Gelled organic liquids.

DESCRIPTION

Rationale of the Invention

The present invention relates to gelled organic liquids whose structure has been modified from free flowing liquids to non-flowing liquids and is considered solid according to ASTM D4359-84. More particularly, this invention relates to organic liquids that can be used as fuels that are gelled to the extent that they are considered solid according to ASTM D4359-84.

In many products it is necessary to substantially increase the viscosity of organic liquids and these organic liquids may be mixed with water. It is simpler to apply an organic liquid to a surface when it is in a thick state than as a free flowing liquid. This is particularly the case on vertical surfaces. Most usefully thickened products include organic based paints, paint and corrosion removers, nail varnish removers, lotions, creams, balms, shampoos, household and commercial cleaners, drill lubricating fluids, lighter fuels and charcoal fluids. There are, however, many other uses for thickened organic liquids. When the organic liquid is gelled, it will also have a significantly reduced evaporation rate. Due to a substantially reduced evaporation rate, the effectiveness of the organic liquid is greater.

BNSDOCID: <EN

101311B I>

<img file="PT101311B_D0001.tif" />

A particularly useful area for gelled organic liquids is gelled fuels. These can be fuels for stationary or mobile use. Gelled fuels in transport vehicles reduce the risk of fire in an accident. These gelled fuels may be used in cars, trucks, buses, boats and airplanes and may be gelled gasoline or diesel. In addition, gelled fuels can be used as fixed sources of heat, particularly for cooking. A fuel chosen for such purpose is an alcohol, usually methanol or ethanol, but may also be propanol, butanol, pentanol or hexanol. Both methanol and ethanol are fuels commonly used for cooking. In one use, methanol or gelled ethanol is in a container with a capacity of about 200 or 500 ml. This container is placed under a brook and ignited to keep the broiler's food warm. These containers will be burning for about 2 to 5 hours, depending on the volume of fuel in the container.

Fuels that are intended to be used effectively without a wick carrying the fuel to a burning surface must be gelled. In addition, these fuels must be gelled to be classified as solid according to ASTM D4359-84. The fuel must not separate from the gel at rest or at the time of pressure application. The main reason is safety. If a gelled fuel is classified as a solid according to ASTM D4359-84, it will be subject to less stringent transportation and storage regulations.

A gelling agent commonly used for commercial fuels, such as methanol or ethanol, is nitrocellulose. Nitrocellulose retains fuel in a sponge-like matrix. However, it is not a true gel.

BNSDOCID: &lt;EN 101311B l&gt;

<img file="PT101311B_D0002.tif" />

Part of the fuel may be physically separated from nitrocellulose, resulting in free fuel being present in a container. This is not desirable.

US Patent 3,759,674 discloses dispersions of certain ethylene-acrylic acid copolymers and water-amine emulsifiers to form stable gels when mixed with alcohols. The dispersions contain from 10 to 20 parts by weight of ethylene acrylic acid copolymer and about 3 to 4 parts by weight of an amine emulsifier. There will be about 10 to 30% by weight solids. In US Patent No. 3,148,958 discloses the gelling of an alcohol fuel through the use of neutralized carboxy vinyl polymers with a weak amine base. This results in a gelled alcohol fuel said to have good burning characteristics. US Patent 4,261,700 and US Patent 4,365,971 both disclose the use of an ethylene-acrylic acid copolymer-based gelling agent, Carbopol 934, for an alcohol fuel. Carbopol 934 is neutralized to form the gel by means of a weak amine base. US Patent 3,214,252 discloses the use of olefin-maleic anhydride copolymers as gelling agents for alcohols. These are gelled by compounds capable of providing a hydroxyl group. US Patent 4,536,188 discloses the incorporation of alcohol-soluble metal compounds in an alcohol-based fuel to increase the visibility of otherwise invisible flames. Also known from US Patent 2,890,257 is the addition of silica gel or activated aluminas to stabilize naphtha fuels. These are not gelled fuels. Gelling of a number of solvents using amine neutralized polyacrylic acid polymers is also known.

BNSDOCID: &lt;EN 101311B!&gt;

<img file="PT101311B_D0003.tif" />

The disclosures of these references are interesting, but there are no guidelines for gelling a solvent through an alkaline compound, namely an amine-neutralized anionic polymer, containing an auxiliary rheological additive to increase the anionic polymer linearity. An auxiliary rheological additive is a substance that increases the viscosity of an amine-neutralized anionic polymer solution. When the anionic polymer is dissolved and neutralized, there is an increase in linearity of the anionic polymer. This linearity is further enhanced by the use of an auxiliary rheological additive. It has also been found that when the solvent is a fuel, namely an alcohol-based fuel, the use of a polymer structuring agent, namely an amphoteric metal oxide and optionally a fatty acid or fatty acid salt, causes more effective burning of the fuel. It appears that a solid amphoteric metal oxide reduces the tendency of the firing surface to form a continuous skin seal. When a skin seal is formed, fuel must burst through that film or scab to burn. This causes noise and uneven burning. This is not the case when an amphoteric oxide auxiliary rheological additive is used. There is also a better gel.

Brief Summary of the Invention

The present invention is directed to the production of better gelled solvents and in particular organic solvents. Gelled organic solvents include alkanes, alkenes, aromatics, acids, ketones, aldehydes, oils, ethylene glycols, polyethylene glycols, amines, alcohols and esters. Gelled solvents have a wide area of ​​use. A specific area of ​​use is as gelled fuels, and in a form

<img file="PT101311B_D0004.tif" />

as gelled fuels for cooking and heating foods.

The gelled solvents will contain from about 0.1 to 10% by weight of an anionic polymer neutralized by a base, 0.1 to 10% by weight of an auxiliary rheological additive, the remainder consisting of at least one solvent. , and mainly an organic solvent. The neutralized anionic polymer is preferably an anionic cross-linked polymer neutralized by^van amine, namely a cross-linked polyacrylic acid polymer and has a molecular weight of about 60,000 to 10,000,000. The polyacrylic acid polymer is neutralized by means of an amine base. The presence of an auxiliary rheological additive, which serves to further unwind the anionic polymer and thereby increase its linearity, enhances the thixotropic properties of the gelled organic solvent. There is a viscosity increase of about 10 to 300% relative to the viscosity of a similar gelled solvent which does not contain the auxiliary rheological additive.

Detailed Description of the Invention

The present invention relates to gelled solvents and in particular to gelled organic solvents. Gelled organic solvents may contain some water, but since the organic factor is predominant, it will be considered to be a gelled organic solvent. The water content may range from about 0 to about 45 wt%, and in many cases 0.1 to 35 wt% of the gelled composition. In a particular embodiment, the invention is directed to gelled fuels. The organic fuel component may be an alkane, alkene, alcohol, an aromatic or mixtures of these hydrocarbons. In a form of

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Preferred embodiment, the fuel is an alcohol of 1 to 6 carbon atoms.

