the same way. In either case, the amount of modification used should be sufficient to reduce the volatilized ammonia derived from the feces of poultry, compared to poultry receiving the same feed and / or water, but without the modifications. Similarly, mammalian feed and water can be improved by adding the copolymers of the invention, again in amounts sufficient to reduce volatilized ammonia derived from mammalian feces, compared to animals that

<td>received the</td><td>I think myself</td><td>and / or water,</td><td>but</td><td>without the S</td>

<td>modifications.</td><td></td><td></td><td></td><td></td>

<td>The</td><td>modifications</td><td>Complete</td><td>they should</td><td>contain</td>

preferably at least about 30 to 60% by weight of the

120 Total copolymer solids of (most preferably about 35 to 50% by weight solids), and about 40 to 70% by weight of water (most preferably about 50-65% water). However, the modifications may also include other ingredients apart from the two copolymers of partial salts and water, such as pH adjusting agents, pH regulating agents, preservatives and emulsifiers. Any of these other ingredients is preferably used at a lower level, for example, from about 1 to 10% by weight. The pH of the complete modifications should be acidic, preferably approximately 1-5, most preferably approximately 2-4.

A preferred modification comprises an aqueous mixture that includes a partial calcium salt of a Class I copolymer and a partial ammonium salt of a Class I copolymer, the partial calcium salt copolymer solids must be present in an amount greater than the amount of the ammonium partial salt copolymer solids therein. That is, taking the total weight of both copolymer salt solids as 100% by weight, the calcium partial salt copolymer solids should be present at a level of about 50 to 80% by weight (most preferably about 55 to 75% by weight, and more preferably from about 6 0 to 65% by weight), and the solids of

121 Partial ammonium salt copolymer should be present at a level of from about 20 to 50% by weight (most preferably from about 25 to 45% by weight, and more preferably from about 35 to 40%) by weight). Furthermore, the individual copolymer salts in water must both have a pH in the order of about 1-4.

Generally speaking, modifications of the invention are administered to animals by adding the modifications to the animal feed in another conventional manner, and / or adding the modifications to the animal water source, or both.

In the case of poultry, use can be made of commercially available or customized poultry feeds, which are typically substantially dry and particulate in nature. Such feeds typically contain yellow corn at a level of about 45 to 65% by weight, along with soybeans at a level of about 18 to 45% by weight. These feeds also commonly include a variety of other ingredients, such as animal meal, fats, salt, limestone or oyster shells, amino acids, vitamins and minerals, and have protein assays (N x 6.25) of approximately 15-32%, and a metabolizable energy (ME) value of approximately 1100 to 1600 kcal / .453 kg. More information on conventional bird feeds can be found at

122

Poultry Nutrition and Feeding, section 12, Animal Nutrition Handbook 316-331 (2009), which is incorporated herein by reference in its entirety. Modifications of the invention, typically in aqueous liquid form, are sprayed or otherwise applied to dry poultry feed ingredients with mixing, to substantially intercalate the copolymer materials with food ingredients. The improved feed is then fed ad libitum to poultry. Complete water / salt copolymer modifications should be present in an improved feed at a level of about 0.05 to 0.25% by weight (more preferably about 0.1 to 0.2% by weight), where the total weight of the supplemented or modified feed it is taken as 100% by weight. This corresponds to a level of about 0.015 to 0.15% by weight (more preferably 0.03 to 0.12% by weight) of copolymer solids per se in poultry feed.

<td></td><td>In</td><td>the case</td><td>of</td><td>the adition of</td><td>the</td><td>modifications</td>

<td>Complete</td><td>of</td><td>water / salt</td><td>of</td><td>copolymer a</td><td>Water</td><td>for birds of</td>

<td>corral,</td><td>the</td><td colspan="2">use would be</td><td>typically</td><td>to</td><td>a level of</td>

<td colspan="3">about</td><td colspan="2">0.01 to 0.25%</td><td>in</td><td>volume plus</td>

preferably about 0.05 to 0.2% by volume, where the total amount of supplemented or modified water is taken as 100% by volume. This corresponds to a level of

123 approximately 0.003 to 0.15% by volume (most preferably 0.0045 to 0.12% by volume) of the copolymer solids per se in poultry water. Since the preferred partial salt copolymers of the invention and the MTM® product are soluble in water, the complete modifications are easily mixed and uniformly dispersed in the poultry water.

Modifications of the invention, used with either poultry feed or poultry water, can be fed to virtually any poultry, eg, chicken, duck, goose, peacock, swan, ostrich, pigeon, turkey. , Guinea fowl, pheasant, ostrich and emu.

When complete modifications are employed to supplement mammalian animal feed and / or water, the same general techniques and amounts of complete modifications and copolymers are employed. For example, the modifications can be mixed directly with the feed or used as a top dressing on it. Similarly, the animals' water supply is completed as previously described. The fact that the copolymers are soluble in water facilitates their greater use. Modifications of the invention can be fed to a wide variety of farm animals, for example mammals such as cows, sheep, pigs, and horses.

124

As indicated above, it is preferred that the modifications of the invention be used in the form of aqueous mixtures containing copolymer salts. However, and especially in the case of modifications to poultry or animal waters, the copolymer solids can be added as is, and not in a complete water / copolymer modification. In such cases, the above addition intervals of the copolymers themselves are applicable.

9. Pesticide adjuvants

The Class I polymers of the invention can be used to improve the efficacy of a broad spectrum of pesticides. As used herein, pesticide refers to any agent with pesticidal activity (eg, herbicides, insecticides, fungicides, and nematocides) and is preferably selected from the group consisting of insecticides, herbicides, and mixtures thereof, but usually excluding materials that affirmatively have a plant fertilizing effect, for example, sodium borate and zinc compounds such as zinc oxide, zinc sulfate and zinc chloride. Well known pyrethroid and organophosphate pesticides are suitable for use in the invention, as are glyphosate and glufosinate herbicides.

In some cases, the polymer, which can be in the form of free, partial acid, or complete salt, is

125 it is in aqueous dispersion and has a pH of about 1-10, most preferably about 2 to 7, and more preferably 2-4, 7, and 8 to 9; pH is often determined by the type of pesticide used, as some may be unstable at low pH ranges, while others decompose at higher pH ranges. The polymers can be mixed with the pesticide to form a mixture that can then be applied to the soil, in foliar applications, on hard surfaces, in the form of aerosols, as additives for liquid or solid compositions (for example, manure), or in any another context where pesticide activity is desired. Alternatively, the pesticide and polymer can be simultaneously or sequentially (typically within 24 hours of each other) applied to the soil. When mixed compositions are used, they are typically in the form of aqueous dispersions, which generally have water, pesticide and polymer fractions. Other minor ingredients can also be used in the compositions such as surfactants and pH adjusting agents, or any of the other aforementioned builders or additives known in the art. Compositions comprising a polymer of the invention and micronutrients have also been shown to be very effective, with micronutrients selected from the group consisting of Mn, Zn, Cu, Ni, Co, Mo, V, Cr, Fe, and B, with a combination of Mn, Zn, Cu and being particularly preferred.

