Patent GB-1000421-A (GB)
Title: Silicone intermediates and silicones
IPC: C08G77/00
Filed: 1963-08-27
Abstract: Organo-silicon compounds containing the group (X=NO)aR13- aSiR111Si, wherein X is a radical of general formula <FORM:1000421/C3/1> where R11 is a saturated divalent hydrocarbon or halohydrocarbon radical, R1 is a monovalent hydrocarbon halohydrocarbon or cyanoalkyl radical, R is a saturated monovalent hydrocarbon or halohydrocarbon radical, R111 is a saturated divalent aliphatic hydrocarbon radical containing at least two carbon atoms, are prepared by reacting (a) a silane of general formula (X=NO)a YSiR3- a, where Y is an alkenyl radical and either (b) a silane of general formula HaR1mSi(ON=X)4- am, wherein m is 0-3, or (c) a siloxane polymer having at least one silicon-bonded hydrogen atom in the molecule. The preparation of reactants (a) and (b) is given in the parent Specification 975,603. Suitable R and R1 groups are alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl and their halogenation products. In addition R1 may be cyanoalkyl. R11 may be alkyl, cycloalkyl or fully or partially halogenated alkyl groups. R111 groups specified are -(CH2)2-, -(CH2)3, -(CH2)18- and -CH2-CH(CH3). CH2-. Suitable catalysts for the reaction are platinum, platinum salts, chloroplatinic acid and ultraviolet light.  When the reactant (b) is a silane the product is of general formula [(X=NO)aSi(R1)3- aR111]d Si(R1)m(ON=X)4- dm where a is 1-3, d is 1-4 and m is 0-3.  When the reactant is a siloxane (c), the product contains at least one siloxane unit of general formula <FORM:1000421/C3/2> and any remaining units are of the formula <FORM:1000421/C3/3> where c is 0-3.  The products of the invention may be co-reacted by exposing to atmospheric water vapour, if necessary at elevated temperatures or in the presence of condensation catalysts, e.g. amine phosphates, amine carboxylates and the carboxylates of quaternary ammonium compounds, lead and tin.  Suitable additives are plasticizers, e.g. trimethylsiloxyend-blocked dimethyl siloxanes; reinforcing fillers, e.g. fume silicas, silica aerogels and precipitated silicas; non-reinforcing fillers, e.g. diatomaceous earth, crushed quartz and metal oxides; fibrous fillers, e.g. asbestos or glass; pigments, sun-screen agents, oxidation inhibitors, graphite and carbon black. Many examples are given.  Uses.-In adhesives, caulking and coating compositions (see Division B2), plasticizer.ALSO:Coating and adhesion compositions suitable for glass, porcelain, metals, wood, organic plastics and other heat-sensitive materials comprises organo-silicon compounds which may be silanes or siloxanes, which contain a group of general formula (X = NO)aR13-aSi R111Si ­ wherein X is a radical of general formula R2C= or <FORM:1000421/B1-B2/1> where R11 is a divalent hydrocarbon or halohydrocarbon radical, R is a saturated monovalent hydrocarbon or halohydrocarbon radical, R1 is a monovalent hydrocarbon, halohydrocarbon, or cyanoalkyl radical or a hydrogen atom, R111 is a divalent saturated alkyl radical and a is 1-3. Curing is effected by exposure to atmospheric moisture at room temperature, or at an elevated temperature, or in the presence of condensation catalysts, e.g. amines and their phosphates and carboxylates, quaternary ammonium carboxylates, lead octoate, dibutyltin-diacetate, dibutyltin-dilaurate and stannous octoate. The silicon compounds which contain two oxime radicals per molecule may be mixed with polyfunctional materials, e.g. Si(ON = X)4 or R1Si[OSiR12)nON = X]3. Suitable additives are plasticizers, e.g. trimethylsiloxy-end-blocked dimethyl siloxanes; reinforcing fillers, e.g. fume silicas, silica aerogels, and precipitated silicas; non-reinforcing fillers, e.g. diatomaceous earth, crushed quartz, and metal oxides; fibrous fillers, e.g. asbestos or glass; pigments, sun-screen agents, oxidation inhibitors, graphite and carbon black.