Preparation and properties of ester or cyano group substituted ring-opening polymers and their hydrogenated derivatives

✍ Scribed by Yoshinori Yoshida; Kohei Goto; Zen Komiya

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 178 KB
• Volume: 66
• Category: Article
• ISSN: 0021-8995
• DOI: 10.1002/(sici)1097-4628(19971010)66:2<367::aid-app17>3.0.co;2-v

✦ Synopsis

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 207ЊC, 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 35ЊC, regardless of the monomer structure. These results indicate that the main-chain mobility is the major contribution to the decrease of T g .