| Project/Area Number |
02650665
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
高分子合成
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| Research Institution | Gifu University |
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Principal Investigator |
MIYATA Mikiji Gifu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90029322)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1991: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1990: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Keywords | One-dimensional polymerization / Inclusion polymerization / Space-dependent polymerization / Asymmetric induction / Space analysis / Propagating radicals / Molecular graphics / Host guest / 一次元包接重合 / 空間効果 / 高安定生長ラジカル / ホスト設計 / 空間設計 / 水素結合 / 分子レベル空間 / 分子運動 |
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| Research Abstract |
We studied the efficient asymmetric induction and highly stable propagating radicals in one-dimensional inclusion polymerization. The polymerization is dependent on a space at a molecular level, although we usually ignore the space effect at a macroscopic level. In order to clarify the effect, we compared the behavior of the former polymerization with the latter one. The results are summarized as follows :
1. We carried out the inclusion polymerization of conjugated butadiene monomers by using cholic acid, deoxycholic acid and their derivatives. Deoxycholic acid and apocholic acid, served as a pair of hosts appropriate for a research of the space effect. It was found that the asymmetric induction and the stability of the propagating radicals depend on the channel size.
2. We used molecular graphics for a comparison of the size and shape of the channel. We adopted the data determined from X-ray crystal structure analysis. From the analysis of lots of the cross sectional figures, we found that the size and shape of the pocket of the channel play a decisive role in the polymerization reaction.
3. We succeeded in observing ESR spectra of the propagating radicals derived from conjugated butadiene monomers. It was so far very difficult due to the instability. The included radicals are difficult to recombine in the channels. Furthermore. the ESR spectra are in some cases greatly different. This is based on the molecular motion of the-radicals in the channels. We now find a close relationship among the stability of the radicals, the rate and the selectivity of the polymerization reaction.
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