METATHESIS COPOLYMERIZATION OF NORBORNENE WITH PHENYLACETYLENE AND ITS RING-SUBSTITUTED DERIVATIVES CATALYZED BY WCL6 .1. PRODUCT CHARACTERIZATION

In the copolymerization of phenylacetylene (PA) with norbornene (NBE) catalysed by WCl6, both monomers reacted simultaneously, the relative reaction rate of PA being several times higher than that of NBE. The product consisted of polymeric (84 wt%, M(n)BAR=41000) and oligomeric (16 wt%, M(n)BAR=several hundreds) parts. According to g.p.c., u.v. and n.m.r. analyses, the former part was a PA-NBE copolymer, while the latter was a mixture of PA oligomers. The PA-NBE dyads could be directly observed in the 2-D H-H COSY n.m.r. spectrum of the polymeric part. The p-CF3 and o-CF3 derivatives of PA showed reactivities close to that of NBE (relative rates approximately 1.4:1 and approximately 1.3:1, respectively). The oligomeric by-products were less in these systems, and the formation of copolymers was similarly confirmed.