DE3145452C2 - - Google Patents

Description

The invention relates to organophilic, organic clay complexes, those in organic liquids to form a gel are dispersible in it. Depending on the composition of the Gels such gels can be suitable as greases, Oil-based sludges, drilling fluids or packer liquids oil-based, paint varnish varnish remover, An coats, sand binders for molding sand molding, Adhesives and sealants, printing inks or inks, laminating polyester resins, polyester gel covers and the like.

It is known that organic compounds containing a cat contain ion, under favorable conditions by Ionaus swap with tones that are a negative layer git ter and exchangeable cations contain, with formation organophilic, organic clay products. If the organic Cation at least one alkyl group with at least 10 Koh Contains lenstoffatomen, such organotones have the Property of swelling in certain organic rivers candy on; see, for example, US-PS's 25 31 427 and 29 66 506, both of which are incorporated herein by reference, and the book "Clay Mineralogy", 2nd edition, 1968, by Ralph E. Grim (McGraw-Hill Book Company, Inc.), especially Kapi tel 10, Clay-Mineral-Organic Reactions; Pages 356-368 -  Ionic Reactions, Smectite; and pages 392-401 - Organo philic clay-mineral complexes.

It is also known that organic compounds contained in Anionic form, usually of negative charge clay surfaces are repelled rather than attracted. This effect is called "negative adsorption". However, positive adsorption of anions can occur ten under conditions in which such compounds in the molecular, i.e. undissociated form; 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 implementing with halloysite, material of the Kaolinite group, with formation of intersalads. The Inter Salad formation was achieved by grinding the mineral with moist crystals of salts of carboxylic acids low molecular weight or by contacting the Minerals with saturated solutions. This interlayer Complex contained all of the salt and water. The Intersalat material, however, was made by washing with water removed what is either used to hydrate the intermediate layer or collapse of the original space led. There was no sign of a change in the basal region stop at montmorillonite, which is treated with salts unlike halloysite; see The American Minerologist, Volume 44, 1959, by K. Wada, "Oriented Pen etration of Ionic Compounds between the Silicate Layers of Halloysite ".

Since the commercial introduction of organoclay in the It became known in the early 1950s that a maximum gelling (thickening) effectiveness of these  Organotone is achieved by adding a polar, orga low molecular weight material to the Zu composition. Such polar, organic materials variously as a dispersant, dispersing aid fen, solvating agents, dispersing agents and the like. designated; see, for example, US Pat. Nos. 2,677,661 (O'Halloran); 27 04 276 (McCarthy et al.); 28 33 720 (Stratton); 28 79 229 (Stratton); 32 94 683 (Stansfield et al.). The use of such dispersion aids proved prove to be unnecessary when using specially constructed, or ganophilic clays that differ from substituted, quaternary Derive ammonium compounds; see U.S. Patents 41 05 578 (Finlayson et al.) And 42 08 218 (Finlayson).

In contrast to the known organoclay compositions could now be a self-activating rheolo within the scope of the invention be provided by the addition of polar Solvent activators do not require this tone is made by reaction of an organic cation, one organic anions and a smectite-type clay, as in standing defined.

The invention thus relates to a gel-forming, organo phile clay containing the reaction product of

