PREPARATION AND PROPERTIES OF ESTER OR CYANO GROUP SUBSTITUTED RING-OPENING POLYMERS AND THEIR HYDROGENATED DERIVATIVES

摘要

Ester or cyano substituted tetracyclo[4.4.0.1(2,5).1(7,10)] dodec-3-enes (1) were synthesized and their metathesis ring-opening polymerization was examined. The tungsten-based ternary catalyst system polymerized them very well. The polymers showed high glass transition temperatures (T-g) and no evidence of crystallization (e.g. the T-g of the polymer derived from 8-methyl-8-methoxycarbonyl substituted monomer (1a) was 207 degrees C, and colorless transparent films could be casted from the solution of the polymer). The stability of these high T-g polymers were too unstable, so practical thermal molding methods could not be applied to them. The hydrogenation of these polymers with a palladium catalyst decreased T-g and greatly increased thermal stability. The physical and thermal properties of the hydrogenated polymers were thoroughly investigated. Monomer 1 was successfully copolymerized with other cyclic olefins. The resultant copolymers were hydrogenated, giving thermally stable polymers. In all cases examined in this study, a decrease of T-g by hydrogenation was about 35 degrees C, regardless of the monomer structure. These results indicate that the main-chain mobility is the major contribution to the decrease of T-g. (C) 1997 John Wiley & Sons, Inc. [References: 28]