The combination of the base-neutralized and normally amine-neutralized anionic cross-linked polymer and the auxiliary rheological additive results in better thixotropic properties. The auxiliary rheological additive will increase the viscosity of the gelled solvent by about 10 to 300%. This is a significant increase for the addition of a relatively small amount of additive.

Polymeric thickening agents and auxiliary rheological additives both contribute to the viscoelastic rheology of the thickened compositions of the present invention. As used herein, the term viscoelastic or viscoelasticity means that elastic modules (storage) (G^z) and the viscous modules (loss) (G^zz) are both substantially independent of tension, at least in a range of applied torsional force from 1 to 150 micro Nm (Newton meter). More specifically, the composition is considered to be linear viscoelastic for purposes of this invention if, above the torsional force range of 1 to 150 micro Nm, the elastic modulus G^z has a minimum fur value. 2 . 2 minus 2,500 dynes / cm, preferably at least 3,500 dynes / cm 2. . .2 the range being less than 500 dynes / cm, preferably less than 400 dmes / cm, and most preferably less than 370 dmes / cm. Typically, the variation in loss modulus G^z'will be less than G^z. Another feature of preferred linear viscoelastic compositions is that the ratio of G^zz/ G^z (tg5) is less than 1, preferably less than 0.4, and more preferably less than 0.2, at least in a torsional force range of 1 to 150 micro Nm

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By way of explanation, the elastic modulus (storage) G 'is a measure of energy stored and recovered when a stress is applied to the composition, whereas the viscous modulus (loss) G' 'is a measure relative to the amount of energy dissipated. heat form when voltage is applied. Thus, a value of tgí

0.05 &lt;tg &lt;5 &lt;1, preferably

0.2&gt; tg &lt;S &lt;0.8 means that the compositions will retain sufficient energy when a force or voltage is applied. Compositions with tg &lt;S values ​​within these ranges will therefore also have a high cohesive property, particularly when a stress or cut is applied to a portion of the composition to make it flow, the surrounding parts will follow it. As a result of this cohesive characteristic of the viscoelastic compositions in question, the compositions will flow easily, evenly and evenly, thereby contributing to the physical (phase) stability of the formulation that characterizes the present compositions. Viscoelastic property also contributes to improved physical stability against phase separation of any undissolved suspended particles, providing resistance to particle movement due to the stress exerted by a particle in the surrounding fluid medium.

One way to further improve the structuring of gel formulations for better viscosity as well as G 'and G' values ​​is to form a solution of an organic solvent, a neutralized cross-linked anionic polymer, namely a thickening agent. polyacrylic acid binding

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neutralized by mixing at room temperature to a slightly elevated temperature, followed by mixing to neutralize anionic groups, namely carboxylic acid groups, by the addition of another basic material, namely an organic amine, to form a neutralized cross-linked anionic polymer, for example, a cross-linked polyacrylic acid polymer having a molecular weight of about 60,000 to 10,000,000. To the amine-neutralized anionic cross-linked polymer solution is added with admixture an auxiliary rheological additive, namely an amphoteric metal oxide, which is an insoluble colloidal particulate such as aluminum oxide and / or a fatty acid and / or a salt of a fatty acid. The neutralized crosslinked anionic polymer, namely a crosslinked polyacrylic acid polymer, in combination with the auxiliary rheological additive provides better G 'and G' 'values ​​as well as better viscosity of the organic polymeric solution, which has a pH of about 7 to 14, compared to the use of neutralized anionic crosslinked polymer alone. There is a theory that the improvement in viscosity results from an increase in solids content and the association of amphoteric metal oxide and neutralized anionic crosslinked polymer in the organic solvent, and the polymeric chain of the anionic crosslinked polymer is unwound. neutralized, namely polyacrylic acid, which causes further structuring of the polymeric structure within the organic solvent. To the solution of the neutralized cross-linked polyacrylic acid polymer, solvent and auxiliary rheological additive, various other ingredients may be added to form combustible compositions, an after shave gel, a detergent composition, a hard surface cleaning composition or any of the following. of the aforementioned compositions. Other commercial and industrial compositions may be formed for a variety of applications, such as cleaning agents for

<img file="PT101311B_D0008.tif" />

fabrics, shampoos, floor cleaners, tile cleaners, ointments and pastes, oven cleaners, pharmaceutical suspensions, concentrated carbon pastes, oil drilling sludges, spot cleaners and paints based on organic solvent. These compositions may be formulated by the addition of appropriate chemicals to the neutralized cross-linked polyacrylic acid polymer solution, organic solvent and auxiliary rheological additive to form the desired composition. The organic solution of organic solvent, neutralized anionic crosslinked polymer, namely polyacrylic acid polymer, and auxiliary rheological additive, namely an amphoteric metal oxide, has a complex viscosity at room temperature at 10 radians / second 2 from 1 to 1,000 dynes / second / cm, more preferably 30 to 800 dynes / second / cm. The organic solution is comprised of 0.1 to 10.0 wt.%, More preferably 0.2 to 4.0 wt.% Of an auxiliary rheological additive, 0.1 to 10.0 wt.%. more preferably 0.1 to 5.0% by weight of a base neutralized crosslinked anionic polymer, namely an amine neutralized crosslinked polyacrylic polymer, the remainder being an organic solvent, mixtures of organics , or mixtures of organic solvents and water, polymer solution has a value G^r of at least 2 500 solvents in which the dynes / cm² at a frequency of 10 radians / second, a G 'value of at. 2 minus 200 dynes / cm at a frequency of 10 radians / second and the G '' / G 'ratio is less than 1 and G' is substantially constant over a torsional force range of 1 to 150 micro Nm

If the organic solution has a G 'value of at least 80 2 dynes / cm at a frequency of 10 radians / second, and the G' '2 value is at least 10 dynes / cm at a frequency of 10 radians / second, where G 'is substantially constant over a torsional force range of 1 to 100 micro Nm and the ratio of G' '/ G' is lower

BNSDOCID: &lt;EN 101311B l&gt;

<img file="PT101311B_D0009.tif" />

. With a yield stress of at least 5 dynes / cm, more preferably 1 to 1200 dynes / cm, the organic solution will be a gel that can function as a suspending medium for a series of solid particles, immiscible liquid droplets or gas bubbles. . Solid particles, liquid droplets or gas bubbles may be inorganic, organic or polymeric. 0 Solid material, liquid droplets or gas bubbles that are not soluble in the solvent should not decompose in the solvent or react with the anionic groups of the anionic polymer. The concentration of solid particles, liquid droplets or gas bubbles in the suspension medium is from 0.1 to 70% by weight, more preferably 1 to 50% by weight.

