FI74887B - ORGANIC FILM REQUIREMENTS FOR THE FRAMEWORK OF FRAMSTAELLNING AV DETTA. - Google Patents

Description

1 74887

This invention relates to organophilic organic clay complexes which are dispersible in and form a gel in organic liquids. Depending on the composition of the gel, such gels can be used as lubricating greases, oil-based sludges, oil-based sealants, paint and alkyd varnish and cellulose varnish removers, paints, binders in foundry molding sand, adhesives and sealants, printing inks, printing inks, polyester like.

It is well known that those organophilic compounds which contain a cation react under preferred conditions with ion exchange with those clays which contain a negative layer lattice and which contain variable cations to form organophilic organic products. If the organic cation contains at least one alkyl group containing at least 10 carbon atoms, then such organic clays have a swelling property in certain organic liquids. See, for example, U.S. Patent Nos. 2,531,427 and 2,996,506, which are incorporated herein by reference, and Clay Mineralogy, Second Edition, 1968 by Ralph E. Grim (McGraw-Hill 25 Book Company, Inc.), specifically Chapter 10, Clay-Mineral Complexes.

It is also known that organic compounds in anionic form usually reject rather than attract a negatively charged clay surface. This effect is referred to as negative adsorption. However, positive adsorption of anions can occur under conditions where such compounds are present in molecular form, i.e., in undissociated form. See "Chemistry of Clay-Organic Reactions" 1974, 35 by B.K.G. Theng, Jonn Wiley & Sons.

In contrast to the above, Wada found that this phenomenon 2 74887, i.e., adsorption, occurs with certain ionic compounds when they react with halloucites, which are substances of the Kaolinite group, to form interlayers. Intermediate deposition was activated by grinding the mineral with wet crystals of salts of low molecular weight carboxylic acids or by combining the mineral with saturated solutions. This interlayer complex contained pure salt as well as water. The interlayer was removed by washing with water, which caused either the hydration of the interlayer or its shrinkage to its original size. No evidence of a change in baseline size was observed when treating montmorillonite with salts in contrast to the hallozite account. See The American Minerolo-gist, Volume 44, 1959, by K.Wada, "Oriented 15 Penetration of Ionic Compounds between the Silicate Layers of Halloysite".

Since the commercial introduction of organic clays in the early 1950s, it has become well known that the greatest efficiency of gel formation (thickening) from these 20 organo clays is obtained by adding a low molecular weight polar organic substance to the composition. Such polar organic materials have alternatively been referred to as dispersants, dispersants, solvents, dispersants, and the like. See, for example, U.S. Patent Publications: 0'Hallora 2,677,661? McCarthy et al. 2,704,276; Stratton 2 833 720? Stratton 2,879,229; Stansfield et al. 3,294,683. The use of such dispersing aids was found to be unnecessary with the use of specially designed organophilic clays derived from substituted quaternary ammonium compounds. See U.S. Patent Publications: Finlayson et al. 4,105,578 and Finlayson et al. 4,208,218.

It has now surprisingly been found that, unlike previous organic clay compositions, a self-Akti-35-enabling Theological Agent is formed which does not require the addition of such polar solvent activators when this agent

It 3 74887 is prepared by the reaction of an organic cation, an organic anion and a smectite-type clay.

The invention thus relates to an organophilic clay gel former with unexpectedly increased dispersibility in an anhydrous system and which is the reaction product of the following components: a) a smectite-type clay with a cation exchange capacity of at least 75 milliequivalents per 100 g of clay; an organic anion of 5 to 100 milliequivalents of valence per 100 g of smectite-type clay, calculated on the basis of 100% active clay, and c) an organic cation of the formula R "t" 15 j 1 R4 * - R2 R3 20 wherein R1 is βι A β-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 aliphatic diatoms, or a mixture thereof, R 2 is a long-chain alkyl group having 12 to 60 carbon atoms, R 1 and R 2 ^ each independently represents an O, unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 30 to 6 carbon atoms, an aralkyl group having an alkyl moiety sa is 1 to 22 carbon atoms, an alkyl group having 1 to 22 carbon atoms, or a mixture thereof, and X is phosphorus or nitrogen, 74887 which organic cation is present in an amount sufficient to at least satisfy the cation exchange capacity of the smectite-type clay and the cation of the organic anion. the cation-5 exchange sites of the smectite-type clay are substituted by an organic cation and the complex formed by the organic cation and the organic anion is interlayed with the smectite-type clay, preferably 80 to 200 milliequivalents of organic cation per 100 g of clay, based on 100% active clay by.

The organophilic clays of the invention can be prepared by mixing an organic anion with clay and water at a temperature of 20 to 100 ° C, preferably 35 to 77 ° C, long enough to produce a homogeneous mixture followed by adding an organic cation sufficiently to satisfy the cation's cation exchange capacity and organic cation capacity. The order in which the organic cation and anion are added is irrelevant as long as a sufficient amount of organic cation is added. In fact, suitable amounts of the organic cation and the sodium salt of the organic anion in solution (water and / or 2-propanol) can be premixed on a 20-90% suspension base to form a complex of the organic cation and the organic anion and then added as a solution to react with the clay slurry. After the addition of the organic anion and the organic cation, the mixture is allowed to react with simultaneous stirring at a temperature of 20 to 100 °, preferably 35 to 77 ° C, long enough to form a complex of the organic cation and the organic anion interlayer with the clay, and the clay cation exchange sites are substituted with organic. cation. Reaction temperatures below 20 ° C and above 100 ° C are not recommended, although they are useful.

The addition of the organic cation and the organic anion can be done either separately or in a complex. By using organophilic clays in emulsions, the drying and grinding steps can be eliminated. When clay, organic cation and water are mixed in concentrations such that

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5 74887 no sludge is formed, the filtration and washing steps can be eliminated.

The clay is dispersed in water at a concentration of about 1 to 80%, preferably 2 to 7%, to form a clay slurry.

The aqueous clay may optionally be centrifuged to remove non-clay contaminants at a concentration of about 10 to 50% in the starting clay composition. The slurry is usually preheated with simultaneous stirring to a temperature in the range of 35 to 77 ° C before the addition of organic starting materials.

