Patent GB-730379-A (GB)
Title: Method of preparing organic silicon compounds
IPC: C07F7/18
Filed: 1951-10-22
Abstract: Resinous condensation products are obtained by reacting at least one hydrocarbon comprising a saturated, unsaturated, open chain and/or ring compound with a halogen free silicon compound having at least one Si-H bond at a temperature between 150 DEG  and 160 DEG  C., preferably about 450 DEG  C., and under a subatmospheric pressure. The hydrocarbons may be substituted and contain halogen, oxygen, nitrogen or sulphur.  Suitable silicon reactants are silane and its homologues, silenes, siloxanes, siloxene and its derivatives, and polymeric silicon dihydride.  The organic reactant may have single or multiple bonds, e.g. pentane, cyclohexane and ethylene and their homologues may be used. Suitable substituted organic compounds for use in the above process are ethers, esters, aldehydes, ketones and organic oxides and halogen compounds especially chlorides such as methyl ethyl, propyl, vinyl and allyl chloride.  Oily condensation products obtained by the above process may be thickened by heating with the exclusion of oxygen, or may be allowed to harden by exposure to the air, e.g. to form a coating on a surface.  In addition to the resinous condensation products obtained by the above process, organic silicon compounds having 1 to 3 hydrogen atoms attached to a silicon atom may be prepared and may be subjected to oxidation or hydrolysis to form silicones having similar uses to the oily condensation products referred to above.  In the examples resinous condensation products are obtained by reacting silane with each of the following reactants:-ethylene, ethylene oxide, ether and acetone.  A polymeric oil having the composition (SiClR)x, where R represents CH3, C2H5 and C3H7, and a solid polymeric substance having the empirical formula (Si2ClR)x, where R represents butyl, are obtained by reacting silane and vinyl chloride.  A solid polymer of the formula (CH3Si)x is isolated from the product obtained by reacting ethylene and silane.ALSO:Organic-silicon compounds which contain in the molecule one silicon atom or a plurality of silicon atoms either directly bound to each other or through one or more carbon atoms by reacting at least one hydrocarbon comprising a saturated, unsaturated, open-chain and/or ring compound with a halogen-free silicon compound having at least one Si-H bond at a temperature between 150 DEG  and 600 DEG  C., preferably about 450 DEG  C., and under a sub-atmospheric pressure.  The hydrocarbons may be substituted and contain halogen, oxygen, nitrogen or sulphur.  Suitable silicon reactants are silane and its homologues, silenes, siloxanes, siloxene and its derivatives and polymeric silicon dihydride. The organic reactant may have single or multiple bonds such as pentane, ethylene and cyclohexane and their homologues. Substituted organic compounds which may be used are ethers, esters, aldehydes, ketones and organic oxides, and halogen compounds especially chlorides such as methyl, ethyl, propyl and allyl chloride.  The reaction between silane and the oxygen containing hydrocarbons such as diethyl ether, acetone or ethylene oxide produces primarily alkoxy silanes of the type ROSiH3. In the case of diethyl ether high-boiling substances containing Si-H bonds are obtained, e.g., a compound of the type (H5C2O)2HSiOSiH(OC2H5)2.  Othe types of compounds which are prepared may contain one hydrocarbon radical attached to silicon as in CH3SiH3 or C2H5SiH3, or may be of the formula R2SiH2 as exemplified by (CH3) (C2H5)SiH2, (CH3) (C3H7)SiH2 or (C2H5)2SiH2, or compounds of the type R3SiH and R4Si, in which one or more hydrogen atoms may also be substituted by silicon-hydrocarbon radicals to form, for instance, a compound of the formula (C2H5)2CH3SiCH2SiCH3(C2 H5)2.  Products containing hydrogen attached to silicon may be subjected to oxidation or hydrolysis to form compounds having Si-OH or Si-O-Si bonds.  In the examples: (1) monosilane and ethylene are reacted in accordance with the above process to produce the compounds CH3SiH3, C2H5SiH3, (CH3)3 Si H, (CH3)4 Si, (C3 H7 CH3 Si H2, (C2H5) CH3 Si H2, (C2H5)2\t Si H2, (C2H5)3 Si H, Si2 (CH3) (C2 H5)4 H, Si2 (CH3)3 (C2 H5)3 and Si2 (C2 H5)3 (C3 H7) H2; (2) monosilane and ethylene oxide are reacted to form the compounds C2H5OSiH3 and C3H7OSiH3 (3) monosilane and diethyl ether are reacted to form the compound C2H5OSiH3 together with a high-boiling fraction containing the compound (H5C2O)2HSiOSiH(OC2H5)2; (4) monosilane and acetone are reacted to form the compound C3H7OSiH3; (5) monosilane and vinyl chloride are reacted to form a volatile portion containing compounds of the type R2SiHCl, RSiH2Cl and R3SiCl, where R represents CH3, C2H5 and C3H7; (6) monosilane and ethylene are reacted as in (1) and the compounds (C3H7)C2H5SiH2, Si2C9H24 and Si(C4H10)4 are additional compounds prepared; (7), (8) siloxene is reacted with pentane and with cyclohexane to form the compounds CH3SiH3, C2H5SiH3, (CH3)2SiH2 and (C2H5)2SiH2; (9) polymeric silicon dihydride and ethylene are reacted to form the products specified in (7).  The following additional products are referred to: (C3H7)CH3Si (OC2H5)2, (C2H5)3(CH3)5Si3, (C2H5)6(CH3)4Si4, C3H7OSi(OC2H5)3 and C3H7OSi(OCH3)3.