| Project/Area Number |
62470098
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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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 | TOHOKU UNIVERSITY |
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Principal Investigator |
KOBAYASHI Shiro Department of Molecular Chemistry and Engineering Faculty of Engineering, Tohoku University, 工学部, 教授 (10026198)
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| Co-Investigator(Kenkyū-buntansha) |
UYAMA Hiroshi Department of Molecular Chemistry and Engineering Faculty of Engineering, Tohoku, 工学部, 助手 (70203594)
SUH Kyung-Do Department of Molecular Chemistry and Engineering Faculty of Engineering, Tohoku, 工学部, 助手 (80196675)
SHODA Shin-ichiro Department of Molecular Chemistry and Engineering Faculty of Engineering, Tohoku, 工学部, 講師 (10143364)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥5,500,000 (Direct Cost: ¥5,500,000)
Fiscal Year 1988: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1987: ¥4,400,000 (Direct Cost: ¥4,400,000)
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| Keywords | Poly(beca-ketone) / Isopropoxyacetylene / t-Butoxyacetylene / Transition metal catalyst / Poly(isoproxyacetylene) / 遷移金属触媒重複 / t-ブトキシアセチレン / アルキルチオアセチレン / アルコキシアセチレン / VI族遷移金属触媒 / ポリ(アルコキシアセチレン) / 含イオウモノマー / ケテンケオアセタール / ケテンチオアセタールSーオキシド |
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| Research Abstract |
Poly(beta-ketones) are a class of biologically important polymers having keto groups alternatively in the carbon-carbon main chain. They are called "poly-ketides" or "acetogenins", which are involved as precursor in the biosynthesis of aromatic natural products in plants. The present study deals with synthesis of poly (beta-ketones) having a well-defined structure by a new method of polymerization followed by acid-hydrolysis of the product polymers.
Isopropoxyacetylene is polymerized in the presence of transition metal catalyst such as WCl_6 and MoCl_5 to give brownish materials. The structure of the isolated polymers has been confirmed as poly(isopropoxyacetylene) by NMR and IR spectroscopy. The polymerization of t-butoxyacetylene by WCl_6 catalyst gave polymer containing a small amount of an isomerized unit. The less acidic catalysts, W(OCH_6)_nCl_<6-n> (n=4,5), however, yielded desired polymer almost exclusively. The hydrolysis of poly(t-butoxyacetylene) was carried out in a mixture of hydrochloric acid and dioxane at room temperature. The IR spectrum of the product indicated that poly(t-butoxyacetylene) was easily hydrolyzed to afford the corresponding poly(beta-ketone) efficiently. On the other hand, poly (isopropoxy acetylene) was less reactive toward the acid hydrolysis.
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