Copolymerization of elemental sulfur with cyclic(arylene disulfide) oligomers

Abstract

Copolymerization reactions between cyclic(arylene disulfide) oligomers were studied. The cyclic disulfide oligomers derived from 4,4′-isopropylidene bisbenzenethiol gave soluble polysulfanes via copolymerization with S8. The copolymerization reactions were studied both in solution and melt by GPC and NMR. Solution copolymerization reactions can only form polysulfanes with up to three to four sulfur linkages; however, melt copolymerization reactions gave polysulfanes with up to seven sulfur linkages (average). The melt copolymerization reactions between cyclic disulfide oligomers derived from 4,4′-thiobis(benzenethiol) and S8 were studied using DSC, TGA, and DMTA. With increasing contents of sulfur in the polysulfanes, Tgs, 5% weight losses by TGA, and tan δ decreased. With seven sulfur linkages in the polymer, it is a rubber with a Tg of 12°C, a 5% weight loss by TGA of 249°C, and tan δ of 44°C, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2961–2968, 1997