LU83759A1 - ANIONICALLY MODIFIED ORGANOPHILIC CLAYS AND PROCESS FOR THEIR PREPARATION - Google Patents

Description

* I

The present invention relates to organophilic complexes of clay and organic compounds which can be dispersed in organic liquids to form a gel therein. Depending on their composition, these gels can be useful in lubricating greases, oil-based sludges, oil-based liquids for fillers, paint and varnish removing agents, paints, sand binders foundry, adhesives and sealants, inks, polyester resins for lamination, polyester gel coatings, etc.

It is well known that organic compounds containing a cation react under favorable conditions, by ion exchange, on clays which contain a negative layer network and exchangeable cations by forming "organophilic products of clay and compounds. If the organic cation contains at least one alkyl group containing at least 10 carbon atoms, these organo-clays have the property of swelling in certain organic liquids.

(See for example US Patents 2,531,427 and 2,966,506 20 and the book "Clay Mineralogy", 2nd edition, 1968, by Ralph E. Grim (McGraw Hill Book Co., Inc.) "especially Chapter 10, Clay -Mineral-0rganic Reactions, pages 356 to 368 of Ionie Reactions, Smectite and pages 392 to 401 of Organophilic Clay-Mineral Complexes).

• S 25 “Π is also known that organic compounds in the anionic form are usually repelled, rather than attracted, by the clay surface with a negative charge * 30. This effect is called negative aeborpt ion. However, positive adsorption of anions may occur under conditions where such compounds exist in molecular form, i.e., not dissociated (See "Chemistry of Clay -Organic Reactions", 1974, by BKG Theng , 3ohn Wiley, & Sons). 35 On the other hand, Wada has found that this phenomenon, namely adsorption, does indeed occur with certain ionic compounds when they are reacted on a material of the group "". Λ

V

2 of halloysite or kaolinite to form intersalification products. Intersalification was accomplished by milling the mineral with wet crystals of low molecular weight carboxylic acid salts or by contacting the mineral with saturated solutions. This interlayer complex contains whole salt, as well as water. However, the intersalting product was removed by washing with water, which resulted either in hydration of the intermediate layer, or in crushing restoring the original spacing. No trace of variation in basal spacing was found with a montmorillonite treated with salts, unlike halloysite. (See The American Minerologist, volume 4-4-, 1959, by K. Wada, "Oriented Penetration of Ionie Compounds between the Silicate Layers of 15 Halloysite").

Since the commercial introduction of organic clays in the early 1950s, it is well known that maximum gelation (thickening) efficiency of these organic clays is achieved by adding a low-weight polar organic body to the composition. molecular. Such polar organic bodies have been called, depending on the case, dispersing agents, dispersing aids, solvating agents, etc. (See for example US Patents 2,677,661, 2,704,276, 2,833,720, 2,879,229 and 3,294. 683). We had found. It was unnecessary to use such dispersing aids when using specially designed organophilic clays derived from substituted quaternary ammonium compounds. (See US patents 4,105,578 and 4,208,218).

Unlike previous organo-clay compositions, a self-activating rheological agent was unexpectedly prepared which does not require the addition of activators of the polar solvent type and which is formed by the reaction a-35 * + 3 an organic cation, an organic anion and a smectite-type clay.

An organophilic clay-type gelling agent having increased dispersibility in non-aqueous systems has been unexpectedly found and consists of the reaction product of: (a) a salt having an organic cation whose cation responds to the formula: + 10 R,

R - X -R

| R3 15 _ _ wherein R ^ is a ψ-unsaturated alkyl group, ^ a hydroxyalkyl group containing 2 to 6 carbon atoms or a mixture thereof, R ^ a long-chain alkyl group containing 12 to 60 carbon atoms , R ^ and represent, individually, an unsaturated p-alkyl group, K a hydroxyalkyl group containing 2 to 6 carbon atoms, an aralkyl group, an alkyl group having 1 to 22 carbon atoms, or mixtures of these, and X represents the. 3 phosphorus or nitrogen, 25 (b) an organic anion, and - s (c) a smectite type clay having a cation exchange capacity of at least 75 milliequivalents per 100 g of clay, such so that an organic cation and organic anion complex is interposed with the smectite-type clay and that the cation exchange sites of the smectite-type clay are substituted by the organic cation.

To prepare the organophilic clays of the invention, the organic anion can be mixed with clay and water, preferably between 20 and 100 ° C and more preferably between 35 and 77 ° C, for a time. sufficient to obtain a homogeneous mixture and then add the organic cation in sufficient quantities to satisfy the cation exchange capacity of the clay and the cationic capacity of the organic anion. The order of addition of the organic cation and the organic anion is not important, as long as a sufficient amount of organic cation is added. In fact, it is possible to mix the appropriate amounts of organic cation and sodium salt of the organic anion, in solution (in water and / or in 2-propanol) containing 20 to 90% solids, to form a complex of organic cation and d organic anion, then add the solution to the clay slurry to react the whole. After the addition of the organic anion and the organic cation, the mixture is reacted with stirring between 20 and 100 ° C., to: preferably between 35 and 77 ° C, for a time sufficient to allow the formation of an organic cation and organic anion complex which is intercalated with the clay, the cation exchange sites of the clay being substituted by the organic cation. Reaction temperatures below 20 ° C or above 100 ° C are usable, but are not preferred.

The organic cation and the organic anion can be added either separately or as a complex. When organophilic clays are used in emulsions, the drying and grinding steps can be eliminated. When the clay, organic cation, organic anion and water are mixed in concentrations such that no slurry is formed, the filtration and washing steps can be eliminated.

Preferably, the clay is dispersed in water at a concentration of from about 1 to 80%, preferably from 2 to 7%, to form a slurry of clay. The clay slurry can optionally be centrifuged to remove impurities extraneous to the clay, which constitute about 10 to 50% of the initial clay composition. The slurry is generally preheated with stirring to a temperature of 35 to 77 ° C. before adding the organic reagents.

The amount of organic anion added to the clay for the purposes of the invention should be sufficient to impart to the organophilic clay the desired increased dispersion characteristic. This quantity is defined by the ratio of milli-equivalents which is the number of milliequivalents (M.E.) of the organic anion contained in the organoclay per 100 g of clay, based on 100% active clay. The organophilic clays of the invention must preferably have a ratio of milliequivalents of anion of between 5 and 100, and more preferably between 10 and 50.

Preferably, the organic anion is added to the reagents at the desired milliequivalents ratio, in the form of a solid 1 or an aqueous solution, with stirring, to obtain a homogeneous mixture.

The organic cation must 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, a cation supplement can be used in addition to the total exchange capacity of the clay and anion. It has been found that it is sufficient to use at least 20 90 M.E. of organic cation to satisfy part of the total need for organic cation. It is acceptable to use 80 to 200 M.E., and preferably 100 to 160 M.E.

