Abstract
4-Chloromethylstyrene has been synthesised by a route commencing with p-toluidine. This monomer has been polymerised, alphaalpha1-azoisobutyro-nitrile being used as initiator, and copolymerised with styrene. Polystyrene has been converted by chloromethylation into poly-(chloromethylstyrene). The polymers and copolymers have been characterized by the determination of their logarithmic viscosity numbers in toluene at 25°. Poly(chloromethylstyrenes) have been converted, via the thiouronium chlorides, into poly(mercaptomethylstyrenes), and reactions typical of thiols of low molecular weight have been successfully applied to these polymers, resulting in the formation of poly(carbamoylmethyl vinyl-benzyl sulphide), poly[di(4-vinylbenzylthio)mercury], and poly-(2-cyanoethyl vinylbenzyl sulphide). Alkaline solutions of poly(mercaptomethylstyrene) have been oxidized with iodine, and atmospheric oxygen. The rate constants of the reactions between sodium benzyl oxide and benzyl chloride, 4-chloromethylcumene, and the polymeric chloromethyl compounds, in benzyl alcohol at 70.55 +/- 0.05, have been determined. The results have been discussed in relation to polar and other effects, to chain-coiling, and to the spacing-out of reactive groups in the copolymer.