• a. a smectite-type clay with a cation exchange ver like at least 75 milliequivalents / 100 g of clay;
• b. an organic anion of one of the following acids in the acidic or in the salt form
  • a) benzoic acid, o-, m- and p-phthalic acid;
  • b) alkyl carboxylic acids of the formula H- (CH₂) _n -COOH, in which n is a number from 2 to 20,
  • c) alkyl dicarboxylic acids having the formula HOOC- (CH₂) _n -COOH, where n is 0 to 8;
  • d) citric acid, tartaric acid, malic acid, mandelic acid and 12-hydroxy-stearic acid;
  • e) naphthalic acid;
  • f) benzenesulfonic acid, phenolsulfonic acid, dodecyl benzenesulfonic acid, benzenesulfonic acid, benzenetrisulfonic acids, p-toluenesulfonic acid; Methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, butanedisulfonic acid;
  • g) phosphites, ie diesters of phosphorous acid of the formula HO-P (OR) ₂, wherein R is an alkyl group having 1 to 22 carbon atoms;
  • h) phosphates, ie diesters of phosphoric acid of the general formula wherein R is an alkyl group having 1 to 22 carbon atoms;
  • i) phenol, hydroquinone; t-butyl catechol; p-methoxyphenol; and naphthols; t-butyl catechol; or ferrocyanide, ferricyanide, sodium tetraphenylborate;
    in an amount of 5 to 100 milliequivalents per 100 g of smectite-type clay, on a 100% active clay basis and
• c. an organic cation of the general formula wherein R₁ is selected from the group of a β, γ-unsaturated alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms, selected from cyclic groups and aliphatic groups having 2 to 6 carbon atoms with the hydroxyl substitution at C₂ to C₆, and mixtures thereof; R₂ is a long chain alkyl group having 12 to 22 carbon atoms; R₃ and R₄ are individually selected from the group of a β, γ-unsaturated alkyl group, a hydroxyalkyl group with 2 to 6 carbon atoms, selected from cyclic groups and aliphatic groups with 2 to 6 carbon atoms with the hydroxyl substitution at C₂ to C₆, an alkyl group with 1 up to 22 carbon atoms and mixtures thereof; and X is phosphorus or nitrogen; wherein the β, γ-unsaturated alkyl group of R₁, R₃ and R₄ is selected from cyclic groups or acyclic alkyl groups with less than 7 carbon atoms, and further the organic cation in an amount of 80 to 200 milliequivalents per 100 g of clay, to 100% more active Clay base, is present in order to satisfy at least the cation exchange capacity of the smectite-type clay and the cation activity of the organic anion, the cation exchange sites of the smectite-type clay being substituted with the organic cation, and an organic cation-organic anion complex is incorporated is in the tone.

The invention further relates to a method for producing the Tone defined above, which is characterized in that one

• a. an aqueous slurry of a clay from Smectite type with a cation exchange capacity of too forms at least 75 milliequivalents per 100 g of clay, wherein the clay ranges from about 1 to about 80% by weight of the Slurry lies;
• b. the slurry to a temperature of 20 to Heated to 100 ° C;
• c. about 5 to 100 milliequivalents of an organic Anion according to claim 1 resulting compound per 100 g of clay, based on 100% active clay and an organic cation compound dung according to claim 1, wherein the organic cation compound in an amount of 80 to 200 milliequivalents per 100 g of Tones, on a 100% active clay basis, is used to at least the cation exchange capacity of the clay from Smectite type and the cationic activity of the organic Anions are sufficient while the reaction solution is stirred becomes; and
• d. the mixture for sufficient time to form of the reaction product that converts an organic includes cation-organic anion complex, which is incorporated is in the smectite-type clay, and what the cations are made of exchanges of clay of the smectite type are substituted with the organic cation.

The measures described can be filtering, washing, drying and grinding follow.

The organophilic clays according to the invention can thus be produced are obtained by mixing the organic anion with the Clay and water at a temp temperature between 20 and 100 ° C, preferably between 35 and 77 ° C, for a sufficient time to prepare egg a homogeneous mixture, followed by the addition of the organic cations in sufficient amounts to eliminate the cations exchange capacity of the sound and the cationic capacity of the organic anions. The order of addition of the organic cation and the organic anion not significant as long as a sufficient amount of the orga African cations is added. In fact, they can appropriate amounts of organic cation and sodium salt of the organic anion in solution (water and / or 2-propanol) with a solid base of 20 to 90% are mixed to form an organic cation orga African anion complex and then as a solution be added for reaction with the clay slurry. After the addition of the organic anion and the organic The mixture becomes cationic with stirring at a temperature from 20 to 100 ° C, preferably 35 to 77 ° C, while sufficient time to implement the formation of an organic to enable cation-organic anion complex, which in the clay is stored, and the cation exchange sites of the clay are substituted by the organic cation.

The addition of the organic cation and the organic type ions can be done either separately or as a complex. When using the organophilic clays in emulsions drying and grinding stages can be omitted. The clay, the organic cation, the organic anion and water mixed in such concentrations that no slurry is formed, so the filtra tion and the washing stages are left out.  