126

Polymers supplemented with micronutrients can be used with glyphosate, to avoid the characteristic blocking reactions between glyphosate and micronutrients.

The amount of polymer in the pesticidal compositions of the invention can vary within wide limits, and the main consideration is the cost of the polymer. Generally, the polymer should be present at a level of from about 0.05 to 10% by weight (most preferably from about 0.1 to 4% by weight, and more preferably from about 0.2 to 2% by weight) based on the total weight of the pesticidal composition taken as 100% by weight.

The pesticides used in the compositions of the invention are widely selected from insecticides and herbicides. In the context of insecticides, pyrethroids and synthetic organophosphates are particularly preferred. For example, permethrin (C21H20C1203, 3- (2,2-dichloroethenyl) -2,2-dimethyl-l-cyclopropan-carboxylate methyl (CAS # 52645-53-1) and biphentrin (C23H22C1F302, (2-methyl- 3-phenylphenyl) methyl (1S, 3S) -3 - [(Z) -2chloro-3,3,3-trifluoroprop-l-enyl] -2,2-dimethylcyclopropan-l-carboxylate, CAS # 82657-04-3) are suitable pyrethroids. A typical organophosphate pesticide useful in the invention is malathion (C10H1906PS2, 2-dimethoxyphosphinothioylthio) butanedioic acid diethyl ester, CAS # 121-75-5).

More generally, the following insecticides are

127 Useful in the invention:

antibiotic insecticides: allosamidine, thuringiensine macrocyclic lactone insecticides avermectin insecticides: abamectin, doramectin, emamectin, eprinomectin, ivermectin, selamectin insecticides, milbemycin spinectin, ilbemectin, milbemycin: calcium arsenate, copper acetoarsenite, copper arsenate, lead arsenate, potassium arsenite, sodium arsenite botanical insecticides: anabasine, azadirachtin, dlimonene, nicotine, pyrethrins (kinerins (kinerin I, kinerin II), jasmoline II, jasmoline II, pyrethrin I, pyrethrin II), quasia, rotenone, ryania, barley carbamate insecticides: bendiocarb, carbaryl benzofuranyl methylcarbamate insecticides:

benfuracarb, carbofuran, carbosulfan, decarbofuran, furathiocarb dimethylcarbamate insecticides: dimethane, dimethylan, hiquincarb, pyrimicarb oxime carbamate insecticides: alanicarb, aldicarbium, butocarboxim, butoxycarboxim, methomyl, nitromocarboxy, methicarboxy, butylcarboxy, methomyl, carmine

128 Thiofanox Phenyl Methyl Carbamate Insecticides:

alixicarb, aminocarb, bufencarb, butacarb, carbanolate, chloetocarb, dicresyl, dioxacarb, EMPC, etiofencarb, fenetacarb, fenobucarb, isoprocarb, methiocarb, metolcarb, mexacarbonate, promacyl, promecarb, propoxurcar, tripoxurkyl, propoxurcarb, X, X, X, X, X, X, X, X, of diatoms, silica gel diamide insecticides: chloranraniliprole, chiantraniliprole, flubendiamide dinitrophenol insecticides: dinex, dinoprop, dinosam, DNOC fluorine insecticides: Barium hexafluorosilicate, cryolite, sodium fluoride, sodium hexafluorosilicate, sulfluramid formamidine insecticides: amitraz, chlordimeform, formetanate, formparanate fumigant insecticides: acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform, chloropicrin, para-dichlorobenzene, 1,2-dichloropropane, ethyl formate, ethylene dibromide, ethylene chloride, ethylene oxide, hydrogen cyanide, iodomethane, methyl bromide, methylchloroform, methylene chloride, naphthalene, phosphine, sulfuryl fluoride, tetrachloroethane

129 inorganic insecticides: borax, boric acid, calcium polysulfide, copper oleate, diatomaceous earth, mercury chloride, potassium thiocyanate, silica gel, sodium thiocyanate, see also arsenical insecticides, growth regulating fluoride Chitin synthesis inhibiting insects: Bistrifluron, Buprofezine, Chlorfluazuron, Cyromazine, Diflubenzuron, Flucicloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Penfluron, Teflubenuron, Juvenile Hormone Triflumuron, Phenylurphenuriphenyl, Phenyluroprene, Phenyluroprene I, juvenile hormone II, juvenile hormone III moulting hormone agonists: chromafenozide, halofenozide, methoxyphenozide, tebufenozide moulting hormones: a-ecdysone, ecdysterone moulting inhibitors: diofenolan precocenes: precocene I, precocene II, precocene III unregulated insect growth regulators: diciclanyl insecticides, nereistoxin analogs: bensultap, cartap, thiocyclam, thiosultap nicotinoid insecticides: flonicamid

130 nitroguanidine insecticides: clothianidin, dinotefuran, imidacloprid, thiamethoxam nitromethylene insecticides: nitenpyram, nitiazine pyridylmethylamine insecticides: acetamiprid, DDTylor-DDT, -T-chlorpid, dichloropyridine) HCH (gamma-HCH, lindane), methoxychlor, pentachlorophenol, TDE cyclodiene insecticides: aldrin, bromotorne, chlorbicycle, chlordane, chlordecone, dieldrin, dilor, endosulfan (endosulfan-alpha), endrin, HEOD, heptachlor, HHDN, isobenzan, isodrine, kelevan, mirex organophosphate organophosphate insecticides, chlorphenes, chlorphenes, brompins, chlorphenes, brompins dicrotophos, dimethylvinfos, fospirate, heptenofos, methocrotophos, monovinophos mevinphos, naled, naphthalophos, phosphamidon, propaphos, TEPP, organotiophosphate insecticidal tetrachlorvinphos: aliphatic organothiophosphate insecticide dioxabenzophos, phosmethyl, phentoate: acetion, amiton, cadusafos, chloretoxy, chlormephos, demefion (demefion-0, demefion-S), demeton (demeton-O, demeton-S), demeton-methyl (demeton-Omethyl) methyl, demeton-S-methyl), demeton-Smethylsulfone, disulfotonsulfone, ethion, ethoprophos, IPSP, isothioate, malathion, methacrypha, oxidemeton-methyl,

131 aliphatic amide organophiophosphate insecticides: amidition, cyanthoate, dimethoate, ethoxymethyl, formothion, mecarbam, omethoate, protoate, sophamide, chlorothophosphate, -methyl heterocyclic organothiophosphate insecticides: azametiphos, coumafos, coumitoato, dioxatión, endotion, menazon, morfotion, fosalona, pyrachlophos, piridafentión, quinotion