The estimated minimum yield strength of the gel suspension medium, which is required to suspend each solid spherical particle, liquid droplet or gas bubble, so that the particles, droplets or bubbles remain suspended for at least seven days in the medium. gel suspension is expressed by the equation:

<img file="PT101311B_D0010.tif" />

(ZlP) gR³ minimum yield stress = ----------- 3A where R is the radius of each solid particle, liquid droplet and / or gas bubble; g is equal to the gravitational constant; ? P is equal to the difference between the density of the gel suspension medium and the density of each solid particle, liquid droplet or gas bubble and A is equal to the surface area of ​​each solid particle, liquid droplet or gas bubbles.

In addition, and as an explanation, it should be clearly emphasized that, to minimize the sedimentation rate and amount of solid particles that are insoluble in the suspension medium, the suspension medium must have independent voltage modules. For materials that exhibit stress independence of viscoelastic modules (G '), these materials tend to exhibit a critical property known as yield stress, which prevents sedimentation of insoluble particles from the suspension medium. It is also very important to understand the data as presented in this invention that by linear viscoelastic gel is meant that G 'is substantially constant in a torsional force range of 1 to 150 micro Nm The estimated minimum yield strength for the gel, which is required to suspend each spherical particle in the gel, so that each particle does not precipitate from the gel, is expressed by the equation:

(Z \ P) gR³ minimum yield stress = ------------- dines / cin

3A where R is equal to the radius of each solid particle, A is equal to the surface area of ​​each solid particle, g

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is equal to the gravitational constant and? P is equal to the difference between the density of the gel and the density of each solid particle.

Illustrative of amine-neutralized anionic polymers contemplated within the scope of the present invention in addition to polyacrylic acid polymers, namely Carbopol: sulfonated polymers containing a sulfonate functionality as defined in US Pat. 3,642,728, 4,608,425, 4,619,773, 4,626,285, 4,637,882, 4,640,945, 4,647,603, 4,710,555, 5,730,028, 4,963,,032, 4,970,260 and 4,975,821, all of which are these patents incorporated herein by reference, as well as polymers and monomers containing a carboxylic acid functionality as defined in US Pat. 4,612,332, 4,673,716, 4,694,046, 4,694,058, 4,709,759, 4,734,205, 4,780,517, 4,960.S21 and 5,036,136, all of which are incorporated herein by reference, as well as copolymers containing a maleic anhydride functionality such as a cross-linked Gantrez, provided that there is an association between the salts of these amine-neutralized polymers in the above patents, and the auxiliary rheological additive sufficient to create a viscoelastic gel having the properties G 'and G' 'as defined herein.

Examples of crosslinked polyacrylic acid-type thickening agents are products sold by BF Goodrich under its trademark Carbopol, especially Carbopol 941, which is the most ionic insensitive in this class of polymers, and Carbopol 676 and Carbopol 940 and Carbopol 934. . Carbopol resins, also known as Carbomer, are high molecular weight hydrophilic crosslinked acrylic acid polymers having an average equivalent weight of 76 and the general structure illustrated by the following formula:

<img file="PT101311B_D0012.tif" />

<img file="PT101311B_D0013.tif" />

Carbopol 941 has a molecular weight of 1,250,000, Carbopol 940 has a molecular weight of approximately 4,000,000 and Carbopol 934 has a molecular weight of approximately 3,000,000. Carbopol resins cross-link with polyalkenyl polyether, for example 1%. of a sucrose polyallyl ether having an average of 5.8 allyl groups for each sucrose molecule. More detailed information on Carbopol resins can be found at BFGoodrich, see, for example, BFGoodrich catalog GC-67, Carbopol Water Soluble Resins.

While good results have been obtained with the Carbopol 941 polyacrylic resin, other light crosslinking polyacrylic acid type thickening agents may also be used in the compositions of this invention. As used herein, the term polyacrylic acid type refers to homopolymers of acrylic acid or methacrylic acid or copolymers of these acids, their salts, esters or amides, with each other or with one or more other ethylenically unsaturated monomers, such as for example styrene, maleic acid, maleic anhydride, 2-hydroxyethylacrylate, acrylonitrile, vinyl acetate, ethylene, propylene and the like.

Carbopol 600 series resins are most useful in the present invention. They are high weight polyacrylic acids.

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molecular, salt-insensitive, cross-linking with polyalkenyl ether. Beyond branched nature? of these resins, they are more crosslinked than the 900 series resins and have molecular weights of approximately 1,000,000 to 4,000,000. Among the Carbopol 600 series resins, the Carbopol 614 is very useful. Carbopol 614 is also very stable under any anticipated storage temperature conditions, from freezing temperatures to temperatures as high as 48.89 ° C (120 ° F), preferably 60 ° C (140 ° F) and especially 71, 11 ° C (160 ° F), for periods as long as several days to several weeks or months or more.

Homopolymers or copolymers are characterized by their high molecular weight in the range of 60,000 to 10,000,000, preferably 500,000 to 5,000,000, especially 1,000,000 to 4,000,000, and their organic solvent solubility. These thickening agents are used in their slightly crosslinked form, wherein crosslinking can be achieved by means known in the art with respect to polymers, such as by irradiation or preferably by incorporation into the monomer mixture to be of known cross-linked chemical monomeric agents, typically polyunsaturated (e.g. diethylenically unsaturated) monomers such as, for example, divinyl benzene, diethylene glycol divinyl ether, N, N'-methylene bisacrylamide, polyalkenyl polyethers (such as those described above and the like). Typically, the amounts of crosslinking agent to be incorporated into the final polymer may range from 0.01 to 1.5%, preferably from 0.05 to 1.2%, and most preferably from 0.1 to 0.9%. by weight of crosslinking agent relative to the weight of the total polymer. Generally, those skilled in the art will find that the degree of crosslinking should be sufficient to produce some compound winding.

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101311R I 5 »

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otherwise generally linear polymeric. Of course, the swelling in water of the polymer providing the desired thickening and viscous properties generally depends on one or two mechanisms, namely, conversion of the acid group containing polymers to the corresponding salts, for example sodium, generating negative charges along the spine. dorsal polymer, thereby causing the rolled molecules to expand and thicken the aqueous solution; or by forming hydrogen bonds, for example, between the carboxyl groups of the polymer and a hydroxyl donor. This latter mechanism is especially important in the present invention and therefore preferred polyacrylic acid type thickening agents will contain free carboxylic acid (COOH) groups along the polymer backbone. It is equally clear that the degree of crosslinking should not be so high as to make the crosslinking polymer completely insoluble or non-dispersible in water and / or organic solvents or to inhibit or prevent further curling of polymer molecules in the presence of metal oxide. amphoteric.