The clay is in water at a concentration from 1 to 80% and preferably 2 to 7% with formation a clay slurry dispersed. The clay slurry can optionally be centrifuged to remove non-clay Impurities that make up about 10 to about 50% of the output Form clay composition to remove. The slurry is generally under stirring or moving to a tempera ture of preferably 35 to 77 ° C before adding the organi prewarmed reaction components.

The amount of organic anion that set the tone for it purposes according to the invention should be sufficient around the organophilic clay the improved dispersion charac teristics that are sought to lend. These men ge is defined as the milliequivalence ratio the number of milliequivalents (meq.) of the organic Anions in the organotone per 100 g of clay, 100% more active Clay base, is. The organophilic clays according to the invention have an anion-milliequivalent ratio from 5 to 100 and preferably from 10 to 50 on.

The organic anion preferably becomes the reaction components in the desired milliequivalent ratio as a solid or as a solution in water with stirring or Move added to form a homogeneous mixture.

The organic cation is used in sufficient quantities det to at least the cation exchange capacity of the clay and the cationic activity of the organic An ions to suffice. Additional cation over the sum of the Exchange capacity of the clay and the anion can be optional be used. It has been found that use of at least 90 meq. organic cation is sufficient to part of the total organic cation requirement suffice. The use of amounts from 80 to 200 meq. and preferably from 100 to 160 meq. per 100 g clay, 100% active clay base is usable.  

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

In the organic cation defined above, the individual residues have the following meaning.

R₁

The β, γ-unsaturated alkyl group can be selected from a wide range of materials. These connections can be cyclic or acyclic, unsubstituted or sub be stuck. Contain β, γ-unsaturated alkyl radicals preferably less than 7 aliphatic carbon atoms. β, γ-unsaturated alkyl radicals which are substituted with egg nem aliphatic radical, preferably contain less than 4 aliphatic carbons. The β, γ-unsaturated alkyl rest can be substituted with an aromatic ring, which may conjugate with the unsaturation of β, γ-Re stes, or the β, γ residue is both with an aliphatic residue as well as an aromatic Ring substituted.

Representative examples of cyclic β, γ-unsaturated Alkyl groups are 2-cyclohexenyl and 2-cyclopentenyl. Right presentative examples of acyclic β, γ-unsaturated Al are alkyl groups with 6 or less carbon atoms 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. Representative case games for acyclic-aromatic substituted verb dung is 3-phenyl-2-propenyl; 2-phenyl-2-propenyl and 3- (4-methoxyphenyl) -2-propenyl. Representative examples for aromatic and aliphatic substituted materials en are 3-phenyl-2-cyclohexenyl; 3-phenyl-2-cyclopentenyl; wherein the alkyl group with an aromatic ring substi can be acted upon.  

The hydroxyalkyl group is selected from a hydroxyl substituted, aliphatic radical, wherein the hydroxyl on Carbon is not substituted, which is adjacent to the positively charged atom, and the group has 2 to 6 aliphatic carbons. Representative Examples include 2-hydroxyethyl; 3-hydroxypropyl; 4-hydroxypentyl; 6-hydroxyhexyl; 2-hydroxypropyl; 2-hydroxy butyl; 2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxycyclo hexyl; 3-hydroxycyclohexyl; 4-hydroxycyclohexyl; 2-hydroxy cyclopentyl; 3-hydroxycyclopentyl; 2-methyl-2-hydroxypro pyl; 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 be and has 12 to 22 carbon atoms on.

The long chain alkyl residues can occur naturally come from the oils, including various vegetable varieties cher oils, such as corn or corn oil, coconut oil, soybean oil, Cottonseed oil, castor oil and the like, as well as various those of animal oils or fats, such as tallow oil. The alkyl residues can be petrochemical in the same way, as from α-olefins.

