Aqueous catalytic process for the preparation of thiocarboxylate silane
View Patent ↗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 in the presence of a catalytically effective amount of alkylguanidinium salt.
1. A process for the preparation of thiocarboxylate silane represented by the formula:
G 1 [-Y—S-G 2 (SiX 3 ) c ] a (2)
which comprises reacting an aqueous solution of salt of thiocarboxylic acid represented by the formula:
G 1 (-Y—S − M 30 ) a (4)
with a haloalkyl silane represented by the formula:
L f G 2 (-SiX 3 ) c (5)
with continuous agitation, at a temperature of between 40° C. and 95° C. and in the presence of a catalytically effective amount ranging from 1 part per million to 3 weight percent of alkylguanidinium salt phase transfer catalyst represented by the formula:
to provide thiocarboxylate silane containing less than 12 weight percent of siloxane-type by-product(s),
wherein G 1 is R wherein R is chosen independently from the set of groups comprising hydrogen, alkyl groups that may or may not contain unsaturation, alkenyl groups, alkynyl groups, aryl groups, and aralkyl groups, with each R containing from 0 to 30 carbon atoms; G 2 is chosen from the group consisting of —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 — and —CH 2 CH(CH 3 )CH 2 —; Y is carbonyl, C(═O): each occurrence of X is independently a member selected from the group consisting of RO—, and —R, with the proviso that at least one X is not —R; L is a halogen; each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a primary alkyl radical containing 1 to 6 carbon atoms; X − is chosen from the group consisting of chloride and bromide; M + is an alkali metal cation; the subscript a is 1; the subscript c is 1; the subscript f is 1; and the subscript n is 1.
2. The process of claim 1 wherein M 30 is selected from the group consisting of sodium cation and potassium cation.
3. The process of claim 2 wherein L is selected from the group consisting of chloride and bromide.
4. The process of claim 1 wherein the salt of thiocarboxylic acid is present in aqueous solution up to its maximum solubility therein under the reaction conditions.
5. The process of claim 1 wherein additional salt is present during the reaction to increase the ionic strength of the reaction medium thereby increasing the stability of the product thiocarboxylate silane from hydrolysis.
6. The process of claim 5 wherein the additional salt is selected from the group consisting of alkali metal halide, alkali metal carbonate and alkali metal nitrate.
7. The process of claim 5 wherein the concentration of the salt of thiocarboxylic acid in the aqueous solution thereof is from about 20 to about 45 weight percent.
8. The process of claim 1 wherein a stoichiometric excess of salt of thiocarboxylic acid or a stoichiometric excess of haloalkyl silane is present.
9. The process of claim 1 wherein the reaction is carried out in the substantial absence of organic solvent which is insoluble in water or has limited solubility in water under the reaction conditions.
10. The process of claim 1 wherein the reaction is carried out in the presence of organic solvent which is insoluble in water or has limited solubility in water under the reaction conditions.
11. The process of claim 1 wherein the alkylguanidinium salt is at least one member selected from the group consisting of hexaethylguanidinium bromide, tetramethyldibutylguanidinium bromide, hexabutylguanidinium chloride, and mixtures thereof.
12. The process of claim 1 wherein the catalyst is present in the reaction medium at a concentration of from about 10 parts per million to about 1 percent by weight.
13. The process of claim 1 wherein the product thiocarboxylate silane is selected from the group consisting of 2-triethoxysilyl-1-ethyl thioacetate; 2-trimethoxysilyl-1-ethyl thioacetate; 2-(methyldimethoxysilyl)-1-ethyl thioacetate; 3-trimethoxysilyl-1-propyl thioacetate; triethoxysilylmethyl thioacetate; trimethoxysilylmethyl thioacetate; triisopropoxysilylmethyl thioacetate; methyldiethoxysilylmethyl thioacetate; methyldimethoxysilylmethyl thioacetate; methyldiisopropoxysilylmethyl thioacetate; dimethylethoxysilylmethyl thioacetate; dimethylmethoxysilylmethyl thioacetate; dimethylisopropoxysilylmethyl thioacetate; 2-triisopropoxysilyl-1-ethyl thioacetate; 2-(methyldiethoxysilyl)-1-ethyl thioacetate; 2-(methyldiisopropoxysilyl)-1-ethyl thioacetate; 2-(dimethylethoxysilyl)-1-ethyl thioacetate; 2-(dimethylmethoxysilyl)-1-ethyl thioacetate; 2-(dimethylisopropoxysilyl)-1-ethyl thioacetate; 3-triethoxysilyl-1-propyl thioacetate; 3-triisopropoxysilyl-1-propyl thioacetate; 3-methyldiethoxysilyl-1-propyl thioacetate; 3-methyldimethoxysilyl-1-propyl thioacetate; 3-methyldiisopropoxysilyl-1-propyl thioacetate; 3-trimethoxysilyl-1-propyl thiooctanoate, also known as 3-trimethoxysilyl-1-propyl thioloctoate and 3-trimethoxysilyl-1-propyl thiocaprylate; 3-triethoxysilyl-1-propyl thiopalmitate; 3-triethoxysilyl-1-propyl thiooctanoate, 3-triethoxysilyl-1-propyl thiodecanoate; 3-triethoxysilyl-1-propyl thiododecanoate, 3-triethoxysilyl-1-propyl thiotetradecanoate, 3-triethoxysilyl-1-propyl thiobenzoate; 3-triethoxysilyl-1-propyl thio-2-ethylhexanoate and 3-triethoxysilyl-1-propyl thio-2-methylheptanoate.
14. The process of claim 1 wherein the haloalkyl silane is selected from the group consisting of chioromethyltriethoxysilane, 3-chioroethyl-1-triethoxysilane, 3-chioropropyl-1-triethoxysilane and 3-chiorobutyl-1-triethoxysilane.