Patent GB-685542-A (GB)
Title: Improvements in or relating to phenylol silanes and resins prepared therefrom
IPC: C07F7/18
Filed: 1949-11-29
Abstract: The invention comprises a silylphenol-formaldehyde type condensation resin comprising the reaction product of a phenylol silane of the general formula <FORM:0685542/IV (a)/1> wherein R represents an alkyl radical, R1 represents an alkyl or monocyclic aryl radical, a is 2 or 3 and n is 0 or 1, with hexamethylenetetramine, and a process for the preparation of the above resin by heating a phenylol silane of the above general formula with hexamethylene tetramine.  The para isomers of the silylphenols are preferred for resin formation.  The preferred R radical is the methyl radical.  The ratio of reactants may be in the ratio of from 1 to 2 equivalents of hexamethylenetetramine (an equivalent is one-sixth of the molecular weight of the tetramine) for each equivalent of phenylol silane.  A soluble type resin is obtained when a low proportion of hexamethylene tetramine is used or when the reaction is stopped before going to completion.  An insoluble thermoplastic resin is obtained when more hexamethylenetetramine is used or when the reaction is allowed to proceed further by heating, and this resin may be converted to an insoluble infusible state by further heating, if desired more hexamethylenetetramine may be added. The properties of the resin may be varied by incorporating fillers, e.g. wood flour, cotton linters, clays, diatomaceous earth, asbestos, mica, glass fibres, graphite and carbon black.  Modifiers may also be added to the resins, e.g. natural resins, fatty acids, glycerol and alkyd resins.  In examples: (1) p-trimethylsilylphenol is heated at 180 DEG  C. with two equivalents of hexamethylene tetramine to give a solid resin which is ground, is mixed with asbestos powder and hexamethylenetetramine, and is moulded at 150 DEG  C. under a pressure of 2,000 lbs./sq. in.; (6) the viscous non-distillable residue obtained from the reaction of two equivalents of p-chlorophenoxytrimethylsilane, one equivalent of dimethyldichlorosilane and two equivalents of sodium (containing dimethyl - di - (p - hydroxyphenyl) silane as well as complex phenolic siloxanes) is heated to remove hexamethyldisiloxane, hexamethylenetetramine is added, the mixture is heated until it starts to gel and asbestos fibre is then added; the cooled resin is ground and the resulting powder is moulded under heat and pressure.ALSO:The invention comprises organo-silicon compounds of the general formula <FORM:0685542/IV (b)/1> wherein R represents an alkyl radical, R1 represents an alkyl or monocyclic aryl radical, a is 2 or 3 and n is 0 or 1, and a process for the preparation of the above compounds by hydrolysing organo-silicon compounds of the general formula <FORM:0685542/IV (b)/2> wherein R, R1, a and n have the above significance.  The radicals R and R1 may be the methyl, ethyl, octadecyl or cyclohexyl radical and the radical R1 may also be a phenyl radical.  The hydrolysis is preferably carried out in a homogeneous liquid phase, and the rate of hydrolysis may be increased by the addition of a water-soluble acidic or basic material, e.g. acetic or hydrochloric acid or sodium hydroxide. In the examples the following compounds are prepared:-p-Me3SiC6H4OH and its 3.5-dinitrobenzoate and alpha-naphthylurethane, 3-Me-4-M33SiC6H6OH and its p-nitrobenzoate, o-Me3SiC6H4OH and its 3.5-dinitrobenzoate, p - EtMe2SiC6H4OH, 2 - Ph - 4 - Me3SiC6H3OH, Me2Si(C6H4OH)2 and (3-Me-4-OHC6H3)2SiMe2.  Specifications 685,540 and 685,541 are referred to.  Bis - (3 - methyl - 4 - trimethylsiloxyphenyl) di methylsilane is prepared by refluxing one equivalent of dimethyldichlorosilane, two equivalents of 2 - methyl - 4 - chlorophenoxytrimethylsilane and two equivalents of sodium in toluene.