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US 8,008,520 B2Granted
Process for the preparation of thiocarboxylate silane
AssigneeMomentive Performance Materials Inc.
InventorsRichard W. Cruse, Tiberiu L. Simandan
Life of this patent
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Abstract
An aqueous process is described in which thiocarboxylate silane is produced from haloalkyl silane by reaction of the haloalkyl silane with an aqueous solution of thiocarboxylate salt. Also described is a process for the preparation of aqueous thiocarboxylate salt from a sulfide and/or hydrosulfide and an acid chloride and/or acid anhydride.
Claims32
A process for the preparation of a thiocarboxylate silane represented by at least one of the formulae:
- (R—Y—S—)a G2(—SiX3)c (1)
- G1[—Y—S-G2(—SiX3)c]a (2)
- [G1(—Y—S—)a]b [G2(—SiX3)c]d (3)
- wherein:
- each occurrence of G1 and G2 is, independently, a polyvalent alkyl, alkenyl, aryl, or aralkyl group, with each G1 and G2 containing from 1 to 40 carbon atoms;
- each occurrence of R is, independently, selected from the group consisting of hydrogen, and alkyl, alkenyl, alkynyl, aryl, and aralkyl groups, with each R containing from 0 to 30 carbon atoms;
- Y is carbonyl, C(═O);
- each occurrence of X is, independently, selected from the group consisting of RO—, R2C═NO—, R2NO— or R2N—, —R, and —(OSiR2)t(OSiR3) and with the proviso that at least one X is not —R and each occurrence of the subscript t is an integer from 0 to 50;
- each occurrence of the subscript a is independently an integer from 1 to 6;
- each occurrence of the subscript b is independently an integer from 1 to 100;
- each occurrence of the subscript c is independently an integer from 1 to 6;
- each occurrence of the subscript d is independently an integer from 1 to 100;
- and, each occurrence of the subscript f is independently an integer from 1 to 6,
- with the proviso that ab=df;
- which comprises reacting an aqueous solution of a salt of a thiocarboxylic acid represented by the formula:
- G1(—Y—SM)a (4)
- wherein:
- each occurrence of G1 is independently a polyvalent alkyl, alkenyl, aryl, or aralkyl group, with each G1 containing from 1 to 40 carbon atoms;
- each occurrence of M is an alkali metal, ammonium, or a mono-, di-, or tri-substituted ammonium;
- and
- each occurrence of the subscript a is independently an integer from 1 to 6;
- with a silane represented by the formula:
- LfG2(—SiX3)c (5)
- wherein:
- each occurrence of G2 is independently a polyvalent alkyl, alkenyl, aryl, or aralkyl group, with each G2 containing from 1 to 40 carbon atoms;
- each occurrence of L is a halogen atom, sulfonate group, sulfinate group, or carboxylate group;
- each occurrence of X is, independently, selected from the group consisting of RO—, R2C═NO—, R2NO—,R2N—, —R, and —(OSiR2)t(OSiR3), wherein each R is, independently, selected from the group consisting of hydrogen, and alkyl, alkenyl, alkynyl, aryl, and aralkyl groups, with each R containing from 0 to 30 carbon atoms and with the proviso that at least one X is not —R and each occurrence of the subscript t is an integer from 0 to 50;
- each occurrence of the subscript c is independently an integer from 1 to 6;
- and,
- each occurrence of the subscript f is independently an integer from 1 to 6;
- and in the absence or presence of phase transfer catalyst to provide a thiocarboxylate silane.
