| Budget Amount *help |
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1992: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1991: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Research Abstract |
The present project has dealt with the copolymerization of substituted acetylenes with cycloolefines, in which synthesis of novel polymers and exploitation of polymerization catalysts. The results are summarized as follows; 1. Copolymerization of Norbornene with Phenylacetylenes: In the copolymerization of norbornene with phenylacetylene at a 1:1 feed ratio, both monomers were consumed simultaneously and smoothly. The main product of this copolymerization was a methanol- insoluble polymer, which proved to be a copolymer according to gel permeation chromatography, 2-D H-H COSY NMR, and UV-visible spectroscopy. Copolymerization of para- and meta-substituted phenylacetylenes with norbornene provided random copolymers, and the reactivity of phenylacetylene increased with increasing electron-donating nature of ring- substituents. 2. Copolymerization of Phenylacetylene with Cycloolefins: Copolymerization of phenyl- acetylene was examined by using deltacyclene, benzonorbornadiene, cyclopentene, etc as comonomers. Copolymer formation was confirmed by 2-D NMR etc. The reactivity of cycloolefins was interpretable in terms of ring strain, steric hindrance, electron density, and so on. 3. Exploitation of Catalysts Effective in Copolymerization: Various catalysts were examined to find one that is effective in the copolymerization of norbornene with Cl-containing disubstituted acetylenes such as 1-chloro-1-octyne and 1-chloro-2-phenylacetylene. Eventually MoCl_5-nBu_4Sn turned out especially effective. Copolymer formation was confirmed, and the structure-reactivity relationship was studied.
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