Abstract
AbstractThis research deals with comparison of the activity of various Rh catalysts in the polymerization of monosubstituted acetylenes and the effect of various amines used in conjunction with [Rh(nbd)Cl]2 in the polymerization of phenylacetylene. A zwitterionic Rh complex, Rh+(nbd)[(η6‐C6H5)B−(C6H5)3] (3), was able to polymerize phenylacetylene (5a), t‐butylacetylene (5b), N‐propargylhexanamide (5c) and n‐hexyl propiolate (5d), and displayed higher activity than the other catalysts examined, that is [Rh(nbd)Cl]2 (1), [Rh(cod)(O‐o‐cresol)]2 (2), and Rh‐vinyl complex (4). Monomers 5a and 5c polymerized virtually quantitatively or in fair yields with all these catalysts, while monomer 5b was polymerizable only with catalyts 3 and 4. Monomer 5d did not polymerize in high yields with these Rh complexes. The catalytic activity tended to decrease in the order of 3 > 4 > 2 > 1. Although polymerization of 5a did not proceed at all in toluene with [Rh(nbd)Cl]2 alone, it smoothly polymerized in the presence of various amines as cocatalysts. The polymerization rate as well as the molecular weight of polymer depended on the basicity and steric bulkiness of amines. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4530–4536, 2005
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