For convenience of handling, it is preferable. the total organic content of the reaction products of the organophilic clay type of the invention is less than about 50% of the weight of the organoclay. Larger amounts can be used, but the reaction product is difficult to process.

Another process for preparing the organophilic clays of the invention comprises the following steps: (a) dissolving in smectite-type clay, in a proportion of 1 to 80% by weight, (b) heating the slurry to a temperature of 20 to 200 ° C, (c) add 5 to 100 ME of an organic anion per 100 g of clay, based on 100% active clay, and the organic cation in an amount sufficient to satisfy the cation exchange capacity of smectite-type clay ♦ - * * 6 and the cationic activity of the organic anion, while stirring the solution, (d) reacting the mixture for a sufficient time to forming a reaction product comprising a complex of organic cation and organic anion intercalated with smectite-type clay, the cation exchange sites of smectite-type clay being substituted by the organic cation, and (e ) recover the reaction product.

The organic cationic compound useful in the invention can be chosen from a wide range of bodies capable of forming organophilic clay by cation exchange with clay of the smectite type. The organic cationic compound must have a positive charge localized on a single atom or a small group of atoms within the compound. Preferably, the organic cation is chosen from the cations of the quaternary ammonium, phosphonium salts and their mixtures, as well as equivalent salts. Preferably, the organic cation contains at least one member from each of two groups, the first group comprising (a) β, Y unsaturated alkyl groups and (b) hydroxyalkyl groups containing 2 to 6 carbon atoms, the second group comprising long chain alkyl groups. The fragments remaining carried by the central positive atom are chosen from β, Y unsaturated alkyl groups and / or hydroxyalkyl groups containing 2 to 6 carbon atoms and / or aralkyl groups and / or alkyl groups containing 1 to 22 carbon atoms.

A representative form of the cationic compound is r— + î1

30 I

R * -X -R2 R3 in which is an unsaturated alkyl group in -Y a hydroxyalkyl group containing 2 to 6 carbon atoms or a mixture thereof, a long chain alkyl group 7 containing 12 to 60 carbon atoms , and represent, î. individually, an alkyl group unsaturated in a hydroxyalkyl group containing 2 to 6 carbon atoms, an aralkyl group, an alkyl group having 1 to 22 carbon atoms, or mixtures thereof, and X represents phosphorus or l 'nitrogen.

The β, Ύ unsaturated alkyl group can be chosen from a wide range of substances. These compounds can be cyclic or acyclic, substituted or not. Preferably, the alkyl radicals unsaturated in β, Ύ contain less than 7 aliphatic carbon atoms. The unsaturated alkyl radicals at P, T and substituted by an aliphatic radical preferably contain less than 4 aliphatic carbon atoms. The alkyl radical unsaturated at β, y may be substituted by an aromatic ring also conjugated with the unsaturation of the fragment β, Y or the radical, is substituted both by an aliphatic radical and by an aromatic ring.

^ 'Representative examples of β-unsaturated cyclic alkyl groups, Y include 2-cyclohexenyl and 2-cyclopentenyl. Representative examples of β, Ύ unsaturated alkyl groups containing 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, A - hexadienyl. Representative examples of aromatic substituted acyclic groups include 3-phenyl-2-propenyl, 2-phenyl-2-propenyl and 3- (4-methoxyphenyl) -2-propenyl groups. Representative examples of aromatic and aliphatic substituted groups include 3-phenyl-2-cyclohexenyl and 3-phenyl-2-cyclopentenyl; the alkyl group may be substituted by an aromatic ring.

The hydroxyalkyl group may be a hydroxylated aliphatic radical, the hydroxyl group of which is not attached to the carbon atom adjacent to the positively charged atom, the, "8 the group containing 2 to 6 aliphatic carbon atoms. The alkyl group may be substituted by an aromatic ring.

Representative examples are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypentyl, 6-hydroxyhexyl, 2-hydro- <5 xypropyl, 2-hydroxybutyl, 2-hydroxypentyl, 2-hydroxyhexyl, 2-hydroxycyclohexyl, 3-hydroxycyclohexyl , 4-hydroxycyclohexy-le, 2-hydroxycyclopentyle, 3-hydroxycyclopentyle, 2-methyl-2-hydroxypropyl, 3-methyl-2-hydroxybutyl and 5-hydroxy-2-pentenyl.

10 ^ 2_

The long chain alkyl radicals can be branched or not, saturated or unsaturated, substituted or not, and must contain 12 to 60 carbon atoms in the straight chain part.

• * • 5 The straight chain alkyl radicals can be derived from oils of natural origin, in particular various vegetable oils such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil, etc., as well as various animal oils and fats such as tallow oil.

The alkyl radicals can also be obtained petrochemically, for example from olefins.

Representative examples of branched saturated alkyl radicals which are useful include 12-methylstearyl and 12-ethylstearyl. Representative examples of useful branched unsaturated radicals include I2-methyloleyl and 12-ethyloleyl. Representative examples of saturated unbranched radicals are lauryl, stearyl, tridecyl, myristyl (tetradecyl), pentadecyl,, exadecyl, hydrogenated tallow and docosanyl. Representative examples of unbranched, unsaturated and unsubstituted long chain alkyl radicals are oleyl, linoleyl, linolenyl, soybean and tallow.

R3 and

The other groups carried by the positively charged atom 55 are chosen from a) an alkyl group unsaturated at i> 'ï b) a hydroxyalkyl group containing 2 to 6 carbon atoms, both defined above, c) an alkyl group containing! 9 ϊ ί 1 to 22 carbon atoms, cyclic or acyclic, and d) an aralkyl group, that is to say benzyl or substituted benzyl, including v * condensed cyclic fragments containing linear or branched chains5 from 1 to 22 carbon atoms 5 in the alkyl part of the aralkyl group.

The unsaturated alkyl group of and can be a linear or branched group, cyclic or acyclic, substituted or not? containing 1 to 22 carbon atoms.

Representative examples of alkyl groups useful for constituting and are methyl, ethyl, propyl 2-propyl, isobutyl, cyclopentyl and cyclohexyl.

The alkyl radicals can be derived from a source similar to that of the long chain alkyl radical R £ above · "

Representative examples of an aralkyl group, i.e., substituted benzyl or benzyl, include the benzyl group and the compounds derived therefrom, for example, benzyl halides, benzhydryl halides, trityl halides, o (-halo-o (-phenylalkanes) in which the chain contains 1 to 22 carbon atoms, such as l-halo-l-phenylethanes, 1-halo-l-phenylpropanes and 1-halo-l-phenyloctadecanes , substituted benzyl moieties such as those derived from ortho-, meta- and para-chlorobenzyl halides, para-methoxybenzyl halides, ortho-, meta- and para-nltrilobenzyl halides and ottho halides -, meta- and para-alkylbenzyl, the alkyl chain of which contains 1 to 22 carbon atoms, and fragments of the benzyl type with condensed nuclei such as those which are derived from 2-halogér.ométhylnaphtalènes, $ 0 of 9-halo-methyl-ananthracenes and 9- halomethylethyl phenanthrenes, in which the nalogen substituent is chl ore, bromine, iodine or any other similar group capable of being eliminated during the nucleophilic attack of the benzyl-type fragment so that the nucleophile replaces the group eliminated from the benzyl-like fragment.