For the purposes of this invention, the amount of organic anion added to the clay should be sufficient to provide the organophilic clay with the desired altered dispersion properties. This amount is defined as the milliequivalence ratio -15, which is the number of milliequivalents (M.E.) of organic anion per 100 g of clay, calculated on the basis of 100% active clay. The organophilic clays of this invention should preferably have an anion-milliequivalence ratio of 5 to 100, most preferably 20 to 50.

The organic anion is preferably added to the starting materials in the desired milliequivalent ratio as a solid or aqueous solution while stirring to obtain a homogeneous mixture.

The organic cation should be used in an amount sufficient to at least satisfy the cation exchange capacity of the clay and the cationic activity of the organic anion. Optionally, an additional cation greater than the sum of the clay and anion exchange capacities may be used. It has been found that an amount of organic cation of at least 90 milliequivalents is sufficient to satisfy a portion of the total organic cation requirement. Amounts of 80 to 200 M.E. and preferably in amounts of 100 to 160 M.E. use.

For convenience of handling, it is recommended that the total organic matter content of the organophilic clay reaction products of this invention be less than 50% by weight of the organic clay. Larger amounts are useful, but the reaction product is difficult to handle.

6 74887

Another process for preparing the organophilic clays of this invention involves: a) impregnating a smectite-type clay with 1 to 80% by weight of said clay, 5 b) heating the slurry to 20-100 ° C, c) adding an organic anion in an amount of 5-100 milliequivalents per 100 g of clay, based on 100% active clay, and adding the organic cation sufficiently to satisfy the cation exchange capacity of the smectite-type clay and the cationic activity of the organic anion while stirring the reaction mixture, d) reacting the mixture long enough to form an organic solvent; a complex of a cation and an organic anion interlayer with the smectite-type clay, and the cation exchange sites of the smectite-type clay are substituted with the organic cation, and e) recovering the reaction product.

The organic cationic compound useful in the process of this invention can be selected from a wide variety of substances that can form organophilic clay by exchanging cations with a smectite-type clay. The organic cationic compound should have a positive charge localized to a single atom or a small group of atoms in the compound.

The β, γ "'- unsaturated alkyl group in the organic cation can be selected from a wide variety of materials. These compounds can be cyclic or acyclic, unsubstituted or substituted. These β, β-unsaturated alkyl groups contain less than 7 aliphatic carbon atoms. substituted β, β-unsaturated alkyl groups preferably contain less than 4 aliphatic carbons.

The β, β-unsaturated alkyl group may be substituted with an aromatic ring similarly conjugated to the β, β-unsaturation, or the β, β-unsaturated alkyl group may be substituted with both an aliphatic group and an aromatic ring.

Il 7 74887

Typical cyclic β, γ-unsaturated alkyl groups include, for example, 2-cyclohexenyl and 2-cyclopentenyl. Typical examples of N, N-unsaturated alkyl groups having 6 or less carbon atoms include 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, 1,2-dimethylpropenyl, 2,4-pentadienyl and 2,4-hexadienyl. Typical acyclic-10 aromatically substituted compounds include 3-phenyl-2-propenyl, 2-phenyl-2-propenyl and 3- (4-methoxyphenyl) -2-propenyl. Typical examples of aromatically and aliphatically substituted substances are 3-phenyl-2-cyclohexenyl, 3-phenyl-2-cyclopentenyl; The alkyl group may be substituted on an aromatic ring.

The hydroxyalkyl group is selected from a hydroxide-substituted aliphatic group in which the hydroxyl is not substituted on the carbon adjacent to the positively charged atom, and the group has 2 to 6 aliphatic carbons.

The alkyl group may be substituted with an aromatic ring. Examples include 2-hydroxyethyl, 3-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.

Alkyl groups as R e may be branched or unbranched, saturated or unsaturated, substituted or unsubstituted, and should have 12 to 60 carbon atoms in the straight chain portion of the group.

35 Long chain alkyl groups can be derived from naturally occurring oils, including various vegetable oils such as corn, coconut, soybean, cottonseed, castor oil and the like, as well as various animal oils or fats such as tallow oil. Alkyl groups may be petrochemically derived, such as those derived from alpha-olefins.

Typical examples of useful branched saturated alkyl groups include 12-methyl-5-stearyl and 12-ethylstearyl. Typical examples of useful unsaturated branched groups are 12-methyloleyl and 12-ethyloleyl. Typical examples of unbranched saturated groups include lauryl, stearyl, tridecyl, myristal (tetradecyl), pentadecyl, hexadecyl, hydrogenated tallow and docosonyl. Typical examples of unbranched unsaturated and unsubstituted long chain alkyl groups are oleyl, linoleyl, linolenyl, soy and tallow.

The remaining groups attached to the positively electrically charged atom, i.e., the groups and R 1, are selected from the group consisting of: a) β, β-unsaturated alkyl group, b) a hydroxyalkyl group having 2 to 6 carbon atoms, both as as described above, c) a cyclic or acyclic alkyl group having 1 to 22 carbon atoms, and d) an aralkyl group, i.e. benzyl or a substituted benzyl group, including fused ring systems, having a linear or branched chain of 1 to 22 carbon atoms in the alkyl portion of the aralkyl.

The unsaturated alkyl group of the group R 1 or R 2 may be linear or branched, cyclic or acyclic, substituted or unsubstituted, and contains 1 to 22 carbon atoms.

Typical examples of useful alkyl groups Reiki and Reiki are methyl, ethyl, propyl, 2-propyl, iso-butyl, cyclopentyl and cyclohexyl.

Alkyl groups can be derived from similar starting materials as above for the long chain alkyl groups of R2.

Typical examples of an aralkyl group comprising benzyl and substituted benzyl groups include benzyl, and those derived from, for example, benzyl halides, benzhydryl halides, tri-

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9,74887 of style halides, 1-halo-1-phenylalkanes having 1 to 22 carbon atoms in the alkyl chain, such as 1-halo-1-phenylethane, 1-halo-1-phenylpropane and 1-halo-1-phenyloctadecane, such as substituted benzyl groups which can be derived from orthometha- and para-chlorobenzyl halides, para-methoxybenzyl halides, ortho-, meta- and para-nitrilobenzyl halides, and ortho-, meta- and para-alkylbenzyl halides in which alkyls are 1 to 22 carbon atoms, and fused benz-10-type ring moieties which can be derived from 2-halomethylnaphthalene, 9-halomethylanthracene and 9-halomethylphenanthrene, wherein the halo group is defined as a chlorine, bromine or iodine group, or any such leaving group as a group in the mucleophilic reaction of the benzyl-15 moiety such that the nucleophile replaces the leaving group of the benzyl-like moiety.

