Patent GB-942812-A (GB)
Title: Improvements in or relating to the production of organo-silicon compounds
IPC: C08G77/48
Filed: 1960-06-10
Abstract: Organo-silanes or siloxanes containing sulphate ester groups attached to silicon atoms through carbon links are prepared by reacting a silane of the formula: <FORM:0942812/C3/1> where R is a monovalent hydrocarbon or halo-hydrocarbon radical, M is a divalent hydrocarbon or halo-hydrocarbon radical containing at least 3 carbon atoms and of which the terminal groups are separated by at least 1 carbon atom, Y is halogen or alkoxy, x and y are 0 to 3 and their sum not greater than 3, or a siloxane derived from such a silane, with sulphuric acid, its anhydride, chlorosulphoric acid or amidosulphonic acid, at a temperature up to 180 DEG C. and, if desired, in the presence of a solvent. Examples of silane starting materials are gamma-acetoxy propyl methyl dichlorosilane, gamma-propionoxy propyl trichlorosilane and delta-acetoxy butyl ethyl dichlorosilane.  The siloxanes derived from these materials may also contain other units and the whole siloxane may be of the formula (B): <FORM:0942812/C3/2> where m and n are 0 to 3, p, q and r are up to 500 and q+r\sF1. In all cases the products contain the group: <FORM:0942812/C3/3> The sulphated silanes may be equilibrated with siloxanes, e.g., with cyclic trisiloxanes, alpha-omega dichlorosiloxanes and siloxanes containing terminal hydroylysable groups together with internal groups of the formula: <FORM:0942812/C3/4> The sulphated silanes or the equilibrates may be hydrolysed to give the acid sulphates of siloxanes. Any of the products may be neutralised by reaction with organic hydroxy compounds or with bases. In this way, surface-active compounds are prepared, and water-insoluble hydroxy compounds such as cellulose and its derivatives are solubilised, although the preferred hydroxy compounds are short-chain aliphatic alcohols. In the Examples: (1) gamma-acetoxy-propyl-methyldichlorosilane is cohydrolysed with dimethyldichlorosilane and trimethylchlorosilane and reacted with conc. H2SO4, the resultant mixture being dissolved in aqueous NH3; (2) allyl alcohol is reacted with tetramethylcyclotetrasiloxane to provide hydroxy propyl groups and the product reacted with H2SO4; (3) the reaction product of gamma-acetoxypropylmethyldichlorosilane and chlorosulphonic acid is reacted with hexamethyltrisiloxane, and in (6) with Cl(CH3)2 Si-O-[(CH3)2SiO]n Si(CH3)2Cl, where n=5.7; (7) the reaction product of (6) is heated with a chlorodimethylsiloxy end-blocked siloxane containing groups of the formula (c) wherein R1= CH3, and is neutralised with sodium bicarbonate; (10) gamma-acetoxy propylmethyldichlorosilane is reacted with chlorosulphonic acid and the product reacted with n-octyl alcohol and ethylamine; (17) the product of (10) is reacted with a chlorodimethylsiloxy end-blocked siloxane of the type used in (7), and then with isopropylamine; (20) the procedure of (17) is repeated using a different amount of siloxane and adding polyethyleneglycol monomethyl ether (mol. wt. 440) to the final reaction mixture.  Uses: emulsifiers, detergents, impregnating and waterproofing materials for textiles, leather, paper, glass, wood and brick.  Specification 899,148 is referred to.ALSO:Textiles, leather, paper, glass, wood and brickwork are impregnated and waterproofed by polysiloxanes containg a sulphate group connected to silicon through a divalent hydrocarbon radical of at least 3 carbon atoms (see Division C3).