Patent GB-1093555-A (GB)
Title: Choloromethylated silicon compounds
IPC: C07F7/18
Filed: 1965-12-31
Abstract: A lubricant or hydraulic fluid comprises siloxanes of the formula <FORM:1093555/C4-C5/1> where Ar is an arylene radical, R is an alkylene radical, R1 is a monovalent hydrocarbon radical, n is 0 or 1, a is 1-3, b is 0-2, provided that the sum of a+b does not exceed 3.  The siloxane may also include units of the formula <FORM:1093555/C4-C5/2> where m is 1-3.ALSO:The invention comprises chloromethylated silicon compounds of the formulae <FORM:1093555/C3/1> or <FORM:1093555/C3/2> where Ar is an arylene radical, R is an alkylene radical, R1 is a monovalent hydrocarbon radical, X is halogen or an -OR11 group, where R11 is alkyl, n is 0 or 1, a is 1 to 3 and b is 0 to 2, provided that the sum of a + b does not exceed 3, except when X is chlorine when it does not exceed 2. The compound of Formula II may also comprise units of the formula <FORM:1093555/C3/3> where m is 1 to 3.  Compounds of Formula I may be obtained by chlorine thyration of silanes of the formula <FORM:1093555/C3/4> where Ar1 is a monovalent aryl radical corresponding to the arylene radical Ar defined above, with chloromethylmethyl ether and SOCl2, optionally in the presence of a catalytic amount of ZnCl2, and suitably at temperatures of 35-120 DEG C., and an inert solvent, e.g. n-hexane, benzene, toluene, xylene, n-heptane or dioxan may be present.  When X is fluorine in Formula (IV), the presence of SOCl2 is not necessary in the reaction mixture. The compound of Formula I may be hydrolysed and condensed in a conventional manner either alone, to give a compound consisting of units of Formula II, or together with another silane to give a siloxane comprised of units of Formulae II and III.  Alternatively, silanes of Formula IV may be hydrolysed and condensed either alone or together with silanes of Formula V to produce siloxanes which may then be chloromethylated with chloromethylmethyl ether, optionally in the presence of a catalytic amount of ZnCl2.  When X is halogen other than fluorine in compounds of Formula I, such halogen may be replaced by reacting the silane with a compound of the formula R11-OH or by reaction with an anhydride e.g. acetic anhydride, such reactions suitably being effected in the presence of an acid acceptor e.g. triethylamine. When X is fluorine in Formula I, it may be replaced by heating in contact with a silicon compound containing at least one alkoxy group directly attached to silicon, e.g. methyl triethoxy silane, phenyltributoxy silane, tetramethylsilicate, in the presence of a redistribution catalyst e.g. tetrabutyltitanate, aluminium trichloride, tin dichloride or zirconium tetraethoxide. The arylene radical Ar in Formula I may be monocyclic, bicyclic or a fused ring, it may be unsubstituted or substituted with inert substituents and it may suitably contain 6 to about 18 carbon atoms.  The alkylene radical R in Formula I may be straight or branched chain, it may be unsubstituted or substituted with inert substituents and may suitably contain 1 to about 12 carbon atoms.  The monovalent hydrocarbon radical R1 in Formula I generally contains 1 to about 18 carbon atoms and it may be straight or branched chain alkyl, alkenyl, cycloaliphatic, aryl, aralkyl or alkaryl and may be unsubstituted or substituted with inert substituents. The alkyl radical R11 may be substituted or unsubstituted and straight or branched chain.