New Catalysts for Polymerizations of Substituted Acetylenes

A variety of transition metal catalysts have been developed for the polymerizations of different types of substituted acetylenes. [Rh(nbd)Cl]2 (nbd = 2,5-norbornadiene) and WCl6—Ph4Sn/dioxane are effective catalysts for polymerizations of acetylenes containing polar functional groups such as cyano, ether, and ester units. Stereoregular poly(phenylacetylenes) are produced by aqueous polymerizations catalyzed by Rh complexes including [Rh(nbd)Cl]2, [Rh(cod)Cl]2, Rh(cod)(pip)Cl, [Rh(cod)Cl]2(pda), Rh(cod)(bbpmt), Rh(cod)(NH3)Cl, [Rh(cod)(mid)2]PF6, Rh(nbd)(tos)(H2O), and Rh(cod)(tos)(H2O) (cod = 1,5-cyclooctadiene, pip = piperidine, pda = o-phenyldiamine, bbpmt = bis(4-t-butyl)-2-pyridylmethanethiolate, mid = N-methylimidazole, and tos = p-toluenesulfonate). Air- and moisture-stable metal carbonyl complexes W(CO)3(mes) (mes = mesitylene) and Mo(CO)4(nbd) effectively initiate polymerizations of phenylacetylene and 1-chloro-1-octyne without the use of cocatalyst and photoirradiation. A number of transition metal compounds including TaCl5, NbCl5, Mo(CO)4(nbd), [W(CO)3cp]2 (cp = cyclopentadiene), PdCl2-ClSiMe3, and Pd/C-ClSiMe3 catalyze polycyclotrimerizations of terminal and internal diacetylenes (diynes) such as 1,8-nonadiyne, 1,9-decadiyne, 3,9-dodecadiyne, and 1,9-bis(trimethylsilyl)-1,8-nonadiyne, yielding soluble hyperbranched poly(phenylenealkenes) under mild conditions.