Patent GB-1113121-A (GB)
Title: New silicone organic polymer graft copolymers their production and use
IPC: C08F255/02
Filed: 1965-04-02
Abstract: Gel-free silicon-containing graft polymers are produced by grafting in the presence of a free radical generator (1) an olefinic silicone compound which comprises:  (A) a silane having the formula RaR1bSiX4- (a + b) wherein R is an olefinically unsaturated monovalent hydrocarbon group, R1 is a monovalent hydrocarbon group free of aliphatic unsaturation, a has a value from 1 to 3, b has a value from 0 to 2 and (a + b) has a value from 1 to 3 and X is a hydroxyl group or a hydrolysable group that is non-reactive under the grafting conditions (e.g. methoxy, acetoxy, t-butoxy, propionoxy, phenoxy or a fluorine atom); (B) a siloxane consisting of units of the formula <FORM:1113121/C3/1> wherein the various symbols are as defined above; or (C) a siloxane consisting of 2-98 mole per cent of units as defined above and 2-98 mole per cent of units of the formula <FORM:1113121/C3/2> wherein R1 is as defined above and c has a value of from 1 to 3 to (2) a polyoxyalkylene consisting of at least 6 recurring oxyalkylene units, which may contain terminal ether or ester groups.  The free radical generator can be ionizing radiation (e.g. beta particles, U.V. light, gamma rays, X-rays, protons, deuterons, alpha particles), azo compounds or organic peroxides. In a preferred procedure, the graft polymer is obtained by slowly and simultaneously adding the olefinic silicone compound and a peroxide catalyst containing a peroxy group (-O-O-) linked to a tertiary carbon atom, to a polyoxyalkylene at a suitably elevated temperature; preferred peroxides include t-butyl hydroperoxide, di-t-butyl peroxide and dicumyl peroxide.  The polyoxyalkylene can also serve as liquid medium for the grafting process, or an added solvent may be used, e.g. benzene, toluene or xylene, to obtain a homogeneous solution.  The graft copolymers are useful wetting agents, e.g. in paints, inks and mould release compositions, and can be used as rubber lubricants.  They are also useful additives in compositions containing thermoplastic polymers, e.g. polystyrene, polyethylene, polyalkyl acrylates and polyvinyl chloride.  Also, they can be used as stabilizers for urethane foams, which stabilized products are obtained by reacting and foaming a mixture comprising an organic compound containing at least two OH groups reactive with isocyanates, an organic isocyanate containing at least two isocyanate groups, a catalyst for the reaction of the hydroxy and isocyanate compounds to produce a polyurethane, a blowing agent, and the graft copolymer stabilizer.  The hydroxy compound is preferably a polyether (although compounds such as hydroxyl-containing polyesters, polyamides and polyamines may also be used). Foaming agents include methylene chloride, water, halofluorocarbons, nitrogen, carbon dioxide, methane, helium and argon.  Suitable catalysts for polyurethane formation include amines, organotin compounds, organometallic compounds of lead, arsenic, antimony or bismuth, organic titanium halides, inorganic halides of the aforementioned metals, titanium and copper chelates, polystannates, mercury compounds, phosphines, inorganic or organic bases, and chelates of Be, Mg, Zn or Cd.  The composition for producing the foams may also contain diol forming modifiers, cross-linking agents, flame retardants, thermal stabilizers, plasticizers, fillers, pigments, dyes, antioxidants, antiozonants, deodorants and fungicides.  The production of urethane foams is illustrated in Examples 1 and 2.ALSO:Graft copolymers, which are useful as lubricants for metal-to-metal moving surfaces and as textile lubricants, comprise the product obtained by graft polymerizing on to a preformed polyoxyalkylene certain silane or siloxane compounds containing olefinic unsaturation (see Division C3).