The amount of anionic cross-linked polymer, namely high molecular weight cross-linked polyacrylic acid or other high molecular weight hydrophilic cross-linked polyacrylic acid type thickening agent, required to provide the desired rheological property of viscoelasticity generally within the range 0.1 to 10%, preferably 0.1 to 5% by weight based on the weight of the composition, although the amount depends on the specific crosslinking agent, ionic strength of the composition, hydroxyl donors and the like.

The auxiliary rheological additive is a colloidal thickener and is preferably an amphoteric metal oxide having dispersing particles with an average diameter size of about 0.05 µm.

<img file="PT101311B_D0016.tif" />

at 2.0 micron, more preferably about 0.05 to about 1.1 micron. Since their particle size is less than 1 micron, these amphoteric metal oxides are non-abrasive. The metal oxide dispersion contains about 60 to about 90 wt% metal oxide and the dispersion has a pH of about 3 to about 4. When the acid oxide dispersion of the metal oxide is added to the neutralized anionic polymer base solution, the acid oxide dispersion of the metal oxide is neutralized, thereby rendering the dispersion of the metal oxide effective as an auxiliary rheological additive. A preferred metal oxide is aluminum oxide. Useful aluminum oxide dispersions are sold by Vista Chemical Company of Houston, Texas, under the tradename Dispal Alumina 23 N4-80, Dispal Alumina 23 N4-20 or Dispal Alumina T23. The auxiliary rheological additive may also contain a fatty acid or a fatty acid salt and further a fatty acid or a fatty acid salt alone or in combination with the amphoteric which may function as an auxiliary rheological additive.

The anionic crosslinked polymer may be neutralized with an organic amine. The organic amine that may be used to neutralize the anionic polymer may be a primary, secondary or tertiary aliphatic amine, aromatic amine or a heterocyclic amine, with aliphatic amines being especially preferred. For example, in the case of an amine-neutralized Carbopol cross-linked polymer, some amines that can be used to neutralize the Carbopol cross-linked polymer are diisopropanol-amine, Ethomeen C-25, Di-2-ethylhexyl amine. triethanolamine, triamylamine, dimethylaminopropionitrile, alamine, dodecylamine, an ethylene / vinyl pyridene copolymer and morpholine. Mixed systems of an alkaline metal neutralized anionic cross-linked polymer and an anionic cross-linked polymer may sometimes be used.

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wherein the ratio of metal neutralized polymer to amine neutralized polymer may be from 100/1 to 1/100 and more preferably 10/1 to 1/10. The selection of neutralizing agent for the anionic polymer is governed, in part, by the solvent system of the composition. Typical solvents which can be used to dissolve amine-neutralized anionic crosslinked polymers and which are consequently gelled are shown in Table I. Gelling occurs with the use of the aforementioned amines.

<img file="PT101311B_D0018.tif" />

TABLE I% Solvent A% Solvent B (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)

Ethanol

<td colspan="2">10 DMF</td><td colspan="2">X</td>

<td>90 Ethanol 10 Methanol</td><td>X</td><td>X</td><td>X</td>

<td>90 Ethanol 10 Water</td><td>X</td><td>X</td><td>X</td>

<td>Ethyl formamide</td><td>X</td><td>X</td><td>X</td>

<td>Ethylene glycol</td><td>X</td><td>X</td><td></td>

<td>90 Ethylene Glycol 10 DMF</td><td>X</td><td>X</td><td></td>

<td>90 Ethylene Glycol 10 Methanol</td><td>X</td><td>X</td><td></td>

<td>90 Ethylene Glycol 10 Water</td><td>X</td><td>X</td><td></td>

<td>Ethylene oxide</td><td></td><td>X</td><td>X</td>

<td>Glycerol</td><td>X</td><td></td><td></td>

<td>80 Hexane 20 methanol</td><td></td><td></td><td></td>

<td>90 Isopropanol 10 Water</td><td></td><td>X</td><td></td>

<td>90 Methoxylene 10 Methanol</td><td></td><td></td><td></td>

<td rowspan="2">Methanol 90 Methanol ....... 10 DMF</td><td>X</td><td>X</td><td>X</td>

<td>X</td><td>X</td><td>X</td>

Methyl

<td>Celosolve</td><td>X</td><td>XX</td>

<td>n-methyl-2- pyrrolidone</td><td> —</td><td>X</td>

<img file="PT101311B_D0019.tif" />

TABLE I% Solvent A% Solvent B (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)

Mineral alcohols

Methanol

<td>Nitrobenzene</td><td colspan="3">X</td>

<td>90 Nitrobenzene 10 DMF</td><td></td><td>X</td><td></td>

<td>90 Nitrobenzene 10 Methanol</td><td></td><td>X</td><td></td>

<td>Phenyl acetate</td><td></td><td></td><td>X</td>

<td>90 Alcohol Diacetone 10 Water</td><td></td><td>X</td><td>X</td>

<td>Diethyl Acetamide</td><td></td><td>X</td><td>X</td>

<td>Diethyl formamide</td><td></td><td>X</td><td>X</td>

<td>90 Diethyl formamide 10 DMF</td><td></td><td>X</td><td>X</td>

<td>90 Diethyl formamide 10 Methanol</td><td></td><td>X</td><td>X</td>

<td>Diethylene glycol</td><td>X</td><td>X</td><td>X</td>

<td>Dimethyl acetamide</td><td></td><td>X</td><td>X</td>

<td>1.4 Dioxane</td><td></td><td></td><td>X</td>

<td>Dipropyl Sulfone</td><td></td><td>X</td><td>X</td>

<td>Dimethyl formamide (DMF)</td><td>X</td><td>X</td><td>X</td>

<td>95 DMF 5 Ethylene glycol</td><td></td><td>X</td><td>X</td>

<td>90 DMF 13th Methanol</td><td>X</td><td>X</td><td>X</td>

<td>90 DMF 10 Water</td><td> —</td><td>X</td><td></td>

<td colspan="2">X</td><td>•P</td>

<td>X</td><td>X</td><td></td>

<td>X</td><td>X</td><td></td>

<td>X</td><td>X</td><td></td>

X

X

XX

XXX

<td>X</td><td>X</td><td>X</td>

<td></td><td>X</td><td></td>

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TABLE I% Solvent A% Solvent B (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)

DMF

Acetonax x

DMF

Toluenox

<td>Dimethyl Sulfoxide (DMSO)</td><td>X</td><td>X</td><td>XX</td><td>X</td><td>X</td>

<td>90 DMSO 10 DMF</td><td>X</td><td>X</td><td>X</td><td></td><td></td>

<td>90 DMSO 10 Methanol</td><td></td><td>X</td><td>X</td><td></td><td></td>

<td>90 DMSO 10 Water</td><td></td><td>X</td><td></td><td></td><td></td>

<td>Ethanol</td><td>X</td><td>X</td><td>X</td><td>X</td><td></td>

<td>95 Ethanol 5 Ethylene glycol</td><td>X</td><td>X</td><td>X</td><td></td><td></td>

