Abstract
(o-Alkylphenyl)acetylenes (alkyl: Et, n-Bu, n-C6H13, n-C8H17, and iso-Pr) polymerized in high yields with W and Mo catalysts. MoCl5-based catalysts, which are not very active to phenylacetylene (PA), exhibited high activity like the WCl6 counterparts. The weight-average molecular weights (Mw) of the polymers having o-n-alkyl groups were in the range 2×104—55×104, being similar to or slightly higher than those of poly(PA), while the highest Mw value of poly(o-iso-Pr-phenylacetylene) [poly(iso-PrPA)] reached 1×106. The formed polymers were dark red, and had the structure –[- CH = C(C6H4-alkyl) -]n–. They were thermally more stable than poly(PA) according to the thermogravimetric analysis. The polymers with long o-n-alkyl groups were soluble in aliphatic solvents (e.g., hexane) unlike poly(PA), and their softening points were lower. Poly(o-iso-PrPA) was film-forming, and fairly gas-permeable (PO2, 27 barrers, PO2/PN2 2.2).
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