Patent GB-802969-A (GB)
Title: A process for the preparation of organosilicon compounds
IPC: C07F7/08
Filed: 1956-11-26
Abstract: Organosilanes and siloxanes, mostly containing acyloxy-, carboxyester- and halophenoxy-substituted groups, are prepared by reacting a tertiary amine salt of an acidic organic compound, the acidic compound having a dissociation constant greater than 1 X 10-7 and the organic radicals attached to nitrogen in the amine salt being alkyl radicals of 1 to 4 carbon atoms, with a silicon compound containing at least one monohalogenated alkyl radical attached to at least one silicon atom.  Suitable acidic compounds for preparing the amine salts are mono- and di-carboxylic acids, which may be substituted, and halogenated phenols; benzene sulphonic acid is also mentioned.  Specified compounds are of the groups: saturated aliphatic acids, aromatic acids, unsaturated, including di- and tri-olefinic and acetylenic acids, dicarboxylic acids which are straight and branched chain, saturated and unsaturated, aliphatic, cycloaliphatic and aromatic; hydroxy, alkoxy, aryloxy and haloaryloxy-substituted aliphatic, aromatic and cycloaliphatic acids; and halogenated hydrocarbon carboxylic acids.  Mixtures of acids and/or amines may be used in the formation of the salt.  The organosilicon reactant may be monomeric or polymeric, and the siloxanes may be copolymeric. Many examples of these compounds are given.  Reaction is preferably effected in the liquid phase at elevated temperatures, and a solvent such as a hydrocarbon, halohydrocarbon or ether, is desirable.  Instead of reacting with the amine salt per se, the silicon compound may be mixed with the amine and acidic compound, followed by heating.  When the acidic reactant is unsaturated, a polymerization inhibitor is preferably added, e.g. hydroquinone or N,N1-diphenyl-phenylene diamine.  The products may be used as moulding and laminating resins, electrical insulation, gaskets, sun-screen agents, ingredients in paints, waxes and polishes, lubricants, lubricant additives, rust inhibitors, emulsifiers, and as reactants for other functional compounds.  In the examples: (1) tetramethyldisiloxane-bis-(1,3-methylacetate) is prepared from acetic acid, triethylamine, or trimethyl-ortributylamine, and [ClCH2(Me))2Si]2O; (2) tetramethyldisiloxane - bis - (1,3 - methylmethacrylate) is prepared from methacrylic acid, triethylamine and [ClCH2(Me)2Si]2O; (3) using 2,4-dichlorophenoxyacetic acid, the product is tetramethyldisiloxane - bis - (1,3 - methyl - 2,4 - dichlorophenoxyacetate); (4) tetramethyl-disiloxane - bis - (1,3 - methylformate) is similarly prepared; (5) the product of (2), but differently prepared, is mixed with hexamethyldisiloxane, sulphuric acid and trifluoroacetic acid to give pentamethyldisiloxane-methyl methacrylate; (6) tetramethyldisiloxane - bis - (1,3-methyl acrylate) and pentamethyldisiloxane methyl acrylate are similarly prepared; (7) diethoxymethylsilylmethylacrylate is prepared from triethylamine, acrylic acid and (chloromethyl)-diethoxy methyl silane; (8) the compound having the average structure <FORM:0802969/IV (a)/1> is prepared from adipic acid, triethylamine and [ClCH2(Me)2Si]2O; (9) maleic acid is substituted for the adipic acid of Example (8); (10) dimethylphenylsilylmethyl acetate and dimethylphenoxysilyl methyl acetate are prepared; (11) starting from chloromethyl pentamethyl disiloxane, pentamethyl disiloxane methyl acrylate is prepared in one step, together with hexamethyl disiloxane and tetramethyl disiloxane - bis - (1,3 - methyl acrylate); (12) a copolymer containing the units ClCH2Si(Me)O, Me3SiO0.5, PhEtSiO, SiO2, cyclohexylmethylsiloxane, BzMeSiO and ViMeSiO is reacted with triethyl ammonium acetate to produce a copolymer containing the units CH3CH2COOCH2SiMeO; (13) MeCHOHCOOCH2CH2SiMe3 is prepared from ClCH2CH2SiMe3, triethylamine and lactic acid; (14) the disiloxanes (HOC6H4COOCH2Me2Si)2O, (HOCH2COOCH2Me2Si)2O and <FORM:0802969/IV (a)/2> are prepared using salicylic, glycollic and 12-hydroxystearic acids respectively; (15) (Cl2C6H3COOCH2Me2Si)2O and (HOOC.C6H4COOCH2Me2Si)2O are prepared from 4,6-dichlorobenzoic and terephthalic acids respectively; (16) (Cl5C6OCH2Me2Si)2O is prepared from pentachlorophenol; (17) <FORM:0802969/IV (a)/3> is prepared from adipic acid, triethylamine and chloromethyl heptamethyl cyclotetrasiloxane; (18) replacing the acetic acid of Example (1) by phenoxyacetic and ethoxyacetic acids produces the compounds <FORM:0802969/IV (a)/4> and <FORM:0802969/IV (a)/5> Specifications 768,790, 769,632, 769,953, 787,046 and 787,209 are referred to.