<td>90 Ethanol 10 Ethylene Glycol</td><td>X</td><td>X</td><td>X</td><td></td><td></td>

<td>90 Acetone 10 Methanol</td><td></td><td>X</td><td>X</td><td>X</td><td></td>

<td>80 Acetone 20 methanol</td><td></td><td>X</td><td>X</td><td>X</td><td></td>

<td>90 Acetone 10 Water</td><td></td><td>X</td><td>X</td><td>X</td><td></td>

<td>80 Acetone 20 Water</td><td>X</td><td>X</td><td>X</td><td>X.</td><td></td>

<td>Acetonitrile</td><td>X</td><td>X</td><td>X</td><td></td><td>X</td>

<td>95 Acetonitrile 5 'Ethylene Glycol</td><td>X</td><td>X</td><td>XX</td><td>X</td><td>X</td>

<td>90 Acetonitrile 10 DMF</td><td></td><td>X</td><td></td><td>X</td><td></td>

BNSDOCID: &lt;EN

101311B I

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TABLE I

<td></td><td>% Solvent A % Solvent B (1)</td><td> (2)</td><td> (3)</td>

<td></td><td>90 Acetonitrile 10 Methanol</td><td>X</td><td>X</td>

<td> ·-·</td><td>90 Acetonitrile 10 Water</td><td>X</td><td>X</td>

<td></td><td>Acetyl Acetone</td><td></td><td>X</td>

<td>t</td><td>Acrylonitrile</td><td></td><td>X</td>

<td></td><td>Aniline</td><td></td><td>X</td>

<td></td><td>Benzonitrile</td><td></td><td>X</td>

<td></td><td>Benzilic alcohol</td><td>X</td><td>X</td>

<td></td><td>Butyl Carbitol</td><td></td><td></td>

<td></td><td>Butyl Celosolve</td><td></td><td></td>

<td></td><td>Butyrol Acetone</td><td>X</td><td></td>

<td></td><td>Butyrolactone</td><td>X</td><td>X</td>

<td></td><td>70 Carbitol 30 Methanol</td><td></td><td>X</td>

<td></td><td colspan="2">90 carbon tetrachloride 10 Methanol</td><td>X</td>

<td></td><td>Alcohol ketone</td><td></td><td>X</td>

<td></td><td>90 Alcohol Diacetone 10 DMF</td><td></td><td></td>

<td></td><td>90 Alcohol Diacetone 10 Ethylene Glycol</td><td></td><td>X</td>

<td></td><td>90 Alcohol Diacetone 10 Methanol</td><td></td><td>X</td>

x

X

X

X

X

X

<td> (4) (5) (6)</td><td> (7) (8) (9) (10) (11</td>

<td>XX</td><td></td>

<td>XXX</td><td>xxxx</td>

<td>X</td><td></td>

<td>X</td><td></td>

<td>X</td><td></td>

<td>X</td><td>XX</td>

<td>X</td><td></td>

<td>X</td><td></td>

<td>X</td><td></td>

<td>X</td><td></td>

n-propanol n-propanol

Water x

TABLE I% Solvent A% Solvent B (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)

<td>Propiolactone</td><td>X</td><td>X</td><td colspan="3">X</td>

<td>Propionitrile</td><td></td><td>X</td><td>X</td><td></td><td>XX</td>

<td>Propylene glycol</td><td>X</td><td>X</td><td>X</td><td>X</td><td></td>

<td>90 Propylene Glycol 10 Methanol</td><td>X</td><td>X</td><td></td><td></td><td></td>

<td>90 Propylene Glycol 10 Water</td><td>X</td><td>X</td><td></td><td></td><td></td>

<td>Styrene</td><td>X</td><td>X</td><td>X</td><td></td><td>X</td>

<td>90 Toluene 10 Ethanol</td><td></td><td></td><td></td><td></td><td>X</td>

<td>90 Toluene 10 Methanol</td><td></td><td></td><td></td><td></td><td>X</td>

<td>Water</td><td>X</td><td>X</td><td>X</td><td>XXX</td><td>XX</td>

X

Xylene

Methanol

Orthoxylene

Methanol

Paraxylene

Methanol (1) Diisopropanolamine (2) Ethomeen (BASF-Wyandatte Corp) (3) Di2 (ethylhexyl) amine (4) Triethylamine (5) Triamylamine (6) Jeffamine D-1000 (Jefferson Chemical Company Inc.), ( 7) b-Dimethylaminopropionithrite (8) Armeen (Armak Industrial Chemical Division) (9) Alamine 7D (Henkel Corporation) (10) Dodecylamine (11) Morpholine

<img file="PT101311B_D0021.tif" />

or polyvalent fatty acid, may be auxiliary rheological or in the aforementioned colloids. Although long chain or its salt used alone in combination with monovalent oxides an amphoteric additive is not yet perfect or salt contributes it is posed to the rheology and hypothesis that it is hydrogen or agent that is clearly the way acid stability of the composition, may function as a cross-linking agent.

Preferred long chain fatty acids are higher aliphatic fatty acids having from 8 to 22 carbon atoms, more preferably from 10 to 20 atoms, more preferably from 12 to 18 carbon atoms, and the carboxyl group carbon atom of the radical acid. Aliphatic may be saturated or unsaturated and linear or branched. Straight chain fatty acids are preferred. Mixtures of these acids, derivatives of natural sources such as tallow acid, coconut fatty acid, soybean acid, acid mixtures, etc. may be used. Stearic acid and mixed fatty acids, for example stearic acid / palmitic acid are preferred.

carbon, including accord. 0 can be saturated such as fat from these

When the fatty acid free acid form is used directly, it will generally associate with any potassium and sodium ions to form the corresponding alkali metal fatty acid soap. However, the fatty acid salts may be added directly to the composition as sodium salt or potassium salt, or as a polyvalent metal salt, although the alkali metal salts of the fatty acids are the preferred fatty acid salts.

Preferred polyvalent metals are the bivalent and trivalent metals of Groups IIA, IIB and IIIB, namely magnesium,

BNSDOCID: &lt;EN

101311B I&gt;

<img file="PT101311B_D0022.tif" />

calcium, aluminum and zinc, although other polyvalent metals may also be used, in particular those of Groups IIIA, IVA, VA, IB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of Elements. Specific examples of such other polyvalent metals include Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, etc. Generally, metals may be present in the bivalent to pentavalent state. Preferably, the metal salts are used in their higher oxidation state.

The amount of fatty acid stabilizer or colloidal fatty acid salt and / or thickener required to achieve the desired increase in physical stability will depend on factors such as the nature of the fatty acid or salt thereof, the nature and amount of the polymeric thickening agent, nature and quantity of organic solvent and other ingredients, as well as anticipated storage and shipping conditions.

