Patent GB-1388941-A (GB)
Title: Organosilicone polymers
IPC: C08G77/46
Filed: 1972-04-07
Abstract: 1388941 Organosilicone polymers; polyurethane foams UNION CARBIDE CORP 7 April 1972 [8 April 1971] 16243/72 Headings C3T C3R and C3S An organosilicone polymer comprises monomeric units (A), (B) and (C) wherein: (A) is SiO 4/2 , (B) has the unit formula (C) has the unit formula wherein R and R<SP>1</SP> is a C 1 -C 12  monovalent hydrocarbon group free of aliphatic unsaturation, d = 4-30, n = 2-4 provided at least 75% wt. of the poly-(oxyalkylene chain) is constituted of oxyethylene units, -L- is a bivalent organic radical, preferably a C 2 -C 14  hydrocarbon radical particularly -C m H 2m - where m = 2-4, W is a monovalent organic radical preferably R<SP>1</SP>, R<SP>1</SP>NHCO or R<SP>1</SP>CO-, e = 1, 2, f = 0, 1 provided e + f = 1-2; each of g and h = 0-3, g + h = 3, and wherein the mole ratio of the (A) : (B) units ranges from 0À4 : 1 to 2 : 1, the mole ratio of the (C) : (B) units ranges from 0À2 : 1 to 2 : 1, and the siloxane content ranges from 15-50% wt. based on the total weight of the (A), (B) and (C) units, the remaining weight being constituted of said [WO-(C n H 2n O) d -L-] groups. The polymers may be prepared when L=C m H 2m  by (I) cohydrolysing in an aqueous reaction mixture reactants (A<SP>1</SP>), (B<SP>1</SP>) and (C<SP>1</SP>) where (A<SP>1</SP>) is a compound of the formula X p Si(OY) q (OCOY) r  where X is halogen, Y is a hydrocarbon radical, each of p, q and r = 0-4, p + q + r = 4, (B<SP>1</SP>) is a compound of the formula E<SP>0</SP> e Si(R f )(X) s - (OY) t (OCOY) u  wherein E is hydrogen or the group [WO(C n H 2n O) d -C m H 2m -], each of s, t and u = 0-3, s + t + u = 2-3 and e + f + s +t + u = 4, and (C<SP>1</SP>) is a compound of the formula E<SP>11</SP> g Si(R<SP>1</SP>) h Z wherein E<SP>11</SP> has the same definition as E, and Z is X, -OY, -OCOY or OH and, when g is zero Z can additionally be -OSiR<SP>1</SP> 3 , the aqueous reaction mixture containing 0À4-2 moles (A<SP>1</SP>) per mole of (B<SP>1</SP>) and 0À2-2 moles of (C<SP>1</SP>) per mole of (B<SP>1</SP>); (II) cocondensing the resulting hydrolysate to give the organosilicone polymer when E and E<SP>11</SP> are the [WO(C n S 2n O) d - -C m H 2m -] groups, and (III) when E and E<SP>11</SP> are hydrogen reacting the product of the said condensation reaction with an organic compound of the formula WO(C n H 2n O) d C m H 2m-1 , in the presence of a Pt catalyst, to provide the organosilicone polymer. The polymers have an average molecular weight of from 1000-20,000. In Examples 1-13 polymers comprising the following units in varying molar proportions: (A) SiO 4/2 ; (B1) CH 3 O(C 2 H 4 O) 7À2 -C 3 H 6 -Si- (CH 3 )O 2/2  or (B<SP>2</SP>) C 6 H 5 CH 2 O-(C 2 H 4 O) 6À6 - C 3 H 6 -Si(CH 3 )O 2/2  and (C) (CH 3 ) 3 SiO 1/2  are prepared by the above cohydrolysis condensation reaction of Si(OC 2 H 4 ) 4  and the corresponding dichlorosilanes and monochlorosilane of units B1, B2 and C. The dichlorosilanes are prepared by reacting CH 2  = CH.CH 2 (OC 2 H 4 ) 7À2 - OCH 3  or CH 2  = CH.CH 2 (OC 2 H 4 ) 6À6 -OCH 2 C 6 H 5  with methyldichlorosilane in the presence of H 2 PtCl 6  as catalyst. In Examples 14, 15 polymers comprising the above A, B2 and C units are modified by reaction with methyl isocyanate in the presence of N-ethyl-morpholine. The organosilicone polymers can be used as surfactants in the production of flexible flameretardant polyester urethane foam, the process comprising reacting and foaming a mixture of (a) a polyester polyol containing an average of at least 2-OH groups per molecule, (b) an organic polyisocyanate containing at least 2 isocyanato groups per molecule, (c) an amine catalyst, (d) a blowing agent which is preferably water and/or a fluorocarbon, and (e) the above organosilicone polymer as foam stabilizer. The mixture may contain an organic flame retardant which preferably contains phosphorus and/or halogen, many examples of which are listed. The catalyst and foam stabilizer may be introduced to the reaction mixture as an aqueous premixture containing as additional components an organic acidic component preferably C 15-20  aliphatic carboxylic acids, e.g. tall oil, a water soluble silicon free organic surfactant and/or a glycol; preferably hexylene glycol. Many examples of the additional components are listed; as well as the polyester polyol and polyisocyanate reactants. In Examples 16-30 foams are produced from the following formulation in p.b.w.:- surfactant-0À35, 0À5 or 1; polyester polyol-100, which is a commercial polyester produced from adipic acid, diethylene glycol and trimethylol propane in a mole ratio of 1 : 1 : 0À2; N-ethylmorpholine-1À9; hexadecyldimethylamine- 0-3; water-3À6; tolylene diisocyanate-45À2; and tris-(2-chloroethyl)phosphate-7À0 as flame retardant, the surfactants being selected from the organosilicone polymers prepared in examples 1-15. In Examples 31-37 foams are prepared from a similar formulation except that the phosphate flame retardant is omitted. In Examples 38-44 foams are produced by substituting the surfactant of the above first formulation with 1 p.b.w. of a blend comprising the organosilicone polymer surfactant, tall oil, hexylene glycol, alone and together with a silicon-free anionic surfactant or non-ionic surfactant and the inhibitor 2,6-di-tertiary butyl p-cresol.