DE3145452A1 - Gel-forming, organophilic clay and process for its preparation - Google Patents

Abstract

There is described a gel-forming, organophilic clay or a gel-forming composition based on organophilic clay, which comprises the reaction product of an organic cation compound, of an organic anion and of a clay of the smectite type having a cation-exchange capacity of at least 75 mequivalents/100 g of clay. The organic cation compound has the following formula <IMAGE> in which R1 is selected from the group comprising a beta , gamma -unsaturated alkyl group and a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long-chain alkyl group having 12 to 60 carbon atoms; R3 and R4 are independently selected from the group comprising a beta , gamma -unsaturated alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having 1 to 22 carbon atoms and mixtures thereof; X is selected from a group comprising phosphorus and nitrogen. The reaction is carried out in such a manner that an organic cation/organic anion complex is incorporated in the clay of the smectite type and the cation exchange sites of the clay of the smectite type are substituted by the organic cation.

Description

description

The invention relates to organophilic, organic clay complexes, which in organic liquids are dispersible therein to form a gel. Ever Depending on the composition of the gel, such gels can be suitable as lubricating greases, Oil-based muds, drilling fluids or oil-based packer fluids, paint-varnish-paint remover, Paints, sand binders for molding sand molding, adhesives and sealants, Printing inks, laminating polyester resins, polyester gel coatings and the like ..

It is known that organic compounds containing a cation react under favorable conditions by ion exchange with clays that have a negative Contain layer lattices and exchangeable cations, with the formation of organophilic, organic clay products. If the organic cation has at least one alkyl group contains at least 10 carbon atoms, such organoclays have the Property of swelling in certain organic liquids; See, for example U.S. Patents 2,531,427 and 2,966,506, both of which are incorporated herein by reference, and U.S. Patent Nos. 2,531,427 and 2,966,506 Book "Clay Mineralogy", 2nd edition, 1968, by Ralph E.

Grim (McGraw-Hill Book Company, Inc.), especially Chapter 10, Clay-Mineral-Organic Reactions; Pages 356-368 - Ionic reactions, smectites; and pages 392-401 - Organophilic Clay-Mineral Complexes.

It is also known that organic compounds that are in anionic Form, usually repelled by negatively charged clay surfaces than to be attracted.

This effect is known as "negative adsorption".

However, a positive adorpion of anions can occur under conditions in which such compounds in the molecular, i.e. undissociated form, exist; see Chemistry of Clay - Organic Reactions ", 1974, by B.K.G.Theng, John Wiley & Sons.

In contrast, Wada found that this phenomenon, i.e. the Adsorption, with certain ionic compounds, occurs when reacting with Halloysite, a material of the kaolinite group, with the formation of intersalates. The sub Salad formation was achieved by grinding the mineral with moist crystals of salts of the carboxylic acids of low molecular weight or by contacting of the mineral with saturated solutions. This interlayer complex contained that complete salt as well as water. The intersalat material, however, was made by washing removed with water, either for hydration of the intermediate layer or for Collapse of the original space. For a change in the basal space there was no evidence of montmorillonite treated with salts was, in contrast to halloysite; See The American Minerologist, Vol. 44, 1959, by K. Wada, "Oriented Penetration of Ionic Compounds between the Silicate Layers of Halloysite ".

Since the commercial introduction of organoclays in the early 1950s For years it has been known to have maximum gelling (thickening) efficiency of these Organotones is achieved by adding a polar, low molecular weight organic material to the composition. Such polar, organic materials have been used variously as dispersants, dispersing aids, Solvating agents, dispersing agents and the like.

designated; See, for example, U.S. Patents 2,677,661 (O'Halloran); 2,704,276 to McCarthy et al .; 2,833,720 to Stratton; 2,879,229 to Stratton; 3,294,683 (Stansfield et al.). The use of such dispersion aids was found to be unnecessary when using specially structured, organophilic clays that differ from substituted, derive quaternary ammonium compounds; See U.S. Patents 4,105,578 (Finlayson et al.) and 4,208,218 (Finlayson).

In contrast to the known organoclay compositions, surprisingly a self-activating, rheological agent made with the addition of polar Solvent activators are not required, this agent being manufactured by Reaction of an organic cation, an organic anion and a clay from Smectite type.

A gel-forming, organophilic clay with improved dispersibility in non-aqueous systems has surprisingly been found which contains: the reaction product of (a) an organic cation salt compound in which the organic cation has the following formula: wherein R1 is selected from the group consisting of a β, γ-unsaturated alkyl group and a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 12 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a β-unsaturated alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having 1 to 22 carbon atoms, and mixtures thereof; X is selected from a carbon consisting of all phosphorus and nitrogen; (b) an organic anion; and (c) a smectite-type clay having a cation exchange capacity of at least 75 meq / 100 g of the clay; wherein an organic cation-organic anion complex is intercalated with the smectite-type clay and the cation exchange sites of the smectite-type clay are substituted with the organic cation.

The organophilic clays of the invention can be made by mixing the organic anion with a clay and water together, preferably at a temperature between 20 and 1000C, preferably between 35 and 770C, for a sufficient time to produce a homogeneous mixture the addition of the organic cation in sufficient quantities to improve the cation exchange capacity of the clay and the cationic capacity of the organic anion. The chronological order the addition of the organic cation and the organic anion is not important, as long as a sufficient amount of the organic cation is added. Indeed can use the appropriate amounts of organic cation and sodium salt of the organic Anions in solution (water and / or 2-propanol) on a solids basis of 20 to 90% are premixed to form an organic cation-organic anion complex and then as a solution for implementation with the clay slurry can be added.