Generally, however, amounts of fatty acid salt or fatty acid stabilizing agents in the range of 0.02 to 2%, preferably 0.04 to 1%, more preferably 0.01 to 0.8%, and most preferably. 0.08 to 0.4%, provide long-term stability and no phase separation, either at rest or during transport, at both low and high temperatures, as required for a commercially acceptable product.

Another means for improving the thickening of the polymer solutions of the present invention is to use, in combination with the neutralized anionic polymer, an inorganic colloidal layered clay, namely laponite clay, smectite clay, or attapulgite clay. The concentration of clay in the present composition is about 0.1 to

BNSDOCID: &lt;EN

101311B I&gt;

<img file="PT101311B_D0023.tif" />

about 10.0 wt%, more preferably about 0.2 to about 4 wt%.

Smectic clays include montmorillonite (bentonite), hectorite, smectite, saponite and the like. Montmorillonite clays are preferred and are marketed under names such as Thixogel (Trade Mark) No. 1 and Gelwhite (Trade Mark) GP, H, etc., by Georgia Kaolin Company; and ECCAGUM (Trademark) GP, H, etc. by Luthern Clay Products. Attapulgite clays include materials marketed under the name Attagel (Trade Mark), ie Attagel 40, Attagel 50 and Attagel 150 by Engelhard Minerals and Chemicals Corporation. Also useful for this purpose are mixtures of smectite and attapulgite types, by weight ratio of 4: 1 to 1: 5. Thickening or suspending agents of the above types are well known in the art and are described, for example, in the above-mentioned US Patent 3,985,668.

The layered clay minerals suitable for use in the present invention belong to the geological classes of layered smectites, kaolins, illites, chlorites, attapulgites and mixed clays. Typical examples of specific clays belonging to these classes are:

smectites, for example montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidelite, volchonskoite, vermiculite;

kaolin, for example, kaolinite, dickite, nacrite, antigorite, anauxite, haloisite, indelite, chrysolite;

illites, for example, bravaisite, muscovite, paragonite, phlogopite, biotite;

chlorites, for example, corrensite, peninite, donbassite, sudoite, penine, clinochlorine;

RN.Rnnnin · '-pt mi5' 11R I -b.

attapulgites, for example sepiolite, polygorsky; layered mixed clays, for example alevardite, vermiculitebiotitis.

The layered clay minerals may be of natural or synthetic origin. Preferred clay minerals for use in the present invention are natural or synthetic hectorites, montmorillonites and bentonites, and of these hectorites are especially preferred. Many of the above clays are marketed and typical examples of commercial hectorites are Laponites from Laporte Industries Ltd., England; Veegum Pro · 'and Veegum F ”from RT Vanderbilt, USA, National Lead Comp. Barasyms, Macaloids and Propaloids, Baroid Division, USA

A useful procedure for preparing the present gelled organic liquids is to dissolve the anionic polymer in the organic solvent. This is usually achieved with moderate mixing. Mixing proceeds until there is a homogeneous solution. The auxiliary rheological additive, alone or in the form of an aqueous or organic dispersion or solution, is then added to the anionic polymer solution. The addition is made with moderate mixing. An amphoteric oxide as a dispersion in water or an organic liquid is added. After the auxiliary rheological additive has been added and a homogeneous mixture has formed, the amine is added to neutralize the polymer. During the initial addition, the homogeneous mixture may thicken rapidly and then become viscous. This is to be expected. The amine is added while the homogeneous mixture is being vigorously mixed. 0 The resulting gelled organic liquid has very good thixotropic properties.

BNSDOCID: &lt;EN

101311B I&gt;

<img file="PT101311B_D0024.tif" />

EXAMPLES 1-6

In this set of operations, Examples 1-3 are ethanol-based combustible gel compositions, which contain a polyacrylic acid but not alumina thickening agent, while Examples 4-6 are ethanol-based combustible gel compositions, which contain contain a thickener of polyacrylic acid and alumina. The polyacrylate polymer is Carbopol 676 ”from BF Goodrich and the alumina is Dispal Alumina 23N4-80” available from Vista Chemical Corporation.

Gelled ethanol compositions were prepared according to the following procedure. The Carbopol 676 ”polymer was slowly sieved (16 or 20 mesh) and added to the ethanol with mixing at a temperature of about 25 ° C and the mixing operation continued for fifteen minutes. An alumina solution was prepared by slowly adding, with mixing, Dispal Alumina 23N4-80 and mixing continued for approximately ten minutes. Diisopropanolaraine was added, with mixing and at room temperature, to the Dispal Alumina 23N4-80 water solution and mixing continued for ten minutes. To the Carbopol 676 polymer solution and ethanol was rapidly added, with mixing, the diisopropanolamine and Dispal Alumina 23N4-80 ”solution and mixing continued for two minutes.

The composition of the gelled ethanol is given in Table 2. The viscosity of the gelled ethanol is given in Table 3. The viscosity is a Brooksfield viscosity at 10 rpm with a # 7 spindle at room temperature. Alumina-containing compositions are found to have a higher initial and long-term viscosity than non-alumina-containing compositions. In addition, with the

BNSDOCIDkEN 101311B I&gt;

<img file="PT101311B_D0025.tif" />

Over time the alumina-containing compositions maintain a higher viscosity compared to the non-alumina-containing compositions.

BNSDOCID: &lt;EN 101311B l&gt;

<img file="PT101311B_D0026.tif" />

TABLE 2

EXAMPLE

<td>COMPONENTS</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>

<td>Polyacrylate Polymer</td><td> 0,75</td><td> 0,65</td><td> 0,55</td><td> 0,75</td><td> 0,65</td><td> 0,55</td>

<td>Ethanol</td><td> 71</td><td> 71</td><td> 71</td><td> 71</td><td> 71</td><td> 71</td>

<td>Water</td><td> 27,25</td><td> 27,35</td><td> 27,45</td><td> 26,75</td><td> 26,85</td><td> 26,95</td>

<td>Alumina</td><td> 0</td><td> 0</td><td> 0</td><td> 0,5</td><td> 0,5</td><td> 0,5</td>

<td>Diisopropanolamine</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

QMennrin · dt mis-HR I

TABLE 3

EXAMPLE

<td>Days</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>

<td>Initial</td><td> 86 000</td><td> 76 000</td><td> 68 000</td><td> 116 800</td><td> 103 600</td><td> 89 200</td>

<td> 1</td><td> 86 400</td><td> 76 000</td><td> 71 200</td><td> 131 600</td><td> 116 400</td><td> 92 000</td>

<td> 2</td><td> 87 200</td><td> 81 200</td><td> 63 200</td><td> 136 400</td><td> 120 000</td><td> 102 800</td>

<td> 7</td><td> 86 400</td><td> 84 000</td><td> 76 400</td><td> 130 000</td><td> 126 000</td><td> 113 600</td>

