Synthesis of amorphous poly(thioarylene)s via oxidative polymerization of diaryl disulfides

Abstract

Amorphous poly(thioary1ene)s containing a methyl substituent and/or an ether bond in the main chain were prepared via oxidative polymerization of diaryl disulfides using 2,3-dichloro-5,6-dicyanobenzoquinone. The resulting poly(thio-2,6-dimethyl-l,4-phenyleneoxy-l,4-phenylene) having alternating ether and thioether bonds shows a better solvent solubility and has a higher glass transition temperature (Tg) (1 82 "C) than non-substituted poly(thio-l,4-phenylene). Polymerization of methyl substituted diphenyl ether derivatives with disulfur dichloride has been also developed for a one-pot synthesis of amorphous poly(thioary1ene)s.

Preparation of Poly(thioarylene)s from Cyclic Disulfide Oligomers

“…Poly(thioarylene)s are generally prepared by the condensation of dichloroaromatic compounds with sodium sulfide in N -methylpyrrolidinone (NMP). − In recent years, several new synthetic methods have been developed. Oxidative polymerization of diaryl disulfides has been extensively studied by Tsuchida et al. − In addition, poly(thioarylene)s have been synthesized via electrophilic substitution reactions utilizing aryl alkyl sulfides, methyl phenyl sulfoxide, and sulfur chloride . However, the use of large amount of strong acids in all of these reactions is a major drawback.…”

Novel Synthesis of Poly(thioarylene)s via Reaction between Arenethiols and Bromo Compounds with a Free Radical Initiator

“…Melt copolymerization of 1,4-diiodobenzene and sulfur, , thermal polymerization of bis(4-iodophenyl) disulfide, and copolymerization of cyclic(arylene disulfide) oligomers with dihaloaromatic compounds , have been described as proceeding by free radical mechanisms. The polymerization of salts of 4-bromobenzenethiol is believed to be a single-electron transfer process. , Electrophilic substitution reactions have been extensively studied by Tsuchida. − …”

“…14,15 Electrophilic substitution reactions have been extensively studied by Tsuchida. [16][17][18][19] There are two reports related to the use of a catalytic process or an initiator for the preparation of PPS. Tsuchida et al reported that high molecular weight PPS was obtained via a soluble precursor by catalytic oxidative polymerization of methyl phenyl sulfide with oxygen in the presence of cerium ammonium nitrate (CAN) catalyst in the presence of strong acid.…”