After adding the organic anion and the organic cation the mixture is stirred at a temperature of 20 to 1000C, preferably 35 to 770C, reacted for sufficient time to form an organic Allow cation-organic anion complex to be incorporated into the clay is, and the cation exchanges of the clay are made by the organic cation substituted.

Reaction temperatures below 200C or above 1600C are applicable, but not preferred.

The addition of the organic cation and the organic anion can either separately or as a complex.

When using the organophilic clays in emulsions, this can be Drying and grinding steps can be omitted.

Become the clay, the organic cation, the organic anion and water mixed in such concentrations that no slurry is formed, so the filtration and washing steps can be omitted.

The clay is preferably in water at a concentration of about 1 to 80%, and preferably 2 to 7%, dispersed to form a clay slurry. The clay slurry can optionally be centrifuged to remove non-clay contaminants, which constitute from about 10 to about 50% of the starting clay composition. the Slurry is generally stirred or agitated to a temperature in the range preheated from 35 to 770C before adding the organic reaction components.

The amount of organic anion that makes up the clay for the invention Purposes added should be sufficient to give the org.lnophile tone the improved To impart dispersion characteristics which are aimed at. This amount will defined as the milliequivalent ratio that the number of Milliequivalents (mEquiv.) Det; organic anions in the organic clay per 100 g clay, on a 100.6 active tone basis. The organophilic clays of the invention should preferably an anion-milliequivalent ratio of 5 to 100 and particularly preferred from 10 to 50.

The organic anion is preferably one of the reducing components in the desired milliequivalent ratio as a solid or as a solution in water with stirring b.

Moving joined to form a homogeneous mixture.

The organic cation should be used in sufficient quantity at least the cation exchange capacity of the clay and the cationic activity of the organic anion. Additional cation over the sum of the exchange capacity of the clay and the anion can optionally be used. It was found that the Use of at least 90 meq. Of organic cation is sufficient to produce one part of the total organic cation requirement. The use of sets of 80 to 200 meq.

and preferably from 100 to 160 meq. is useful.

To facilitate handling, it is preferred if the entire organic content in the organophilic clay reaction products of the invention less than about 50% by weight of the organic clay. Higher amounts are useful, however the reaction product is difficult to process.

Another method for making the organophiles of the present invention Clays are: (a) a smectite-type clay in water at 1 to 80 wt% Tor. to slurry; (b) heating the slurry at a temperature of 20 to 1000C; (c) 5 to 100 mAequiv. of an organic anion / 100 g clay, on a 100% active clay basis, and adding the organic cation in an amount sufficient to increase the cation exchange capacity the smectite-type clay and the cationic activity of the organic anion suffice while the reaction solution is agitated or stirred; (d) the mixture to react for a sufficient time to form a reaction product that contains an organic cation-organic anion complex that is embedded with the smectite-type clay, the cation exchange sites of the smectite-type clay are substituted with the organic cation; and (e) recovering the reaction product.

The organic cation compound useful in the present invention can be selected from a wide range of materials that are suitable to form an organophilic clay by cation exchange with the smectite-type clay. The organic, cationic compound must have a positive charge that on a single atom or on a small group of atoms within the compound is located. The organic cation is preferably selected from the group of quaternary ammonium salts, phosphonium salts and mixtures thereof and of equivalents Salt. The organic cation preferably contains at least one material selected from each of two groups, the first group consisting of (a) a β> y-unsaturated Alkyl group and (b) a hydroxyalkyl group having 2 to 6 carbon atoms, and the second consists of a long chain alkyl group. The remnants of the central, positive atoms are chosen from one material, from a ß, y-unsaturated Alkyl group and / or a hydroxyalkyl group with 2 to 6 carbon atoms or an aralkyl group and / or an alkyl group having 1 to 22 carbon atoms.

A representative formula for the cationic compound is wherein R1 is selected from the group of a β, γ-unsaturated alkyl group and a hydroxyalkyl group having 2 to 6 carbon atoms; R2 is a long chain alkyl group having 12 to 60 carbon atoms; R3 and R4 are selected from a group consisting of a β, γ-unsaturated alkyl group, a hydroxyalkyl group; Init 2 to 6 carbon atoms, an aralkyl group and an alkyl group having 1 to 22 carbon atoms; and X is phosphorus or nitrogen.

R1 The β, -unsaturated alkyl group can be selected from one of wide range of materials. These compounds can be cyclic or acyclic, be unsubstituted or substituted. Preferably contain ß, - unsaturated alkyl radicals less than 7 aliphatic carbon atoms.

β, γ-unsaturated alkyl radicals which are substituted with an aliphatic Remainder, preferably contain less than 4 aliphatic carbons. The ß, y-unsaturated The alkyl radical can be substituted by an aromatic ring, which is optionally conjugated with the unsaturation of the β, 7 radical, or the β, y radical is both substituted with an aliphatic radical as well as with an aromatic ring.