<td> 14</td><td> 90 000</td><td> 90 400</td><td> 78 000</td><td> 134 000</td><td> 127 200</td><td> 116 000</td>

<td> 28</td><td> 93 200</td><td> 89 200</td><td> 82 000</td><td> 132 000</td><td> 126 400</td><td> 110 400</td>

<td> 42</td><td> 94 000</td><td> 96 000</td><td> 84 000</td><td> 130 000</td><td> 132 400</td><td> 110 400</td>

<td> 56</td><td> 81 600</td><td> 93 600</td><td> 78 000</td><td> 128 400</td><td> 125 600</td><td> 126 000</td>

<td> 84</td><td> 104 000</td><td> 89 200</td><td> 81 600</td><td> 159 600</td><td> 132 000</td><td> 128 000</td>

RNsnncm · cPT

101311R I

<img file="PT101311B_D0027.tif" />

EXAMPLES 7-12

In this set of operations, Examples 7-9 are methanol-based combustible gel compositions containing a polyacrylate but not alumina thickening agent, while Examples 10-12 are methanol-based combustible gel compositions containing a polyacrylate and alumina thickening agent. The polyacrylate polymer is Carbopol 676 from BF Goodrich and the alumina is Dispal Alumina 23N4-80 available from Vista Chemical Corporation.

Gelled methanol compositions were prepared according to the following procedure. The Carbopol 676 polymer was slowly sieved (16 or 20 mesh) and added to the methanol with mixing at a temperature of about 25 ° C and mixing continued for fifteen minutes. An alumina solution was prepared by slowly adding, with mixing, Dispal Alumina 23N4-80 and mixing continued for approximately ten minutes. Diisopropanolamine was added, with mixing and at room temperature, to the Dispal Alumina 23N4-80 solution of water and mixing continued for ten minutes. To the Carbopol 676 polymer solution and methanol was rapidly added, with mixing, the diisopropanolamine and Dispal Alumina 23N4-80 solution and mixing continued for two minutes.

The composition of the gelled methanol is given in Table 4. The viscosity of the gelled methanol is given in Table 5. The viscosity is a Brooksfield 10 rpm viscosity with a # 7 spindle at room temperature. Alumina-containing compositions are found to have an initial and long-term viscosity greater than that of non-alumina-containing compositions. In addition, as

BNSDOCID: &lt;EN

101311B I&gt;

<img file="PT101311B_D0028.tif" />

Over time alumina-containing compositions maintain higher viscosity compared to alumina-containing compositions.

one no

RKiennrm · --dt

TABLE 4

EXAMPLE

<td>COMPONENTS</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td><td> 11</td><td> 12</td>

<td>Polyacrylate Polymer</td><td> 0,75</td><td> 0,65</td><td> 0,55</td><td> 0,75</td><td> 0,65</td><td> 0,55</td>

<td>Methanol</td><td> 72</td><td> 72</td><td> 72</td><td> 72</td><td> 72</td><td> 72</td>

<td>Water</td><td> 26,25</td><td> 26,35</td><td> 26,45</td><td> 25,75</td><td> 25,85</td><td> 25,95</td>

<td>Alumina</td><td> 0</td><td> 0</td><td> 0</td><td> 0,5</td><td> 0,5</td><td> 0,5</td>

<td>Diisopropanolamine</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

RMftnnrm ·

-io-is-i-go i

<img file="PT101311B_D0029.tif" />

TABLE 5

EXAMPLE

<td>Days</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td><td> 11</td><td> 12</td>

<td>Initial</td><td> 82 400</td><td> 73 200</td><td> 60 000</td><td> 100 400</td><td> 97 600</td><td> 66 000</td>

<td> 1</td><td> 94 000</td><td> 79 200</td><td> 58 000</td><td> 118 800</td><td> 114 400</td><td> 84 800</td>

<td> 2</td><td> 87 200</td><td> 84 000</td><td> 64 800</td><td> 132 000</td><td> 127 600</td><td> 106 000</td>

<td> 7</td><td> 98 400</td><td> 79 200</td><td> 71 200</td><td> 136 000</td><td> 117 600</td><td> 80 000</td>

<td> 14</td><td> 91 600</td><td> 91 600</td><td> 76 400</td><td> 124 000</td><td> 112 000</td><td> 112 000</td>

<td> 28</td><td> 84 400</td><td> 80 000</td><td> 70 400</td><td> 144 000</td><td> 132 000</td><td> 116 800</td>

<td> 42</td><td> 92 400</td><td> 86 800</td><td> 81 600</td><td> 156 800</td><td> 137 600</td><td> 92 000</td>

<td> 56</td><td> 94 400</td><td> 77 200</td><td> 79 600</td><td> 144 000</td><td> 134 800</td><td> 109 200</td>

BNSDOCID: &lt;EN

1013118 I

<img file="PT101311B_D0030.tif" />

EXAMPLE 13

The composition of Example 6 was prepared and filled into filled alumina molded containers having an inner diameter of 8.64 cm and a height of 6.35 cm. The top opening is 5.08 cm. The average weight of the gelled ethanol fuel is 221.7 g.

A container is placed under a shed containing 3 liters of water at 43 ° C in the receptacle for the water of the sheath and 2 liters of water at 43 ° C in the food. This container is set on fire and, from the thermoelements in the water and food receptacles, the water temperatures in these receptacles are recorded. The average data on operations are as follows:

Burning time - 131 minutes

Burning speed - 1.49 g / min

Min.para 65,5 ° C

Water Recap - 24.25 minutes

Min.para 65,5 ° C

Food - 54 minutes

Min.para Max.T ° C

Water Recording - 122 minutes

Min.para Max.T ° C

Rec.Food - 129.75 minutes

Max.T ° C

Water - 99.1 ° C

Max.T ° C

Rec.Food - 89.1 ° C

QMcnnrin ·&gt; dt

Q11Q

<img file="PT101311B_D0031.tif" />

This example reveals that canned fuels have a satisfactory burn time as well as temperature profile.

EXAMPLE 14

The fuels of Example 13 were tested for compliance with those tested to ASTM D 4359-84. The title of this test is Determining Whether A Material Is A Liquid Or A Solid (Determination Whether A Material Is A Liquid Or A Solid). The fuels were placed in 1/4 gallon cans until filling to at least 85% level. The cans were sealed by friction caps and placed in an oven at 38 ° C ± 3 ° C for 24 hours. The cans were then removed from the oven and the lids removed. The cans were placed at rest in an inverted position for 3 minutes. The level of gelled fuel in the can was measured at the beginning and end of the 3 minute period. A flow of 5 cm or less is acceptable and the material is considered to be a solid. The canned fuel samples that were tested showed no flow. They have been classified as solids according to ASTM D 4359-84.