10

A quaternary compound is formed from the organic cationic compound described above and from an anionic radical which may be Cl, Br, I, OH, or a mixture thereof.

Preferably the anion is a chloride or bromide anion or a mixture thereof, more preferably a chloride anion, although other anions, for example acetate, hydroxy, nitrite, etc., may be present in the cationic organic compound to neutralize the cation.

Organic cationic salts can be prepared by known methods, such as those described in US Patents 2,355,356, 2,775,617 and 3,136,819.

The organic anions useful in the invention can be chosen from a wide range, provided that they are capable of reacting on an organic cation and of forming intercalations with a smectite-type clay in the form of a cation complex. organic and organic anion. The molar mass (mass of the gram molecule) of the organic anion is preferably 3000 maximum and preferably 1000 maximum, and it contains at least one acidic fragment per molecule as indicated herein. The organic anion is preferably derived from an organic acid having a pK ^ of less than about 11.0. As indicated, the acid must contain at least one ionizable hydrogen atom having the preferential PK ^, so as to allow the intercalation reaction between organic cation and organic anion.

One can also use any compound which can give by / hydrolysis the desired organic anion. Representative compounds are: 1) acid anhydrides, especially acetic anhydrides,? 30 maleic, succinic and phthalic, 2) acid halides, in particular acetyl chloride, octanoyl chloride, lauroyl chloride, lauroyl bromide and benzoyl bromide, 3) of 1,1, 1-trihalides, in particular 1,1,1-trichloro-35 ethane and 1,1,1-tribromooctane, and 4 ·) orthoesters, in particular 1 'orthof ethyl ormiate and ethyl orthostearate.

; ï 11

The organic anions can be in acid or saline form. The salts can be chosen from alkali or alkaline-earth metal, ammonium and organic amine salts. Representative salts are those of hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, ammonium and organic amines such as ethanolamine, diethanolamine, triethanolamine, methyl- diethanolamine, butyl-diethanolamine, diethylamine> dimethylamine, triethylamine, dibutylamine, etc., as well as their mixtures. As an alkaline salt, the sodium salt is especially preferred.

. Examples of the types of acid-functional organic compounds which are useful in the invention include: 1) Carboxylic acids, in particular: a) Benzenecarboxylic acids such as benzoic, ortho-, meta- and para-phthalic, benzene- 1,2,3-tricarboxylic, 1,2-benzene, ή - tricarboxylic, benzene-1,3,5-tricarboxylic, benzene-1,2, 4-, 5-tetracarboxylic, benzene-1,2,3, 4-, 5.6 hexa-carboxylic acid (mellitic acid), 20 b) alkylcarboxylic acids corresponding to the formula H-ÎCH ^^ - COOH in which £ is a number from 0 to 20, in particular acetic, propionic, butanoic acids , pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, undecanoic, lauric, tridecanoic, tetradeca-25 noic, pentadecanoic, hexadecanoic, heptadecanoic, octadecanoic (stearic), nonadecanoic, eicosanoic); c) alkyldicarboxylic acids corresponding to the formula H00C- (CH ^) n-C00H in which ια is from 0 to 8, such as oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic acids; d) hydroxyalkylcarboxylic acids, such as citric, tartaric, malic, mandelic and 12-hydroxystearic acids; e) unsaturated alkylcarboxylic acids, such as maleic, fumaric and cinnamic acids; f) aromatic carboxylic acids with condensed nuclei, such as naphthalenic acids and anthracenecarboxylic acid, and g) cycloaliphatic acids, such as cyclohexane-carboxylic, cyclopentanecarboxylic and furanecarboxylic acids, 2) organic sulfuric acids. comprising: 5 a) sulfonic acids, in particular: (1) benzenesulfonic acids such as benzene-tallow acids, phenolsulfonic, dodecylbenzenesulfonic, benzenisulfonic, benzenetrisulfonic, para-toluenesulfonic, 10 (2) alkylsulfonic acids such as acids methanesulfonic, ethanesulfonic, butanesulfonic, butane-disulfonic, alkyl sulfosuccinates such as dioctyl-succinylsulfonic acid and alkyl-polyethoxy-, succinylsulfonic acid; B) alkyl sulphates, such as monolauryl sulphate and monooctadecyl sulphate, 3) organophosphorus acids, comprising: a) phosphonic acids corresponding to the formula: 0

20 II

RPC (OH) 2 wherein R is an aryl or alkyl group containing 1 to 22 carbon atoms; b) phosphinic acids corresponding to the formula: 1 ‘25 0

II

R2P0H

wherein R is an aryl or alkyl group containing 1220 ® 22 carbon atoms, for example dicyclohexylphosphinic, dibutylphosphinic and dilaurylphosphinic acids; c) thiophosphinic acids corresponding to the formula:

S

II

R2psh in which R is an aryl or alkyl group containing 1 to 22 carbon atoms, for example diisobutyl-dithiophosphinic, dibutyl-dithiophosphinic, dioctadecyl-i j. 1 13 dithiophosphonic; d) phosphites, that is to say diesters of phosphorous acid, corresponding to the formula (HO-POR)) wherein R is an alkyl group containing 1 to 22 carbon atoms, for example dioctadecyl phosphite , and e) phosphates, that is to say diesters of phosphoric acid, corresponding to the formula: 0

II

io ho-p- (or) 2 in which R is an alkyl group containing 1 to 22 carbon atoms, for example dioctadecyl phosphate.

4) Phenols, such as phenol, hydroquinone, tert-butylcatechol, p-methoxyphenol and naphthols.

^ 5) Thioacids corresponding to the formulas:

S

II

R-C-OH

and 20 0 i R-C-SH, and

S

25 I '

s R-C-SH

in which R is an aryl or alkyl group containing 1 to 22 carbon atoms, for example thiosalicyli-30 thiobenzoic, thioacetic, thiolauric and thiostearic acids.

6. Amino acids, such as naturally occurring amino acids and their derivatives, such as 6-amino-hexa-noic acid, 12-aminododecanoic acid, N-phenylglycine and 3-aminocrotonic acid.

7) Polymer acids drawn from acid monomers in which the acid function remains in the polymer chain, j! 14 such as polymers and copolymers of low molecular weight acrylic acid, and styrene / maleic anhydride copolymers.