Representative examples of cyclic β, -y-unsaturated alkyl groups are 2-cyclohexenyl and 2-cyclopentenyl. Representative examples of acyclic β, γ-unsaturated alkyl groups with 6 or fewer carbon atoms are propargyl; 2-propenyl; 2-butenyl; 2-pentenyl; 2-hexenyl; 3-methyl-2-butenyl; 3-methyl-2-pentenyl; 2,3-dimethyl-2-butenyl; 1,1-dimethyl-2-propenyl; 2-dimethylpropenyl; 2,4-pentadienyl; and 2,4 - hexadienyl. Representative examples of acyclic - aromatic substituted compounds are 3-phenyl-2-propenyl; 2-phenyl-2-propenyl and 3- (4-methoxyphenyl) -2-propenyl. Representative examples of aromatic and aliphatic substituted materials are 3-phenyl-2-cyclohexenyl; 3-phenyl-2-cyclopentenyl; wherein the alkyl group may be substituted with an aromatic ring.

The hydroxyalkyl group is selected from a hydroxyl-substituted, aliphatic radical in which the hydroxyl is unsubstituted on the carbon, the is adjacent to the positively charged atom, and the group has 2 to 6 aliphatic Carbons on. The alkyl group can be substituted with an aromatic ring be. Representative examples include 2-hydroxyethyl; 3-hydroxypropyl; 4-hydroxypentyl; 6-hydroxyhexyl; 2-hydroxypropyl; 2-hydroxybutyl; 2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxycyclohexyl; 3-hydroxycyclohexyl; 4-hydroxycyclohexyl; 2-hydroxycyclopentyl; 3-hydroxycyclopentyl; 2-methyl-2-hydroxypropyl; 3-methyl-2-hydroxybutyl; and 5-hydroxy-2-pentenyl.

R2 The long-chain alkyl radical can be branched or unbranched, saturated or unsaturated, substituted or unsubstituted and should be 12 to 60 carbon atoms have in the straight-chain part of the remainder.

The long chain alkyl radicals can be from naturally occurring oils originate, including various vegetable oils, such as corn or corn oil, coconut oil, Soybean oil, Cottonseed oil, castor oil and the like., As well as from various animal oils or fats, such as sebum oil. The alkyl radicals can be in be of the same petrochemical nature as that of α-olefins.

Representative examples of useful branched, saturated alkyl radicals include 12-methylstearyl and 12-thylstearyl. Representative examples of useful, branched, unsaturated radicals include 12-methyloleyl and 12-ethyloleyl. Representative Examples of straight, saturated radicals include lauryl; Stearyl; Tridecyl, Myristal or myristyl (tetradecyl); Pentadecyl; Ilexadecyl; hydrogenated sebum and Docosonyl. Representative examples of unbranched, unsaturated and unsubstituted, long chain alkyl groups include oleyl, linoleyl, linolenyl, soy, and tallow.

R3 and R4 The remaining groups on the positively charged atom are selected from a group consisting of (a) a β, γ-unsaturated alkyl group, (b) a hydroxyalkyl group of 2 to 6 carbon atoms, both of the above (c) an alkyl group having 1 to 22 carbon atoms, cyclic or acyclic, and (d) an aralkyl group, i.e. benzyl and substituted benzyl radicals including fused ring radicals with linear or branched chains of 1 to 22 carbon atoms in the alkyl part of the aralkyl.

The unsaturated alkyl group of R3 and R4 can be linear and branched, cyclic and acyclic, substituted and unsubstituted, and 1 to 22 carbon atoms contain.

Representative examples of useful alkyl groups shown as R and R4s useful include methyl; 3 ethyl; Propyl; 2-propyl; Isobutyl; Cyclopentyl and cyclohexyl.

The alkyl radicals can be from a source similar to that of long-chain alkyl radical of the above R2 iö Representative examples of an aralkyl group, i.e.

Benzyl and substituted benzyl radicals include benzyl and the like Materials derived from, for example, benzyl halides, benzhydryl halides, Trityl halides, 1-halo-1-phenylalkanes in which the alkyl chain has 1 to 22 carbon atoms has, such as 1-Ha'logen-1-phenylethane; 1-halo-1-phenylpropane and 1-halo-1 -Phenyloctadecane; substituted benzyl radicals derived from o-, m- and p-chlorobenzyl halides, p-methoxybenzyl halides; o-, m- and p-nitrilobenzyl halides and o-, m- and p-alkylbenzyl halides wherein the alkyl chain has 1 to 22 carbon atoms; and condensed ring radicals of the benzyl type, which are derived from 2-halomethylnaphthalene, 9-halomethylanthracene and 9-halomethylphenanthrene in which the halogen group is defined as chlorine, bromine, iodine or any other suitable group known as leaving group in the nucleophilic attack of the radical of the benzyl type serves, in such a way that that the nucleophile replaces the leaving group on the remainder of the benzyl type.

A quaternary compound is obtained from the above-described, organic, cationic compound, and an anionic residue, the Cl, Br, J, NO2, OH and C2H302 and mixtures thereof can be. Preferably the anion is selected from the group of chloride and bromide and mixtures thereof and is special prefers chloride, although other anions, such as acetate, hydroxide, nitrite, etc., are in the organic, cationic compound for neutralizing the cation is present could be.

Organic, cationic salts can be prepared by known processes as described in U.S. Patents 2,355,356, 2,775,617, and 3,136,819.

