Synthesis of Crystalline Poly(phenyleneether)s by Interfacial Electron-transfer Polymerization
| Project/Area Number |
60550649
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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 | Waseda University |
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Principal Investigator |
TSUCHIDA Eishun School of Science and Engineering, Waseda University, 理工学部, 教授 (90063461)
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| Co-Investigator(Kenkyū-buntansha) |
NISHIDE Hiroyuki School of Science and Engineering, Waseda University, 理工学部, 助教授 (90120930)
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| Project Period (FY) |
1985 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1986: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1985: ¥1,200,000 (Direct Cost: ¥1,200,000)
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| Keywords | Electron-transfer / Interface / Polymerization / Poly(phenyleneether) / 芳香族ポリマー |
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| Research Abstract |
The objective of this research is to study new synthesis procedure of poly(phenyleneether)s with sharp molecular weight distribution and high crystallinity by controlling interfacial electron-transfer of phenol. Anodic oxidation of phenols gave the corresponding poly(1,4-phenyleneoxide)s by selecting the interfacial electron-transfer conditions. The investigators found that phenolate ion is polymerized quantitatively to poly(phenyleneether) in the presence of bromine or alcohol. They act as an electron-transfer mediator in the polymerization. Polymerization of phenol with bisphenol gave the poly(phenyleneether) having phenolic hydroxy groups on both the chain ends. Polymerization of phenols having trimethylsilyl groups also gave corresponding poly(phenyleneether)s. Linear 1,4-phenylene structure of thus formed poly(phenyleneethers)s was confirmed by NMR, IR, and DSC in the reference of model phenyleneether compounds. Electrochemical measurements on the interfacial electron-transfer indicated that the polymerization proceeds within diffusion layer on the electrode interface and this interfacial step controls the reaction selectivity to yield poly(phenyleneether)s. The interfacial electron-transfer procedure was applied to a series of aromatic compounds. Under specififc electron-transfer conditions, benzene derivatives such as p-dimethoxybenzene and cyclicdienes such as cyclohexadiene gave new conjugated polymers: poly(2,5-dimethoxy-1,4-phenylene) and poly(1,4-cyclohexadiene). Strong basic compounds inhibited the polymerization, which suggested that cation radical formed by one-electron transfer on the electrode interface is an active species of this polymerization. As mentioned above, electro-oxidative polymerization of phenols was characterized in connection with the interfacial electron-transfer process on the electrode and was developed as a new polymerization procedure of aromatic polymers.
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Report
(1 results)
Research Products
(12 results)
