POLYMERIZATION OF SULFUR-CONTAINING AROMATIC DISUBSTITUTED ACETYLENESAND POLYMER CHARACTERIZATION

1-Phenylthio-1-alkynes (PhS-C-C-R; R=Me, n-Bu, n-C6H13, n-C6H17, n-C10 H21, and n-C12H25) polymerized in 40-80% yields in toluene at 80 degre es C in the presence of MoCl5-Ph(3)SiH (1:2) catalyst, but did not pol ymerize with the corresponding W catalyst. The produced polymers with R=n-C8H17 and longer were soluble in toluene, chloroform, etc., whose weight-average molecular weights (($) over bar M(w)) reached 2x10(4). 1-Alkyl-thio-2-phenylacetylenes (RS-C=C-Ph; R=Me, Et, n-Bu) polymerize d in 10-20% yields with a WCl6-Ph(3)SiH (1:2) catalyst, while they did not produce any polymer with Mo catalysts. Only the polymer with R=n- Bu was soluble in several organic solvents, whose ($) over bar M(w) wa s ca. 1x10(4). Although 1-phenylthio-2-phenylacety-lene (PhS-C=C-Ph) p olymerized with both MoCl5-Ph(3)SiH and WCl6-Ph(3)SiH, the produced po lymers were insoluble in all solvents. Poly(1-phenylthio-1-dodecyne) a nd poly(1-butylthio-2-phenylacetylene) were yellow solids with absorpt ion maxima at around 280 m; their weight loss in a thermogravimetric a nalysis started at around 200 degrees C.