The quaternary compound is formed from the above organic cationic compound and an anionic group which may be a mixture of Cl, BrI, NC 2, OH and C 2 H 3 ° 2 3a ηϋ “20 den. Preferably, the anion is selected from the group consisting of chloride and bromide and mixtures thereof, and is most preferably chloride, although other anions such as acetate, hydroxide, nitrite, etc. may be present in the organic cationic compound to neutralize the cation.

Organic cationic salts can be prepared by known methods, as disclosed in U.S. Patent Nos. 2,355,356, 2,775,617 and 3,136,819.

The anion useful in the process of this invention may be selected from a wide variety of substances provided that they are capable of reacting with the organic cation and forming interlayers with smectite-type clay as a complex of the organic cation and the organic anion. The molecular weight (molecular weight) of the organic anion is preferably 3,000 or less, most preferably 1,000 or less, and contains at least one acidic moiety per molecule, as disclosed herein. The organic anion is preferably derived from an organic acid having a pK of less than about 11.0. As shown, the starting acid must have at least 1 ionizable hydrogen with the recommended pK, cl 10 74887 for the cationic organic interlayer reaction to occur.

Also useful are all compounds that provide the required organic anion for hydrolysis. Typical 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 chloride, lauroyl chloride, lauroyl chloride, lauroyl chloride, l-trihalides; including 1,1,1-trichloroethane and 1,1,1-tribromooctane, and 4) orthoesters including ethyl orthoformate and ethyl orthostearate.

Organic anions may be in acid form or in salt form. The salts can be selected from alkali metal salts, alkaline earth metal salts, ammonium and organic amines. Typical salts include: hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, ammonium and organic amines such as ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, butyldiethanolamine, diethylamine, dimethylamine, triethylamine, etc., dibutylamine , and mixtures thereof. The most preferred salt is sodium as the alkali metal salt.

Typical examples of acidic functional organic compounds suitable for this invention include: 1) Carboxylic acids, including: a) benzenecarboxylic acids such as benzoic acid, ortho-, meta- and para-phthalic acid, 1,2,3-benzenetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid), b) alkylcarboxylic acids of formula 35 H- (Cl · ^) n-COOH, where n is an integer from 0 to 20, such

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n 74887 include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, tetradecanoic acid, pentadecanoic acid, pentanic acid nonadecanoic acid, eicosanic acid.

c) alkyl dicarboxylic acids of the formula HOOC- (CH2) n-COOH, where n is 0-8, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azalic acid, azelaic acid, sebacic acid, sebacic acid , such as citric acid, tartaric acid, malic acid, mandelic acid and 12-hydroxystearic acid, e) unsaturated alkylcarboxylic acids such as maleic acid, fumaric acid and cinnamic acid anthric acid, and anhydric acid with an aromatic carboxylic acid such as condensed ring, condensed ring, g) cycloaliphatic acids such as cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, furan carboxylic acids.

2. Organic sulfuric acids comprising: a) sulfonic acids comprising: 1) benzenesulfonic acids such as benzenesulfonic acid, phenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid (butenesulfonic acid), benzenesulfonic acid, para-toluenesulfonic acid, para-toluenesulfonic acid, such as acid, sulfosuccinate alkyl esters such as dioctylsuccinylsulfonic acid, and alkyl polyethoxysuccinylsulfonic acid, b) alkyl sulfates such as the lauryl half ester of sulfuric acid and the octadecyl half ester of sulfuric acid.

12 74887 3. Organophosphoric acids comprising: a) phosphonic acids of formula: 0 RP (OH) 2 (III) 5 wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms: b) phosphinic acids of formula:

O

R2POH (IV) 10 wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms, such as dicyclohexylphosphonic acid, dibutylphosphonic acid, and dilaurylphosphonic acid, c) thiophosphinic acids of formula:

S

R2PSH (V) wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms, such as diisobutyldithiophosphonic acid, dibutyldithiophosphonic acid, dioctadecyldithiophosphonic acid, d) phosphites which are HO of the phosphoric acid diester and -Q - (OR) 2 »wherein R is an alkyl group having 1 to 22 carbon atoms, such as dioctadecyl phosphite, and e) phosphates which are diesters of phosphoric acid having the formula:

O

HO-P- (OR) 2 (VI) wherein R is an alkyl group having 1 to 22 carbon atoms such as dioctadecyl phosphate.

4) Phenols such as phenol, hydroquinone, t-butyl catechol, p-methoxyphenol and naphthols.

30 5) Thioacids of the formula:

S O

II t1 R-C-OH and R-C-SH, (VII) (VIII) wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms, such as thiosalicylic acid, thiobenzoic acid, thio-

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13 74887 Acetic acid, thiolauric acid and thiostearic acid.

6. Amino acids such as naturally occurring amino acids and their derivatives such as 6-aminohexanoic acid, 12-aminododecanoic acid, N-phenylglycine and 3-aminocroton-5 acid.

7) Polymeric acids prepared 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) Miscellaneous acids and salts of acids such as ferrocyanide, ferricyanide, sodium tetraphenylborate, phosphofungic acid, phosphopilic acid or any other anion which forms a dense ionic pair with the organic cation, i.e. any anion which forms a solution insoluble in water with an organic cation.

The clays used in the preparation of the organophilic clay gel formers of the present invention are smectite type-20 clays having a cation exchange capacity of at least 75 milliequivalents per 100 g of clay. Particularly preferred clay types are the naturally occurring Wyoming variants of swellable benthic rivets and resemble clays and hectorite, swellable magnesium lithium silicate clay.