The organic anions which are useful in the present invention can can be selected from a wide range of materials provided that they are suitable are to react with an organic cation and inclusions with a tone dated Form smectite-type as an organic cation-organic anion complex. The molecular weight (Gram molecular weight) of the organic anion is preferably 5,000 or less and particularly preferably 1000 or less and contains at least one acidic residue per molecule as described here. The organic anion is preferably derived from an organic acid with a PKA less than about 11.0. As stated, the acid source must have at least one ionizable hydrogen, with preferred PKA so that the formation of the organic cationorganic intercalation reaction can be done.

Any compound that contains the desired organic compound can also be used Anion results in the hydrolysis. Representative compounds include: (1) acidic Anhydrides including acetic anhydride, maleic anhydride, succinic anhydride and phthalic anhydride; (2) acid halides including acetyl chloride, octanoyl chloride, Lauroyl chloride, lauroyl bromide and benzoyl bromide; (3) 1,1 including 1-trihalides 1,1 1-trichloroethane and 1,1,1-tribromooctane; and (4) orthoesters including ethyl orthoformate and ethyl orthostearate.

The organic anions can be in the acidic or salt form. Salts can be selected from alkali metal salts, alkaline earth metal salts, ammonia and organic amines. Representative salts include: hydrogen, lithium, sodium, Potassium, magnesium, calcium, barium, ammonium and organic amines such as ethanolamine, Diethanolamine, triethanolamine, methyldiethanolamine, butyldiethanolamine, diethylamine, Dimethylamine, triethylamine, dibutylamine, etc., and mixtures thereof. The most preferred Salt is sodium as an alkali metal salt.

Examples of types of suitable acidic, functional, organic compounds useful in the present invention include (1) carboxylic acids including a) benzenecarboxylic acids such as benzoic acid, o-, m- and p-phthalic acid, 1,2,3-benzenetricarboxylic acid; 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid; 1 2,4,5-benzene tetracarboxylic acid; 1 2,3,4 5,6-benzene hexacarboxylic acid (mellitic acid); b) Alkylcarboxylic acids of the formula H- (CH2) n-COOH, where n is a number from 0 to 20, such compounds including: acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid , Tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, eicosonic acid or eicosanoic acid; c) alkyldicarboxylic acids with the formula HOOC- (CH) n-COOH, in which n is 0 to 8, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; d) Hydroxyalkyl carboxylic acids, such as citric acid, tartaric acids, malic acid, mandelic acid and 12-hydroxystearic acid; e) unsaturated alkyl carboxylic acids such as maleic acid, fumaric acid and cinnamic acid; f) condensed, ring aromatic carboxylic acids, such as naphthalic acid and anthracene carboxylic acid; and g) cycloaliphatic acids, such as cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, furancarboxylic acids; (2) organic sulfuric acids including a) sulfonic acids including (1) benzenesulfonic acids such as benzenesulfonic acid, phenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid; (2) alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, butanedisulfonic acid, sulfosuccinate alkyl esters, such as dioctylsuccinylsulfonic acid and alkylpolyethoxysuccinylsulfonic acid; b) alkyl sulfates, such as the lauryl half esters of sulfuric acid and the octadecyl half esters of sulfuric acid; (3) Organophosphoric acids including a) phosphonic acids of the formula wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms; b) phosphinic acids of the formula wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms such as dicyclohexylphosphinic acid, dibutylphosphinic acid and dilaurylphosphinic acid; c) thiophosphinic acids of the formula wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms such as diisobutyl-dithiophosphinic acid, dibutyldithiophosphinic acid; Dioctadecylditlliophosphinic acid; d) phosphites, ie diesters of phosphorous acid of the formula HO-P (OR) 2, in which R is an alkyl group having 1 to 22 carbon atoms, such as dioctadecyl phosphite; and e) phosphates, ie diesters of phosphoric acid of the formula wherein R is an alkyl group having 1 to 22 carbon atoms such as dioctadecyl phosphate; (4) phenols such as phenol; Hydroquinone; t-butylcatechol; p-methoxyphenol; and naphthols; t-Butylbranzkate- (5) thioacids of the formula quin; wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms such as thiosalicylic acid; Thiobenzoic acid; Thioacetic acid; Thiolauric acid; and thiostearic acid; (6) Amino acids such as the naturally occurring amino acids and their derivatives such as 6-aminohexanoic acid, 12-aminododecanoic acid, N-phenylglycine and 3-aminocrotonic acid; (7) polymeric acids made from acidic monomers in which the acidic function remains in the polymer chain, such as low molecular weight acrylic acid polymers and copolymers and styrene-maleic anhydride copolymers; (8) various acids and acid salts such as ferrocyanide, ferricyanide, sodium tetraphenylborate; Phosphotungstic acid, phosphosilicic acid, or any other such anions which form a close ion pair with an organic cation, that is, any anion which forms a water-insoluble precipitate with an organic cation.

The for the production of the gel-forming, organophilic clay according to The clays used in the invention are smectite-type clays which have cation exchange capacity of at least 75 meq / 100 g clay. Particularly cheap types of clays are the naturally occurring wyoining varieties of swellable bentonites and similar clays as well as hectorite, a swellable magnesium-lithium silicate clay.

The clays, particularly the bentonite type clays, are preferred converted to the sodium form if they are not already in that form. This can be conveniently achieved by preparing an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form. Alternatively, the clay can be mixed with water and a soluble sodium compound, such as sodium carbonate, Sodium hydroxide and the like, are mixed, followed by shearing on the mixture with a drum mill (pugmill) or an extruder or a Extruder.