Representative examples of useful, branched, sown saturated alkyl residues include 12-methylstearyl and 12-ethyl stearyl. Representative examples of useful, ver branched, unsaturated radicals include 12-methyloleyl and 12-ethyl oleyl. Representative examples of unbranched, saturated residues include lauryl; Stearyl; Tridecyl, Myristal or myristyl (tetradecyl); Pentadecyl; Hexadecyl; hydrogenated sebum and docosonyl. Representative examples for unbranched, unsaturated and unsubstituted, long chain alkyl radicals include oleyl, linoleyl, linolenyl, Soy and tallow.  

R₃ and R₄

The remaining groups on the positively charged atom who selected from a group consisting of (a) one β, γ-unsaturated alkyl group, (b) a hydroxyalkyl group pe with 2 to 6 carbon atoms, both be were written and (c) an alkyl group with 1 to 22 Koh Oil atoms, cyclic or acyclic.

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

Representative examples of useful alkyl groups that as R₃ and R₄ are useful include methyl; Ethyl; Propyl; 2-propyl; Isobutyl; Cyclopentyl and cyclohexyl.

The alkyl residues can come from a similar source, like the long chain alkyl radical of the above R₂.

A quaternary compound is derived from the above written, organic, cationic compound and an anionic radical, the Cl, Br, J, NO₂, OH and C₂H₃O₂ and mixtures thereof can be formed. Preferably that is Anion selected from the group of chloride and bromide and Mixtures of these and is particularly preferred chloride, whether probably other anions, such as acetate, hydroxide, nitrite, etc., in the organic, cationic connection to the neutral sation of the cation may be present.

Organic, cationic salts can according to known Ver drive are produced, as in US Pat. Nos. 23 55 356, 27 75 617 and 31 36 819.

The organic anions useful in the present invention have a molecular weight (gram molecular weight) of preferably 3,000 or less, and more preferably 1,000 or less, and contain at least one acidic residue per molecule as described herein. The organic anion is preferably derived from an organic acid with a pK _A less than about 11.0. As indicated, the acid source must have at least one ionizable hydrogen, with preferred pK _A , so that the formation of the organic cation-organic intercalation reaction can take place.

The organic anions can be in acidic or in salt Form. Salts can be selected from alkali metal salts, alkaline earth metal salts, ammonia and organi amines. Representative salts include: hydrogen, Lithium, sodium, potassium, magnesium, calcium, barium, Ammonium and organic amines such as ethanolamine, diethanol amine, triethanolamine, methyl diethanolamine, butyl diethanol amine, diethylamine, dimethylamine, triethylamine, dibutyl amine, etc. and mixtures thereof. The most preferred salt is Sodium as an alkali metal salt.

Specific examples of some of the types mentioned include:

Type b): acetic acid, propionic acid, butter acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tri decanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid, eic acid), nonadecanoic acid
Type c): oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid;
Type g): dioctadecyl phosphite; and
Type h): dioctadecyl phosphate.

The ge to produce the gel-forming, organophilic clay Clays used in accordance with the invention are clays of smectite Type that have a cation exchange capacity of at least 75 mEq. / 100 g clay. Particularly cheap types of clays are the naturally occurring Wyoming varieties swellable bentonites and similar clays as well Hectorite, a swellable magnesium-lithium silicate clay.  

The clays, particularly the bentonite type clays, are preferably converted to the sodium form when not already exist in this form. This can be useful be targeted by making an aqueous clay slurry and slurry flow through a bed of cat ion exchange resin in sodium form. Alternatively, you can the clay with water and a soluble sodium compound, such as sodium carbonate, sodium hydroxide and the like followed by shear on the mixture with a drum mill or an extruder or an extruder.

Smectite-type clays occur naturally or can be synthetic be made table, either by pneumatolytic or hydrothermal synthesis processes. Examples of sol che clays are montmorillonite, bentonite, beidellite, hectorite, Saponite and stevensite. The cation exchange capacity of the Smectite-type clays can be made according to the known ammonium acetate Method to be determined.

The inventive sets discussed above tongues are widely used as rheological additives sets in non-aqueous, fluid system or liquid Systems in general.