- benzothiopyran organothiophosphate insecticides: dithicrophs, ticrophos

- Benzothriazine organothiophosphate insecticides : azinphosthyl, azinphosyl isoisole organothiophosphate insecticides: dialiphos, isoxazole organotiophosphate phosphospyridine pyrophosphospyriphospyridinyl pyrophyriphosphate: -methyl

- insecticides of pyrimidine organothiophosphates: butathiophos, diazinon, etrimfos, lirimfos, pirimifos-ethyl, pirimifos-methyl, primidofos, pirimitato, tebupirimfos

132

- quinoxaline organothiophosphate insecticides: quinalphos, quinalphos-methyl thiadiazole organothiophosphate insecticides: atidation, lithidation, methidathion, protiation triazole organothiophosphate insecticides: isophosphosophilic organophilophosphate: azotoate, bromofos, bromofos-ethyl, carbofenotion, clortiophos, cyanophos, citioato, dicapton, diclofention, etafos, famfur, fenclorfos, fenitrotión, fensulfotion, fentión, fentión-ethyl, heterofos, jodfenfos, mesulfenfos, fosniclor, profenofos, protiofos, sulprofos, temefos, trichlormetafos-3, triphenophos phosphonate insecticides: butonate, trichlorfon phosphonothioate insecticides: phenyl ethylphosphonothioate insecticides: Phonophos, Phenylphosphonothioate Insecticides Trichloronat: Cyanophenes, EPN, Leptophos Insecticide Phosphoramidate:

<td>cruphomate,</td><td>fenamiphos,</td><td>party,</td><td>mephospholan,</td><td>phosfolan,</td>

<td colspan="2">pyrimetaphos insecticides</td><td colspan="2">phosphoramidothioate:</td><td>acetate,</td>

isocarbophos, isophenphos, isophenphos-methyl, methamidophos, piIpropetamphos phosphorodiamide insecticides: dimefox, mazidox,

133 mipafox, schradan insecticides oxadiazine: You indoxacarb insecticides oxadiazolone: metoxadiazone insecticides phthalimide: dialifos, phosmet, tetramethrin pyrazole insecticides: chlorantraniliprole, cyantraniliprole, dimetilan, tebufenpyrad, phenylpyrazole tolfenpyrad insecticides: acetoprole, ethiprole, fipronil, pyrachlofos, pirafiuprol, pyriprole, vaniliprol pyrethroid insecticides pyrethroid ester insecticides: acrinatrine, alethrin (bioaletrine), bartrine, biphentrine, bioethanometrine, cyclethrin, cycloprotrine, cyphuthrine (beta-cyfluthrin), cyhalothrin, (gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin (alpha-cypermethrin) cypermethrin), cyphenothrin, deltamethrin, dimefluthrin, dimethrin, empentrin, fenfluthrin, fenpirithrin, fenpropathrin, fenvalerate (sphevalerate), flucitrinate, fiuvalinate (tau-fluvalinate), furethrin, imiprotrin, metoflutrine Permethrin (Biopermethrin, Transpermethrin), Phenothrin, Pralethrin, Profiutrin, Piresmethrin, Resmethrin (Bioresmethrin, Cismethrin), Tefluthrin, Teralethrin, Tetramethrin, Tralometrine, Pyrutheproxen, Fetheproxen, Phethropheproxin

134 pyrimidine amine silafluofen: flufenerim, pyrimidiphen pyrrole insecticides: chlorfenapir tetramic acid insecticides: spirotretramat tetronic acid insecticides: spyromesifen thiazolidine insecticides see also unclassified insecticide chitin synthesis inhibitors: closantel, copper naphthenate, crotamiton, EXD, fenazaflor, fenoxacrim, hydramethylnon, isoprothiolane, malonoben, metaflumizone, nifiuridide, pliphenate, pyridaben, pyridalyl, pirifluquinazon, rafoxanide, sulfoxaflor, triarate, triarate.

The above insecticides, and links for further identification and description of insecticides, can be found at http://www.alanwood.net/pesticides/class_insecticides.html, which is incorporated herein in its entirety.

A particularly preferred herbicide is glyphosate (C3H8N05P, [(phosphonomethyl) amino] acetic acid, CAS # 1071-83-6). Other herbicides that can be used in the invention include:

amide herbicides: alidochlor, amicarbazone, beflubutamide, benzadox, benzipram, bromobutide, cafenstrol,

135

CDEA, cyprazole, dimethenamide (dimethenamide-P), diphenamide, epronaz, etnipromid, fentrazamide, flucarbazone, flupoxam, fomesafen, halosafen, isocarbamide, isoxaben, napropamide, naptalamide, propizamide, propizamide, propizamide, propizamide chloranocryl, cisanilide, clomeprop, cipromid, diflufenican, etobenzanid, fenasulam, flufenacet, flufenican, ipfencarbazone, mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanopyridine, benzene-propyl,: chloroacetanilide herbicides: acetochlor, alachlor, butachlor, butenachlor, delachlor, diethathyl, dimethachlor, metazachlor, metolachlor (S-metolachlor), pretilachlor, propachlor, propisoclor, prinachlor, terbuchlor, tenylchlor, xylchloride, fluoroflum, benzoflum, chlorofluorin metosulam, perfluidone, pyrimisulfan, profluazol sulfonamide herbicides: asulam, carbasulam, fenasulam orizaline, penoxsulam, piroxsulam, see also sulfonylurea herbicides thioamide herbicides: bencarbazone, chlortiamide antibiotic herbicides: bilanafos aromatic acid herbicides:

136 benzoic acid herbicides: chloramben, dicamba,

2,3,6-TBA, tricamba pyrimidinyloxybenzoic acid herbicides:

bispiribac, piriminobac pyrimidinylhi obenzoic acid herbicides:

piritiobac italic acid herbicides: chlorthal picolinic acid herbicides: aminopyralid, clopiralid, picloram quinolincarboxylic acid herbicides: quinclorac, quinmerac arsenical herbicides: cacodylic acid, CMA, DSMA, hexaflurate, potassium arsenite, of benzoylcyclohexanedione: mesotrione, sulcotrione, tefuryltrione, tensotrione benzofuranyl alkyl sulfonate herbicides: benfuresate, ethofumesate benzothiazole herbicides: Benazolin, Benzthiazuron, Fentiaprop Mefenacet, Metabenztiazuron Carbamate Herbicides: Asulam, Carboxazole, Chlorprocarb, Dichlormate, Fenasulam, Karbutylate, Terbucarb Carbanilate Herbicides: Barban, CMPC, Carbasulam, Carbetamide, Chlorp, Chloroform , fenmedipham-ethyl, profam, swep