Smectite-type clays occur naturally or can be synthetic can be produced, either by pneumatolytic or hydrothermal synthesis methods. Examples of such clays are montmorillonite, bentonite, beidellite, hectorite, saponite and stevensite. The cation exchange capacity of the smectite-type clays can be according to the known ammonium acetate method can be determined.

The organophilic clays according to the invention can be prepared by mixing the clay, organic cation, organic anion and water with each other, preferably at a temperature in the range from 20 to 100 ° C, particularly preferably 35 to 77 ° C, for a sufficient period of time to store the organic cation and organic anion complex with the clay parts, followed of filtering, washing, drying and grinding.

not find compositions of the invention discussed above Widely used as rheological additives in non-aqueous, fluid systems or liquid systems in general. ü The non-aqueous, fluid compositions, in which the self-activating organophilic clays are useful include paints, Varnishes, enamels, waxes, epoxy compounds (epoxies), putties or sealants, adhesives, Cosmetics, printing inks, polyester laminating resins and polyester gel coatings and the like. These fluids can be prepared by any known method, such as, for example, according to US Pat. No. 4,208,218, including colloid mills, roller mills, Ball mills and high speed dispersers in which the pigment materials in the organic vehicle due to the high shear force used in processing be well dispersed.

The gelling organophilic clay is used in such compositions used in amounts sufficient to achieve the desired rheological properties to achieve, such as a high viscosity at low shear rates, the control or Control of sagging of fluid films and prevention of settling and hard-clumping pigments contained in the non-aqueous, fluid compositions available. The amounts of gel-forming, organophilic clay present in the non-aqueous Fluid systems used should preferably be from about 0.1 to about 15% by weight based on the weight of the non-aqueous fluid system being treated, and preferably about 0.3 to 5.0% to give the desired rheological effects.

The following examples serve to explain the invention, without to restrict them. All percentages in the present description relate to unless otherwise stated, by weight.

A simple, functional test has been developed to identify the improved Dispersion characteristics of the organophilic clays used according to the invention wld be illustrated in the following examples, to show and to the potential achievable results when using the compositions according to the invention illustrate. This test is referred to as the "Solvent Compatibility Test". The solvent compatibility test is carried out taking a sample of organophilic clay, which is sieved in 10 ml of various solvents that are contained in separate measuring cylinders of 10 ml. The organophilic clay is in added to such an extent that the particles are evenly wetted and clumping cannot occur. The samples are being equilibrated left after all of the organophilic clay has been added (about 30 minutes). That The volume occupied by the orzJrllophilic clay is then divided into n tenths Milliliters recorded; this number is referred to as the "swell volume".

The mixture is mixed 50 times, i.e. 10 times horizontally and 40 times vertically, shaken vigorously and left to stand overnight.

The volume occupied by the organophilic clay is again in tenth of a milliliter recorded; this value is referred to as the "settling volume".

The swelling volume gives an indication of the tolerance of the organic portion of the organophilic clay unit; the solvents investigated; the settling volume gives an indication of the easy dispersibility of the cr-nou phile Clays in this solvent under low shear conditions.

Since for the rate of the fl'insiebensbzw. Letting in the organo clay in the solvent and the force with which. the sample is shaken, variations can occur, the numerical values are not absolute. Slight differences in volumes are not considered significant as the values are for comparison purposes only should.

The gel-forming, organophilic clays according to the invention, which are used in the Examples used were prepared by the following procedure, unless otherwise stated.

A D% clay slurry (sodium form of Wyoming bentonite) was made and the slurry is heated to 60.degree. C. with stirring. The organic anion was added to the clay slurry and reacted for about 10 minutes, followed by the Addition of the organic cation. The amounts of organic materials are in the Tables given and as milliequivalents of the organic cation and organic Anions per 100 g of clay on a 100% active clay basis.

The mixture was then agitated for a sufficient period of time Period of time implemented to complete the reaction (generally 10 to 60 minutes). Of the Organoclay was collected on a vacuum filter. The filter cake was filled with hot Washed (40 to 800C) water and dried at 600C. The dried organ clay was milled using a hammer mill or similar milling device to reduce the particle size and then through a sieve with a clear mesh size sieved from 0.074 mm (200 mesh).

Example 1 Allylmethyl-di- (hydrogenated tallow) -ammonium chloride (abbreviated as Am2HT).

824.7 g methyl di (hydrogenated tallow) amine, about 350 ml isopropyl alcohol, 250 = g NaHCOD, 191.3 g allyl chloride and 10 g allyl bromide (as a catalyst) were in a 4 1 reaction vessel equipped with a condenser and a mechanical stirrer, brought in. The mixture was heated and gently refluxed. Periodically Samples were filtered away and titrated with standardized HCl and NaOH.

The reaction was considered complete when 0.09o 'amine HCl and 1.8% amine was present. The final analysis showed an effective gram molecular weight of 831.17.

EXAMPLE 1 e 2 to 4 A 30% clay slurry of the sodium form of Wyoming bentonite in Examples 2 and 3 and hectorite in Example 4 heated to 60 ° C. with stirring. A solution of organic, cationic compound, Ethanol methyl di (hydrogenated tallow) ammonium chloride [Em2HT] for example 2 and AM2HT prepared in Example 1 for Examples 3 and 4 were added to the Added clay slurry and stirred for 20 minutes. The organoclay was on a vacuum filter collected. The filter cake was washed with 600C water and dried at 600C. The dried organoclay was ground using a hammer mill for Reduce the particle size and then pass through a sieve with a clear Mesh size of 0.074 mm (200 mesh) sieved.

