| Project/Area Number |
06651029
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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 | Tokushima University |
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Principal Investigator |
SATO Tsuneyuki Faculty of Engineering, University of Tokushima Professor, 工学部, 教授 (20047187)
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| Co-Investigator(Kenkyū-buntansha) |
SENO Makiko Faculty of Engineering, University of Tokushima, 工学部, 助手 (40226676)
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| Project Period (FY) |
1994 – 1995
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| Project Status |
Completed (Fiscal Year 1995)
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| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1994: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Keywords | Radical Polymerization / Vinyl Ether / Fumarate Ester / Addition-Abstraction Mechanism / ESR Spectrum / Propagation Rate Constant / Main Chain Structure / Polyether / ラジカル共重合 / ポリエステル |
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| Research Abstract |
We have developed a novel type of radical polymerization which propagates through addition-abstraction mechanism. Three monomers suitable for the addition-abstraction polymerization were prepared and their polymerization behaviors were investigated.
3,3-Dicyanopropyl vinyl ether (DCPVE), a vinyl ether, was easily polymerized with t-butyl peroxide. The molecular weight of the resulting polymer was in the range of 3000-4000. ^1H-and ^<13>C-NMR analysis of polymer structure revealed that the polymerization almost quantitatively proceeds through addition-abstraction mechanism. Radical copolymerization of DCPVE with some vinyl monomers were examined on the basis of monomer reactivity ratios and structures of copolymers. The copolymerizations also involve the addition-abstraction mechanism to a considerable extent.
Ethyl o-formylphenyl fumarate (EFPF) was polymerized by radical initiators in a fairly yield. The polymerization was found to proceed in a complicated manner involving vinyl addition and intramolecular hydrogen-abstraction. The molecular weight of poly (EFPF) was in the range of 1600-2900. The polymerization system involved ESR-observed propagating radicals. The rate constants of propagation and termination were estimated on the basis of ESR data. Copolymerizations of EFPF with vinyl monomers were also examined.
Ethyl o- (4-phenyl-1,3-dioxolan-2-yl) phenyl fumarate (EPDPF) was synthesized from EFPF and stirene glycol. EFDPF was also radically polymerized. ^1H- and ^<13>C-NMR analysis of poly (EFDPF) showed that the polymerization proceed in a manner involving vinyl addition, intramolecular hydrogen-abstraction, and further ring-opening of cyclic acetal at higher temperatures.
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