137 Climaxhene exima herbicides: aloxidim, butroxidim, clethodim, cloproxidim, cycloxidim, profoxidim, setoxidim, tepraloxidim, tralcoxidim, cyclopropyl isoxazyl, fx, zinc, dichloroxylamine,: Dinitroanlline uracil herbicides: benfluralin, butraline, dinitramine, ethalfluraline, flucloraline, isopropaline, metalpropalin, nitraline, orizaline, pendimethalin, prodiamine, profluralin, trifiuralin, dinitrophenol herbicides: dinophenate, dinopropin, dinosine, dinoterb, DNOC, nitrophenyl ether herbicides: acifiuorfen, aclonifen, bifenox, clomethoxyphene, chlornitrofen, etnipromid, fluorodifen, fluoroglycophen, fluoronitrofen, fomesafen, furiloxifene, halosafen, lactofen, nitrofluorfen, oxifluorophene, dichlorophenyl herbicides: hexachloroacetone, iodomethane, methyl bromide, monochloroacetic acid, SMA, TCA imidazolinone herbicides: imazamethabenz, imazamox,

138 imazapic, imazapir, imazaquin, imazetapir inorganic herbicides: ammonium sulfamate, borax, calcium chlorate, copper sulfate, ferrous sulfate, potassium azide, potassium cyanate, sodium azide, sodium chlorate, sulfuric acid nitrile herbicides: bromobonyl , bromoxynil, chloroxynil, diclobenyl, iodobonyl, ioxinil, pyraclonil organophosphate herbicides: amiprofos-methyl, anilophos, bensulide, bilanafos, butamifos, 2,4-DEP, DMPA, EBEP, fosamina, glufosinate (glufosinate-P), glyphosate, oxadiazolone herbicide piperofos: dimefuron, methazole, oxadiarzol, oxadiazole herbicide: , phenoxasulfone, isouron, isoxaben, isoxaclortol, isoxaflutol, monisouron, pyroxasulfone, topramezone phenoxy herbicides: bromophenoxim, clomeprop, 2,4-DEB,

2,4-DEP, difenopenten, disulfide, erbon, ethnipromid, phenteracol, trifopsima

<td></td><td>herbicides</td><td>phenoxyacetics:</td><td>4-CPA,</td><td>2,4-D,</td><td>3,4-DA,</td>

<td>MCPA,</td><td>MCPA-thioethyl, herbicides</td><td>2,4,5-T phenoxybutyrics:</td><td>4-CPB,</td><td>2,4-DB,</td><td>3,4-DB,</td>

<td>MCPB,</td><td colspan="3">2,4,5-TB phenoxypropionic herbicides:</td><td>cloprop,</td><td>4-CPP,</td>

dichlorprop (dichlorprop-P), 3,4-DP, fenoprop, mecoprop, (mecoprop-P)

139 aryloxyphenoxypropionic herbicides: clorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop, (fenoxaprop-P), fentiaprop, fluazifop, (fluazifop-P), haloxifop, (haloxifop-P), isoxapiropop, metam P), trifop phenylendi amine herbicides: dinitramine, prodiamine pyrazole herbicides: azimsulfuron, diphenzoquat, halosulfuron, metazachlor, metazosulfuron, pyrazulfuron, pir oxa s ul f ona benzoylpyrazole herbicides: Benzophenap, Pyrasulfotol, Pyrazolinate, Pyrazoxyphene, Topramezone Phenylpyrazole Herbicide: Fluazolate, Nipiraclofen, Pinoxaden, Pyridazine Herbide Pyridazin, Pyridaflora, Pyridazin, Pyridazin, Pyridazin, Chlorida pyridine: aminopiralid, cliodinate, clopiralid, diflufenican, dithiopyr, flufenican, fluroxipir, haloxidine, picloram, picolinafen, pyriclor, piroxsulam, tiazopir, pyrimidine quarantine, quarantine, iprimidam herbicides: iprimidam, thiochloride herbicides:

140 thiocarbamate herbicides: butylate, cycloate, dialates, EPTC, esprocarb, etiolate, isopolinate, methiobencarb, molinate, orbencarb, pebulate, prosulfocarb, piributicarb, sulphalate, tiobencarb, thiocarbazil, trialate, vernolato, vernolato, tiocarbonate thiourea: metiuron triazine herbicides: dipropetrin, indaziflam, triazifiam, trihydroxytriazine chlorotriazine herbicides: atrazine, chlorazine, cyanazine, cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine, propazine, sebuthylazine, simazine, terbuthylazine, trietazine herbicides methoxitriazina: atraton, metometon, prometon, secbumeton, simeton, terbumeton herbicides metiltiotriazina: ametryn, aziprotryne, Cyanatrin, Desmethrin, Dimethamethrin, Metoprotrine, Promethrin, Symmetrine, Terbutrin Triazinone Herbicides ametridione, amibuzin, hexazinone, isomethiozin, metamitron, metribuzin triazole herbicides: amitrol, cafenstrol, epronaz, flupoxam triazolone herbicides: amicarbazone, bencarbazone, carfentrazone, flucarbazone, ipfencarbazone, propoxicarbazone

141 triazolopyrimidine herbicides: chloransam, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, piroxsulam

<td>herbicides</td><td>of</td><td>uracil:</td><td>benzfendizona, bromacil,</td>

<td colspan="2">butafenacil, flupropacil, terbacil</td><td>isocyl,</td><td>lenacil, saflufenacil,</td>

<td>herbicides</td><td>of</td><td>urea:</td><td>benztiazuron, cumiluron,</td>

cycluron, dicloralurea, diflufenzopir, isonoruron, isouron, metabenztiazuron, monisouron, noruron phenylurea herbicides: anisuron, buturon, clorbromuron, chloreturonuronuronuronuronuron , methyldimron, methobenzuron, methobromuron, methoxuron, monolinuron, monuron, neburon, parafiuron, phenobenzuron, siduron, tetrafiuron, tidiazuron sulfonylurea herbicides: pyrimidinylsulfonylurea herbicides: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulforon, flazasulfuron, flucetosulfuron, flupirsulfuron, sulfururururur, sulfur, sulfur, sulfur, sulfur, sulfur trifloxysulfuron triazinyl sulfonylurea herbicides: chlorsulfuron,

142 Cinosulfuron, Ethametsulfuron, Iodosulfuron, Metsulfuron, Prosulfuron, Tifensulfuron, Triasulfuron, Tribenuronon, Triflusulfuron, Tritosulfuron Thiadiazolylurea Herbicides: Butiuron, Etidimuron, Tebutiuron, Thiazafluron, Tidiazuron Herbicides Not Classified: Acrolein, Allyl Alcohol, Aminocyclopyrachlor, Azafenidine, Bentazone, Benzobicyclone, Bicyclopyrone, Butidazole, Calcium Cyanamide, Cambendichlor, Chlorphenac, Chlorfenprop, Chlorfluranol, Curenol, Dimethyline, Curenol, Curenol, Curenol fluridone, flurochloridone, flurtamone, flutiacet, indanofan, methyl isothiocyanate, OCH, oxaziclomefone, pentachlorophenol, pentoxazone, phenylmercury acetate, prosulfalin, pyribenzoxim, pyriftalid, quinoclamine, rodethanil, sulglicapin, tidiazimin, tridiphan, trimeturon, tripropindan, tritac. The above herbicides, and links for herbicide identification and description, can be found at http://www.alanwood.net/pesticides/class_herbicides.html, which is incorporated herein in its entirety. The following are the most preferred insecticides for use in the invention: botanicals, carbamate, diamide, fumigants, insect growth regulators,

143 nicotinoids, organochlorines, organophosphates, phthalimide, pyrazole, pyrethroids, pyrethroid ester, pyrethroid ether, pyrimidine amine, pyrrole, thiazole, thiazolidine and thiourea.

