Novel Polymers by the Radical Polymerization via Addition-Abstraction Mechanism

通过加成-抽象机制进行自由基聚合的新型聚合物

• 批准号: 06651029
• 负责人: SATO Tsuneyuki
• 金额: $ 1.34万
• 依托单位: Tokushima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06651029/
• 关键词: 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

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.

我们开发了一种新型的自由基聚合，通过加成-夺取机制传播。合成了3种适用于加成-抽离聚合的单体，研究了它们的聚合行为。所得聚合物的分子量为3000 - 4000。聚合物结构的~1H-NMR和~1C-NMR分析表明，聚合几乎定量地通过加成-夺取机理进行。<13>根据单体竞聚率和共聚物结构，研究了DCPVE与某些乙烯基单体的自由基共聚合。在自由基引发剂存在下，邻甲酰基苯基富马酸乙酯（EFPF）以较高的产率聚合。发现聚合以复杂的方式进行，涉及乙烯基加成和分子内氢提取。聚（EFPF）的分子量在1600 - 2900范围内。聚合体系涉及ESR观察到的传播自由基。根据ESR数据估计了增长和终止的速率常数。研究了EFPF与乙烯基单体的共聚反应，以EFPF和苯乙烯二醇为原料合成了邻（4-苯基-1，3-二氧戊环-2-基）苯基富马酸乙酯（EPDPF）。EFDPF也被自由基聚合。对聚（EFDPF）的~1H-和~1C-NMR分析表明，聚合反应是以乙烯基加成、分子内夺氢和在较高温度下环缩醛进一步开环的方式进行的。<13>

项目成果

Tsuneyuki Sato: "Radical Polymerization Behavior of Ethyl ortho-Formylphenyl Fumarate Involving Intramolecular Hydrogen Abstraction" J.Polym.Sci. : Part A : Polym.Chem.33. 2865-2873 (1995)

Tsuneyuki Sato：“涉及分子内氢提取的邻甲酰基苯基富马酸乙酯的自由基聚合行为”J.Polym.Sci。

Tsuneyuki Sato: "Radical Polymerization of 3,3-Dicyanopropyl Vinyl Ether via Addition-Abstraction Mechanism" Eur. Polym. J.(in press).

Tsuneyuki Sato：“通过加成-抽象机制进行 3,3-二氰基丙基乙烯基醚的自由基聚合”Eur。

Tsuneyuki Sato: "Radical Polymerization of 3,3-Dicyanopropyl Vinyl Ether via Addition-Abstraction Mechanism" Eur.Polym.J.(in press).

Tsuneyuki Sato：“通过加成-抽象机制进行 3,3-二氰基丙基乙烯基醚的自由基聚合”Eur.Polym.J.（出版中）。

Tsuneyuki Sato: "Radical Polymerization Behavior of Ethyl ortho-Formyl Fumarate Involving Intramolecular Hydrogen Abstraction" J.Polym.Sci. : Part A : Polym.Chem.33. 2865-2873 (1995)

Tsuneyuki Sato：“涉及分子内氢提取的原甲酰富马酸乙酯的自由基聚合行为”J.Polym.Sci。

Tsuneyuki Sato: "Radical Polymerization Behavior of Ethyl ortho-Formylphenyl Fumarate Involving Intramolecular Hydrogen Abstraction" J. Polym. Sci.: Part A : Polym. Chem.33. 2865-2873 (1995)

Tsuneyuki Sato：“涉及分子内氢提取的邻甲酰基苯基富马酸乙酯的自由基聚合行为”J. Polym。