Clays, especially bentonite-type clays, are preferably converted to the sodium form if they are not already in this form. This can be conventionally carried out by preparing an aqueous clay slurry and passing the slurry through a cation exchange resin bed in sodium form. Optionally, the clay may be mixed with water and a soluble sodium compound such as sodium carbonate, sodium hydroxide and the like, after which the mixture is ground in a clay mill or extruder.

Smectite-type clays occur in nature or can be synthetically prepared by either a pneumatolytic or hydrothermal synthesis process. Typical such clays are montmorillonite, bentonite, beidellite, hectorite, saponite and stevensite. The cation exchange capacity of smectite-type clays can be determined by a well-known ammonium acetate method.

The organophilic clays of this invention can be prepared by mixing clay, organic cation, organic anion and water together, preferably at 20-100 ° C, more preferably 35-77 ° C long enough for the organic cation and organic anion complex to interlay with the clay particles. after which it is filtered, washed, dried and ground.

The compositions of the invention described above have a wide range of uses in general as theological additives in anhydrous liquid systems.

Anhydrous liquid compositions in which self-activating organophilic clays are useful include paints, varnishes, enamels, waxes, epoxies, mastics, adhesives, cosmetics, inks, polyester laminating resins and polyester gel coatings, and the like. These liquids can be prepared by any conventional method, as disclosed in U.S. Patent No. 4,208,218, these methods include colloid mills, roller mills, ball mills, and high speed dispersers in which the pigments disperse well in the organic medium by the high shear rates used in processing.

The organophilic clay gelling agent is used in such compositions in an amount sufficient to provide the desired Theological properties such as high viscosity at low shear rates, control of softening of liquid films, and prevention of settling and hard compaction of pigments in anhydrous liquid compositions. The amount of organosilic clay gel formers used in anhydrous liquid systems should preferably be about 0.1-15% based on the weight of the treated anhydrous liquid system and preferably 0.3-5.0% to obtain the desired theological effects.

The following examples are provided to illustrate the invention, but are not intended to limit it. All percentages given in the instructions are by weight unless otherwise indicated.

A simple, suitable test is designed to illustrate the dispersion properties of the organophilic clays used in the present invention and are shown in the following examples to demonstrate the potential results obtained using the compositions of this invention. The test is called the solvent miscibility test. The solvent miscibility test is performed by taking a sample of the organophilic clay and screening the sample into 10 ml of various solvents in separate 10 ml calibrated cylinders. The organophilic clay is added at such a rate that the particles wet evenly and in such a way that no clumping is allowed. The samples are allowed to equilibrate after all the organophilic clay has been added (approximately 30 minutes). The volume taken up by the organophilic clay is then recorded in tenths of milli-25 meters, this figure is called the expansion volume.

The mixture is stirred vigorously 50 times, 10 times horizontally, 40 times vertically and allowed to stand overnight. The volume taken up by the organophilic clay is again recorded as tenths of a milliliter, this value being called the settling volume.

The expansion volume indicates the miscibility of the organic part of the organophilic clay with the solvents studied. The settling volume shows the ease of dispersion of the organophilic clay in this solvent at low shear rates.

ie 74 8 87

The figures are not absolute because the screening rates of the organic clay in the solvent and the intensity of mixing of the sample vary. Small differences in volumes are not considered significant, rather the values are for comparison only.

The organophilic clay gel formers used in the examples were prepared as follows, unless otherwise indicated. 3% clay slurry (sodium form of Wyoming bentonite) was heated with stirring to 60 ° C. The organic anion was added to the clay slurry and allowed to react for about 10 minutes, after which the organic cation was added. The amounts of added organic substances are shown in the tables and are expressed in milliequivalents of organic cation and organic anion per 100 g of clay, per 100% active clay base. The mixture was then allowed to react with simultaneous stirring long enough for the reaction to be complete (usually 10-60 minutes). The organic clay is collected on a vacuum filter. The filter cake is washed with hot (40-80 ° C) water and dried at 60 ° C. The dry organoclay is ground using a hammer mill or similar grinding agent to reduce particle size and then passed through a 200 mesh screen.

Example 1

Allylmethyl dide (hydrogenated tallow) ammonium chloride 25 (abbreviated AM2HT).

824 g of methyldi (hydrogenated) amine, about 350 ml of isopropyl alcohol, 250 g of NaHCO 3, 191.3 g of allyl chloride and 10 g of allyl bromide (as catalyst) were placed in a 4-liter reaction vessel equipped with a condenser and a mechanical stirrer. The mixture was heated and allowed to recover slowly. Samples were periodically removed, filtered and titrated with standardized HCl and NaOH. The reaction was considered complete with 0.0% amine HCl and 1.8% amine. The final analysis showed 35 effective molecular weights of 831.17.

Il 17 74887

Examples 2-4 3% clay slurry, in Examples 2 and 3, the sodium form of Wyoming bentonite and hectorite in Example 4 were heated to 60 ° C with stirring. To the clay slurry was added a solution of the organic cation compound, ethanol-methyl (hydrogenated) ammonium chloride (EM2HT) to Example 2 and AM2HT prepared from Example 1 to Examples 3 and 4, and stirred for 20 minutes. Organoclay was collected on a vacuum filter. The filter cake was washed at 60 ° C with water and dried at 60 ° C. The dried organoclay was ground using a hammer mill to reduce particle size and then screened through a U.S. standard 200-mesh screen.

Examples 5-24 These examples illustrate the preparation of the organophilic clays of this invention using organic anions and allylmethyldi (hydrogenated) ammonium chloride (AM2HT) as the organic cation. As a comparative example, a conventional organophilic clay with AM2HT as an organic cation is shown. The compositions are shown in Table I and the solvent miscibility results in Table I (a). The data show the excellent dispersion properties of the organophilic clays of the invention compared to organophilic clays prepared without an organic anion.

18 74887

Table I

Eg Organic anion (salt) Organic Organic n.:o anion M.E. cations M.E.

