Patent GB-1017697-A (GB)
Title: New phosphite esters
IPC: C08K5/529
Filed: 1962-09-14
Abstract: A halogen-containing synthetic resin is stabilized by incorporating therewith a phosphite ester of the formulae:  <FORM:1017697/C3/1> <FORM:1017697/C3/2> or <FORM:1017697/C3/3> wherein n is 0 or 1, R1 is an aryl, aralkyl or alkaryl group or an alkyl group which may be substituted with a halogen atom, a cyano group or a group -OR in which R is alkyl, alkenyl, aryl, alkaryl, aralkyl, acyl or abietyl group and R2, R3 and R4 which may be the same or different are groups of the formula:-  <FORM:1017697/C3/4> or alkyl, cycloalkyl, alkaryl, aralkyl or aryl groups which may be substituted by halogen (see Division C2).  The resin may be chlorinated polyethylene, or polyvinylidene chloride but is preferably a vinyl halide resin or a copolymer of vinyl chloride with an ethylenically unsaturated compound, e.g. a copolymer of vinyl chloride with vinyl-acetate, -propionate, -butyrate or -benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate or other alkyl fumarate or maleate, an alkyl acrylate or methacrylate, methyl a -chloroacrylate, styrene, trichloroethylene, a vinyl ether, a vinyl ketone, 1-fluoro-1-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene- and chloroallylidene diacetate, or a copolymer of vinyl chloride, vinyl acetate and maleic anhydride (86:13:1). Conventional resin additives, e.g. plasticizers, pigments, fillers, dyes, U.V. light absorbing agents and densifying agents may also be present and specified additional additives are di-2-ethylhexyl phthalate, dibutyl and dihexyl sebacates, tricresyl phosphate, barium and cadmium laurates, calcium stearate, cadmium octoate, barium octoate and barium octyl phenolate.  The oxetane ring-containing phosphites of Formulae I, II and III may be polymerized, e.g. by contacting with boron fluoride or its complexes to form flameproof oxetane polymers and may also be used as cross-linking agents with 3,3-bis-(chloromethyl) oxetane.ALSO:The invention comprises compounds of the general formulae <FORM:1017697/C2/1> <FORM:1017697/C2/2> <FORM:1017697/C2/3> in which n is 0 or 1, R1 is an aryl, aralkyl or alkaryl group or an alkyl group which may be substituted with a halogen atom, a cyano group or a group -OR in which R is an alkyl, alkenyl, aryl, alkaryl, aralkyl, acyl or abietyl group and the groups R2, R3 and R4 which may be the same or different represent a group of the formula <FORM:1017697/C2/4> in which n is 0 or 1, or an alkyl, cycloalkyl, alkaryl, aralkyl or aryl group which may be substituted by halogen.  The compounds of Formulae I and II may be obtained by reacting as appropriate 1 to 3 moles of an oxetane ring-containing alcohol of the formula <FORM:1017697/C2/5> or 1 mole of an oxetane ring-containing alcohol of the formula <FORM:1017697/C2/6> or 1 mole of each of the alcohols IV and (V) with 1 mole of a trisubstituted phosphite of the formula (R4O)P(OR2)(OR3) in the presence of an alkaline catalyst.  Compounds of Formula (III) may be obtained by reacting 3 moles of an alcohol of Formula V with 2 moles of a phosphite of the formula (R4O)-P(OR2)(OR3) in the presence of an alkaline catalyst.  Also, compounds of Formula I and III may be obtained by reacting the alcohol of Formula IV or V with one or two moles, respectively, of PCl3 in the presence of 3 or 6 moles, respectively, of a hydrogen chloride acceptor, e.g. a tertiary amine such as pyridine or triethylamine. Suitable alkaline catalysts in the transesterification reaction are sodium-phenolate, -methylate, -decylate, and -cresylate, sodium hydroxide, sodium and alcohol, or potassium phenolate and suitable trisubstituted phosphites for use as starting materials are triphenyl, tri-p-tolyl, tri-p-chlorophenyl, tridecyl, tricyclohexyl, trimethyl, tribenzyl and diphenyl decyl phosphites. The phenol or alkanol formed is suitably removed by vacuum distillation. Compounds of Formula II in which R4 is the oxetane ring-containing group may also be obtained by reacting a compound of Formula II, in which R4 is other than the oxetane ring-containing group with an oxetane ring-containing mono-alcohol. Several examples are given and the products are useful as stabilizers for halogen-containing synthetic resins and may be polymerized to form flame-proof polymers (see Division C3). Specification 758,450 is referred to.