Patent GB-769497-A (GB)
Title: Organosilicon alcohols
IPC: C07F7/18
Filed: 1954-12-08
Abstract: The invention comprises silanes and siloxane alcohols produced therefrom, the silanes having the general formula (YOR)R1bSiX3, where Y is an acyl or trihydrocarbonylsilyl radical, R is a divalent saturated aliphatic radical containing at least 3 carbon atoms or a divalent saturated cycloaliphatic hydrocarbon radical, the YO-group being attached to a carbon atom which is at least 3 carbon atoms from the silicon, R1 is a monovalent hydrocarbon or halogenated hyrocarbon radical free from aliphatic unsaturation, X is Cl, Br or H and b is 0 or 1.  The silanes are prepared by reacting a hydrogen-containing silane of the formula R1bSiX4-b, at least one X being H, with an unsaturated aliphatic or cycloaliphatic ester containing one CH2=CH linkage where there is at least one CH2 group between the ester oxygen atom and the =CH carbon atom, the ester being one of an unsaturated aliphatic or unsaturated cyclo- or poly-cyclo-aliphatic alcohol containing at least 3 carbon atoms and either a saturated organic acid or an acidic trihdrocarbonylsilyl compound.  A catalyst such as benzoyl peroxide or tert. butyl perbenzoate may be used. Specified esters are allyl acetate, trimethallyloxysilane, undecenyl acetate, oleyl propionate, 4-cyclohexenol acetate and compounds of the formulae <FORM:0769497/IV(a)/1> and <FORM:0769497/IV(a)/2> The siloxane alcohols, prepared by hydrolysing the above silanes, have the unit formula (HOR)R1bSiO 3-b/2 When the radical Y in the silane is trihydrocarbonylsilyl, hydrolysis is effected by merely adding to water preferably in the presence of a solvent, e.g. toluene or ether. When Y is acyl, dilute aqueous alkali is used.  One or more of the hydrolysates may be subjected to catalytic polymerization.  Examples of R radicals are propylene, butylene, octadecylene and those of the formulae <FORM:0769497/IV(a)/3> and <FORM:0769497/IV(a)/4> Examples of R1 radicals are methyl, ethyl, octadecyl, cyclohexyl, cyclopentyl, phenyl, tolyl, benzyl, naphthyl, xenyl, chlorophenyl, dibromoxenyl, tetrafluoroethyl, pentafluorobutyl and a ,a ,a -trifluorotolyl.  The siloxanes may be copolymerized with other siloxanes and, alone or when copolymerized, may also be reacted with polyfunctional organic compounds, e.g. dicarboxylic acids or anhydrides, di-isocyanates or one or more siloxanes such as those described in Specifications 769,496 and 769,498.  A polyhydric organic alcohol may be included in such a reaction.  In the examples:  (1) 3-phenylsilylpropoxytrimethyl silane is prepared from allyloxytrimethyl silane and monophenylsilane in the presence of tert. butyl per benzoate.  The siloxane of unit formula C6H5[HO(CH2)3] SiO is obtained by hydrolysis with dilute NaOH; (2) 3-amylsilylpropoxytrimethyl silane is prepared as in (1) using mono-amyl silane and from it is obtained the siloxane [(C5H11) HO(CH2)3SiO]x; (3) 3-phenylsilylpropyl acetate is prepared from allyl acetate and monophenyl silane and is hydrolysed in aqueous ethanol containing catalytic amounts of piperidine and NaOH to give the siloxane [OSi(C6H5)(CH2)3 OOCCH3]x. Hydrolysis in the absence of piperidine-1(4) gives the siloxane [HO(CH2)3 (C6H5)SiO]x; (5) a modified alkyd resin is prepared from soya oil fatty acids, pentaerythritol, phthalic anhydride and the siloxane of Example (4). A solution in Stoddard solvent containing driers forms a varnish, and mixing with titanium dioxide forms a paint; (6) the silane acetate, C6H5SiH2(CH2)11 OOCCH3, prepared from undecenyl acetate and monophenyl silane, is hydrolysed to [HO(CH2)11C6H5 SiOx; (7) the silane Br3Si(CH2)3OOCCH3 is prepared from allyl acetate and tribromosilane and hydrolysed to [CH3COO(CH2)3SiO1,5]x which is converted by refluxing in aqueous ethanol containing NaOH to [HO(CH2)3SiO1,5]x; (8) the compound Cl3Si(CH2)3OOCCH3 is prepared from allyl acetate and trichlorosilane; (9) the compound MeSiBr2(CH2)3OSiMe3 is prepared from methy dibromosilane and allyloxytrimethylsilane, and on hydrolysis gives [HO(CH2)3MeSiO]x; (10) the compound ClC6H4SiH2(CH2)3 OSiMe3 is prepared from chlorophenyl silane and allyloxytrimethylsilane and is hydrolysed to [HO (CH2)3(ClC6H4)SiO]x; (11) a copolymeric siloxane containing the units HO(CH2)3SiO1,5, C6H5(Me)SiO, C6H5(C2H3)SiO and Me3SiO0,5 is obtained by cohydrolysing Br3Si(CH2)3 OSiMe3, phenylmethyldichlorosilane and phenylvinyldichlorosilane; (12) the silane <FORM:0769497/IV(a)/5> is prepared from monophenyl silane and <FORM:0769497/IV(a)/6> and is hydrolysed to the siloxane of unit formula <FORM:0769497/IV(a)/7>