Patent GB-1102733-A (GB)
Title: Halogen-rich phosphites, phosphates, thiophosphates and phosphonates
IPC: C07F9/12
Filed: 1965-09-22
Abstract: The invention comprises phosphate, thiophosphate, phosphite and phosphonate esters within the following formulae <FORM:1102733/C3/1> or <FORM:1102733/C3/2> where R1 is polyhalophenyl, R3 and R5 are hydroxyalkyl, R2 is alkylene, R4 and R6 are alkylene, hydroxyalkylene or oxyalkylated hydroxyalkylene, x, y and z are zero or a positive integer, R7, R9, R10 and R11 are alkylene, alkyleneoxyalkylene or alkylenepoly (oxyalkylene) each optionally substituted by oxyalkylated hydroxy, R8 is a ring polyhalosubstituted alkylidene bisphenol residue, s, t, v and w are each 0 or 1 with the proviso that not more than one of w and t is 0 and v is not 0 when s, t or w is 0, X is O or S, and the halogens are Cl or Br. The phosphites are prepared by transesterification of an optionally oxyalkylated polyhalophenol or of a bisphenol with a tertiary phosphite containing the remaining R groups; phosphates by peroxidic oxidation of the phosphites or by reacting alkylene oxides with R1(OR2)x.OP(O)(OH)2 or R1(OR2)xOP(O)Cl2; phosphonates by Arbuzov rearrangement of the phosphites with a catalytic amount of an alkyl halide or a halohydrin, and thiophosphates by heating the phosphites with sulphur.  The above compounds are used to prepare polyurethanes, which may be foamed by the inclusion of water or fluorohaloalkanes, by reaction with conventional polyisocyanates.  A one-step or two-step procedure may be used. Conventional catalysts, thickeners, fillers and surfactants may be present.  The above phosphorus-containing polyols may be the sole hydroxy reactant or may be mixed with, for example, glycols, polyglycols, thiodiglycol, glycerol, trimethylolalkanes, propylene oxide/polyol reaction products, trimethylolphenol, pentaerythritol, blown linseed or soya oil, castor oil, hydroxyamine, hydroxy-containing polyesters, polyglycol phosphites or phosphonates, pentahydroxyethyldextrose.ALSO:The invention comprises phosphate, thiophosphate, phosphite and phosphonate esters within the following formulae <FORM:1102733/C2/1> <FORM:1102733/C2/2> where R1 is polyhalophenyl, R3 and R5\t are hydroxyalkyl, R2 is alkylene, R4 and R6 are alkylene, hydroxyalkylene or oxyalkylated hydroxyalkylene, x, y and z are zero or a positive integer, R7, R9, R10 and R11 are alkylene, alkyleneoxyalkylene or alkylenepoly (oxyalkylene) each optionally substituted by oxyalkylated hydroxy, R8 is a ring polyhalosubstituted alkylidene bisphenol residue, s, t, v and w are each 0 or 1 with the proviso that not more than one of w and t is 0 and v is not 0 when s, t or w is 0, X is O or S, and the halogens are Cl or Br. The phosphites are prepared by transesterification of an optionally oxyalkylated polyhalophenol or of a bisphenol with a tertiary phosphite containing the remaining R groups; phosphates by peroxidic oxidation of the phosphites or by reacting alkylene oxides with R1(OR2)xOP(O)(OH)2 or R1(OR2)xOP(O)Cl2; phosphonates by Arbuzov rearrangement of the phosphites with a catalytic amount of an alkyl halide or a halohydrin, and thiophosphates by heating the phosphites with sulphur.