B e i s p i e 1 e 5 to 24 These examples show the production of organophilic clays-according to the invention-using various organic Anions and of allylmethyl di (hydrogenated tallow) ammonium chloride (AM2HT) as an organic Cation. A common organophilic clay using AM2TIT as organi, clles Cation is used as a comparative experiment. The compositions are in the table I and the solvent compatibility results are shown in Table I (a).

The data demonstrate the superior dispersion characteristics of the present invention organophilic clays versus organophilic clays made in the absence of the organic anion.

The abbreviations listed below are used in the following tables used: MÄV = milliequivalent ratio QuV = swelling volume AV = settling volume.

Table 1 Bei- Organic Anion (Salt) Organic Organic.

game an cation no. ion MÄV MÄV 5 Na benzoate 15 115 6 same as above 22.5 122.5 7 ditto 30 130 8 ditto 10 110 9 ditto 22.5 130 1Ö Na-p-phenolsulfonate 15 115 11 ditto 30 130 12 ditto 22.5 122.5 13 ditto 10 110 14 Na salicylate 30 130 15 ditto 22.5 122.5 16 ditto 15 115 17 sodium dioctadecyl phosphite 22.5 122.5 18 benzoic acid 22.5 122.5 19 disodium phthalate 22.5 122.5 20 sodium octoate 22.5 122.5 21 sodium stearate 22.5 122.5 22 Na laurate 22.5 122.5 23 Na 12 hydroxystearate 22.5 122.5 24 Na3 citrate 22.5 122.5 Comparison none - 114 Table I (a) Solvent Compatibility Solvent e.g. toluene methyl isobutyl ketone 60/40 diisodecyl phthalate / toluene heptane No. QuV AV QuV AV QuV AV QuV AV 5 10 100 12 19 10 8 18 27 6 10 100 11 18 8 10 28 33 7 15 100 11 17 8 8 28 42 8 8 76 10 20 7 8 10 12 9 8 80 14 20 10 10 30 44 10 12 78 13 16 11 14 14 18 11 12 48 12 18 8 10 22 68 12 8 100 12 14 10 12 27 32 13 12 68 13 17 10 11 9 12 14 16 100 14 19 10 14 26 34 15 11 100 12 18 9 10 23 29 16 12 100 12 17 9 9 16 22 17 7 100 12 16 10 5 20 26 18 8 32 13 17 7 8 22 70 19 10 100 14 18 9 8 20 52 20 12 36 14 20 7 8 32 57 21 11 100 13 19 8 11 58 44 22 12 100 13 17 8 9 32 37 23 14 100 12 18 10 10 37 44 24 10 100 12 20 10 11 34 52 cf. 15 88 13 16 16 20 7 11 E i e 1 e 25 to 45 These examples show dic production of organophi ion clays according to the invention using various of organic anions and of diallyl di (hydrogenated tallow) ammonium chloride as (2A2HT) organic cation. A common organophilic clay using 2A2HT as organic cation is used as a comparative experiment. The compositions are in Table II and the solvent compatibility results in Table II (a). The data demonstrate the substantially superior dispersion characteristics of the present invention organophilic clays versus organophilic clays made in the absence of the organic anion.

Table II Example organic anion (salt) Organ.An- Organ.Kat-No. ion MÄV ion MÄV 25 Na salicylate 22.5 129.4 26 Na naphthalene-1-carboxylate 22.5 129.4 27 Na p-toluate 22.5 122.5 28 Na borate 22.5 122.5 29 Disodium phthalate 22.5 122.5 30 Na benzoate 22.5 129.4 31 Na ferricyanide 22.5 122.5 32 Na tetraphenylborate, 22.5 122.5 33 Na-1-butanesulfonate 22.5 122.5 34 Na-p-toluenesulfonate 22.5 122.5 35 Na-benzenesulfonate 22.5 122.5 36 Na-benzene-1,3-sulfonate 22.5 122.5 37 p-phenol sulfonate 22.5 122.5 38 Na 12 hydroxystearate 22.5 122.5 39 Na oleate 22.5 122.5 40 Na stearate 22.5 122.5 41 Na laurate 22.5 122.5 42 Na octoate 22.5 122.5 43 Na 2-ethylhexanoate 22.5 122.5 44 sodium hexanoate 22.5 122.5 45 sodium dodecylbenzenesulfonate 22.5 122.5 cf. none none 110 Table II (a) Solvent Compatibility Solvent Ex. Toluene methyl isobutyl ketone 60/40 diisodecyl phthalate / toluene lacquer solvent no. QuV AV QuV AV QuV AV QuV AV 25 34 18 12 26 26 14 37 12 16 13 13 14 80 27 13 28 12 16 10 12 14 23 28 10 57 11 17 11 10 16 100 29 15 37 12 18 12 11 16 22 30 54 18 13 87 31 9 53 11 16 10 13 18 33 32 10 5 11 14 9 10-33 12 73 10 12 10 12 15 88 34 13 18 11 14 11 12 14 82 35 12 16 12 14 10 12 16 88 36 14 38 12 15 12 13 14 22 37 14 45 12 11 12 12 14 80 38 14 46 12 14 10 14 16 84 39 16 30 12 18 12 12 14 78 40 14 100 18 32 16 90 18 94 41 14 32 12 18 10 10 16 80 42 14 52 12 20 12 14 16 100 43 14 64 10 16 10 12 15 80 44 10 54 12 20 10 14 17 82 45 12 12 12 13 9 10 12 50 cf. 14 33 12 14 12 15 16 22 Ex. 1 e 46 to 58 These examples illustrate the preparation of organophilic clays according to the invention using various organic anions and ethanol dimethyl hydrogenated tallow ammonium chloride (e2MHT) as an organic cation. A common organophilic clay using E2MHT as the organic cation is used as a comparative experiment. The compositions are given in Table III and the solvent compatibility results in Table III (a).