The non-aqueous, fluid compositions in which the self-activating, organophilic clays are useful to hold paints, varnishes, enamels, waxes, epoxy compounds manures, putties or sealants, adhesives, Cosmetics, printing inks or inks, polyester-laminating Resins and polyester gel coatings and the like. These fluids can be made by any known method, such as, for example, according to US-PS 42 08 218 Lich colloid mills, roller mills, ball mills and high mills Speed dispersers in which the pigment materials in the organic vehicle by the at the Processing applied, high shear force well dispersed will.  

The gel-forming, organophilic clay is combined in such a way used in quantities sufficient to meet the requirements achieve desired rheological properties, such as high viscosity at low shear rates, the tax or sagging of fluid films and preventing settling and hard clumping of pigments in the non-aqueous, fluid together settlements exist. The amounts of gel-forming, orga nophile clay used in the non-aqueous fluid system should preferably be about 0.1 to about 15% based on the weight of the treated non-aqueous fluid systems, and preferably about 0.3 to 5.0% to provide the desired rheological effects.

The following examples serve to explain the inven dung without restricting it. All percentages in the unless otherwise stated given on the weight.

A simple, convenient test was developed to test the improved dispersion characteristics of the organophilic Clays used in the present invention and in the following Examples are illustrated to show and around the potentially achievable results when using the inventions to illustrate compositions according to the invention. This The test is referred to as the "solvent compatibility test" net. The solvent compatibility test is carried out performs taking a sample of the organophilic clay that is sieved in 10 ml of different solvents, which in separate measuring cylinders of 10 ml are included. The orga nophile clay is added to such an extent that the particles are wetted evenly and clumping cannot occur. The samples become equilibrium setting left after the whole organophile Clay was added (about 30 minutes). That through the organo The volume taken up by the phile tone is then in tenths of a milliliter recorded; this number is called that "Source volume" referred to.

The mixture is 50 times, i.e. 10 times horizontally and 40 times vertical, shaken vigorously and left overnight. The volume taken up by the organophilic clay becomes recorded again in tenths of a milliliter; this value is referred to as the "sediment volume".

The source volume gives an indication of the contracts the organic portion of the organophilic clay the solvents examined; the sales volume there an indication of the easy dispersibility of the organo  phile clays in this solvent with low shear conditions.

As for the rate of screening or shrinking the Organotons in the solvent and the force with which the Sample is shaken, variations may occur the numerical values are not absolute. Minor differences in Volumes are not considered significant since the Values should only be used for comparison purposes.

The gel-forming, organophilic clays according to the invention which used in the examples were as follows Procedure prepared unless otherwise stated. A 3% clay slurry (Wyoming sodium form Bentonite) was prepared and the slurry with stirring heated to 60 ° C. The organic anion became the clay Slurry given and reacted for about 10 min followed from the addition of the organic cation. The amounts of orga African materials are given in the tables and as Milliequivalents of organic cations and organic Anions per 100 g of clay, on a 100% active clay basis. The mixture was then agitated during a sufficient time to complete the response den (generally 10 to 60 min). The organ sound was collected on a vacuum filter. The filter cake was washed with hot (40 to 80 ° C) water and at 60 ° C dried. The dried organoclay was ground and ter using a hammer mill or similar grinding device for reducing particle size and beyond through a sieve with a mesh size of 0.074 mm sieved.  

Example 1 (Preparation of Organic Cationic Compound) Allylmethyl-di- (hydrogenated tallow) ammonium chloride (abbreviated as Am2HT)

824.7 g of methyl di (hydrogenated tallow) amine, about 350 ml of iso propyl alcohol, 250 g NaHCO₃, 191.3 g allyl chloride and 10 g Allyl bromide (as a catalyst) was in a 4 liter reaction vessel equipped with a cooler and a mechanical one Stirrer, introduced. The mixture was warmed and gentle kept under reflux. Periodically samples were removed filtered and titrated with standardized HCl and NaOH. The reaction was considered complete when 0.0% Amine HCl and 1.8% amine were present. The final Analysis showed an effective gram molecular weight of 831.17.