_ratio_ratio_ 5 5 Na-benzoate 15 115 6 Na-benzoate 22.5 122.5 7 Na-benzoate 30 130 8 Na-benzoate 10 110 9 Na-benzoate 22.5 130 10 10 Na-p-phenol sulphonate 15 115 11 Na- p-phenol sulphonate 30 130 12 Na-p-phenol sulphonate 22.5 122.5 13 Na-p-phenol sulphanate 10 110 14 Na salicylate 30 130 15 15 Na salicylate 22.5 122.5 16 Na salicylate 15 115 17 Na -dicktadecyl phosphate 22.5 122.5 18 Benzoic acid 22.5 122.5 19 Disinitrate 22.5 122.5 20 20 Na-buttoate 22.5 122.5 21 Na-stearate 22.5 122.5 22 Na- laurate 22.5 122.5 23 Na-12-hydroxystearate 22.5 122.5 24 Na 2 -citrate 22.5 122.5 2 5 Comparative No no 114

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1-3 iT ir 3 t> rl rl rl rl H HHr | rlrlrlr | i- | rlrlHrlrlrlrl H

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Examples 25-45 These examples illustrate the preparation of the organophilic clays of this invention using various organic anions and diallyldide (hydrogenated) ammonium chloride (2A2HT) as the organic cation. Comparative Example 5 shows a conventional organophilic clay using 2A2HT as an organic cation. The compositions are shown in Table II and the solvent mixing results in Table IIa. The data show much better dispersion properties of the organophilic clays of the invention compared to organophilic clays prepared without an organophilic anion.

Il 2i 74887

Table II

Example Organic Antoni (salt). Organic Organic --—--- anion M.E, cation M.E.

ratio ratio_ ^ 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 Dinatriurophthalate 22.5 122.5 30 Na-Benzoate 22.5 129.4 1Q 31 Na-Ferrisyanide 22.5 122.5 32 Na 2 Tetraphenylborate 22.5 122.5 33 Na-1H-butanesulfonate 22.5 122 Na 34 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-Phenolsulfonate 22.5 122, 5 -.e 38 Na-12 * «ydraxin nitrate 22.5 122.5 39 Na-octate 22.5 122.5 40 Na-stearate 22.5 122.5 41 * Na-laurate 22.5 122.5 42 Na-lactate 22.5 122.5 43 Na'-2-ethylhexanoate 22.5 122.5 44 Na-hexanoate 22.5 122.5 45 NarDodkylbenzenesulfonate 22.5 122.5

Comparative no no 110 22 74887 I tn 3 I 3 3 in 3 44 -H> II Fi 111 3 «3rl

-r-4 J + J-rH Λ O PO O IN PO I CetNOOfNO'TOD'rOOOINOtN

_p r * oo γμ o <n oo ro I ooooQOtNooosr-tTvooocoooinrN

o ^ 3 I ----------- • rt ui in ι-H * rt 3 Ό E 3 44 3> X 111 ιβ (rt · Η> Η * * β * oo I ΐΛ ^ ΐί ^ ^ ΐ ^ οοιοιοκιΐ'Ν'ί PJ «-H" '* “-I - - - - - - - - CM 44 II (0> 1 3 13> i 3 n 3 -P 44 - H> me γη cNmpMo - nrocNCMiNmcM'd'rMoo ^ ts ^ roin 3 3 "* ---------------- - - - - - ---- 0 -H PJ 44 -RT

W -P -P

rt -P ..............

1 3 Ή ui * rl | ΌΗ C »Cl ns oi -ri 3

0440) 63 <*) O - Γ4 OfflO - OCS <NOtNVDO (NOOes <S

* r <44 3 3> - - - - - ------------ -

s i h m u O -H 0 -H H

so —i 4J 3 * r: _ CM 44_______

c I 3 O

m -H -H 44 3 3 44 ή 3 3 3 o> 1 3>> rt>, 44 I 3 rt "L JY mr« J eovCVOr ^ aocDVOrtlNrtVi / l - rt'OOfMOOO ^ orort · r! 'H ti ” ”J - - - - - - - - - - - - - - - PO - (N - Γ4 - - 44 j 3 3 -rt -rt 44 X) PJ 6 44

• H O

O 01 ------

44 H I

0) I CO 10 0) · Η · Η 3 1-4 · ι4 f- rt 3> iC3> IN N - N - - O - (Ν <Ν (ΝΓΝΓ400 (Ν (ΝΟ <Ν (Ν (Ν O)) > i OW 3 ^ ----------------

6 44 44 -H -I

• HQ) Q) 3 Ή 44 a 44 CM 44 _________ O Cl 3 l 3 3 -H 3 13 PJ 3 UI> ^ r ^ ooi ^ r-rt'fOinpocovoooinvooooJiNrt'rt'tNro H 44 · Η3 <ΌΡ0Γ4 »ΛΡ0ΐΛΐη r ~ - - ro ^ rTrrooroinvOt / i - ro h -H tn 6> - · <-

3 3 3 -H

O 3 PJ 44 44 44 _______ 44 3 I --- 3 -t M m Ή O Ή 3 3 £ 4 jj> rt · M O 1/1 σΐΟΓΜΓΟΓΜτΤντρνΟτΤΌ'τΤ ^ ΤΟΓΝ'Τ

Eh tn 3

• rt —I

3 'rt __CM -P__

rt I

44 -rt I 44 O invor ^ eeeio - (No. ^ / / Ivor-ooffio - (NrOrt ·! /! ^ • rt 4> ME 3 3 _> Ή 11 23 74887

Examples 46-58 These examples illustrate the preparation of the organophilic clays of this invention using various organic anions and ethanol dimethyl (hydrogenated) ammonium chloride (E2MHT \) as an organic cation. Comparative Example 5 shows a conventional organophilic clay using E2MHT as an organic cation. The compositions are shown in Table III and the results of solvent miscibility in Table III (a) The data describe the significantly better dispersion properties of the organophilic clays of the invention compared to organophilic clays prepared without an organic anion.