28 more elements
A process for the preparation of a thiocarboxylate silane represented by at least one of the formulae:
- (R—Y—S—)a G2(—SiX3)c (1)
- G1[—Y—S-G2(—SiX3)c]a (2)
- [G1(—Y—S—)a]b [G2(—SiX3)c]d (3)
- wherein:
- each occurrence of G1 and G2 is, independently, a polyvalent alkyl, alkenyl, aryl or aralkyl group, with each G1 and G2 containing from 1 to 40 carbon atoms;
- each occurrence of R is, independently, selected from the group consisting of hydrogen, and alkyl, alkenyl, alkynyl, aryl, and aralkyl groups, with each R containing from 0 to 30 carbon atoms;
- Y is carbonyl, C(═O);
- each occurrence of X is, independently, selected from the group consisting of RO—, R2C═NO—, R2NO—, R2N—, —R, and —(OSiR2)t(OSiR3) and with the proviso that at least one X is not —R and each occurrence of the subscript t is an integer from 0 to 50;
- each occurrence of the subscript a is independently an integer from 1 to 6;
- each occurrence of the subscript b is independently an integer from 1 to 100;
- each occurrence of the subscript c is independently an integer from 1 to 6;
- each occurrence of the subscript d is independently an integer from 1 to 100;
- and, each occurrence of the subscript f is independently an integer from 1 to 6,
- with the proviso that ab=df;
- which comprises:
- (a) charging a reactor with aqueous NaSH;
- (b) adding acyl chloride and a phase transfer catalyst in either order of addition to the agitated aqueous NaSH solution and continuing agitation until reaction is complete, wherein the acyl chloride is represented by the formula:
- G1(—Y-L)a (8)
- wherein:
- each occurrence of G1 is independently R1 or a polyvalent alkyl, alkenyl, aryl or aralkyl group containing from 1 to 40 carbon atoms, where R1 is selected from the group consisting of hydrogen, and alkyl, alkenyl, alkynyl, aryl, and aralkyl groups with each R1 containing from 0 to 30 carbon atoms;
- Y is a carbonyl, C(═O);
- each occurrence of L is a halogen selected from the group F, CI, Br and I, sulfonate, sulfinate, or carboxylate;
- and
- each occurrence of the subscript a is independently an integer from 1 to 6;
- and the phase transfer catalyst is represented by the formula:
- (R1R2R3R4Q+)n A−n (9)
- wherein each occurrence of R1, R2, R3 and R4, is, independently, an R, where each occurrence of R is, independently, selected from the group consisting of hydrogen, and alkyl, alkenyl, alkynyl, aryl, and aralkyl groups, with each R containing from 0 to 30 carbon atoms;
- Q is nitrogen or phosphorus;
- A−n is fluoride, chloride, bromide, iodide, sulfate, bisulfate, carbonate, bicarbonate, hydroxide phosphate, carboxylate, thiocarboxylate, sulfide, or hydrosulfide;
- (c) adding a silane to the aqueous solution obtained in step b with optionally addition of phase transfer catalyst in either order and agitating the solution until the desired extent of reaction is reached, wherein the silane is represented by the formula:
- LfG2(—SiX3)c (5)
- wherein:
- each occurrence of G2 is, independently, a polyvalent alkyl, alkenyl, aryl or aralkyl group, with each G2 containing from 1 to 40 carbon atoms;
- each occurrence of L is a halogen atom, sulfonate group, sulfinate group, or carboxylate group;
- each occurrence of X is independently, selected from the group consisting of RO—, R2C═NO—, R2NO—, R2N—, —R, and —(OSiR2)t(OSiR3), wherein each R is, independently, selected from the group consisting of hydrogen, and alkyl, alkenyl, alkynyl, aryl, and aralkyl, groups, with each R containing from 0 to 30 carbon atoms and with the proviso that at least one X is not —R and
- each occurrence of the subscript t is an integer from 0 to 50;
- each occurrence of the subscript c is independently an integer from 1 to 6;
- and,
- each occurrence of the subscript f is independently an integer from 1 to 6;
- (d) separating the organic phase from the aqueous phase;
- and
- (e) optionally filtering and/or removing residual volatile components by evaporation using heat and/or vacuum.
39 more elements
Dependencies are inferred from the claim text.