Synthesis and properties of poly(1-naphthylacetylene) and poly(9-anthrylacetylene)

Abstract

Polymerizations of 1-naphthylacetylene (1-NA) and 9-anthrylacetylene (9-AA) by various transition metal catalysts were studied, and properties of the polymers were clarified. 1-NA polymerized with WCl6-based catalysts to offer dark purple polymers in good yield. Especially, a binary catalyst composed of WCl6 and Ph3Bi gave a polymer with high molecular weight (Mw = 140×103) and sufficient solubility in common solvents. The use of Mo and Rh catalysts, in contrast, resulted in the formation of insoluble red poly(1-NA)s. 9-AA gave insoluble polymers by both WCl6- and MoCl5-based catalysts in moderate to good yields. Copolymerization of 9-AA with 1-NA by WCl6–Ph3Bi provided a soluble copolymer which exhibited the largest third-order nonlinear optical susceptibilities (χ(3)(−3ω; ω, ω, ω) = 40×10−12) among all the substituted polyacetylenes synthesized so far. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 277–282, 1999