8) Various acids and acid salts such as ferrocyanide, ferricyanide, sodium tetraphenylborate, phosphotungstic acid, phosphosilicic acid or any such anion which can form a tight ion pair with an organic cation , that is to say any such anion which forms a water-insoluble precipitate with an organic cation.

The clays which are used to prepare the gelling agents of the organophilic clay type of the invention are clays of the smectite type which have a cation exchange capacity of at least 75 milliequivalents per 100 g of clay. Particularly suitable types of clay are varieties of swelling bentonite which occur naturally in Wyoming and similar clays, as well as hectorite which is a swelling clay of magnesium and lithium silicate.

Preferably, the clays, and especially the benzonite type clays, are converted into the sodium form, if they are not already in this form. This can be done advantageously by preparing an aqueous slurry of clay and passing it through a layer of cation exchange resin in the sodium form. The clay can also be mixed with water and a soluble sodium compound, such as sodium carbonate, sodium hydroxide, etc., and then shear the mixture with a kneader or an extruder.

Smectite clays are found in nature or can be synthetically prepared by pneumatolytic or hydrothermal synthesis methods. Examples of these clays are montmorillonite, bentonite, beidellite, hectorite, saponite and stevensite. The cation exchange capacity of smectite-type clays can be determined by the well known ammonium acetate method.

The organophilic clays of the invention can be prepared by mixing the clay, the organic cation, the organic anion and the water, preferably at a temperature of 20 to 100 ° C, more preferably 35 at 77 ° C., for a time sufficient for the organic cation and the organic anion to complex to intercalate with the clay particles, then by filtering, washing, drying and grinding.

The compositions of the invention, described above, find wide utility as rheological additives in non-aqueous liquid systems in general.

Non-aqueous liquid compositions in which self-activating organophilic clays are useful include paints, varnishes, enamels, waxes, epoxy resins, sealants, adhesives, cosmetics, inks, polyester resins for lamination and polyester gel coats, etc. These liquids can be prepared by any conventional method, as described in US Patent 4 · .208,218, for example using colloid mills, rolling mills, ball mills and high speed dispersers in which the pigments disperse well in the organic vehicle, as a result of the high shear applied.

Organophilic clay type gelling agents are used in such compositions in amounts sufficient to obtain the desired rheological properties, for example a high viscosity at low shear rates, a limitation in the flow of liquid films, and preventing the deposition and agglomeration of pigments present in non-aqueous liquid compositions. The amounts of gelling agent of the organophilic clay type which is used in the non-aqueous liquid system should preferably be from 0.1 to 15% approximately, relative to the weight of the system and preferably from 0.3 to 5.0. % to give the desired rheological effects.

The following examples are given to illustrate the invention, but do not limit it. All percentages shown are by weight unless otherwise noted.

A simple and convenient test has been devised to illustrate the increased dispersion characteristics of. λ 16 organophilic clays used in the invention and it is described in the examples below to show the results which it is possible to obtain using the compositions of the invention. This is called a compatibility test with solvents. To do this, we take a sample of organophilic clay which is sieved in 10 ml of various solvents contained in separate graduated cylinders of 10 ml. The organophilic clay is added at a rate such that the particles are uniformly wetted and that agglomeration cannot occur. The samples are allowed to equilibrate after all the organophilic clay has been added (about 30 minutes). We then note the volume occupied by organophilic clay, in tenths of a milliliter; this - number is called the swelling volume.

The mixture is vigorously stirred 50 times, 10 times horizontally and 40 times vertically and allowed to stand overnight. The volume occupied by organophilic clay is again noted, in tenths of a milliliter; this quantity is called the volume of sedimentation. The volume of swelling gives an indication of the compatibility of the organic part of the organophilic clay with the solvents tested; the volume of sedimentation gives an indication of the ease of dispersion of the organophilic clay in this solvent, under conditions of low shear.

Due to variations in the speed at which the organo-clay is sieved in the solvent and the vigor with which the sample is taken, the figures are not absolute. Small differences in volume are not considered significant; values are intended for comparison only.

The organophilic clay type gelling agents according to the invention, used in the examples, are prepared by the following method, unless otherwise indicated. A 3% clay slurry (sodium form of Wyoming bentonite) is formed and it is heated to 60 ° C. with stirring. The organic anion is added and reacted for about 10 minutes, then the organic cation is added. The quantities of organic matter added are indicated in the tables and expressed in milliequivalents of the organic cation and of the organic anion per 100 g of clay, on the basis of clay active at 100%. The mixture is then reacted with stirring, sufficient time to complete the reaction (generally 10 to 60 minutes). The organoclay is collected on a vacuum filter. The cake is washed with hot water (4-0 at 8G ° C) and dried at 60 ° C.

The dried organo-clay is ground using a hammer mill or similar fragmentation apparatus to reduce the particle size, then passed through a sieve = 74 j / m openings.

EXAMPLE 1 "Chloride d 1 allyl-methyl-di- (hydrogenated tallow) -ammonium (abbreviated AM2HT)

824.7 g of methyl-di- (hydrogenated tallow) -amine, about 350 ml of isopropyl alcohol, 250 g of NaHCO 2 were placed in a 4-liter reactor equipped with a condenser and a mechanical stirrer. , 191.3 g of allyl chloride and 10 g of allyl bromide (as catalyst). The mixture was heated and left under mild reflux. Periodically, samples were taken, filtered and titrated with standardized HCl and NaOH. The reaction was considered complete when there was 0.0% amine hydrochloride and 1.8% amine. The final analysis indicated a / mass. molar: effective 831.17.

EXAMPLES 2 to 4

A 3% clay slurry which was the sodium form of Wyoming bentonite in Examples 2 and 3 and the hectorite in Example 4 was heated to 60 ° C with stirring.

A solution of cationic compound which was ethanol-methyl-di- (hydrogenated tallow) -ammonium chloride (EM2HT) for Example 2 was added to the slurry of clay and 1ΆΜ2ΗΤ prepared in Example 1 for Examples 3 and 4, and stirred for 20 minutes. The organoclay was collected on a vacuum filter. The cake was washed with water at 60 ° C and dried at 60 ° C. The dried organo-clay 18 was ground in a hammer mill to reduce the particle size, then passed through a sieve with 74 µm openings.

EXAMPLES 5 to 24

These examples demonstrate the preparation of organophilic clays of the invention with various organic anions and, as organic cation, allyl-methyl-di- (hydrogenated tallow) -ammonium chloride (AM2HT). As a comparative example, a conventional organophilic clay is used using the organic cation AM2HT. The compositions are indicated in Table I and the compatibility with the solvents in Table I (a). The data show the superior dispersion characteristics of the organophilic clays of the invention, in comparison with organophilic clays prepared in the absence of the organic anion.

