Preparation and properties of novel aromatic poly(thioethers) derived from 4,4′-thiobisbenzenethiol

A series of amorphous and semicrystalline aromatic poly(thioethers) have been prepared by the reactions of 4,4'-thiobisbenzenethiol and activated dihalides. Azo group activated dihalide monomer was prepared by the reactions of 4-fluoronitrosobenzene with a suitable diamine. The keto and phosphine sulfide containing monomers were synthesized by Friedel-Crafts acylation reactions of suitable halobenzenes with appropriate acid chlorides. Potassium carbonate mediated reactions in dimethylacetamide afforded moderate to high molecular weight polymers. Polymers with high melting points were prepared by using diphenyl sulfone as a co-solvent. The poly(thioethers) exhibit high glass transition temperatures and/or high melting points. In addition, the polymers exhibit excellent thermal stability.