The following are the most preferred herbicides for use in the invention: amide, aromatic acid, benzothiazole, carbamate, carbonylate, cyclohexene oxime, dicarboximide, dinitroaniline, dinitrophenol, diphenyl ether, imidazolinone, organophosphates, oxadiazolone, oxazole, phenoxy, phenoxy pyridine, pyridazinone, quaternary ammonium, thiocarbamate, thiocarbonate, thiourea, triazine, triazinone, triazole, triazolone, triazolopyrimidine, urea, and unclassified.

The following are the most preferred fungicides for use in the invention: dithiocarbamates, nitrial, benzimidazoles, dicarboximides, sterol (SI) inhibitors / demethylase (DMI) inhibitors, carboxamides / anilides, strobilurins, phenylpyrrole, finilamide, aromine hydrocarbin, polyoxine, pyridine amine, cyanoimidazole, carbamate, and phosphonate.

Example 8 - Evaluation of partial salt of tetrapolymer as an adjuvant for pesticides

In this test, the efficacy of the ammonium / sodium tetrapolymer partial salt B previously described as a glyphosate adjuvant was compared with an aqueous mixture containing 4.0 wt% of a maleic-itaconic polymeric ammonium partial salt, having equimolar amounts of remains

144 of maleic and itaconic acid and a pH of approximately 2 (referred to herein as partial ammonium salt ΜΙ) ·

Glyphosate assay dispersion treatments were prepared as follows, using 50 mL of glyphosate dispersion in each treatment:

Treatment A - glyphosate alone

Treatment B - glyphosate + 1.0% (v / v) MSO

<td>Treatment</td><td>C -</td><td>glyphosate</td><td> +</td><td> 0.50%</td><td>(v / v)</td><td>Salt</td><td>. partial</td>

<td>ammonium MI + 1.0%</td><td>(v / v)</td><td>from MSO</td><td></td><td></td><td></td><td></td><td></td>

<td>Treatment</td><td>D -</td><td>glyphosate</td><td> +</td><td> 0.50%</td><td>(v / v)</td><td>of</td><td>salt B of</td>

<td>tetrapolymer + 1.0%</td><td>(v / v)</td><td>from MSO</td><td></td><td></td><td></td><td></td><td></td>

<td>Treatment</td><td>E -</td><td>glyphosate</td><td> +</td><td> 0.50%</td><td colspan="3">(v / v) from CS</td>

<td>Treatment</td><td>F -</td><td>glyphosate</td><td> +</td><td> 0.50%</td><td>(v / v)</td><td>Salt</td><td>. partial</td>

<td>ammonium MI + 0.50%</td><td>(v / v</td><td>j from CS</td><td></td><td></td><td></td><td></td><td></td>

<td>Treatment</td><td>G -</td><td>glyphosate</td><td> +</td><td> 0.50%</td><td>(v / v)</td><td>of</td><td>salt B of</td>

<td>tetrapolymer + 0.50%</td><td>(v / v</td><td>j from CS</td><td></td><td></td><td></td><td></td><td></td>

<td>Treatment</td><td>H -</td><td>glyphosate</td><td> +</td><td> 0.50%</td><td>(v / v)</td><td>of</td><td>salt B of</td>

tetrapolymer

Glyphosate used in all formulations was isopropylamine glyphosate sold under the name gold star glyphosate, and was prepared as an aqueous dispersion in a 50 mL tube, using the conventional commercial concentration, namely 946 ml (32 oz. ) of glyphosate per acre. The other components were mixed with glyphosate to

145 complete the treatments. The materials added were partial ammonium MI salt, methylated seed oil surfactant (MSO), and ChemSurf 90 (CS). The latter product is a commercially available aqueous surfactant containing 90% alkylarylpolyoxane ether, isopropanol, and free fatty acids, and is manufactured by Chemorse, Ltd. of Des Moines, IA.

Twenty-four 17.14-centimeter (6.75-inch) soil pots were planted with pre-germinated pods containing two rudis (Amaranthus rudis) plants known to be resistant to glyphosate herbicides. The plants were allowed to reach 10 to 15 cm in height, after which they were sprayed with the previous treatments using a calibrated CO2 pressurized conical nozzle manual sprinkler to supply 0.230 mL of treatment to each pot, which is equivalent to a mixture 40-liter tank sprayed on one acre.

A numerical scale based on observations of live plants was used to measure the efficacy of each treatment, with 0.0 being no effect and 5.0 being totally effective. Three repeated observations were made on day 6 and day 12 after spraying, with the cumulative means of all replicates representing the efficacy of the corresponding treatment. The results of this series of tests are set forth in Tables 3 and 4 below.

146

Example 8, Table 1 - Observations on Day 6

<td>Group ID</td><td>Rep 1</td><td>Rep 2</td><td>Rep 3</td><td>Half</td>

<td>Treatment A</td><td> 3.0</td><td> 4.0</td><td> 0.0</td><td> 2.3</td>

<td>Treatment B</td><td> 5.0</td><td> 4.0</td><td> 0.5</td><td> 3.2</td>

<td>Treatment C</td><td> 3.0</td><td> 3.0</td><td> 0.5</td><td> 2.2</td>

<td>Treatment D</td><td> 4.0</td><td> 4.0</td><td> 4.0</td><td> 4.0</td>

<td>Treatment E</td><td> 5.0</td><td> 3.0</td><td> 3.0</td><td> 3.7</td>

<td>Treatment F</td><td> 4.5</td><td> 5.0</td><td> 5.0</td><td> 4.8</td>

<td>Treatment G</td><td> 5.0</td><td> 1.0</td><td> 3.0</td><td> 3.0</td>

<td>Treatment H</td><td> 5.0</td><td> 4.0</td><td> 2.5</td><td> 3.8</td>

Example 8, Table 2 - Observations on Day 12

<td>Group ID</td><td>Rep 1</td><td>Rep 2</td><td>Rep 3</td><td>Half</td>

<td>Treatment A</td><td> 3.0</td><td> 3.5</td><td> 0</td><td> 2.2</td>

<td>Treatment B</td><td> 5.0</td><td> 5.0</td><td> 0.5</td><td> 3.5</td>

<td>Treatment C</td><td> 5.0</td><td> 2.5</td><td> 0</td><td> 2.5</td>

<td>Treatment D</td><td> 3.5</td><td> 3.0</td><td> 5.0</td><td> 3.8</td>

<td>Treatment E</td><td> 5.0</td><td> 3.0</td><td> 5.0</td><td> 4.3</td>

<td>Treatment F</td><td> 5.0</td><td> 5.0</td><td> 5.0</td><td> 5.0</td>

<td>Treatment G</td><td> 5.0</td><td> 2.5</td><td> 3.0</td><td> 3.5</td>

<td>Treatment H</td><td> 5.0</td><td> 5.0</td><td> 2.5</td><td> 4.2</td>

As illustrated in the data above, the tetrapolymer products of the invention provided increased adjuvant activity in almost all cases, compared to the non-polymer partial salts and MI ammonia tests. This result was especially evident with

147 treatments D and F, where observations from day 1 show easily discernible differences between treatments with and without the tetrapolymer additive.

