NOVEL ONE-POT POLYMER SYNTHESES BASED ON DITHIOLS OBTAINED FROM A 5-MEMBERED CYCLIC DITHIOCARBONATE AND DIAMINES

Novel one-pot syntheses of sulfur-containing polymers from a five-memb ered cyclic dithiocarbonate (5-phenoxymethyl-1,3-oxathiolane-2-thione (1)) and diamines were examined. Polydisulfides with (M) over bar(n) 5 400 similar to 15 800 were obtained in the oxidation polymerizations o f dithiols 2, which were obtained in situ by the reactions of 1 and di amines. When 1,12-dodecanediamine was employed, a polydisulfide with r elatively high (M) over bar(n) was obtained, while in the case of m-xy lylenediamine, the polymerization was accompanied by intermolecular cy clization to give a polydisulfide with low (M) over bar(n). Polythiour ethanes with (M) over bar(n) 6 500 similar to 17 200 were obtained in the polyaddition of 2 with 4,4'-methylenebis(phenyl isocyanate). The y ields and (M) over bar(n) values increase with increasing methylene ch ain length of 2. Polythioethers with (M) over bar(n) 2 600 similar to 19 900 were obtained by the polycondensations of 2 with alpha,alpha'-d ibromo-p-xylene. The glass transition temperature (T-g) of the polymer decreases with increasing methylene chain length in the main chain.