15 TABLE I

Example Report Report No. Organic anion (salt) ME of organic cation anion ME _ _ organic 5 Na benzoate 15 115 6 Na benzoate 22.5 122.5 20 7 Na benzoate 30 130 8 Na benzoate 10 110 9 Na benzoate 22 , 5 130 10 p-Phenosulfonate Na 15 115 5 11 p-Phenosulfonate Na 30 130 25 12 p-Phenosulfonate Na 22.5 122.5 13 p-Phenosulfonate Na 10 110 14 Salicylate Na 30 130 15 Salicylate Na 22.5 122.5 16 Na salicylate 15 115 30 17 Dioctadecyl phosphite 22.5 122.5 18 Benzoic acid 22.5 122.5 19 Disodium phthalate 22.5 122.5 20 Na octoact 22.5 122 , 5 21 Na stearate 22.5 122.5 35 22 Na laurate 22.5 122.5 23 12-Na hydroxystearate 22.5 122.5 24 Trisodium citrate 22.5 122.5

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O DD

P 0 c 33 43 ε 0 0 ε p

3 p oOiAooaoououaoouvûpour ^ aoooupou ^ OLA P C P P P P P PP P P P P P P P P P P

o o> ct | -ο ς- C p 4-3 0 Ifl

COULD

O- 3 ε mvor'.coo \ opourn4ÎLn \ 0r'.®ONOPO4rei.d- α.

0 ppppppppppououououou ε X ο LU C_3 * 20

Examples 2¾ to 45

These examples illustrate the preparation of organophilic clays of the invention with various organic anions and, as the organic cation, diailyl-di- (hydrogenated tallow) ammonium (2A2HT) chloride. As a comparative example, a conventional organophilic clay using the organic cation 2A2HT is presented. The compositions are indicated in Table II and the compatibility with the solvents in Table II (a). The data illustrate the very superior dispersion characteristics of the organophilic clays of the invention, in comparison with organophilic clays prepared in the absence of the organic anion.

TABLE II

- Example Organic anion (salt) Report by M.E. Report by M.E.

15 n ° ___ organic ion of cation orqan.

25 Na salicylate 22.5 129.4 26 Na napthalene-l-carboxylate 22.5 129.4 27 p-Toluate Na 22.5 122.5 28 · Na borate 22.5 * 122.5 2Q 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 1-Na butanesulfonate 22.5 122.5 25 34 Na p-toluenesulfonate 22.5 122.5 35 Na benzenesulfonate 22.5 122.5 36 Na benzene-i, 3-sulfonate 22.5 122.5 37 p-Phenolsulfonate 22.5 122.5 38 Na 12-hydroxystearate 22.5 122.5 30 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 2-Na Ethylhexanoate 22.5 122.5 44 Na Hexanoate 22.5 122.5 45 Na Dodecylbenzenesulfonate 22.5 122.5

Comparative None none 110 21 c ο

• H

OJ -P HJ Ό a)

U -P

3 <D C

+ -> E 4) “ΰ O m O N Μη I 00 M COfMO-d-OD ί OOON O W

C 3 = PJ 00 PJ O PJ 00 ι "Β I 00 OC 00 M 00 CO Γ '0V 00 O 00 00 UB PJ

· "I— | P P p o on

CL> VU B

- P 3 O

a a> -P

a c P <u c tu ε b ε <u> 3 P J- ^ l-VOVÛ ΟΙιΛί VOÎOtOd · ®VO «inis PJ V0

P P t (- P i — i p P P I P -P ”p (P P P P P P P P P p P P

O oc

"Λ> O

in c

"p. O

O P P <U -P

>. -a oo

O P

'4) 4) C

ό ε ω ο 03 ε tn .dp · ρ ojmtMOP nmoiMN pj m oj .d · pj OOd-roi Οιλ P "PD O PPPPP PPPPP ppppp OB P P P P P P P> '4) __Ό vo t0

tU <U O C

"/ 4) 4) -P

dd 0) 3C C

t. P P <ü C b o <u ε fl p + jg 0

> <0 3 P OB Ο Ή PJ ΟΛΟΗ ΟΝΛίΟΜ vflONOO 0 \ PJ

t PPP Ρ p Ρ P P pp ppi — ipp ppppp p O J = o c ° a> o <0 _ cn tn c

0 O

m p «>« p

dd C T3 P

v ^ O (0

O C P (D P

P 4) B '4) ε C

p>> O 34) 00 tfl vfl | s ® C0 B0 d · PJ d- d "uB p d" 00 ΝΦΟΌΟ PB d "

". P ρε PPPPP ppppp p p p p p PB p OJ p PJ PP

_ 10 ”>, O P

P ° P> "O

<C '4) CO 3' 4) UJ P -J3 tn -J P g

S Ί! -η 4) P

<· Η I Ο C

h- -Q P 4) p >> O ε

'p -C ε 4) N N P Μ PPOP (MNNNW CO (V! N O N PJ PJ

μ P 3 P P P P P P P P P P P P P P P P iP P P P P

ü? '4) P P

- 2- ε o c ε> o O O) w c o

• H

4) P

a b

P

4) C

ε 4) wd-r-OO ^ r- "d · P" * UB PB C0 vo O0 ιΛ B0 O O CM PJ d · d "(Μ Β

- 4) 3ε Β B (\ J 1Γ \ Β UB ιΛ P »Ρ ι-i B J- d * B Ο <" Ρ | UB Β0 UB PB

C Ρ Ρ ρ / 4) Ο Ό 3> '4) - ρ λ ο Ρ

4) Ρ Ο C

4) α) ε ε ο 3Ρ d "PB Ο UB OB Ο PJ PB PJ d" d- d1 ΒΟ d- d "d" d "Ο PJ d" lp pt (p *) Ip Pp Ip (P Ip (p Ip rp p «4 Ip | p pm) PH-) fp pp pp oc> oo

"P

P + J

CL B

ε w 3o 1Λ tfl [N 00 0 \ O PJ PB d- uB B0 1 ^ · 00 CB Ο P (Μ B d ιΛΒ r: cc \ i oj rvi cm cm bbbbbbbbbbb d- d · d · d- d · d - at.

*. ε

üJ O

o 22 1 *

Examples 46 to 58

These examples demonstrate the preparation of organophilic argil® of the invention with various organic anions and, as organic cation, ethanol-dimethyl- (hydrogenated tallow) 5-ammonium chloride (E2MHT). As a comparative example, a conventional organophilic clay is used using E2MHT as an organic cation. The compositions are indicated in Table III and the compatibility with the solvents in Table III (a). The data illustrate the very superior dispersion characteristics of the organophilic clays according to the invention, in comparison with organophilic clays prepared in the absence of the organic anion.

TABLE III

Report Report

Example Organic anion (salt) M.E. of anion M.E. of cation n ° _i________ organic organic 4-6 Na benzoate 22.5 114.

