Patent GB-1062647-A (GB)
Title: Organic phosphites and synthetic resin compositions containing the same
IPC: C07F9/6574
Filed: 1963-09-09
Abstract: The invention comprises organic phosphites, having in the molecule at least one alkylene glycol monocarboxylic acid ester group having 4 to 44 carbon atoms, the carboxylic acid radical in the said ester group being free from a ,b -ethylenic unsaturation. The phosphites may have all the valences of the phosphite oxygen atoms satisfied by the said groups, or one or two of these valences may bear alkyl, aryl, alkaryl, or heterocyclic groups, or hydrogen atoms. The preferred phosphites have the formula <FORM:1062647/C2/1> wherein R is a nitrogen-free C1 to C23 saturated or unsaturated straight or branched chain or cyclic organic radical which is free from a ,b -ethylenic unsaturation, Y is a straight or branched saturated or unsaturated C2 to C20 hydrocarbon chain, and Z is one or a plurality of radicals which, taken singly or together, are sufficient to satisfy the remaining two phosphite oxygens, and may be hydrogen, or two monovalent or one divalent group or groups, and can be or can include alkylene glycol ester radicals of the type R-COO-Y-, as above. The compounds are prepared by transesterification between alkyl, aryl, or alkaryl phosphites and glycol-monocarboxylic esters, at elevated temperature under anhydrous conditions, preferably in the presence of alkaline catalysts-e.g. alkali or alkaline earth metal salts whose 1% aqueous solution exceeds pH 10.  First aryl and then alkyl groups are replaced progressively, depending upon the molar quantity of glycol ester used, to give products with varying degrees of glycol esterification.  Examples are given for the preparation of: diphenyl - mono - (2,2,4 - trimethyl pentanediol monoisobutyrate) phosphite; tris - (2,2,4-trimethyl pentanediol monoisobutyrate) phosphite; and 2 - ethylhexyl - bis - (ethylene-glycol monophenyl acetate) phosphite; and for the use of these compounds as stabilizers for polyolefin and polyvinyl chloride resins (see Division C3).ALSO:Polyolefin and polyvinyl chloride resin compositions contain stabilizers which are organic phosphites having in the molecule at least one alkylene glycol monocarboxylic acid ester group having 4 to 44 carbon atoms, the carboxylic acid radical in the said ester group being free from a ,b -ethylenic unsaturation.  The phosphite oxygens may all have their valences satisfied by such ester groups, or one or two of these valences may bear alkyl, aralkyl, aryl or heterocyclic groups or hydrogen.  Preferred phosphites have the formula <FORM:1062647/C3/1> wherein R is a nitrogen free, C1 to C23 saturate or unsaturated straight or branched chain or cyclic organic radical which is free from a ,b -ethylenic unsaturation, Y is a straight or branched chain saturated or unsaturated hydrocarbon chain, and Z is one or a plurality of radicals, which taken singly or together, satisfy the remaining two phosphite oxygens, and may be hydrogen, or two monovalent groups or one divalent group and can be or can include alkylene glycol ester groups of the type R-COO-Y-, as above.  Resins may be polyvinyl chloride, which includes any polymer having, to at least some extent, a repeating unit of the structure <FORM:1062647/C3/2> and a chlorine content in excess of 40%, the group X being either hydrogen or chlorine; this includes after chlorinated polyvinyl chlorides, and co-polymers having a major proportion of polyvinyl chloride and a minor proportion of, e.g. vinyl acetate, fumaric acid or esters, styrene, chlorinated polyethylene, and copolymers of acrylonitrile, chlorinated polyethylene, and styrene.  Rigid polyvinyl chlorides or those plasticized with known plasticizers are also included.  Polyolefin resins which may be stabilized with the phosphites are polyethylenes and higher polyolefins, and also numerous polyolefin copolymers are mentioned.  The phosphite stabilizers, optionally together with known stabilizers may comprise 0.1 to 1% by weight of the compositions. Examples are given for the preparation of the phosphites (see Division C2), and for the following compositions: (1) Polyvinyl chloride homopolymer, Ba-octyl phenolate, Cd-2-ethylhexoate, and Diphenyl mono (2,2,4-trimethyl pentane diol mono iso butyrate) phosphite; (2) As for (1) but phosphite is Tris - (224 - trimethyl pentane diol mono iso butyrate) phosphite; (3) Polypropylene, Zn-2-ethyl hexoate, 4,41-thio bis (2-tert-butyl-5-methyl phenol), and the phosphite of Example (1); (4) (a) Zn-ethylhexoate, polypropylene, the phisphite used in Example (1), and 1,1,3-tris-(2 - methyl - 4 - hydroxy - 5 - tert. butyl phenyl) butane; (4) (b) As for (4) (a) but with addition of dilauryl thiodipropionate; (5) (a) Polypropylene, 4,41 - n - butylidene - bis-(2 - tert. butyl - 5 - methyl phenol, 2 - ethyl hexyl-bis (ethylene glycol monophenyl acetate) phosphite, and Zn-ethyl hexoate; (5) (b) As for (5) (a) but with addition of dilauryl dithiopropionate.