Patent GB-975603-A (GB)
Title: Improvements in or relating to organosilicon compounds
IPC: C07F7/08
Filed: 1961-12-08
Abstract: The invention comprises silanes of the general formula (X=NO)a SiR14-a, and siloxane copolymers containing the group Si(ON=X), wherein X is R2C= or <FORM:0975603/C3/1> wherein R11 is a divalent hydrocarbon or halogeno substituted hydrocarbon radical, R is a hydrocarbon or halogeno substituted hydrocarbon radical and each may be the same or different, R1 is a hydrocarboxn, halogeno substituted hydrocarbon, cyano alkyl group, or hydrogen atom and may be the same or different, and a is 1, 2, 3, or 4.  Specified R and R1 groups include alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, aralkyl, and alkaryl radicals and these may be substituted by Cl, F, Br or I. Specified R11 groups are: -CH2(CH2)3CH2-, -CH2(CH2)4-CH2-, -C6H4.C6H4-, <FORM:0975603/C3/2> and <FORM:0975603/C3/3> The silanes are prepared by mixing an oxime X=NOH with HalaSiR14-a in the temperature range of 20-100 DEG C. in the presence of acid acceptor. Specified oximes are acetophenone oxime, acetone oxime, benzophenone oxime, 2-butanone oxime, 3-methyl -2- butenone oxime, d-camphor oxime, a -d-carbone oxime, 2-nonaxone oxime, 5-methyl -2- hexanone oxime, 2-pentanone oxime, diisopropylketone oxime, cyclopentanone oxime, cyclohexanone oxime, acrylophenone oxime, 1-acetonaphthone oxime-1-phenyl -2- butanoneoxime, chloro-cyclohexanone oxime, perfluorocyclobutanone oxime, 4-phenyl -2- butanone oxime, 5-isopropyl -2-methyl acetophenone oxime, 12-tricosanone oxime, a -bromo-2, 4, 6-trimethyl-isobutyrophenone oxime, a -bromoacetophenone oxime, anthrone oxime, p-chloro acetophenone oxime and p-a -dibromo acetophenone oxime.  The polysiloxane copolymers consist of units <FORM:0975603/C3/4> wherein b is 0, 1, or 2, d is 1, 2, or 3, and b+d<4, with conventional siloxane units.  One method of preparation comprises reacting a hydroxy-end-blocked siloxane, having units of the general formula <FORM:0975603/C3/5> wherein c is 0, 1, 2 or 3, with a silane R1bSi(ON=CR2)4-6 wherein b is 0, 1 or 2. An alternative method comprises reaction of a halogeno endblocked siloxane with the oxime. These halogeno end blocked siloxane are prepared by reaction of a halogeno-silane R1bSiZ4-6 where b is as above and Z is halogen, in the presence of a hydrogen halide acceptor, such as pyridine, with a hydroxylated organo silicon compound.  Specified hydroxylated organo-silicon compounds are silanediols, silanetriol and hydroxy-end-blocked siloxanes, as above. Halogeno silane and hydroxylated organo-silicon compound must be such that there is at least one R1 radical per silicon in the resulting halogeno-siloxane. The compounds cure in the presence of water vapour to give rubbery or resinous materials.  Elevated temperatures or catalysts such as amino compounds or metal carboxylates may be used.  They may be modified by presence of fillers, e.g. reinforcing silica fillers with or without organosilyl groups attached to the surface, non-reinforcing fillers such as coarse silicas or metallic oxides, asbestos and glass, graphite and carbon black.  Examples describe the preparation of (1) a dimethyl polysiloxane having as end-units (Me2C=NO)2 SiMeO0.5; (3) MeSi(ON=CMe2)3; (5) Si(ON=CMe2)4; (6) (Me2C=NO)3SiO 1/2 ; (7) Me2Si(ON=CMe2)2 (8) Me3SiON=CPh2; (10) MeHSi(ON=CMe2)2; (14) (Me2C=NO)2SiMeO-(SiHMeO)7SiMe-(ON=CM2) 2. Many other examples are given, including vinyl, cyano, chlorine, bromine and fluorine-substituted compounds.  Uses;  Caulking and coating applications on glass, porcelain, wood, metals, and organic plastics.ALSO:Surfaces such as wood, glass, porcelain, metals and plastics may be coated with a composition comprising a silane of the formula (X=NO)aSiR14-a or a copolymeric siloxane containing units of the formula <FORM:0975603/B1-B2/1> where X is R2C= or <FORM:0975603/B1-B2/2> , wherein R and R11 are respectively monovalent and divalent hydrocarbon or halohydrocarbon radicals, R1 is a hydrocarbon, halohydrocarbon or cyanoalkyl group or a hydrogen atom, a is 1 to 4, b is 0 to 2, d is 1 to 3 and b+d is less than 4 (see Division C3).  The compositions may contain other polysiloxanes as well as fillers, e.g. fume and precipitated silicas, silica aerogel, diatomaceous earth, quartz, titania, ferric oxide, zinc oxide, asbestos glass, graphite and carbon black.  They may be applied in organic solvents and the compounds cure on exposure to atmospheric moisture; this may be accelerated by amino or carboxylate catalysts.