Granted Patent B2

US 9,290,520 · App. 14/088,825 · Granted Mar 22, 2016

Abstract

Claims (57)

1. A process for the preparation of a cyclic and bridging dialkoxy silane composition comprising at least one component having a chemical structure selected from the group consisting of:

wherein:

each occurrence of the —SiX u Z b v Z c w group is independently selected from the group consisting of —SiXZ c , —SiZ b Z c , —SiX 2 Z b , —SiXZ b 2 and —SiZ b 3 ;

each occurrence of R is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl group, alkenyl group, aryl group, and aralkyl group, with each R, other than hydrogen, containing from 1 to 18 carbon atoms;

each occurrence of G is independently selected from the group consisting of hydrogen, a monovalent alkyl, alkenyl, aryl or aralkyl group containing from 1 to 30 carbon atoms, and polyvalent group containing from 1 to 30 carbon atoms derived from an alkyl, alkenyl, aryl or aralkyl group;

each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 1 O(R 4 CR 5 ) f O—, R 1 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO—, R 1 R 2 N—, —R 1 , and —(OSi R 1 R 2 ) t (OSi R 1 R 2 R 3 ), wherein each occurrence of R 1 , R 2 and R 3 is independently R;

each occurrence of Z b , which forms a bridging structure between two different silicon atoms, is independently selected from the group consisting of (—O—) 0.5 and [—O(R 4 CR 5 ) f O—] 0.5 , wherein each occurrence of R 4 and R 5 is independently R;

each occurrence of Z c , which forms a cyclic structure with a single silicon atom, is independently given by —O(R 4 CR 5 ) f O— wherein each occurrence of R 4 and R 5 is independently R;

each occurrence of the subscripts, u, n, v, w, f, p, r, q, j, t, and s, and k, is independently given by u is 0 to 3; n is 1 to 100, with the proviso that when n is greater than 1, v is greater than 0 and all the valences for Z b have a silicon atom bonded to them; v is 0 to 3; w is 0 to 1 with the proviso that u+v+2w is 3; f is 1 to 15; p is 0 to 5; r is 1 to 3; q is 0 to 6; j is 0 to 1, with the proviso that when j is 0 p is 1; t is 0 to 50; s is 1 to 3; and k is 1 and wherein that each of the above structures comprise at least two hydrolysable bridging dialkoxy group, Z b , or at least one hydrolysable cyclic dialkoxy group, Z c ,

the process comprising reacting an aqueous solution of a salt of at least one thioacid with at least one cyclic and bridging dialkoxy haloalkyl silane and, optionally, at least one haloalkyl silane to provide cyclic and bridging dialkoxy silane composition.

2. The process of claim 1 , wherein the cyclic and bridging dialkoxy haloalkyl silane is:

[L r -G-(SiX u Z b v Z w ) s ] n ,

and the structure for the thiocarboxylate salt is selected from the group consisting of the formula:

[(ROC(═O)) p -(G) j ]-Y 1 —SM and

(Z c w Z b v X u Si) q -G-Y 1 —SM

wherein

each occurrence of M is independently selected from alkali metal; ammonium; and mono-, di-, or tri- substituted ammonium;

each occurrence of Y 1 is carbonyl;

each occurrence of R is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl group, alkenyl group, aryl group, and aralkyl group, with each R, other than hydrogen, containing from 1 to 18 carbon atoms;

each occurrence of G is independently selected from the group consisting of hydrogen, monovalent alkyl, alkenyl, aryl or aralkyl group containing from 1 to 30 carbon atoms, and polyvalent group containing from 1 to 30 carbon atoms derived from alkyl, alkenyl, aryl or aralkyl group;

each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 1 O(R 4 CR 5 ) f O—, R 1 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO—, R 1 R 2 N—, —R 1 , and —(OSi R 1 R 2 ) t (OSi R 1 R 2 R 3 ), wherein each occurrence of R 1 , R 2 and R 3 is independently R;

each occurrence of Z b , which forms a bridging structure between two different silicon atoms, is independently selected from the group consisting of (—O—) 0.5 and [—O(R 4 CR 5 ) f O—] 0.5 , wherein each occurrence of R 4 and R 5 is independently R;

each occurrence of Z c , which forms a cyclic structure with a single silicon atom, is independently given by —O(R 4 CR 5 ) f O— wherein each occurrence of R 4 and R 5 is independently R;

each occurrence of L is independently chloro or bromo, and

each occurrence of the subscripts, f, j, n, p, q, u, v, w, r, t, and s is independently given by f is 1 to 15; j is 0 to 1, with the proviso that when j is 0 p is 1; n is 1 to 100, with the proviso that when n is greater than 1, v is greater than 0 and all the valences for Z b have a silicon atom bonded to them; p is 0 to 5; q is 0 to 6; u is 0 to 3; v is 0 to 3; w is 0 to 1 with the proviso that u+v+2w is 3; r is 1 to 3; t is 0 to 50, and s is 1 to 3 and wherein the structure, [L r -G-(SiX u Z b v Z w ) s ] n , comprises at least two hydrolysable bridging dialkoxy groups, Z b , or at least one hydrolysable cyclic dialkoxy group, Z c .

3. The process of claim 1 , wherein the reaction temperature is about 40 to about 85° C. and the pressure is ambient.

4. The process of claim 1 , wherein the reaction is carried out in the presence of at least one phase transfer catalyst of the formula:

(R 6 R 7 R 8 R 9 N + ) m A −m

wherein each occurrence of R 6 , R 7 , R 8 and R 9 is independently R, where R is selected from the group consisting of hydrogen, straight, cyclic or branched alkyl group-alkenyl group, aryl group, and aralkyl group, with each R, other than hydrogen, containing from 1 to 18 carbon atoms; N is nitrogen; A −m is a monovalent or polyvalent anion selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, bisulfate, carbonate, bicarbonate, hydroxide, phosphate, carbox late and h drosulfide, where the minus sign denotes that the species is an anion, and m denotes the number of negative charges on the anion; and the subscript m is a positive integer of from 1 to 6.