24 74 8 87

Table III

Pre- Organic Anion Organic Organic Mark (Salt) Anion Cation 5 No._M.E. ratio M.E. ratio 46 Na-benzoate 22.5 114 47 "30 130 48" 22.5 122.5 49 Na-phenolate 22.5 122.5 10 50 Na-tetraphenylborate 22.5 122.5 51 Na-ferrocyanide 22, 5 122.5 52 Na-fluorescein derivative 22.5 122.5 15 53 Rose benzal 22.5 122.5 54 Disodium phthalate 22.5 122.5 55 Na-laurate 22.5 122.5 56 Na-octate 22, 5 122.5 57 Na stearate 22.5 122.5 20 58 Na abietate 22.5 122.5

Comparative no no 108.1

II

25 7 4 8 8 7 3 m! 3 13 and 44 m 3:

m -h> ^ I

piri coMrrcooovoooo I i i i i »r 'S 5" J r-rlMMMMrOM | | I I | «-

• H i-H 3 iH

β 4-1 -H

3 44 3 I___

4J W

Qi -H tn 0) £ 3

^ 3, β νβΟ> βΟΟΙ ^ «- ΜΙ | | I IM

tn * - M * - M M »—MM I | | I I r- • h m 3

3 · Η H

A E Ή _-M ______ i i tn S *. ri l 3 JP, mii Μ \ Χ> · * ΤιΛνΓ) ΟΙΛΜ · -0000 <ΝΜΟ M 44 · Η> tu m E 3

Ό \ (0 3 rH

0 -H (3 +4 -rl

tn 4J 4J

• rl + 4--

1 3 I

• d * 'd "S3 ο * ί · ^ · <ο · ησ'θ ^ οοττ ^ · θΜα5 iB (11 E 3 O 4J <U 3> J" H 3 tn 13

tn x i h ή tn rH

3 β O -rl o 3 -rt -rl

3 -rltOrH + LAE-P

3> t! --------- 3 p

H 44 3 | IM

H + j -H -H 3 13 H -H 1-4 rH 3 M 3 O> i 4 ^ 'd ^ »α, νονοοοοαοΓ-ονοοο'ΛΜσι O 44> i Mp3 MMMMfinMMmMMr-mr- 44 3 44 3 3 Ή 44 M 3 i3 44 -rl 3 Λ 44 rH β O --—----

3 3 M

3 E -Hl

E-H -H I M M

+4 Ή "d 3 OOeiOOOOOINPlr- ΜΟΟΜΜΡΟΓ- 44 H -H E 3 * - * - Mr-r-M * - MM -— M * - Mr- O> h β 3> 3>, 0313

• H + J +4 -H M rH

μ) 3 3 3 -H -H

JS 44 A E 44___

M

I 3 OOvOMPMVOOVDVOmorrOOO

rj 13 »- ^ (ΝΜΜΜΠΜΠΓΟΠΜΓΟ 3 M> 44 -H 3

• H M E rH

β 3 3 -H

3 41 44 44 3 ______— ·

3 M

Ή 3 mo ^ ooM ^ vovocovor-r-r — vo O | 3 · - m · - · ——> - · - r -'— · - ^ 3> 3 M I 3> H M rH Q) 3 Ή * H; 1

A E 44 -H

—------ 3 η

• H 4J

440, βΡ'Οοσ, Ο’-ΜΓΗνιηνοΓ’ΟΟίι I 44 ·· ^^^^ ιηΐΛίπιπιπιπίΛίΛιπΟ • H Jh β> M 3 w e 26 7 4 8 8 7

Examples 59-72 These examples illustrate the preparation of the organophilic sayi of this invention using various organic anions and various quaternary ammonium chlorides as the organic cation. As a comparative example 5, a conventional organophilic clay using ethanolmethyldide (hydrogenated) is used as an organic cation. The compositions are shown in Table IV and the solvent miscibility results in Table IV (a). The data describe the much better dis-1Q transition properties of the organophilic clays of the invention compared to organophilic clays prepared without an organic anion.

Il e 27 74887

G <D

0) T3 c x;

• H G

G -H (fl G G iDLOLDinio m m m m m m in

GO * * · * * - * * · -H

CT> -HMfSrs | (N (NCNOCN (N <NCN (N <NCNLn <D

S-LC »(NfNirsj (NCN | f o (N (N (NTN (N <N <N> -I

o g g

G tU

(I) x3

G -C

-H -H G

GCcnminininin m in m m m in m <n GO '*** «^ ^ ^ ^ ^ *> (Ö-H * CNCN (NCNCNO (NCN (N (N <NCNlCNin 00

CJi-PWCNCNCNCNCNrOCNCNCNCNCNCNCNi — I O

P G · rHI rH t — li — I I — It — I I — It — It — It — It — It — It — It — I t — I

0 44 g

P

• H -P -P -H -P -P

id m id w • h ρ o c (dm

0 -P -H

• Η Ή CO f — I Ή -H

G -Ρ -Η -Η -P -H ip -p -rH -H .p -P

(0 + J -Ρ -Ρ -Ρ -Ρ -P W> i + J-P-P-P-P

+ J-P-P-P-P G 44 44 · Η -Ρ -Ρ -P (d rd G g-P-PGGGOO-pggggg

0) GGGGGOOiO-PGGGOO

G t-i (d (dP-Pcn <i) rd (dt — it — irHwcn

• P GOPGCD-PI-PGGGG-P-P

G H -> - PG (1) -HGO>; (l) 4J-P-PGG -h rd m ^ id-PjacutHOHmmmcucD o)

rd I Ο Ή w G, Q ^ · Ρ O I I I Λ XX

tn (n I I I I I <n Ό I cscncnii p rd <d (d (d rd rd I I rd rd rd rd rd rd

> O ZZZZZZGGZZZZZ

H 2 2 -

•B

O 1-1 ^ · Η · Η · Η · Η · Η -— * · - '-—- -—' rd

^ I — I t — 1 t — 1 t — 1 rH -Η · Η · Η Ή -P

G G G G G G »—1 r — l I — I I — I

rH -P-P-P-P-PGidrdid G

G -P -P -P -P -Η -P

G YYYYMM Η -P

Eh -pPPP-PGGGG> · id -PPPPPPPPPP> · -Ρ -Ρ -Ρ -Ρ p GGGGG-PPP-P44i — It-Hi — It — I T3 • H PPPPPGGGGOGrdGrd ip G OOTJOOPPPPO-PPPP Si o> i> i> i> i> raOra, devil w