Example 9 - Class I tetrapolymers as adjuvant herbicides

Glufosinate assay

In this series of tests, commercially available Liberty glufosinate herbicide obtained from Bayer CropScience was supplemented with a T5 partial sodium ammonium salt polymer (pH 2.5) in two different amounts.

Tank mixes were first made by mixing 10 liters of deionized water and Liberty herbicide at an amount equal to 857 mL (29 ounces) per acre. The polymer was then added in an amount of 0.50% v / v 1% v / v immediately prior to spray application.

Liquid herbicide mixtures were targeted at 12 "tall 305 mm (Amaranthus rudis) rudis that have known resistance to glyphosate and triazine herbicides. All treatments were applied at 40 L / acre using a TeeJet 8002 EVS nozzle in a DeVries Research sprayer, at an amount of 857 mL (29 ounces) per acre of Liberty herbicide. After 15 days, the weight percentage of biomass was measured for each remaining plant. The control (without polymer) exhibited 45% of the remaining biomass,

148 while the 0.5% test tetrapolymer gave 20% of the remaining biomass, and the 1% test tetrapolymer gave 10% of the remaining biomass.

Dicamba test

In this series of tests, commercially available Clarity Dicamba herbicide obtained from BASF Corporation was supplemented with a T5 partial sodium salt polymer (pH 8.0) in two different amounts.

Tank mixes were first made by mixing 40 liters of deionized water and Clarity herbicide at an amount equal to 406 ml (16 ounces) per acre. The polymer was then added in an amount of 0.50% v / v or 1% v / v immediately prior to spray application.

The liquid herbicide mixtures were directed to horse grass (Conyza canadensis) in the full rosette state which has known resistance to glyphosate herbicides. All treatments were applied at 40 L / acre using a TeeJet 8002 EVS nozzle in a DeVries Research sprayer, at an amount of 406 ml (16 ounces) per acre of Clarity herbicide. After 7 days, the weight percentage of biomass was measured for each remaining plant. The control (no polymer) exhibited 65% of the remaining biomass, while the 0.5% test tetrapolymer gave 45% of the remaining biomass, and the tetrapolymer of

149 Testing at 1% gave 50% of the remaining biomass. After 14 days, the control had 20% of the remaining biomass, the 0.5% test tetrapolymer gave 5% of the remaining biomass, and the 1% test tetrapolymer gave 15% of the remaining biomass.

2,4-D test

In this series of tests, commercially available 2,4-D diethylamine salt herbicide was supplemented with a polymer of sodium salt and partial ammonium salt T5 (pH 2.5) in two different amounts.

Tank mixes were first made by mixing 40 liters of deionized water and 2,4-D herbicide at a dose equivalent to 946 mL (32 ounces) per acre. The polymer was then added in an amount of 0.50% v / v or 1% v / v immediately prior to spray application.

Liquid herbicide mixtures were directed at horsetail (Conyza canadensis) in the full rosette state which has known resistance to glyphosate herbicides. All treatments were applied at 40 L / acre using a TeeJet 8002 EVS nozzle in a DeVries Research sprayer, at an amount of 946 mL (32 ounces) per acre of herbicide. After 7 days, the weight percentage of biomass was measured for each remaining plant. The control (without polymer) exhibited 70% of the remaining biomass, while the

150 The 0.5% tetrapolymer test gave 60% of the remaining biomass, and the 1% tetrapolymer test gave 65% of the remaining biomass. After 14 days, the control had 25% of the remaining biomass, the 0.5% tetrapolymer test gave 10% of the remaining biomass, and the 1% tetrapolymer test gave 15% of the remaining biomass.

10. Nitrification / inhibition of urease / phosphate binding

The Class I polymers of the invention have also been found to serve as useful inhibitors for nitrification processes in soil, and also to inhibit phosphate urease and binding activities therein. In this way, the increase in crop yields was achieved due to the fact that they occur naturally and nitrogen and phosphate sources from the supplied fertilizers are used more efficiently by plants. The polymers of the invention can be applied directly to the soil in aqueous dispersion or in solid form and in amounts effective for the control of nitrification, urease activity, and phosphate binding; more commonly, however, the polymers are used in combination with the solid ammonia fertilizer (eg, urea), or with liquid fertilizers (eg, gaseous or liquid UAN fertilizers) containing ammoniacal nitrogen.

As used herein,

151 Ammoniacal Nitrogen is a broad term encompassing fertilizer compositions containing ammoniacal nitrogen (NH4), as well as fertilizer compositions and other compounds that are ammoniacal nitrogen precursors or that cause ammoniacal nitrogen to be generated when fertilizers or compounds undergo various reactions such as hydrolysis . To give a single example, the polymers of the invention can be applied to or mixed with urea or other nitrogen-containing fertilizers having ammoniacal nitrogen therein as is. However, such fertilizers will undergo reactions in the soil to generate ammoniacal nitrogen in. if you. Therefore, in this example urea or other precursor nitrogen-containing fertilizers are considered to contain ammonia nitrogen.

When Class I polymers are used in the form of aqueous dispersions in close contact with or dispersed in ammonia nitrogen fertilizers, the fertilizer / polymer mixture is typically applied to the soil adjacent to the growing plants or is pre-applied to the subject soils to nitrification. Aqueous polymer blends are typically used with liquid and dry fertilizers at relatively low levels of up to about 2% by volume (eg 0.01 to 2% by volume), based on the total volume of liquid fertilizer material taken

152 as 100% by volume. In such uses, it is also preferred that the pH levels should be up to about 3, most preferably up to about 2, and more preferably up to about 1. Furthermore, said aqueous dispersions suitably contain from about 10 to 85% by weight solids, most preferably from about 30 to 65% by weight of solids, and more preferably from about 4 0%> by weight of solids.

In preparing the polymer / liquid fertilizer materials of the invention, the ammonia nitrogen-containing fertilizer material was suspended in water and added to the aqueous polymer mixture therewith with mixing. No mixing conditions or temperature regime are required. Surprisingly, these liquid fertilizer materials have been found to be quite stable and resist sedimentation or precipitation of solids during prolonged storage periods of at least about two weeks.

