Ring-opening polymerization of macrocyclic (aromatic disulfide) oligomer derived from 4,4'-oxybis(benzenethiol) was studied. Ring-opening reactions were carried out in nitrogen and oxygen atmosphere, respectively. Oxidation reaction and cross-linking reaction took place in oxygen atmosphere. The melt copolymerization between cyclic 1 and elemental sulfur was studied using DSC, and TGA techniques. With increasing the contents of sulfur in the polymer, the T-g values, and 5% weight loss temperatures decreased. When the ratio of sulfur to cyclic reached 5, the polymer appeared as a rubber with a T-g of 23.0 degreesC and a 5% weight loss temperature of 269.4 degreesC. A series of poly(thiol aromatic)s were prepared from cyclic 1 and dibromo aromatic compounds in diphenyl ether at 260 degreesC. The dibromo aromatic compounds can be bis(4-bromophenyl) ether, 4,4'-dibromobiphenyl, and 1,4-dibromobenzene. 4,4'-Dibromobiphenyl gave poly(thiol aromatic) with a T-g of 122.2 degreesC and a T-m of 221.3 degreesC by reacting with the cyclic 1. (C) 2004 Elsevier Ltd. All rights reserved.