4-7 Na benzoate 30 130 4-8 Na benzoate 22.5 122.5 2Q 49 Na phenolate 22.5 122.5 50 Na tetraphenylborate 22.5 122.5 51 Na ferrocyanide 22.5 122, 5 52 Fluorescein derivative Na 22.5 122.5 53 Rose Benzal 22.5 122.5 25 54 Disodium phthalate 22.5 122.5 55 Na 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 3Q Comparative none none none 108.1 23 c

O 0 · η Ό + J 0 ¢) .U

ε c 30 co cmi -d · co oovocooi i ι i 14 · r- <É * h m <\ i ai (nj (M m μ ι ι ι ι ι. — i O · Η

> -O

0 '0 C 0 0 4 * ^, a -p (U O c js -a a; ε 0 0 ε ή 3 1- \ oovco or> i ”Hr \ ii ι ι ι ι cm

<Η C rH (Ml rH (Ml N ι-Ι N N I 1 I I I rH

ο ο> 5¾

VS

ο "'•« «ι * * Η 0 0 -μ rH TJ 0 5s 45

Ο 0 C

'0 ε 0 03 3ε Ν Ό ί 1Λ VA Ο (Α (ΜΙ -Η ® œ Ν (Μ ο Ο γΗ · Η ι— | r— (r-i rH rH rH rH π-Ι (Μ rH rH rH rH Ή

= 0 O "O

• H> '0 • h o tn Ό <t 0 O 4->

Ό VC "C

Ό 0 0 00 ε +5 +5 C 0 0 c 0/0 ε Ή Ο 4 * "4 4" (A 0 \ O rH CO cf · ί ON ® - <r — 13 3 4— r — 4 rH rH / P Ή / H rH Ή ι — 4 rH “-H Ή

! ” 10 a.m.

> +5000 Ή JS +5> & (o-Q · e

0 S

Η 0 0 hj ® + 5 -W 0 c 03 0 (—i +5 0 +5

M C + * <U C

□ ,, «· 0 ε 0 rj ~!? 0 3 ε 4- CM MO Mû Ο CO CO r ·. Ο MO αθ Mû (Ml 0 \ Μ p> ι — ι -η · η n NNN ca en (mi ai γα ai (mi> hm · η> ri>, ο Ό ZI 0 0 + 5> '0 <<n -2 "» L + J '0 -g —I +5 0 0 CG -H · Η 0 45

<—I 1 C

1— "H Ή 0 0" >> ε ε · “JS zi 0

• H +5 -H —I 00 <JM O 00 ® N 0 \ · + (Μ ® (VI (Μ ® N

+5 ·> <]} o <* - rH rH (MJ ι-H i — i (Ml rH (MI (Mi ι-H (M! RH (Ml rH

0 ε> c a o ε O c

O O

Ή 0 45 o 0

45 0 C

E 0 ao mo CM 00 (Mvoovflvo en O 4 "O co 3 ε i-tj - (\ JiM m n 0 (M m m no oj m

(“5“ H

0 o -a C> '0, 0 0

3 rH

Oh-

45 0 C

Ό 0 ε 0 0 ε ή 3 <Η m ο Cf ® (Μ 4 "MO MO GO ΌΓΗΓ ^ Γ'Ό

(H C rH (Ml rH rH rH rH rH iH rH rH rH rH rH

o o> ÔT ("I-

• H

+5 0 0

rH H

at 0 ε o.

00 MO r- 00 CM O 5 N Λ + f (Λ MO CO ε X C 4- 4 "<f 4- (A VA KM un vn VA VA VA VA VA o

Ul CJ

k 24

Examples 59 to 72

These examples demonstrate the preparation of organophilic clays of the invention with various organic anions and, as organic cation, various quaternary ammonium chloride.

As a comparative example, a conventional organophilic clay is used using ethanol-methyl-di- (hydrogenated tallow) -ammonium as the organic cation. The compositions are indicated in Table IV and the compatibility with the solvents in Table IV (a). The data illustrate the very superior dispersion characteristics of the organophilic clays according to the invention, in comparison with organo clays. philes prepared in the absence of the organic anion.

V

25 C3 ocr

<U --M

c ce + J D0 "p>

ΙΛ 1Λ Λ 1Π Λ lf \ ΙΛ ιΛ ιΛ ιΛΙΛΙΛ C

Q is ^ vr * "" · "#k" s "%" s λ λ λ flj Q_.Q NNNNIMONNIMN N N N ΙΛ 'd)

q. IjJ NMNNNmNNNN <\ l CM (Μ —I Z

Γ3 ·

CC Z

cm <U On 13 £ σ "£ yc ununu ^ mm mmmm m m tn cm

§ .. £ 2, CMCMCMCMCUOCMCMCMCM CM CM CM LA "T

g-TÏOl CMtMOJCMCMmojCMCMCM CM CM CM.-H O

fg Lu P rpr — fr-it— (r-p, -., —a-prp: —H H H H H H

Q £ O

O

rtj Ή Z>

O

<U '<U

-α ό 4J <U (tf

3 3 <U -P <D <D O

a · CT -PO O 3 3 • h -t ό or ~ cr cr 3 Ό P · Η · Ρ * ρ · Η rg Ç <Ό ^ JS ΙΌ ΙΌ -a -Ό Ό -Ό <Ό <Ό σι Λ ζ iS 2 ζ ό ο ο ο ζ ζ 2 · Η Z 4J ® “10“ · Λ ο Ό “<ΰ J) (0 Τ3 Ζ Η · Η · Η 0 0 η 1> Ό Ό -> Τ3 Ό-α- σ-α C ® Ό X Ο Ο Ο -Ρ <η Ο 0 0 Ο · Ρ Τ3 (U Ο 0 0 Ο> -π iOJS 0Î4PJ-Ï + J Ο - * - I -P .ρ +} -Ρ - Ρ h-ι c - ^ (n-pomi0üjx: o (0 <3 ηο 0 ro «a- rtjQiÖPPOlO.Pi-H <—ι, —ι Ο Ο Ρ

^ P.pp0ONOWfl3ie fO rC N N C

UJ jeTjOOn-ICrHOO + J P P C C A3 _l q.o1,0 · ^ -0 ^ “£ p £ jz jz“ 3 o s <o 33 —icn <: tno \ Q.oa. at. l to o z <I- • "“ V> * S ^ / -s ^ (U '(D' »O vfl) c c c c c v $) sg; v <ü% (!)