In the case of solid ammonia fertilizers, the polymers are applied directly to the fertilizer, typically at a level of about 0.01 to 10% by weight, more preferably about 0.05 to 2% or by weight, based on the total weight of the product of polymer / fertilizer taken as 100%> by weight.

Typically, aqueous polymer dispersions are

153 they spray onto solid fertilizers and allow to dry, so that the polymeric dry residue remains on the fertilizer surfaces.

Example 10 - Evaluation of partial tetrapolymer salt as Urease Inhibitor - Method 1

Studies have shown that urea-containing fertilizers can lose up to 3 0% or more of their N if they are not incorporated into the soil within 72 hours by tillage or rain. Volatilization occurs when urea hydrolyzes, that is, it reacts with soil moisture and breaks down. The urease enzyme, which is produced by soil microorganisms, facilitates volatilization. Therefore, best management practices dictate that urease can be inhibited as much as possible.

In this test, the urease inhibiting efficacy of the tetrapolymers of the invention was determined, compared to the prior art maleic acid-itaconic acid partial salts. In the test, 50 mL Erlenmeyer flasks were loaded with 25 mL of 1.0% (w / w) dispersion of urea, and two levels of tetrapolymer salt B, i.e. 0.033% (v / v) (8.25 pL) and 0.066% (v / v) (16.5 pL). Comparative flasks were also prepared containing the same amounts of urea dispersion, but with a 40% solids aqueous dispersion of a partial calcium salt of a maleic acid-itaconic acid polymer as

154 it contains equimolar amounts of maleic and itaconic acid residues, and it has a pH of approximately 2.25-2.75, nominally 2.5 (referred to herein as MI Ca 2.5) and a 40% aqueous dispersion of solids of a calcium salt A partial maleic acid-itaconic acid polymer containing equimolar amounts of maleic and itaconic acid residues, and having a pH of about 1-2, nominally 1.5 (referred to herein as MI Ca 1.5). Control flasks containing no urease inhibiting polymer were also prepared.

A pH meter and electrode are used to record initial pH levels, after which an additional 1.0% (v / v) of the urease enzyme dispersion was added to each flask. PH measurements were taken at time intervals to track the decomposition of urea in the flasks. As urea decomposes, ammonia ions are generated, causing a subsequent increase in the pH of the dispersions. By observing the rate of pH elevation, the effectiveness of urease inhibition can be measured.

155

Example 10, Table 1 - Test 1: Inhibition of urease with

0.033% inhibitor

<td>Polymer Salt</td><td>SalB</td><td>MI Ca 2.5</td><td>MI Ca 1.5</td><td>Control</td>

<td>initial pH</td><td> 4.122</td><td> 4.084</td><td> 3.088</td><td> 7.000</td>

<td>pH at 30 seconds</td><td> 8.400</td><td> 4.818</td><td> 3.362</td><td>9,295 (immediate)</td>

<td>pH at 120 seconds</td><td> 9.105</td><td> 8.389</td><td> 3.753</td><td></td>

<td>pH at 600 seconds</td><td>X</td><td>X</td><td> 6.484</td><td></td>

<td>Increase (600s)</td><td> 4.983</td><td> 4.305</td><td> 3.396</td><td></td>

Example 10, Table 2 - Test 1: Inhibition of urease with

0.066% inhibitor

<td>Polymer Salt</td><td>SalB</td><td>MI Ca 2.5</td><td>MI Ca 1.5</td><td>Control</td>

<td>initial pH</td><td> 3.943</td><td> 3.908</td><td> 3.496</td><td> 7.000</td>

<td>pH at 30 seconds</td><td> 4.087</td><td> 4.055</td><td> 3.559</td><td>9,295 (immediate)</td>

<td>pH at 120 seconds</td><td> 4.601</td><td> 4.345</td><td> 3.801</td><td></td>

<td>pH at 600 seconds</td><td> 9.305</td><td> 6.504</td><td> 4.636</td><td></td>

<td>Increase (600s)</td><td> 5.362</td><td> 2.596</td><td> 1.14</td><td></td>

As illustrated, control flasks without any polymeric urease inhibitor exhibit an immediate pH peak. However, the tetrapolymer salts of the invention gave the urease inhibition functional results compared to the prior art MI Ca 2.5 and MI Ca 1.5 products, in particular at the highest use amount in Table 6.

156

Example 11 - Evaluation of partial tetrapolymer salt as urease inhibitor - Method 2

In this test, the urease inhibiting properties of the tetrapolymers of the invention were determined compared to the prior art MI Ca 2.5 and MI Ca 1.5 products, using a different technique. In particular, nine 50 mL Erlenmeyer flasks were charged with 25 mL each of deionized water, to give three sets of flasks A, B, and C, each set containing three flasks. Then 0.033% (v / v) of MI polymers

Ca 2.5, MI Ca 1.5, salt B were added individually to the three flasks in each set. After the pH levels of the flasks containing water and polymer were stabilized, 1% (v / v) of urease dispersion was added to each of the nine flasks, and the individual flasks containing water were left / Polymer / urease were incubated for three different time periods, namely 1 (set A), 3 (set B) and 10 minutes (set C). The pH levels were taken at this point, followed by the addition of 0.5 mL of 50% (w / w) of urea water dispersion to each flask to obtain a total of 1% (w / w) of urea in each dispersion of flask. The pH measurements were then observed at time intervals

157 30 seconds, 120 seconds and 600 seconds. As the urea degraded in each flask, ammonia was released, causing an increase in pH in the dispersions. By observing the rate of pH increase, the effectiveness of urease inhibition was measured; this amount is directly affected by the amount of incubation time between the three groups.

Example 11, Table 1 - One minute incubation of polymer / urease - Set A

<td>Polymer</td><td>SalB</td><td>MI Ca 2.5</td><td>MI Ca 1.5</td>

<td>Initial pH, H2O and polymer</td><td> 3.974</td><td> 3.856</td><td> 3.588</td>

<td>H2O, Polymer and Ureasa after one minute</td><td> 3.895</td><td> 3.789</td><td> 3.523</td>

<td>3 Os after adding urea dispersion</td><td> 4.194</td><td> 4.003</td><td> 3.695</td>

<td>120 seconds</td><td> 4.510</td><td> 4.353</td><td> 3.763</td>

<td>600 seconds</td><td> 7.934</td><td> 8.907</td><td> 6.176</td>

Example 11, Table 2 - Three minute incubation of polymer / urease - Set B

<td>Polymer</td><td>SalB</td><td>MI Ca 2.5</td><td>MI Ca 1.5</td>

<td>Initial pH, H2O and polymer</td><td> 3.925</td><td> 3.951</td><td> 3.619</td>

<td>H2O, Polymer and Ureasa after one minute</td><td> 4.025</td><td> 3.845</td><td> 3.559</td>