1A4O11D

EXAMPLES 15

<img file="PT101311B_D0032.tif" />

<td></td><td>Carbopol 676</td><td>Hi - Isopropanolamine 85%</td><td>50% NaOH</td><td>Student (Dispa 13N4-80)</td><td>DI water</td><td>95% ethanol</td><td>100% methanol</td><td>Brookfield Initial Viscosity - Spindle # 7, 10rpm TA (cPs)</td>

<td> 15</td><td> 0,85</td><td> 0,35</td><td> ....</td><td> 0</td><td>I 27.8</td><td> 71</td><td></td><td> 86 000</td>

<td> 16</td><td> 0,85</td><td> 0</td><td> 0,08</td><td> 0</td><td> 28,07</td><td> 71</td><td></td><td> 31 600</td>

<td> 17</td><td> 0,85</td><td> ....</td><td> 0,5</td><td> ....</td><td> 28,10</td><td> 71</td><td></td><td> 34 400</td>

<td> 18</td><td> 0.75</td><td> 1,0</td><td> ....</td><td> 0</td><td> 27,25</td><td> 71</td><td></td><td> 86 000</td>

<td> 19</td><td> 0,75</td><td> 1,0</td><td> ....</td><td> 0,5</td><td> 26,75</td><td> 71</td><td></td><td> 116 800</td>

<td> 20</td><td> 0,65</td><td> 1,0</td><td> ....</td><td> 0</td><td> 27,35</td><td> 71</td><td></td><td> 76 000</td>

<td> 21</td><td> 0,65</td><td> 1,0</td><td> ....</td><td> 0,5</td><td> 26,85</td><td> 71</td><td></td><td> 103 600</td>

<td> 22</td><td> 0,55</td><td> 1,0</td><td> ....</td><td> 0</td><td> 27,45</td><td> 71</td><td></td><td> 68 000</td>

<td> 23</td><td> 0,55</td><td> 1,0</td><td> ....</td><td> 0,5</td><td> 26,95</td><td> 71</td><td></td><td> 89 200</td>

<td> 24</td><td> 0,45</td><td>L0</td><td></td><td> 0</td><td> 27,55</td><td> 71</td><td></td><td> 50 000</td>

<td> 25</td><td> 0,45</td><td>1, the</td><td> ....</td><td> 0,5</td><td> 27,05</td><td> 71</td><td></td><td> 59 600</td>

<td> 26</td><td> 0,75</td><td> 1,0</td><td> ....</td><td> 0</td><td> 26,25</td><td></td><td> 72</td><td> 82 400</td>

<td> 27</td><td> 0,75</td><td> 1,0</td><td> ....</td><td> 0,5</td><td> 25,75</td><td></td><td> 72</td><td> 100 400</td>

<td> 28</td><td> 0,65</td><td> 1,0</td><td> ....</td><td> 0</td><td> 26,35</td><td></td><td> 72</td><td> 73 200</td>

<td> 29</td><td> 0,65</td><td> 1,0</td><td> ....</td><td> 0,5</td><td> 25,85</td><td></td><td> 72</td><td> 97 600</td>

<td> 30</td><td> 0,55</td><td>1, the</td><td> ....</td><td> 0</td><td> 26,35</td><td></td><td> 72</td><td> 60 000</td>

<td> 31</td><td> 0,55</td><td> 1,0</td><td> ....</td><td> 0,5</td><td> 25,85</td><td></td><td> 72</td><td> 66 000</td>

<td> 32</td><td> 0,45</td><td> 0,75</td><td> ....</td><td> 0</td><td> 26,80</td><td></td><td> 72</td><td> 45 200</td>

<td> 33</td><td> 0,45</td><td> 0,75</td><td> ....</td><td> 0,5</td><td> 26,30</td><td></td><td> 72</td><td> 40 400</td>

<td> 34</td><td> 0,45</td><td> 1,0</td><td> ....</td><td> 0</td><td> 26,55</td><td></td><td> 72</td><td> 45 200</td>

<td> 35</td><td> 0,45</td><td> 1.0</td><td> ....</td><td> 0,5</td><td> 26,05</td><td></td><td> 72</td><td> 57 200</td>

<td> 36</td><td> 0,35</td><td> 0,65</td><td> ....</td><td> 0,5</td><td> 26,5</td><td></td><td> 72</td><td> 33 200</td>

BNSDOCID: &lt;EN

101311B I&gt;

EXAMPLES 15 - 36

Formulas (15 - 36) were prepared according to the following procedure. The Carbopol 676 polymer was slowly sieved (16 or 20 mesh) and added to the methanol or ethanol with mixing at a temperature of about 25 ° C and mixing continued for fifteen minutes. An alumina solution was prepared by slowly adding, with mixing, Dispal Alumina 23N4-80 and mixing continued for approximately ten minutes. Diisopropanolamine was added, with mixing and at room temperature, to the 23 N4-80 Dispal Alumina water solution and mixing continued for ten minutes. To the Carbopol 676 polymer solution and methanol (or ethanol) was rapidly added, with mixing, the solution of diisopropanolamine and Dispal Alumina 23N4-80 and mixing continued for two minutes. Brookfield viscosities were measured at room temperature using a # 7 spindle at 10 rpm.

RNfinnmn · ^ en

1D1S11R I&gt;

EXAMPLE 37 (Pa.S), the Loss Modules G ''

No. and 10 rad / s (Experience

0.45% Carbopol, Methanol (35) Ethanol (24) = 0.45% Carbopol,

Complex Viscosities were obtained 2)

Storage Modules G '(N / m' (N / m²) Compositions at 150 micro Stress Curve). Methanol (34) = = 0.45% Carbopol plus 0.5% Alumina,

Ethanol (25) = 0.45% Carbopol plus 0.5% Alumina.

<td></td><td>Ethanol (24)</td><td>Ethanol (25)</td><td>Methanol (34)</td><td>Methanol (35)</td>

<td>Complex Viscosity (Pa.s)</td><td> 40,13</td><td> 52</td><td> 39,10</td><td> 75,28</td>

<td>G '(N / m²)</td><td> 398,9</td><td> 517,6</td><td> 389,2</td><td> 750,6</td>

<td>G '' (N / m²)</td><td> 44,58</td><td> 49,48</td><td> 37,64</td><td> 57,79</td>

<td>Yield Stress (N / m²)</td><td> 85,53</td><td> 124,6</td><td> 87,37</td><td> 91,08</td>

Pa = NM²

N / m²

39.10 Pa.s ~ 391.0 dines.cm

389.2 N / m² = 3892 dynes.cm ²

Lisbon, July 16, 1993___________

<img file="PT101311B_D0033.tif" />

J- PEREIRA OF THE CROSS

Official Industrial Property Agent

<img file="PT101311B_D0034.tif" />