U) U) CD D) O

V (ü s (ü v <ü V (ü '<Ü O c O O O

CcCccpppp p Ό „Jn Ό Ό Ό Ό Ό T3 Ό Ό" 0 no C3 ^ '' * -> >> 3 Po °° C) ZZZZ '0)' C Ό £ μ »tj {^ 4 ΛΛ ci CC ** H Ό -a Ό Ό Ό “P“ P “P tp fH oo V®> o> ® p

3 ·> ^ >> 2> »> s · Η · Η * H> r-i >> C Ο) OO en ®H

Π3 £ Cp £: £: Z30330 '0 0 0 0 3 no "w" en Ό ai ρ ρ ρ to U Pa.PPP' - 'w- ^ · -> T3 Ο "Ο Ό Ό" - ·

Ο · Ρ .h Ή · Η * rt I I I I <X3 P>,>,>, I

33ziD3tn (nu3rt4J το jz -g jz <n C ï / 0 jn ΙΛ t / 5 tO · Ρ · Η · Η Ή Ο> * · Η

Ο * _ * - ^ £ 3 .Ο -Ο .Q Ο -C q— <4— <Ρ- _Q

• Η I I 1 I I I I I I · Η · Η · Η I

U —I __> —I. — I I — Ιι — il — irHr-ti—) “P 3 3 3 (0 >>>, >>>>> 1> Y >>>.>, >> P Λ l0 (0>,

O jz £ jijzx: jz £ .jzxzjz 3 ^ ^ JZ

PtjPppppppp cni i i + J '0> .45 Ό Ό Ό' 0 '0' 4) '(U' 0 W, —i, - |, _)> (D

εΐεεεεεεεε ιοοοε

"H .¾ · Ρ · Ρ · Η l ι 1 1 ι ι—) C C C I

"Ο -η Ό Ό Ό Ή ι-Η ^ Ρ r — I γ-η C0 Π3 f £ rp 17 '1 ΙΟΟΟΟ >> ^ JZ JZ JZ Ο

Ή, —Ι'-ΗιΗιΗΟΟΟΟΉ ι — I + J P3 + J C

>) >>>>>>>, mi0iCi0H 10 'φ> φ' JJ HJ

'-iSf'-tr-ir-iJZÆJZJZ ΙΌ · Ρ · Ρ · Η · Η £:' -jiH-j'P'H + J + J + J + JP ΡΡΡΡΡ ”<: <C << uJuuLua ipip-uj <υ ίτ ^ -Ρ Ο. (0 ε ° ρ djCONOi — i (Mcn <j-tr \ vot ^ co ο \ οή <μ re "lAvûvOVOnOvOvOVOvûvO vo [s [ν [sq, * ε LU Ο Ο 26 c ο (U · Η TJ -P fl a -p ε c

3 ΰ OOOOO (\ J rH r ^ o vO VO

H ε Ο Ο Ο Ο rH I I! iA H N Vû H f "p

Ο · Η Ή rH rp rp I I 1 (* VJ

> Ό A Ά C fl fl

-P

Cl

fl -P

X fl C TJ fl ε

a a ε • P

3 <P .TV <j "-d" -3- Ol I ILT (\ J 4 · <Ά 4 *

rH C rp CJ CVI <\ i CVJ rP I I I Μ HHHH Ή O O

> CT)

VS

-V. O

fl fl · Η

rH Ό + J

>. fl

O fl -P

ά ε c ^ TJO 3 fl moooo ao 4 · œ vo oj ιλ fl d · oj cj ·

O 4 ~ r — I S rH i-H rp rp rH r — i rH rH 4 "rH rH rH rH rH

"O * m

• HO> TJ

• H vû Ά TJ fl fl

fl C

T! / fl fl -P

3 TJ C

A rH fl po fl ε fl fl -p ε fl P rP 3 H • ÎOOVOl'sVO OS 4 "CO (\ l <\ l îhimh h C fl rI · Η rH rH rp i — i rH I — i | —i Csl rH * H rp (H t — i fl -PO c

> -C> O

rH a O

O

w c

- *> O

fl fl fl fl · Η

fl C TJ -P

rp o fl

> -P fl -P

MO HJ Ά ε c fl C ü 3 fl H N N CO O C \ J CD - VO 4 · OCMVOOd ·

33> fl -H rP £ CM PS 4 · C'A 4 "rPrHCOfMÛV N N (VI! M H

<fl> >> O * H

Lü Ή * P> TJ

_J 'fl O 3' fl en -p cd xj fl · Η Ο

I— ι-p fl -P

• H · Η fl C

£ 3 I TJ fl • H rH ε

• P>, A A

fl £ £ H

a -p 3 (ρ 4 · VJ co ^ 4- o N 4- vo co 4 · rvj ns vo <\ j

ε Ά rH C rp rH I— | ("VJ H rH rp rp iH <\ l <H rH Ή rH i — I

ο ε ο o o> ct | c o

= A "H

-a -p fl

fl + J

SC VOOCOCOCO N Ο ί O H H (VI fl ΙΛ CD

3 fl et- co MneoNfl ps r \ j cm rp rH

rH ε Ο · Η> T! fl 'fl C- fl / fl

3 -P

rH fl C

O T! fl i— ε fl fl ε h us O vo co Os aoaocvjpj-m vo (sj cm rH oj

3 P rHCVJrHrprH HHHH HHHH rH

rH C

o o

> CT

(p

• H

fl 4J

rp fl a p ε fl AO Ον O H N fl 4 "US VO Γ> CO OJOHN a X C fl vo VO vo VÛ vo vo VO Vû VO vo IV rs | S s LU o

CJ

27 *

Examples 73 to 79

These examples demonstrate the preparation of organophilic clays of the invention with various organic anions and, as the organic cation, diethanol-methyl- (hydrogenated tallow) -ammonium chloride (2EMHT). As a comparative example, a conventional organophilic clay is used using 2EMHT as an organic cation. The compositions are indicated in Table V and the compatibility with the solvents in Table V (a). The data illustrate the much superior dispersion characteristics of the organophilic clays of the invention, as compared to organophilic clays prepared in the absence of the organic anion.

TABLE V

Example Report of Report of .n ° Organic anion (salt) M * E * flag M.E, of cation l-> _. __organic organic 73 Na benzoate 15 115 74 · Na benzoate 15 122.5 75 Disodium phthalate 22.5 122.5 76 Na octoate 22.5 122.5 20 77 Na laurate 22.5 122.5 78 Stearate Na 22.5 122.5 79 Na abietate 22.5 122.5