The data show the considerably superior dispersion characteristics of the organophilic clays according to the invention in comparison with organophilic clays without organic anion.

Table III Example Organ.An- Organ.Kat-No. Orean anion (salt) ion MÄV ion MÄV 46 Na benzoate 22.5 114 47 ditto 30 130 48 ditto 22.5 122.5 49 Na phenolate 22.5 122.5 50 Na tetraphenylborate 22.5 122.5 51 Na ferrocyanide 22.5 122.5 52 Na fluorescein derivative 22.5 122.5 53 rose benzal 22.5 122.5 54 disodium phthalate 22.5 122.5 55 sodium laurate 22.5 122.5 56 Na octoate 22.5 122.5 57 Na stearate 22.5 122.5 58 Na abietate 22.5 122.5 Compare none none 108.1 Table III (a) Ex. Toluene methyl isobutyl ketone 60/40 diisodecyl phthalate / toluene heptane No. QuV AV QuV AV QuV AV QuV AV 46 13 18 18 24 10 12 16 18 47 20 46 19 29 14 16 20 32 48 14 22 20 26 14 14 16 24 49 18 28 28 26 14 15 20 28 50 12 22 28 30 13 15 20 28 51 14 26 22 38 9 10 17 26 52 16 30 19 28 10 13 21 30 53 16 26 21 27 11 12 22 28 54 18 36 22 30 18 21-55 16 33 18 26 14 18-56 17 30 22 28 14 18-57 17 24 12 16 10 12-58 17 30 23 32 12 12-comp. 6 8 17 19 8 10 12 14 EXAMPLE 59 to 72 These examples illustrate the preparation of organophilic clays according to the invention using various organic anions and various quaternary ammonium chlorides as organic Cation. A common organophilic clay and dispatch of ethanolmethyl-di- (hydrogenated tallow) as the organic cation is used as a comparative experiment. The compositions are given in Table IV; the solvent compatibility results in table IV (a). The data show the essential superiority in the dispersion characteristics of the organophilic clays according to the invention in comparison with organophilic clays without organic anion. Table IV Ex. Organic Cation Organic Anion organ. Organ.

No. Cation Anion MÄV MÄV 59 Allyl-dimethyl-hydrogenated tallow Na2-phthalate 122.5 22.5 60 ditto Na octoate 122.5 22.5 61 ditto Na laurate 122.5 22.5 62 ditto Na stearate 122.5 22.5 63 same as Na abietate 122.5 22.5 64 Ethanol methyl di (hydrogenated tallow) Na benzoate 130 30 65 ditto Na 9,10 epoxystearate 122.5 22.5 66 ditto Na dioctadecyl phosphite 122.5 22.5 67 ditto Na oleate 122.5 22.5 68 diallyl methyloctadecyl Na 2 phthalate 122.5 22.5 69 Triallyl hydrogenated tallow Na2 phthalate 122.5 22.5 70 Triallyl hydrogenated tallow ditto 122.5 22.5 71 ditto Na benzoate 122.5 22.5 72 ditto ditto 115 15 cf.ethanolmethyl-di- (hydrogenated tallow) none 108.2 - Table IV (a) Solvent Compatibility Solvent e.g. toluene methyl isobutyl ketone 60/40 diisodecyl phthalate / toluene heptane No. QuV AV QuV AV QuV AV QuV AV 59 15 46 14 21 14 13 13 20 60 20 80 16 32 18 10 24 100 61 16 78 18 42 16 10 24 100 62 18 78 24 38 17 10 24 100 63 19 78 14 40 16 10 24 100 64 8 72 10 12 9 8 10 12 65 18 50 12 18 14 14-66 12 84 14 81 18 18-67 14 20 16 26 12 16-68 13 51 28 94 22 42 25 51 69 16 31 14 20 14 15 12 17 70 12 22 12 22 11 13 14 20 71 12 25 13 26 12 14 14 26 72 11 15 16 20 11 12 13 16 Comp. 12 18 12 14 11 14 12 16 E xample 1 e 73 to 79 These examples show the preparation of organophilic clays according to the invention using various organic anions and diethanol methyl hydrogenated tallow ammonium chloride (2EMHT) as an organic cation. A common organophilic clay using 2K'IHT as the organic cation is used as a comparative experiment. The compositions are given in Table V; the solvent compatibility results in table V (a). The data demonstrate the significantly superior dispersion characteristics of the organophilic clays according to the invention in comparison with organophilic clays without organic anion.

