Patent GB-842674-A (GB)
Title: Improvements in or relating to organosilicon compounds
IPC: C08G77/38
Filed: 1958-05-06
Abstract: Organosilicon compounds are made by reacting (1) a silicon compound containing at least one Si-bonded H atom per molecule, with (2) a hydroxy compound free from aliphatic unsaturation selected from (A) compounds of the formula ROH where R is an acyl, hydrocarbon or halohydrocarbon radical, (B) compounds of the formula R1a [HO(CH2)b] SiO 3-a\2 , where a and b are each 1, 2 or 3 and R1 is a monovalent hydro-carbon radical, (C) polyhydric alcohols, (D) dicarboxylic acids, (E) alkyd resins containing residual OH groups, and (F) organosilicon compounds containing at least one Si-bonded OH group per molecule, by contacting (1) and (2) in the liquid phase in the presence of chloroplatinic acid. In simple form the reaction is illustrated by the equation: \sYSiH + HO.R-->\sYSiOR + H2.  The silicon reactant may be a monomer, polymer, copolymer or any admixture thereof, e.g. HSiCl3, H2SiBr2, RSiH2Cl, R3SiH, HSi(OR)3, HSi(OR)Cl2, RHSi(OOCR1)2, a polysilane, polysiloxane, polysilcarbane or silazane or any copolymer thereof, and may contain, as Si-bonded radicals, alkyl, aryl, aralkyl, alkaryl, cycloalkyl or halohydrocarbon radicals or radicals containing S, Sn or Ge bonded to carbon.  Numerous examples of hydroxy compounds are given.  The reaction may be effected at room temperature or at temperatures up to 150 DEG C. in the presence of the catalyst which is preferably used in solution in an alcohol.  Inert solvents, e.g. benzene, toluene, xylene and saturated petroleum hydrocarbons, may also be present, some solvents having a beneficial effect on the reaction, e.g. iso-octane in amount equal to or greater than the amount of the alcoholic reactant increased the rate of reaction.  In the presence of chloroplatinic acid the hydroxy compounds reacted with Si-bonded hydrogen in preference to Si-bonded halogen.  The reactants are usually used in amounts to provide from 0,5 to 2 reactive groups per Si-bonded hydrogen.  Products containing residual OH or COOH groups can be reacted respectively with dibasic acid acids or poly-hydric alcohols to yield silicone-alkyl resins which can be used as magnet wire enamel.  In typical examples in which Me and Ph denote methyl and phenyl respectively. (1) PhMe2SiH was reacted at room temperature and in the presence of H2PtCl6.6H2O with various alcohols or phenols represented by the formula ROH; the alcohols used were, in descending order of reactivity-benzyl alcohol, butanol, hexanol, Me3SiCH2OH, ethanol, methanol, p-chlorophenol, isopropanol and t-butanol, and in each case the corresponding product of the formula PhMe2SiOR was obtained: (3) PhMe2SiH was similarly reacted with acetic, malonic, sebacic and phthalic acids to give PhMe2SiOOC.CH3 and the isomers PhMe2SiOOC.CH2.COOH and PhMe2SiOOC.CH2.COOOSiMe2Ph, PhMe2Si OOC.(CH2)3COOH and PhMe2SiOOC.(CH2)3 COOSiMe2Ph and PhMe2SiOOC.(C6H4).COOH and PhMe2SiOOC(C6H4).COOSiMe2Ph; (4) (Me2H.Si)2O was similarly reacted with isopropanol to yield Me2H.SiOSiMe2(OCH.Me2) and O[SiMe2(OCH.Me2)]2; (5) Me3SiO(Me HSiO)nSiMe3 was similarly reacted with ethylene glycol to yield a polymer containing Si-bonded O.CH2.CH2OH groups; (9) a copolymer composed of PhSiO15, MeSiO1,5 and MeHSiO units was similarly reacted with a viscous polymer of unit formula [(HOCH2) MeSiO] to yield a resinous copolymer; when ethanol was used instead of the hydroxymethylsiloxane, a copolymer containing Si-bonded-OC2H5 groups was produced; (18) HOSi(Me)2O(Me2SiO)3Si(Me2)OH was similarly reacted with Ph2MeSiH to yield a Ph2MeSi-end-blocked polymer.  Specifications 630,952, 631,049 and 692,669 are referred to.