Examples 2 to 4 (comparison)

A 3% clay slurry of Wyoming's sodium form Bentonite in Examples 2 and 3 and hectorite in the case game 4 was heated to 60 ° C. with stirring. A solution of organic, cationic compound, ethanol-methyl di (hydrogenated tallow) ammonium chloride [Em2HT] for be game 2 and AM2HT, produced in example 1, for the example games 3 and 4 were added to the clay slurry and 20 min. The organoclay was on a vacuum filter collected. The filter cake was washed with 60 ° C water and dried at 60 ° C. The dried organoclay was ground using a hammer mill Reduction in particle size and then by one Sieve with a mesh size of 0.074 mm sieved.

Examples 5 to 21

These examples show the production of organophilic To NEN according to the invention using various org  anions and allylmethyl-di- (hydrogenated tallow) ammonium chloride (AM2HT) as an organic cation. A bad one Organophilic clay using AM2HT as an orga African cation is used as a comparison test. The Compositions are in Table I and the solvent Compatibility results are listed in Table I (a). The data show the superior dispersion characteristics ka of the organophilic clays according to the invention in comparison with organophilic clays, made in the absence of organic anions.

The following tables list the following abbreviations used:

MÄV = milliequivalents ratio,
QuV = swelling volume,
AV = sedimentation volume.

Table I

Table I (a)

Compatibility with solvents

solvent

Examples 22 to 38

These examples show the production of organophiles Toning according to the invention using various organic anions and diallyl di (hydrogenated tallow) ammonium chloride as (2A2HT) organic cation. A bad one rich, organophilic clay using 2A2HT as or ganic cation is used as a comparison test. The Compositions are in Table II and the solvents compatibility results are given in Table II (a). The Data show the significantly superior dispersion charac teristics of the organophilic clays according to the invention in ver same with organophilic clays, made in absence of the organic anion.

Table II

Table II (a)

Compatibility with solvents

solvent

Examples 39 to 48

These examples show the production of organophiles Toning according to the invention using various organic anions and ethanol dimethyl hydrogenated tallow ammonium chloride (e2MHT) as an organic cation. A bad one rich, organophilic clay using E2MHT as or ganic cation is used as a comparison test. The Compositions are given in Table III and the Solvent compatibility results in Table III (a). The data show the significantly superior dispersion characteristics of the organophilic clays according to the invention in comparison with organophilic clays, produced without or ganic anion.

Table III

Table III (a)

Examples 49 to 59

These examples illustrate the manufacture of er organophilic clays according to the invention using ver various organic anions and various quaternaries rer ammonium chloride as an organic cation. A common one organophilic clay and use of ethanolmethyl-di ( -hydrogenated tallow) as an organic cation is used as Ver equal attempt used. The compositions are in Table IV given; 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 orga nophilic clays, made without organic anion.  

Table IV

Table IV (a)

Compatibility with solvents

solvent

Examples 60 to 65

These examples show the production of fiction moderate organophilic clays using various organic anions and diethanol-methyl-hydrogenated tallow ammonium chloride (2EMHT) as an organic cation. A bad one Organophilic clay using 2EMHT as an organ African cation is used as a comparison test. The Compositions are given in Table V; the solutions medium tolerance results in Table V (a). The Da ten show the significantly superior dispersion characteristics Risks of the organophilic clays according to the invention in Ver same with organophilic clays, produced without organic Anion.

Table V

Table V (a)

Compatibility with solvents

solvent

Claims (11)

