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    Improvements in metallocenylaryl-substituted organosilicon compounds
    82.
    发明专利
    Improvements in metallocenylaryl-substituted organosilicon compounds 未知

    公开(公告)号：GB1082026A

    公开(公告)日：1967-09-06

    申请号：GB4683065

    申请日：1965-11-04

    Applicant: GEN ELECTRIC

    Inventor： WILKUS EDWARD VINCENT ,  BERGER ABE

    IPC: C07F17/02 ,  C08K5/56

    Abstract: The invention comprises metallocenylaryl-substituted-organosilicon compounds having one or two silylaryl radical of formula A1(A)2SiR11-attached to a metallocene nucleus composed of a transition metal chemically combined with two cyclopentadienyl radicals, whose other free valencies are satisfied with monovalent radicals selected from hydrogen, electron-donating organic radicals, electron-withdrawing organic radicals, and mixtures thereof, where A is selected from hydrogen, halogen radicals, halogenated and unhalogenated monovalent hydrocarbon radicals, cyanoalkyl radicals, fluoroalkyl radicals alkoxy radicals, A1 is selected from A radicals and the hydroxy radical and R11 is an arylene radical. Preferred compounds are those of formulae (1) R3SiR11Z and (2) (R3SiR11)2Z1 where R is selected from hydrogen, halogen radicals, halogenated and unhalogenated monovalent hydrocarbon radicals, cyanoalkyl radicals and fluoroalkyl radicals, R11 is an arylene radical and Z is a metallocene radical of formula -[-Q4C5]M[C5Q5] where M is a transition metal chemically combined with two cyclopentadienyl radicals and Q is a monovalent radical selected from hydrogen, monovalent electron-withdrawing radicals and monovalent electron-donating radicals and Z1 is a divalent metallocene radical of formula -[-Q4C5]M[C5Q4-]-. The compounds of Formula (1) are prepared by reacting a Grignard reagent of formula ZR11MgX with a halosilane of formula R3SiX where R, R11 and Z are as defined and X is a halogen radical while those of Formula (2) are prepared by reacting a di Grignard of formula XMgR11Z1R11MgX with the above halosilane. Examples describe the preparation of trimethylsilylphenylferrocene, 1,11-bis(p-trimethylsilylphenyl) ferrocene and p-trimethylsilylphenylmethenocene. The preparation of polymers, e.g. by hydrolysis, from some of the compounds of the invention is referred to. These polymers may be blended with fillers and may be cured by the use of organotris-cyloxy silanes or by ethylorthosilicate and a metal soap. The compounds of the invention may also be used to stabilize poly-siloxanes against degradation by U.V. rays, heat, oxidation &c.ALSO:Haloarylmetallocenes are prepared by adding with stirring to a solution of 100 parts by weight of a metallocene and 500 parts by weight of 96% sulphuric acid, at a temperature of about 25 DEG C., a mixture obtained by diazotizing 86 parts by weight of a haloaniline in 500 parts by weight of 20% sulphuric acid at 0 DEG C. to 5 DEG C. After 24 hours the mixture is filtered and extracted with benzene and 100 parts by weight of zinc dust are added to the filtrate. The resulting mixture is stirred for about one hour and extracted with ether. The ether is stripped and the residue steam distilled to remove unreacted metallocene. The product is again extracted with ether and recrystallized with 90% acetic acid. Examples describe the preparation of p-bromophenylferrocene, 1,11-bis (p-bromophenyl) ferrocene and p-bromophenylruthenocene.

    Organofunctional (ketoximino) silanes - useful as crosslinkers, chain-extenders and -terminators for curable polydioganosiloxane compsns.
    86.
    发明专利
    Organofunctional (ketoximino) silanes - useful as crosslinkers, chain-extenders and -terminators for curable polydioganosiloxane compsns. 未知

    公开(公告)号：FR2345457A1

    公开(公告)日：1977-10-21

    申请号：FR7608804

    申请日：1976-03-26

    Applicant: GEN ELECTRIC

    Inventor： BEERS MELVIN DALE ,  BERGER ABE ,  SELIN TERRY G ,  HAMILTON STEPHEN BRANCROFT

    IPC: C07F7/08 ,  C08L83/04 ,  C07F7/10

    Abstract: Cpds. of formula (I) are new: (R1)(R2)C=NO)-a -(R3OC(O)R d (I) (where R contains is not >8C and is (halo-, nitro- or alkoxy-) hydrocarbyl or cyanoalkyl; R1 and R2 are 1-8C (halo)alkyl; R3 contains 2-8C and is divalent (halo- or alkoxy-) satd. hydrocarbon; R6 is chosen as for R; a is 1-3; d is 1-3; f is 0-2; and a + d + f = 4). Also claimed is a room temp. vulcanisable fluid compsn. which is stable under anhydrous conditions and curable to an elastic solid in the presence of moisture, the compsn. comprising a silanol chain-stopped polydiorganosiloxane of formula (II): (where R4 and R5 contain is not >8C and are (halo-) hydrocarbyl or cyanoalkyl, and n is 10 - 15,000) and a cpd. of formula (I). (I) acts as a crosslinking, chain extending and/or chain terminating agent for (II), and, unlike prior art such cpds., is stable and does not generate corrosive by-products during the curing or chain extending operation. The mixt. of (I) and (II) is esp. for application with concrete substrates, and acts as a caulking or sealing compsn.

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