5. The process of claim 4 , wherein the phase transfer catalyst is selected from the group consisting of tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydroxide, methyltributylammonium chloride, methyltributylammonium bromide, methyltributylammonium iodide, methyltributylammonium hydroxide, tetraoctyl ammonium chloride, tetraoctylammonium bromide, tetraoctylammonium iodide, tetraoctylammonium hydroxide, methyltrioctylammonium chloride, methyltrioctylammonium bromide, methyltrioctylammonium iodide, methyltrioctylammonium hydroxide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltributylammonium chloride, dibenzyldimethylammonium chloride, dibenzyldimethylammonium bromide, dibenzyldiethylammonium chloride and dibenzyldibutylammonium chloride.

6. A process for the preparation of a cyclic and bridging dialkoxy silane composition comprising at least one component having a chemical structure selected from the group consisting of:

wherein:

each occurrence of the —SiX u Z b v Z c w group is independently selected from the group consisting of —SiXZ c , —SiZ b Z c , —SiX 2 Z b , —SiXZ b 2 and —SiZ b 3 ;

each occurrence of R is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl group, alkenyl group, aryl group, and aralkyl group, with each R, other than hydrogen, containing from 1 to 18 carbon atoms;

each occurrence of G is independently selected from the group consisting of hydrogen, a monovalent alkyl, alkenyl, aryl or aralkyl group containing from 1 to 30 carbon atoms, and a polyvalent group containing from 1 to 30 carbon atoms derived from alkyl, alkenyl, aryl or aralkyl group;

each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 1 O(R 4 CR 5 ) f O—, R 1 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO—, R 1 R 2 N—, —R 1 , and —(OSi R 1 R 2 ) t (OSi R 1 R 2 R 3 ), wherein each occurrence of R 1 , R 2 and R 3 is independently R;

each occurrence of Z b , which forms a bridging structure between two different silicon atoms, is independently selected from the group consisting of (—O—) 0.5 and [—O(R 4 CR 5 ) f O—] 0.5 , wherein each occurrence of R 4 and R 5 is independently R;

each occurrence of Z c , which forms a cyclic structure with a single silicon atom, is independently given by —O(R 4 CR 5 ) f O— wherein each occurrence of R 4 and R 5 is independently R;

each occurrence of the subscripts, u, n, v, w, f, p, r, q, j, p, t, and s, and k, is independently given by u is 0 to 3; n is 1 to 100, with the proviso that when n is greater than 1, v is greater than 0 and all the valences for Z b have a silicon atom bonded to them;

v is 0 to 3; w is 0 to 1 with the proviso that u+v+2w is 3; f is 1 to 15; p is 0 to 5; r is 1 to 3; q is 0 to 6; j is 0 to 1, with the proviso that when j is 0 p is 1; t is 0 to 50; s is 1 to 3; and k is 1 and wherein that each of the above structures comprise at least two hydrolysable bridging dialkoxy group, Z b , or at least one hydrolysable cyclic dialkoxy group, Z c ,

the process comprising reacting a thiocarboxylate-alkoxy silane having an alkoxysilyl moiety with a diol of the general formula:

HO(R 4 CR 5 ) f OH

in the presence of a catalyst to effect the transesterification of the alkoxysilyl moiety of the thiocarboxylate-alkoxy silane and provide the cyclic and bridging dialkoxy silane composition.

7. The process of claim 6 carried out in the presence of a catalyst which is an acid, base or transition metal-containing compound.

8. The process of claim 7 , where the acid is selected from the group consisting of p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, chlorosilanes, chloroacetic acid, phosphoric acid and mixtures thereof; the base is selected from the group consisting of sodium methoxide, sodium ethoxide and mixtures thereof; the transition metal-containing compound is selected from the group consisting of tetraisopropyl titanate, dibutyltin dilaurate, titanium alkoxides, titanium-containing chelates, zirconium alkoxides, zirconium-containing chelates and mixtures thereof.

9. The process of claim 6 , wherein the catalyzed reaction of silane and diol is carried under distillation to remove volatile alcohol by-product.

10. The process of claim 6 , wherein the diol is selected from the group consisting of 1,2-ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 2-methyl-2,4-pentanediol, 1,4-butanediol, 1,6-hexanediol, cyclohexane dimethanol, pinacol and mixtures thereof.

11. The process of claim 6 , where the reaction temperature is about 30 to about 90° C.

12. The process of claim 6 , where the reaction pressure is about 1 to about 80 mm Hg absolute pressure.

13. The process of claim 6 , wherein a molar ratio of at least about 0.5 moles of diol per alkoxy-silyl in the silane is employed.

14. The process of claim 6 , further comprising:

a) reacting, in a thin film reactor, a thin film reaction medium comprising a thiocarboxylate-alkoxy silane, a diol and a catalyst to provide a diol-derived thiocarboxylate-alkoxy silane and a by-product alcohol;

b) vaporizing the by-product alcohol from the film to drive the reaction;

c) recovering the diol-derived thiocarboxylate-alkoxy silane reaction product;

d) optionally, recovering the by-product alcohol by condensation; and,

e) optionally, neutralizing the diol-derived thiocarboxylate-alkoxy silane product to improve its storage stability.

15. The process of claim 14 , where the film is formed in a falling film evaporator device, a wiped film evaporator device or a distillation column.

Assignments (23)