Comparative None None 111.7

Ir 28 - c o

• H

you + J

"Ό 0

0 4P

<H 0 C

> 1 ε 0 ο · 4 · r ~ i i i i r-

-μ 3 ε OJ fM Ή I i l I zH

3 f — i Ή -Q Ο T3 1> '0 C 0 0 Ό

0 45 4P

+ -> -o c 0 45 4P 45 ε «• 45 ε 45 Ο 3 —i vû Ό VÛ I I I I if

0 -H <P zH z-I ι-i I I I 1. — I

O C

> O

ότι c

45 O

<H 0 * H

>> Ό 4P

0 0 0

dd '0 O 0 4P

t- Τΐ ^ εΟΟΝΙΜΟΟΟΝ ip CO

~ Ο 3 0 <-H r-i Ή <\ l fl 0 o ih ε

V> ‘H \ Ω O -P

zp · Η> -C

o -a 0 '0 1 w - c 0 "0/0 to 3 0 ip

0 0 C 0 4P

PH -P 4P TJ C

0 0 _ - (0 ε 00 O O 00 CO 4 · M ifl

^ O 0 ε 0 rP rP

0 0 4P 3 Ή w> + J Æ -H <p 1 0 0 ° · oc

0t> O

0 ~ CT

> '0> 1 4P zP C

3 Η O 0 O

<-H 00 "fl ri

Law · Η 0 0

—1 -O 0 e 4P

CQ · Η C 3CVOmO \ OVO ΛΙ N N

<4J O rP 0 OJ CA f \ l CM OJ H (Λ (M

1—0 + * ο ε

X_ '0>' H

“O -a = Zp '0 O >> 0 O *

-Q

O 0 4P

0 -a c • H 0 1 0 ε "h ε 0:> i 3 H (\ j ιΛ CO φ CO N Γ '0 \ JC —I 4 * N H ^ 1 zp zP —I M z" 1

4P OC

'0> O

ε σ -> c o 0 "H Ό 4P 0

0 4P

ε c 30O0- (MiffM ΓΑ LA if z — i ε Ή —4 —1 zp z — 1

0 OP

C> T3 / 0_ '0 3 0

-H

O

1— 0 4P Ό C 0 0 ε H 0 ^ 3 Ή 05 σ \ O O 0 \ fl Λ 4

i — i P- r-H (—H

O c

> O

σ 4-

0 -H

zH 4P

Q- 0 ε p 0 ofl -f m VO r- CO 0 \ 0 x o r- r- p- i— f- p- p- o.

lu c ε o a; 29 The invention having been thus described, it is clear that it can be modified in many ways. These variants are considered to fall within the spirit and within the scope of the invention.

Claims (17)

30 'λ% * * 1. Gelling agent of the organophilic clay type, characterized in that it consists of the reaction product of: (a) a salt having an organic cation, the cation of which corresponds to the formula: Γ! - JR -X -R _ R3 _ in which is a β ", unsaturated alkyl group, a hydroxyalkyl group containing 2 to 6 carbon atoms or a mixture thereof, R £ a long chain alkyl group containing 12 to 60 carbon atoms , R ^ and R ^ represent, individually, an unsaturated β-alkyl group, Ύ 2 a hydroxyalkyl group containing 2 to 6 carbon atoms, an aralkyl group, an alkyl group having from 1 to 22 carbon atoms, or mixtures of these, and X represents phosphorus or nitrogen, (b) an organic anion, and (c) a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 g of 25 clay, so that a complex of organic cation and organic anion is interspersed with clay of the smectite type and that l The cation exchange sites of smectite-type clay are replaced by the organic cation. 2. Gelling agent according to claim 1, characterized in that the unsaturated alkyl group at p, Y is chosen from cyclic groups, acyclic alkyl groups containing less than 7 carbon atoms, acyclic alkyl groups substituted by aromatic groups and aromatic groups substituted with aliphatic groups. 3. Gelling agent according to claim 1, characterized in that the hydroxyalkyl group is chosen from i> * 31 cyclic groups and aliphatic groups containing 2 to 6 carbon atoms, the hydroxyl substituent being on one of the carbon atoms in C- to C .. C 6 k. Gelling agent according to Claim 1, characterized in that it contains 12 to 22 carbon atoms. 5. Gelling agent according to claim k, characterized in that R £ is a long chain fatty acid group. 6. Gelling agent according to claim 1, characterized in that the organic anion is derived from an organic acid 1Q having a pKA less than about 11.0. 7. Gelling agent according to claim 1, characterized in that the clay of the smectite type is hectorite or bentonite-sodium. * 8. Gelling agent according to claim 1, characterized in that the amount of organic anion is from 5 to 100 milli-equivalents per 100 g of clay, based on 100% active clay. 9. Gelling agent according to claim 1, characterized in that the quantity of organic cation is sufficient to satisfy the cation exchange capacity of the smectite type clay and the cation exchange capacity of the organic anion. 10. Gelling agent according to claim 1, characterized in that the amount of organic cation is from 80 to 200 r 25 milliequivalents per 100 g of clay, based on 100% active clay. 11. Gelling agent according to claim 1, characterized in that the amount of organic cation is from 100 to 160,160 milliequivalents per 100 g of clay, based on 100% active clay. 12. Process for the preparation of a gelling agent of the organophilic clay type, characterized in that it comprises the steps consisting in: (a) preparing an aqueous slurry containing approximately 1 to 80% by weight of clay of the smectite type. (b) heat the slurry to a temperature of 20 to 100 ° C, (c) add about 5 to 100 milliequivalents of an organic g * 32 anion per 100 g of clay, based on 100% active clay , and a cationic organic compound in which the cation corresponds to the formula: rp T r4-X-R2 R3 in which R ^ is an unsaturated P alkyl group, Ύ a hydroxyalkyl group containing 2 to 6 carbon atoms: or a mixture of these, R2 a long chain alkyl group containing 12 to 60 carbon atoms, R ^ and R ^ represent, individually, an unsaturated alkyl group at p, Y, a hydroxyalkyl group containing 2 to 6 atoms carbon, an aralkyl group, an alkyl group having 1 to 22 carbon atoms, or mixtures thereof, and X represents phosphorus or nitrogen, said organic cationic compound being used in an amount sufficient to satisfy the cation exchange capacity of the smectite type clay and the cationic activity of the organic anion, all by stirring the solution, (d) reacting the mixture for a sufficient time to form a product constituting an organic cation and organic anion complex intercalated with smectite-type clay, the cation exchange sites of the clay being substituted "with the organic cation, and (e) recovering the reaction product. 13. Method according to claim 12, characterized in that the organic cation is chosen from quaternary ammonium salts and phosphonium salts, containing at least one linear or branched alkyl group containing 8 to 22 carbon atoms. 14. Method according to claim 12, characterized in that the organic anion is derived from an organic acid having a pK. less than about 11.0. At ito ft 33 15. The method of claim 12, characterized in that the clay of the smectite type is hectorite or bentonite-sodium. 16. The method of claim 12, characterized in that the amount of organic anion is from 10 to 50 milliequivalents per 100 g of clay, based on 100% active clay. 17. The method of claim 12, characterized in that the amount of organic cation is from 80 to 200 10 milliequivalents per 100 g of clay, based on 100% active clay. 18. The method of claim 12, characterized in that the organic anion is added to the smectite type clay before the addition of the organic cationic compound. 19. The method of claim 12, characterized in that the organic anion and the organic cation compound are added to the clay of the smectite type in the form of an organic cation and organic anion complex.