Patent GB-872206-A (GB)
Title: Unsaturated halogen-containing esters of phosphorus oxyacids and copolymers thereof
Inventor: KING FREDERICK ERNEST
IPC: C08F220/42
Filed: 1957-02-11
Abstract: The invention comprises a copolymer of an aliphatic homopolymerizable mono-olefinic compound of dipole moment greater than one and a phosphoric or phosphonic ester of the formula: P(O)(OR)2(OR1) and R1P(O)(OR)2 respectivel wherein R is 2-chloroethyl or 2-bromoethyl and R1 is allyl or methallyl (see Group IV(b) ).  Specified olefinic compounds are the vinyl esters of acetic and propionic acids, the alkyl esters of acrylic and methacrylic acid in which the alkyl group contains 1-4 carbon atoms, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.  Examples are given for the production of copolymers of acrylonitrile with allyl bis (2-chloroethyl) phosphate and bis (2-chloroethyl) allyl phosphonate respectively.  The copolymers can be used in making filaments, films and moulded articles and in treating filaments and other fibrous materials to improve their fire resistance.  The Provisional Specification includes copolymers derived from the aliphatic mono-olefinic compounds and other unsaturated phosphorus esters, e.g. allyl diethyl phosphate, allyl ethylene phosphate, allyl ethylene phosphite, allyl diethyl phosphite, vinyl di (b -chlorethyl) phosphate, b , b -dichlorvinyl di (b -chlorethyl) phosphate, b , b -dichlorvinylethyl di (b -chlorethyl) phosphate and the corresponding phosphites.  The corresponding compounds in which allyl is replaced by methallyl, ethyl is replaced by propyl and ethylene is replaced by 1, 2-propylene are also referred to.ALSO:The invention comprises phosphoric and phosphonic esters of the formula: P(O)(OR)2-(OR1) and R1P(OR)2 respectively wherein R is 2-chlorethyl or 2-bromethyl and R1 is allyl or methallyl.  The phosphoric esters may be obtained by reacting phosphorus trichloride with ethylene chlorhydrin (or bromhydrin) in dry benzene and then reacting with sulphuryl chloride to form the corresponding bis (2-haloethyl) phosphorochloridate which is then reacted with allyl or methallyl alcohol in the presence of benzene and pyridine.  The phosphonic esters may be obtained by reacting phosphorus trichloride or tribromide with ethylene oxide to form the corresponding tris (2-haloethyl) phosphite which is then heated in an autoclave under oxygen-free nitrogen with allyl chloride or bromide or methallyl chloride or bromide to form the bis (2-haloethyl) allyl or methallyl phosphonate the allyl or methallyl bromide being used in the production of the bis (2-bromo-ethyl) allyl or methallyl phosphonate.  The products may be co-polymerized with aliphatic homo-polymerizable monoolefinic compounds having a dipole moment greater than 1 (see Group IV(a)).  The Provisional Specification also describes the production of the following phosphate and phosphite esters: (1) allyl diethyl phosphate by reacting ethanol with phosphorus trichloride in dry ether to form diethyl hydrogen phosphite which is then treated with chlorine at - 10 DEG C. to form diethylchlorphosphate which is then reacted with allyl alcohol and pyridine at 0 DEG C.; (2) allyl di(b -chlorethyl) phosphate by reacting dry ethylene oxide with a solution of POCl3 in dry ether to form di(b -chlorethyl) chlorphosphate which is then reacted with anhydrous allyl alcohol in the presence of pyridine; (3) allyl ethylene phosphate by reacting a solution of POCl3 in dry ether with ethylene glycol and then reacting the product with allyl alcohol as in (2); (4) allyl diethyl phosphite by reacting PCl3 with ethanol in dry ether in the presence of diethylaniline at 0 DEG C. and reacting the product with allyl alcohol as in (2); (5) allyl ethylene phosphite by reacting ethylene glycol with PCl3 in methylene chloride and reacting the product with allyl alcohol as in (2); (6) allyl di(b -chlorethyl) phosphite by using phosphorus chloride instead of oxychloride in (2).  The corresponding allyl di(n-propyl) compounds can be obtained by using n-propanol instead of ethanol in (1) and (4) and the corresponding methallyl compounds may be obtained by using methallyl alcohol.  In (3) and (5) 1,2-propylene glycol may be used instead of ethylene glycol to form the corresponding 1,2 - propylene compounds.  Reference is also made to the production of b ,b -dichlorovinyl di-(b -chlorethyl) phosphate from chloral and tri-(b -chlorethyl) phosphite.