1. Gel-forming, organophilic clay, containing the reaction product of

• a. a smectite-type clay with a cation exchange capacity of at least 75 meq / 100 g of the clay;
• b. an organic anion of one of the following acids in the acidic or in the salt form
  • a) benzoic acid, o-, m- and p-phthalic acid;
  • b) alkyl carboxylic acids of the formula H- (CH₂) _n -COOH, in which n is a number from 1 to 20,
  • c) alkyl dicarboxylic acids having the formula HOOC- (CH₂) _n -COOH, where n is 0 to 8;
  • d) citric acid, tartaric acid, malic acid, mandelic acid and 12-hydroxy-stearic acid;
  • e) naphthalic acid;
  • f) benzenesulfonic acid, phenolsulfonic acid, dodecyl benzenesulfonic acid, benzenesulfonic acid, benzenetrisulfonic acids, p-toluenesulfonic acid; Methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, butanedisulfonic acid;
  • g) phosphites, ie diesters of phosphorous acid of the formula HO-P (OR) ₂, wherein R is an alkyl group having 1 to 22 carbon atoms;
  • h) phosphates, ie diesters of phosphoric acid of the general formula wherein R is an alkyl group having 1 to 22 carbon atoms;
  • i) phenol, hydroquinone; t-butyl catechol; p-methoxyphenol; and naphthols; t-butyl catechol; or ferrocyanide, ferricyanide, sodium tetraphenylborate;
    in an amount of 5 to 100 milliequivalents per 100 g of smectite-type clay, on a 100% active clay basis and
• c. an organic cation of the general formula wherein R₁ is selected from the group of a β, γ-unsaturated alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms, selected from cyclic groups and aliphatic groups having 2 to 6 carbon atoms with the hydroxyl substitution at C₂ to C₆, and mixtures thereof; R₂ is a long chain alkyl group having 12 to 22 carbon atoms; R₃ and R₄ are individually selected from the group of a β, γ-unsaturated alkyl group, a hydroxyalkyl group with 2 to 6 carbon atoms, selected from cyclic groups and aliphatic groups with 2 to 6 carbon atoms with the hydroxyl substitution at C₂ to C₆, an alkyl group with 1 up to 22 carbon atoms and mixtures thereof; and X is phosphorus or nitrogen; wherein the β, γ-unsaturated alkyl group of R₁, R₃ and R₄ is selected from cyclic groups or acyclic alkyl groups with less than 7 carbon atoms, and further the organic cation in an amount of 80 to 200 milliequivalents per 100 g of clay, to 100% more active Clay base, is present in order to satisfy at least the cation exchange capacity of the smectite-type clay and the cation activity of the organic anion, the cation exchange sites of the smectite-type clay being substituted with the organic cation, and an organic cation-organic anion complex is incorporated is in the tone.

2. Gel-forming agent according to claim 1, characterized in that that the organic anion sodium benzoate, sodium lauryl sulfate or Sodium stearate comes from.   3. Gel-forming agent according to claim 1, characterized in that that R₂ is derived from a long chain fatty acid group. 4. Gel-forming agent according to claim 1, characterized in that the organic anion is derived from an organic acid with a pk _A value of less than about 11.0. 5. Gelling agent according to claim 1, characterized in that that the smectite-type clay is selected from hectorite and Sodium bentonite. 6. Gelling agent according to claim 1, characterized records that the amount of the organic cation is 100 to 160 milliequivalents per 100 g of clay, 100% more active Clay base. 7. A process for the preparation of an organophilic, gel-forming clay, characterized in that

• a. forms an aqueous slurry of a smectite-type clay with a cation exchange capacity of at least 75 milliequivalents per 100 g of the clay, the clay ranging from about 1 to about 80% by weight of the slurry;
• b. the slurry is heated to a temperature of 20 to 100 ° C;
• c. about 5 to 100 milliequivalents of an organic anion compound according to claim 1 per 100 g of clay, on a 100% active clay basis and an organic cation compound according to claim 1, wherein the organic cation compound in an amount of 80 to 200 milliequivalents per 100 g of 100% active clay-based clay is used to satisfy at least the cation exchange capacity of the smectite-type clay and the cationic activity of the organic anion while stirring the reaction solution; and
• d. reacting the mixture for sufficient time to form the reaction product comprising an organic cation-organic anion complex intercalated in the smectite-type clay and wherein the cation exchange sites of the smectite-type clay are substituted with the organic cation .

8. The method according to claim 7, characterized in that the amount of the organic anion is 10 to 50 milliequivalents per 100 g of clay, on a 100% active clay basis. 9. The method according to claim 7, characterized in that that the organic anion connection to the Smectite-type clay before adding the organic Cation compound is added. 10. The method according to claim 7, characterized in that the compound resulting in an organic anion and the organic cation compound to smectite-type clay in the form of an organic cation-organic anion complex be added.   11. Use of the gel-forming organophilic clay, such as defined in one of claims 1 to 6, as rheological Additive in non-aqueous fluid systems.