<td>3 Os after adding urea dispersion</td><td> 4.025</td><td> 3.975</td><td> 3.690</td>

<td>120 seconds</td><td> 4.260</td><td> 4.043</td><td> 3.761</td>

<td>600 seconds</td><td> 4.765</td><td> 7.663</td><td> 3.934</td>

158

Example 11, Table 3 - Ten minute incubation of polymer / urease - Set C

<td>Polymer</td><td>SalB</td><td>MI Ca 2.5</td><td>MI Ca 1.5</td>

<td>Initial pH, H2O and polymer</td><td> 3.987</td><td> 3.832</td><td></td>

<td>H2O, Polymer and Ureasa after one minute</td><td> 3.908</td><td> 3.756</td><td></td>

<td>3 Os after adding urea dispersion</td><td> 4.049</td><td> 3.848</td><td></td>

<td>120 seconds</td><td> 4.081</td><td> 3.879</td><td></td>

<td>600 seconds</td><td> 4.140</td><td> 3.951</td><td></td>

<td></td><td>Example</td><td>12 - Class I Polymer as</td><td>inhibitor</td><td>of</td>

<td>enzyme</td><td>urease</td><td></td><td></td><td></td>

<td></td><td>In a</td><td>first series of tests,</td><td>aliquots</td><td>of</td>

<td>2 5 mL</td><td>of 1%</td><td>(p / p) of stock solution</td><td>urea</td><td>I know</td>

they combined in 50 mL Erlenmeyer flasks with four different test formulations at equal levels of 0.666% (v / v). A pH meter and electrode are used to record initial pH levels, and then 1.0% (v / v) urease solution was added to each flask. Measurements of pH over time (at 30 seconds, 120 seconds, and 600 seconds) were observed as a measure of the decomposition of urea, generating ammonia and therefore causing an increase in pH levels. The pH increase rates were a measure of the effectiveness of urease inhibition. Two repetitions A and B were carried out for each test formulation.

159

The test formulations were:

• No. 1 - no polymer, 4% w / w boric acid, 30% w / w lactic acid, remaining water, with added dye.

• No. 2 - T5 polymer as a partial sodium / calcium salt mixed in water, pH around 1.

• No. 3 - 34% w / w Polymer T5 as a mixed partial calcium / sodium salt, 4% w / w Boric Acid, 1.5% w / w Low Molecular Weight Polyvinyl Alcohol, 22% w / w lactic acid, without dye, the balance being water, pH of about 1.

• No. 4 - T5 polymer as a partial sodium / calcium mixed salt in water, pH of approximately 1, with 4.3% w / w boric acid, and 32% w / w lactic acid.

The results of this first series of tests are indicated below.

Example 12, Table 1

<td>Test Formulation</td><td>Repetition</td><td>Initial pH</td><td>pH at 30s</td><td>pH at 120s</td><td>pH at 600s</td>

160

As illustrated in the above data, test formulations containing Class I tetrapolymers without boric acid both gave sustained inability of enzyme urease. Further testing has confirmed that Class I tetrapolymers inhibit urease completely within 10 minutes.

In a second series of tests, the same formulations Nos. 1 to 4 were tested in a different regimen. Specifically, 24.5 ml of water were combined with the test formulations in 50 mL Erlenmeyer flasks to obtain a test formulation level of 0.033% v / v. Immediately thereafter, the enzyme urease was added to each flask in an amount of 1.0% v / v, and allowed to incubate for 60 seconds or 300 seconds. Once the incubations were complete, measurements were taken

<td>initials</td><td>pH and 0.5 ml</td><td>50%</td><td>p / p</td><td>solution</td><td>urea is</td>

<td>added to</td><td>each flask for</td><td>wear</td><td>the</td><td>solutions</td><td>totals to</td>

<td>1% w / w of</td><td>urea and water. TO</td><td>depart</td><td>of</td><td>so,</td><td>They were taken</td>

pH measurements in 60 seconds / 300 seconds, 90 seconds / 330 seconds, 180 seconds / 400 seconds, and 600 seconds / 900 seconds. Furthermore, the ammonia concentrations in the ambient air of the respective flasks were measured after 4 hours as another indicator of urease inhibition. The results of this test are set out below.

161

Example 12, Table 2

<td>Test Formulation</td><td>Incubation period / initial pH</td><td>Waiting time / pH</td><td>Waiting time / pH</td><td>Waiting time / pH</td><td>NH3 / 4 hours</td>

Example 13 - Class I tetrapolymers as phosphorous binding inhibitors

Phosphorus fertilizer can be immobilized or fixed with antagonistic cations in the soil, which translates into 75 to 95% of applied phosphorus being available for absorption by the plant. It has been found that the Class I polymers of the invention are capable of reducing said phosphorous binding by sequestering antagonistic cations in the microenvironments of phosphorous fertilizers.

In a field test, two levels of phosphorus in the form of diammonium phosphate (DAP) were applied by transmission as a fertilizer before planting a cotton field, i.e. 29.44 kg (65 lbs) per

162 acre of DAP and 58.9 kg (130 pounds) of DAP per acre. The tests were two replicates each of an unfertilized control, a DAP control only, and DAP mixed with 0.25% w / w of a Class I polymer formulation. The formulation included 40%> w / w of a salt of Partial zinc / sodium of polymer T5, 5% w / w of zinc, and the rest of water, a pH of approximately 3.

Tissue tests were taken before the first flowering of each plot, and the percentage of phosphorus in the plant tissue was measured. After harvest, fluff yields were measured. The results of the tissue phosphorus test are set forth below in Table 1, while the performance tests are given in Table 2.

Example 13, Table 1

<td>Treatment</td><td>Weight% of Phosphorus in Tissue</td>

<td>unfertilized control</td><td> 0.21</td>

<td>29.44 kg DAP w / polymer</td><td> 0.5</td>

<td>unfertilized control</td><td> 0.21</td>

<td>58.89 kg DAP w / polymer</td><td> 0.51</td>

163

Example 13, Table 2

<td>Treatment</td><td>Lint Yield .453 kg / acre</td>

<td>unfertilized control</td><td> 390</td>

<td>29.44 kg DAP w / polymer</td><td> 896</td>

<td>unfertilized control</td><td> 390</td>

<td>58.89 kg DAP w / polymer</td><td> 900</td>

These results confirm that the use of Class I tetrapolymer with zinc gave a significant increase in tissue phosphorus levels and yields.

The above Examples 5-13 illustrate specific uses of the novel Class I polymers of the invention in various contexts. It is understood that these examples are provided by way of illustration only, and nothing in them should be taken as a limitation of the overall scope of the invention.

It is noted that in relation to this date, the best method known to the applicant for practicing the present invention is the one that is clear from the present description of the invention.

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61870472	United States of America	–	2013-08-27
201361870472	United States of America	P	2013-08-27
61978011	United States of America	–	2014-04-10
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Polyanionic polymers.

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