• H ÄJ345x: x:> i> i>,> i-PGGGG -H

• P I I I I I, G.G, CjC44-P-P-P-P Ό

G -Η -Η · Η · Η Ή 'Ο -Ρ H-> -Ρ -P I

, i4 t — H I — I t— (t— (I — I * H -H * H * P I g rd rd G Ή

ίΡίρίΡίΡ> · ΌΌΌΌ · Η P P P P rH

G ip ip> i ip I I I I i — I Ό T3 Ό t3 O

Q) · Ρ · Ρ · Ρ · Ρ · Ρ · Η · ιΗ · ιΗ · ιΗ5> ·> ι> ι> ι> η c

G 1Ι (1) 1Ι1ΙΙ1ΙΗΗΗΗ> · 4ίχ; £ G

• H gggggiPiPiPiP-ΡΙΙΙΙ -P

C * H * H * H · Η Ή 0) * rH · Η · Η -H Cl) G ΌΌΌΌΌ-P-P-P-PgrHrHrHrH g

G I I I I I CL> OJ CL) CU I> ι O O O I

tn -Η -Η -P -H -H g g g g -H> 1 G G G -H

P rHt — It — IrHrHI I I IrHrHGGG rH

O> i> i rP ip> - · Η · Ρ · Ρ -P> - Η -Ρ -Ρ -Ρ Ο

rH t — I rH t — I rH O O O O rH * rl -rl -rl * P G

rHrHrHrHrHGGGGt — IPPPP -P

<C <<<< GGGGGtHEHEHEH W

+ J -Ρ -Ρ -Ρ -H I

p w w W W Ti -H

44 G

1 44 -P G

• H P O P> cncD ^ ryiOi-HiNm ^ incor ^ oomiOt-HCN <d q)

mgGudioiommioioioioioioior ^ r ^ r- '> rH

28 7 4 8 8 7 I tn

3 P

a) I 3 X M> W -H Id OOOOOCNI I | »-I ^ OVOOV © (OgrH <N O O O O - ~ I I I u-1 - <N fvl« - .- • H W P -H * “*“ * “

G 4-1 -P

Id___

id I

4-> W

Qj -h U)

Q) £ P

K P P ro · »« r «r o I | | m in <<t n * U5> - (N (N IN <N · - I I I (N · - «-« - · - »-

• H (0 id r-4 CLi -H

__ £ · ____ I i to

> 1 P I P

> i DWG ηοοοοοο ^ οονοΜίΛΠ'ί'ΓΜ '»A * A4-H>" ^ ^ ^ O) tn £ rd

P id P H

Ο · Η μ4 4- * Ή tn 4-> 4-1 H 4 -> __ I Id I - • h id -h tn tn rd HC -H 3 ·> Τ®νΟΓ-ίβσ \ 'Ταθ <Ν < Ν * Τ »- <Ν · -« - idtl) £ P ^ ^ ^ - -.-In - - - - - o 4-1 Φ 3> Ί1 4j d tn id

X I Ή Ή H

O -H O Id - · Η «H 4J PL | 4-> c_____ tn -h

id p 4-1 I

3 o h I tn

>> P Ή PIP

M3 -H> 1 <U tn 3 + J J> - --ININOOOINCO - VO'tOfNICO'J- q tn £ (d Nn ^ n ^ i-i-eissiiNNivioi · -

A4 -H 3 Id 3 H

X Ο Λ W 4-> · Η 3 Α4 Ο 4-1 μ α) tn ------- 3 tn -hi id I tn tn

E "· G * H Ή G

Qj, - (., - 1 Pd £> i G 3>

• H> i O tn M

4-> 4- * 4-1 -H Id

4-1 <U tl) Id -H

OSX CU +> 3 • H - 1-DI- ------.-4 3 13 di m 3 S is νοοοο®® <Νο ^ · ο - «- ίΝΐηιηοο ^ οοΓ-Γ'Ι- ' Γ ^ ιΠαΟΙΝιηΠΙΝΟΝ'- · - i / i E m

* H id 3 M

G 1-4 4- * -H

tU 4-1 <L · ________

3 I

m tn tn

O -ι-l H

> t 33 inO'illOOIOOOSN'fnilINM'-M

M K p -— IN -— -— -— ----------------- 3> S * 10 ♦ H rH ^ 22 ϋ —-3 ---- «

. · ~ \ Α> ο - Γ «ΐΓθ ^ · ιηνθΓ ~ ®σιθ - tN + J

I μζ UHVOVOVDVÖVOVDVOvD ^ VOr ^ f ^ -r ** · Lj -H Ρ O <y tn <ϋ - -> wee ^ f 11 29 7 4 8 8 7

Examples 73-79 These examples illustrate the preparation of the organophilic clays of this invention using various organic anions and diethanol methyl (hydrogenated) ammonium chloride (2EMHT) as the organic cation. As a comparative Example 5, a conventional organophilic clay using 2EMHT as an organic cation is shown. The compositions are shown in Table V and the solvent miscibility results in Table V (a). The data describe the much better dispersion properties of the organophilic clays of the invention compared to organophilic clays prepared without an organic anion.

1.. .

3t> 74887

Table y Organic Organic · rv a. anion cations

Example Organic anion (salt) M.E, ratio M.E. ratio

No_________ _ ___ 73 Na-benzoate 15 115 74 Na-benzoate 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

Comparative No No 111.7 3i 74887 IW "" t • H 3 I 3 P (D in 3 PX -H> 3 co 6 3 id id 3 H o Γ ~ ι II ι γ- η-) pi + jh in n * - I i J 1 Ιο .p (0 <d ___

• H I

i-h in in> 1 · Η 3> 10 3 -P 3> VO VO VO | | | ι „3 in id ---- 1 I I I * -

Λ · Η rH

I id -H

C 1¾ -P

—I ----- “h I in r-H -H 3 13 ^> ί 3 0) in 3 ovtNOoov ^ iNao> i <D Λ! -H> --- X qj in e <d

