Patent GB-920515-A (GB)
Title: Improved polymers
Inventor: ERREDE LOUIS ANTHONY
IPC: C08G79/04
Filed: 1959-10-05
Abstract: Polymers are made from a quinodimethane and a compound of phosphorus, arsenic, antimony or bismuth.  Preferred quinodimethanes are p-quinodimethane (p-xylylene) <FORM:0920515/IV(a)/1> 1,4-naphthaquinodimethane <FORM:0920515/IV(a)/2> corresponding heterocyclic quinodimethanes containing at least one heteronitrogen atom vicinal only to carbon atoms, or the nuclear substitution products of the foregoing with fluorine, chlorine or a methyl group. Preferred compounds of the abovementioned elements are those of phosphorus, e.g. phosphine, phosphorus tri- and penta-halides, phosphoryl trihalides, phosphines substituted by one, two or three organic groups, organic phosphonyl halides and esters of phosphorous and phosphonous acid.  Also mentioned is the use of arsenic trichloride.  The polymerization of the quinodimethane and the phosphorus-group element compound may be carried out in the presence or absence of a catalyst, e.g. trichloroacetyl peroxide, aluminium chloride and iodide, boron trifluoride, sodium iodide and nickel iodide.  The reaction may be carried in liquid or vapour phase, in the former case in solution in solvents such as toluene, acetone and hexane, at temperatures which are preferably below 50 DEG C. and are usually below -45 DEG C.  The resulting polymers contain reactive groups which may be converted by appropriate treatment, e.g. hydrolysis, esterification, amination and amidation.  The examples describe the following processes: (6) p-quinodimethane, oxygen and phosphorus trichloride are reacted together in toluene to provide a polymer containing POCl groups which may be converted to phosphonic acid form by treatment with sodium hydroxide; (7) the polymer prepared as in (6) above is treated with methyl alcohol to provide a polymer containing methyl phosphonate groups which cross-links on heating; (8) p-quinodimethane, oxygen and ethyl phos phorus dichloride are reacted in hexane to produce a solid polymer; (9) p-xylylene and phosphorus trichloride are reacted in toluene to produce a polymer which after vacuum drying and exposure to oxygen exhibits phosphonyl chloride groups which may be hydrolysed to phosphonic acid groups; (10) p-xylylene and arsenic trichloride are polymerized together in heptane; (11) p-xylylene and phenylphosphorus dichloride are reacted together in a heptane-p-xylene mixture to produce a polymer containing P-OH bonds as a result of reaction with atmospheric moisture; treatment of this polymer with acetic acid produces a polymer containing phenyl phosphine oxide groups; (12) p-xylylene and phosphorus pentachloride are reacted in toluene to produce a viscous liquid which may be reacted with sodium hydroxide to yield a product which reacts with methanolic solutions of ferric chloride, barium chloride, sodium chloride and silver nitrate; (13) p-xylylene and triethyl phosphite are copolymerized in heptane; (14) p-xylylene and triphenyl phosphine are copolymerized in toluene and (15) p-xylylene and tri-n-butyl phosphine are copolymerized in heptane. Specification 788,662 is referred to.ALSO:2-Chloro-p-quinodimethane is prepared by leading vapours of 2-chloro-p-xylene through a pyrolysis tube heated to 1050 DEG C. and condensing the resultant vapours in toluene at -80 DEG C. to produce a solution of 2-chloro-p-quinodimethane.  Specification 788,662 is referred to.