Patent GB-684662-A (GB)
Title: Improvements in or relating to the preparation of organo silicon derivatives from unsaturated compounds
IPC: C07F7/08
Filed: 1948-02-04
Abstract: Silicones are obtained by the hydrolysis of organo-silicon compounds having hydrolysable groups attached to silicon, e.g. halogen or hydrogen atoms or alkoxy or aryloxy groups (see Group IV (b)).  The hydrolysis may be carried out in an ether solution by pouring on to ice or ice water mixtures.  The silicones may be dissolved in aromatic or aliphatic hydrocarbon solvents, e.g. hexane, benzene or toluene, in ethers, e.g. dimethyl, diethyl, diisopropyl or dibutyl ether, in cyclic ethers, e.g. dioxan, in diethers, e.g. diethyl ether of ethylene glycol or in mixed ethers, and in esters, e.g. ethyl, butyl or amyl acetate, propionate or butyrate.  Any of the above solvents may be added prior to the hydrolysis step referred to above. Fillers which may be added to liquid silicones include inorganic fillers such as mica, clays and asbestos and organic fillers such as the cellulose products, wood or wood fibres, cellulose fibres or paper.  Other components which may be blended with the silicones are natural resins including rosins, copal or shellac, and synthetic resins including the urea aldehyde resins, e.g. urea formaldehyde, phenol aldehyde, melamine aldehyde, aniline aldehyde, acetone formaldehyde, alkyd or cumaronindene resins, vinyl resins, polymerized vinyl derivatives, allyl di-basic acid resins, acrylate and methacrylate resins, and various cellulose derivatives including the ethers and esters such as nitrocellulose, and the organic esters of cellulose such as cellulose acetate.  In an example, a mixture of silane, monochlorosilane, dichlorosilane, trichlorosilane and tetrachlorosilane is heated with ethylene in a bomb, the product is fractionated, and four chlorine-containing fractions are dissolved in benzene and hydrolysed.ALSO:Organo-silicon compounds are prepared by heating a halogen-free organic compound containing an ethylenic linkage with a silicon compound containing a silicon atom, none of the valences of which is satisfied by a halogen atom and at least one of the valences of which is satisfied by a hydrogen atom.  Mixtures of either of the reactants may be employed in the process.  The reaction may be effected in a number of stages to modify the reaction product and the halogen-free organic compound may be introduced at each stage. It is preferred to heat the reactants in a pressure vessel.  The reaction temperature may vary from 50 DEG  to 450 DEG C.  The reaction conditions may be such that an organo-silicon product is formed having a substituent organic group of lower carbon content than the higher derivatives initially formed.  Organo-silicon products containing a hydrolyzable group attached to silicon, e.g. a halogen or hydrogen atom or an aryloxy or alkoxy group, may be hydrolysed.  The silicon compound reactant may be a mono- or poly-silicon compound and may be wholly inorganic, e.g. silane, disilane, or disiloxane may be used, or may have one or more organic substituent groups, e.g. aliphatic, carbocyclic, alicyclic or heterocyclic groups, present in the molecule such as the compounds trimethylsilane and the tributylsilanes.  The silicon compound reactant may contain halogen provided it contains a silicon atom, none of the valencies of which is satisfied by a halogen atom and at least one of the valencies of which is satisfied by a hydrogen atom, e.g. alkyl and aryl substituted silanes may be used and the alkyl and aryl substituents may or may not be halogenated.  The silicon compound reactant may contain other elements, e.g. oxygen, nitrogen or sulphur.  The oxygen may be present in organo-substituted oxygen containing compounds and in organo-substituted oxygen and halogen containing compounds as well as their thio derivatives, e.g. alkoxy, thio-alkoxy, aryloxy and thio-aryloxy silanes such as triethoxysilane and trithiophenoxysilane, and in compounds containing carboxyl acyl groups-particularly those derived from fatty acids, e.g. triacetoxy- and diacetoxy-silane.  The nitrogen may be present directly linked to silicon as in an amino-, imino-, substituted amino-, or substituted imino-silane or a silazane, e.g. N-diethylamino-dimethylsilane and sym.-diethyldisilazane, and the nitrogen containing compounds may be further substituted by halogen and oxygen containing groups.  The ethylenic compound may be an unsubstituted olefin, e.g. ethylene, propene, a butylene or a pentene, or may have substituent groups, e.g. alkyl or other aliphatic groups, aryl or other carbocyclic groups and unsaturated alicyclic groups such as those derived from the cyclo-olefins, as well as other substituent groups including the nitro and nitrile groups.  Diolefins may also be employed, e.g. butadiene, cyclopentadiene and cyclohexadiene, as well as the aryl substituted olefins, e.g. styrene, vinylnaphthalenes, ethylvinyl benzene and allylbenzene, heterocyclic compounds, indene and stilbene.  Other ethylenic compounds mentioned are allyl and vinyl ethers, nitro-olefins, allyl and vinyl esters, esters of acrylic and methacrylic acid, vinyl carbazole, acrolein, ketene, quinone, esters of cinnamic and crotonic acids, esters of maleic acid, particularly diallyl maleate, esters of fumaric acid, maleic anhydride and acrylonitrile.  The reactant containing the ethylenic linkage may also contain silicon.  In the examples: (1) tri-n-butylsilane is heated with ethylene in a bomb to give tri-n-butyl hexyl silane, tri-n-butyl octyl silane and tri-n-butyl decyl silane; (2) a mixture of silane, mono-chlorosilane, dichlorosilane, trichlorosilane and tetrachlorosilane is heated with ethylene in a bomb to give a complex mixture of silicon compounds.  Specification 684,597 is referred to.ALSO:Organo-silicon compounds (see Group IV(b)) and the silicones obtained therefrom (see Group IV(a)) are used as additives for lubricating and hydrocarbon oils, and vegetable oils, e.g. drying oils such as linseed and Chinawood oil, the semi-drying oils such as soya bean oil and the non-drying oils such as castor oil.  The vegetable and other glycerine oils may be blended by cooking.