II 3 Id 3 rH

Ό H ι3 -Ρ -H

0 0 -P

in -P ____

•B

1 H I

Η-P in in ooooaooo-TCNin Ό -P -H 3 - - (d e 3 O 3 3> v * rH in 3

\ 3 * H rH

tn o + j 3 -H

3 c VO UH (¾ -P

3 3 Ή -----—

> -P I

> 3 O -HI in • P 3 rH 3 13 o -P ή> 1 o) in 3 Λί -rl PI> 1 Α! · Η> νθΙΛονθνθ (Ν <Ν (Ν, ¾ Ο -Ρ UI g Id ΐνηπΙΝΝ ^ ΜΝ 3 X 3 3 3 Ή H (D XI ιΧ -Ρ -Ή 3 ιη Ο -Ρ 3 ιη ._______

Eh C Ή I ω 0) I ιη 3 e -η · η 2 • H H rl E C ΜΐηοοοοοοίΝΐ ^ σν «Ρ> 1 C 3 ζ

-Ρ> 1 Ο in JS

O -Ρ -Ρ · Η 'Ί 3 Ο) <ΰ 3 Π • HSX (k ^ * ------- 3 I ^' α) ιη 2 iu.jp Ο ^ ΙΝ ^ ΙΜΠιίΙν ωε> --- - • Η 3 3 * 3 c pi -ρ, 'Ι 0) Μ 0) ^ ___ 3 I ---- ι — ι ιη ιη ο · Η 3 _ _ ρ_, g .j οοονοοσνι-ιιη · »tn 3 3 • H rH> 3 -HQ)

Λ -p. B

, ^ H i) o n ^ u-Ivor-coov,

I .¾ (D

• Ρ P O> in Q) ·· ω e c 32 7 4 8 8 7

It is obvious that the invention thus described can be modified in many ways. Such variations are not to be construed as departing from the scope and spirit of the invention, and all such variations are intended to fall within the scope of the following claims.

Claims (15)

33 74887 Organophilic clay gelling agent, characterized in that it is the reaction product of the following components 5: a) a smectite-type clay with a cation exchange capacity of at least 75 milliequivalents per 100 g of clay, b) an organic anion of 5 to 100 milliequivalents per 100 g per smectite-type clay, calculated on the basis of 100% active clay, and (c) an organic cation of the formula R I1 15 R.- X-R_ Gel former according to claim 1, characterized in that the β, β-unsaturated alkyl group is a cyclic group, an acyclic alkyl group having less than 7 carbon atoms, an acyclic alkyl group substituted by aromatic groups, or an aromatic group substituted by with aliphatic groups. Gel former according to Claim 1, characterized in that the hydroxyalkyl group is a cyclic group or an aliphatic group having 2 to 6 carbon atoms and a hydroxy substitution on carbon C 2 to C 6. Gel former according to Claim 2, characterized in that R 2 is an alkyl group having 12 to 22 carbon atoms. 4 I 2 R3 where R 1 is a Y'-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 aliphatic diatomic atoms, or a mixture thereof, R 2 is a long-chain alkyl group having 12 to 60 carbon atoms, R 1 and R 2 each independently represent a ^ 5, 5-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group having 1 to 22 carbon atoms in the alkyl moiety, an alkyl group having 1 to 22 carbon atoms. - 22 carbon atoms, or a mixture thereof, and X is phosphorus or nitrogen, the organic cation being present in an amount sufficient to at least satisfy the cation exchange capacity of the smectite-type clay and the cationic activity of the organic anion, whereby the cation exchange sites of the smectite-type clay are substituted by organic wherein the complex of organic cation and organic anion is interlayed with smectite-type clay 34 74887, preferably ti organic cation is 80 to 200 milliequivalents per 100 g of clay, calculated on the basis of 100% active clay. 5 R4-f-R2 R3 wherein Gel former according to Claim 4, characterized in that R 2 is a long-chain fatty acid group. The gelling agent of claim 1, wherein the anion is derived from an organic acid having a pK of less than about 11.0. Gel former according to Claim 1, characterized in that the smectite-type clay is hectorite or sodium bentonite. Gel former according to Claim 1, characterized in that the cation is 100 to 160 milliequivalents per 100 g of clay, calculated on the basis of 100% active clay. 9. A process for preparing an organophilic clay gelling agent, characterized in that a) an aqueous slurry is prepared from a smectite-type clay with a cation exchange capacity of at least 75 milliequivalents per 100 g of clay, containing 35 to 1-80% by weight of clay, b) the slurry is heated to 20 to 100 ° C, c) about 5 to 100 milliequivalents of organic anion per 100 g of clay, based on 100% active clay, and a compound containing an organic cation are added to the slurry, the organic cation having the formula ff '* Process according to Claim 9, characterized in that a quaternary ammonium salt or a phosphonium salt having at least 1 linear or branched alkyl group having 12 to 22 carbon atoms is used as the organic cation-containing compound. 36 74887 R 1 is a δ, 5 'unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 aliphatic carbon atoms, or a mixture thereof, R 2 is a long-chain alkyl group having 12 to 60 carbon atoms, R 1 and R 4 each independently represent an β 2, β-unsaturated alkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an aralkyl group having 1 to 22 carbon atoms in the alkyl moiety, an alkyl group having 1 to 22 carbon atoms, or a mixture thereof, and X is phosphorus or nitrogen, the organic cation-containing compound being used sufficiently to at least satisfy the cation exchange capacity of the smectite-type clay and the cationic activity of the organic anion, preferably 80 to 200 milliequivalents of the organic cation-containing compound per 100 g of clay, calculated on the basis of 100% active clay and the reaction mixture is stirred simultaneously, and d) the mixture is allowed to react long enough to form a reaction product containing a complex of an organic cation and an organic anion interlayer with a smectite-type clay and a cation exchange site of the smectite-type clay kat are substituted by an organic cation. Process according to Claim 9, characterized in that the organic anion used is an anion derived from an organic acid having a pK of less than about 11.0. a Process according to Claim 9, characterized in that hectorite or sodium bentonite is used as the smectite-type clay. Process according to Claim 9, characterized in that 10 to 50 milliequivalents of organic anion are used per 100 g of clay, calculated on the basis of 100 active clays. Process according to Claim 9, characterized in that the organic anion is added to the smectite-type clay before the addition of the compound containing the organic cation. A method according to claim 9, characterized in that the organic anion and the organic cation are added to the smectite-type clay as a complex formed by the organic cation and the organic anion. Il 37 74887