Table V Ex. Organ. To organ. Cat no. Organic anion (salt) ion MÄV ion MÄV 13 Na benzoate 15 115 7 same as above 15 122.5 75 Na2 phthalate 22.5 122.5 76 Na octoate 22.5 122.5 77 Na laurate 22.5 122.5 78 Na stearate 22.5 122.5 79 Na abietate 22.5 122.5 Comp. None none 111.7 Table V (a) Solvent Compatibility Solvent e.g. toluene methyl isobutyl ketone 60/40 diisodecyl phthalate / toluene n-butyl acetate No. QuV AV QuV AV QuV AV QuV AV 73 8 10 22 26 8 9 16 20 74 9 14 15 35 10 12 16 24 75 10 12 18 20 10 10 16 17 76 10 14 18 26 8 10-77 9 12 18 26 8 9-78 3 3 12 12 4 4-79 5 5 27 32 2 2-comp. 4 4 19 22 5 8 14 17

Claims (18)

Claims 1. Gel-forming, organophilic clay containing the reaction product of (a) an organic cation salt compound, wherein the organic cation has the following formula: wherein R1 is selected from the group of a p, 7-unsaturated alkyl group and a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 12 to 60 carbon atoms; R3 and R4 are individually selected from the group consisting of a p-unsaturated alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group, an alkyl group having 1 to 22 carbon atoms, and mixtures thereof; X is selected from the group consisting of phosphorus and nitrogen; (b) an organic anion; and (c) a smectite-type clay having a cationic content of at least 75 mfiquiv./100 g of the clay; such that an organic cation-organic anion complex is intercalated with the smectite-type clay and that the cation exchange sites of the smectite-type clay are substituted with the organic cation. 2. Gel-forming agent according to claim Is in which the ß, γ-unsaturated Alkyl group is selected from a group of cyclic groups, acyclic Alkyl groups with less than 7 carbon atoms, acyclic alkyl groups, substituted with aromatic groups, and aromatic groups substituted with aliphatic Groups. 3. A gel-forming agent according to claim 1, in which the hydroxyalkyl group is selected from a group of cyclic groups and aliphatic groups with 2 to 6 carbon atoms, with the hydroxyl substitution at C2 to C6. 4. The gel-forming agent of claim 1, wherein R2 has 12 to 22 carbon atoms having. 5. The gel-forming agent of claim 4, wherein R2 is a long chain Fatty acid group. 6. Gelling agent according to claim 1, in which the organic anion is derived from an organic acid with a PKA less than about 11.0. 7. The gelling agent according to claim 1, wherein the clay is of the smectite type is selected from the group of hectorite and sodium bentonite. 8. The gelling agent of claim 1, in which the amount of the organic Cation is 5 to 100 meq / 100 g of the clay, 100% active clay base. 9. gel forming agent according to claim 1, in which the amount of the organic Cation is sufficient to the cation exchange capacity of the smectite-type clay and to satisfy the cationic exchange capacity of the inorganic anion. 10. Gelling agent according to claim 1, in which the amount of the organic Cation is 80 to 200 meq / 100 g clay, 10Q active clay base. The gelling agent of claim 1, wherein the amount of the organic Cation is 100 to 160 meq / 100 g clay, 100% active clay base. 12. A method of making a gel-forming organophilic clay characterized in that: (a) forming an aqueous slurry of smectite-type clay, the clay ranging from about 1 to about 80 percent by weight of the slurry; (b) heating the slurry to a temperature of 20 to 1000C; (c) about 5 to 100 meq. an organic anion / 100 g clay, 100 active clay base, and adding an organic cationic compound, wherein the organic cation has the following formula wherein R1 is selected from the group consisting of a β, γ-unsaturated alkyl group and a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof; R2 is a long chain alkyl group having 12 to 60 carbon atoms; R3 and R are individually selected from the group consisting of a B -, - unsaturated alkyl group, a hydroxyalkyl group with 2 to 6 carbon atoms, an aralkyl group, an alkyl group with 1 to 22 carbon atoms and mixtures thereof; X is selected from the group consisting of phosphorus and nitrogen; wherein the organic cation compound is used in an amount sufficient to satisfy the cation exchange ability of the smectite type clay and the cationic activity of the organic anion while the reaction solution is being stirred; (d) reacting the mixture for a sufficient time to form the reaction product which comprises an organic cation-organic anion complex intercalated with the smectite-type clay and wherein the cation exchange sites of the smectite-type clay are substituted with the organic cation; and (e) recovering the reaction product. 13. The method according to claim 12, characterized in that the organic cation selects from the group of quaternary ammonium salts, phosphonium salts and sulfonium salts containing at least one linear or branched alkyl group Contain 8 to 22 carbon atoms. 14. The method according to claim 12 or composition, characterized in that that the organic anion is from an organic acid with a pKA of less than about 11.0-stems. Method according to claim 12 or composition, characterized in that that the tone of the SmeIcti-b-yp is chosen from the group of uectorite and sodium bentonite. 16. The method according to claim 12 or composition, characterized in that that the amount of the organic anion is 10 to 50 meq / 100 g of the clay, 100% active Tone base, amounts to. 17. The method according to claim 12 or composition, characterized in that that the amount of the organic cation compound is 80 to 200 meq. / 100 g of clay, 100% active tone base, concerned. 18. The method according to claim 12, characterized in that-the organic Anion is added to the smectite-type clay prior to adding the organic cation compound. -19. Method according to claim 12, characterized in that the organic Anion and the organic cation compound to the smectite-type clay in the form an organic cation-organic anion complex is added.