Organophilic clay complexes, their preparation and compositions comprising said complexes

An organophilic clay gellant which comprises:

• the reaction product of (a) a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay;
• (b) an organic anion derived from an organic acid having a pK.sub.A less than about 11.0 in an amount ranging from 5 to 100 milliequivalents per 100 grams of said smectite-type clay, 100% active clay basis;
• and (c) an organic cationic compound selected from the group consisting of:
• ##STR7## wherein X is nitrogen or phosphorus, Y is sulfur, M.sup.- is selected from the group consisting of chloride, bromide, iodide, nitrite, hydroxyl, acetate, methyl sulfate and mixtures thereof and wherein R.sub.1 is an alkyl group containing 12 to 22 carbon atoms;
• and wherein R.sub.2, R.sub.3 and R.sub.4 are selected from the group consisting of hydrogen, alkyl groups containing 1 to 22 carbon atoms, aryl groups, aralkyl groups containing 1 to 22 carbon atoms on the alkyl chain and mixtures thereof, said organic cationic compound providing organic cation 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 wherein the cation exchange sites of the smectite-type clay are substituted with the organic cation and wherein substantially all of the formed organic cation-organic anion complex is intercalated with the smectite-type clay.

A process for preparing an organophilic clay gellant which comprises:

• (a) preparing a slurry of smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay in water at 1 to 80% by weight of said clay;
• (b) heating the slurry to a temperature between 20.degree. C. and 100.degree. C.;
• (c) adding 5 to 100 milliequivalents of an organic anion per 100 grams of clay, 100% active clay basis and an organic cation containing at least one group having 12 to 22 carbon atoms 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 while agitating the reaction mixture;
• (d) continuing the reaction for a sufficient time to form a reaction product comprising the smectite-type clay having its cation exchange sites substituted with the organic cation and having substantially all of the formed organic cation-organic anion complex intercalated with the smectite-type clay;
• and
• (e) recovering the reaction product.

A process for preparing an organophilic clay gellant which comprises:

• (a) preparing a slurry of smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay in water at 2 to 7% by weight of said clay;
• (b) heating the slurry to a temperature between 20.degree. C. and 100.degree. C.;
• (c) adding an organic cation containing at least one group having 12 to 22 carbon atoms in an amount up to the cation exchange capacity of the smectite-type clay to the clay slurry under agitation to prepare an organophilic clay reaction product;
• (d) adding 5 to 100 milliequivalents of an organic anion per 100 grams of clay, 100% active clay basis, with agitation to prepare a homogeneous mixture;
• (e) adding additional amounts of an organic cation containing at least one group having 12 to 22 carbon atoms to the homogeneous mixture in an amount sufficient to at least satisfy the available remaining cation exchange capacity of the smectite-type clay and cationic activity of the organic anion while agitating the reaction mixture;
• (f) continuing the reaction for a sufficient time to form a reaction product comprising the smectite-type clay having its cation exchange sites substituted with the organic cation and having substantially all of the formed organic cation-organic anion complex intercalated with the smectite-type clay;
• and
• (g) recovering the reaction product.

A process for preparing an organophilic clay gellant which comprises:

• (a) preparing a slurry of smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay in water at 2 to 7% by weight of said clay;
• (b) heating the slurry to a temperature between 20.degree. C. and 100.degree. C.;
• (c) adding 5 to 100 milliequivalents of an organic anion per 100 grams of clay, 100% active clay basis, with agitation to prepare a homogeneous mixture;
• (d) adding an organic cation containing at least one group having 12 to 22 carbon atoms to the homogeneous mixture 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 while agitating the reaction mixture;
• (e) continuing the reaction for a sufficient time to form a reaction product comprising the smectite-type clay having its cation exchange sites substituted with the organic cation and having substantially all of the formed organic cation-organic anion complex intercalated with the smectite-type clay;
• and
• (f) recovering the reaction product.

A process for preparing an organophilic clay gellant which comprises:

• (a) preparing a slurry of smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay in water at 2 to 7% by weight of said clay;
• (b) heating the slurry to a temperature between 20.degree. C. and 100.degree. C.;
• (c) adding with agitation an organic cation-organic anion mixture composed of 5 to 100 milliequivalents of the organic anion per 100 grams of clay, 100% active clay basis, and organic cation containing at least one group having 12 to 22 carbon atoms 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;
• (d) continuing the reaction for a sufficient time to form a reaction product comprising the smectite-type clay having its cation exchange sites substituted with the organic cation and having substantially all of the formed organic cation-organic anion complex intercalated with the smectite-type clay;
• and
• (e) recovering the reaction product.

A thixotropic cross-linkable polyester composition comprising an unsaturated polyester and an unsaturated aromatic monomer having dispersed therein from 0.25 to 10% by weight of an organophilic clay gellant which comprises:

• (a) a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay;
• (b) an organic anion in an amount ranging from 5 to 100 milliequivalents per 100 grams of said smectite-type clay, 100% active clay basis;
• and
• (c) an organic cation containing at least one group having 12 to 22 carbon atoms, said 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 wherein the cation exchange sites of the smectite-type clay are substituted with the organic cation and wherein substantially all of the formed organic cation-organic anion complex is intercalated with the smectite-type clay.

A non-aqueous fluid system which comprises a non-aqueous fluid composition and a self-activating organophilic clay rheological composition useful as an additive for non-aqueous fluid systems which comprises:

• (a) a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay;
• (b) an organic anion in an amount ranging from 5 to 100 milliequivalents per 100 grams of said smectite-type clay, 100% active clay basis;
• and
• (c) an organic cation containing at least one group having 12 to 22 carbon atoms, said 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 wherein the cation exchange sites of the smectite-type clay are substituted with the organic cation and wherein substantially all of the formed organic cation-organic anion complex is intercalated with the smectite-type clay.

A non-aqueous fluid system which comprises a non-aqueous fluid composition and an organophilic clay gellant which comprises:

• the reaction product of (a) a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay;
• (b) an organic anion derived from an organic acid having a pK.sub.A less than about 11.0 in an amount ranging from 5 to 100 milliequivalents per 100 grams of said smectite-type clay, 100% active clay basis;
• and (c) an organic cationic compound selected from the group consisting of:
• ##STR8## wherein X is nitrogen or phosphorus, Y is sulfur, M.sup.- is selected from the group consisting of chloride, bromide, iodide, nitrite, hydroxyl, acetate, methyl sulfate and mixtures thereof;
• and wherein R.sub.1 is an alkyl group containing 12 to 22 carbon atoms and wherein R.sub.2, R.sub.3 and R.sub.4 are selected from the group consisting of hydrogen, alkyl groups containing 1 to 22 carbon atoms, aryl groups, aralkyl groups containing 1 to 22 carbon atoms on the alkyl chain and mixtures thereof, said organic cationic compound providing organic cation 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 wherein the cation exchange sites of the smectite-type clay are substituted with the organic cation and wherein substantially all of the formed organic cation-organic anion complex is intercalated with the smectite-type clay.