The preparation and characterization of novel cocylic(arylene disulfide) oligomers

A series of homo- and cocyclic(arylene disulfide) oligomers were synthesized under high dilution conditions by the catalytic oxidation of arylenedithiols with oxygen in the presence of a copper-amine catalyst in DMAc. The aryl groups contained moieties such as sulfone, ether, and ketone. The free radical ring-opening polymerization of these cyclic(arylene disulfide) oligomers led to the formation of linear poly(thio arylene)s. The homo- and cocyclic(arylene disulfide) oligomers were characterized by gradient high pressure liquid chromatography (HPLC), get permeation chromatography (GPC), ¹H-NMR, and differential scanning calorimetry (DSC) methods. These cocyclic(arylene disulfide) oligomers except those containing sulfone moiety had lower melt flow temperature as low as 140°C and therefore could readily undergo free radical ring-opening polymerization under mild conditions. The glass transition temperatures of these cocyclics ranged from 72.3 to 190.0°C, while the glass transition temperatures of the polydisulfides derived from these cocyclics ranged from 78.4 to 194.5°C. In this article, a new method of preparing arylene dithiols 4,4′-oxybis(benzenethiol) and diphenylmethane-4,4′-dithiol is reported. © 2003 John Wiley and Sons, Ltd.