Synthesis of new degradable polymers containing azo-group in a polymer chain

聚合物链中含有偶氮基团的新型可降解聚合物的合成

• 批准号: 13650940
• 负责人: KAMACHI Mikiharu
• 金额: $ 1.22万
• 依托单位: Fukui University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650940/
• 关键词: Azabutadiene; Ionic Polymerization; Degradable Polymer; Stereoregular Polymer; Crystalline Polymer; Grignard Reagent; 1.4-trans-addition; Functional Polymer; アニオン重合; アザブタジエン誘導体; 結晶性ポリマー; 立体規則性

Azine compounds (azabutadienes) are not polymerized by radical initiators or cationic initiators, but easily polymerized by anionic initiators. In the extension of this finding, anionic polymerizations of α, ω-dialkylazabutadiene were performed with various kinds of initiator, indicating that stereoregular polymers with 1,4-trans monomer unit were obtained with some of anionic initiators. Accordingly, the optimum conditions for the preparation of the stereoregular polymers was investigated by various kinds of anionic initiators, which indicates that alkyl magnesium iodide was the best initiator for the stereoregular polymer with high molecular weight. The thermal degradability of the polymers was investigated by DSC and thermogravitomeric analysis. The stereoregular polymers were completely decomposed to the corresponding olefins and nitrogen above 150℃.The stereoregular have azo-group in trans-form, which can is allowed to isomerize reversibly from trans to cis under irradiation of UV light. The expansion and contraction of polymer molecule was found along with the isomerization from trans to cis. Practical application was investigated in this work.

氮杂化合物(氮杂丁二烯)不能被自由基引发剂或阳离子引发剂聚合，但容易被阴离子引发剂聚合。作为这一发现的延伸，在各种引发剂的作用下，α，ω-二烷基氮杂丁二烯的阴离子聚合反应表明，在某些阴离子引发剂的作用下，得到了具有1，4-反式单体单元的立体规则聚合物。在此基础上，研究了各种阴离子引发剂制备立体正则聚合物的最佳条件，结果表明烷基碘化镁是制备高分子量立体正则聚合物的最佳引发剂。用差示扫描量热法和热重分析法研究了聚合物的热降解性能。在150℃以上，立体正构体完全分解为相应的烯烃和氮气。立体正构体具有反式偶氮基团，在紫外光照射下可以从反式异构化为顺式异构化。随着反式异构化为顺式异构化，聚合物分子发生了膨胀和收缩。这项工作对实际应用进行了研究。

项目成果

蒲池幹治, 松田健太朗, 橋瓜章仁: "アザブタジエン誘導体の重合-分子量および構造制御の検討"Polymer Preprints. 51. 357-357 (2002)

Mikiharu Kamachi、Kentaro Matsuda、Akihito Hashika：“氮杂丁二烯衍生物的聚合 - 分子量和结构控制的研究”聚合物预印本 51. 357-357 (2002)。

Mikiharu.Kamachi: "Search for Highly Resolved Electron Spin Resonance Spectra of Transient Radical in Radical Polymerization"J. Polym. Sci., Polym. Chem.. 40,3. 269-285 (2002)

Mikiharu.Kamachi：“寻找自由基聚合中瞬态自由基的高分辨率电子自旋共振谱”J。

Mikiharu Kamachi, Kentaro Matsuda, Akihito Hashidsume: "Polymerization of Azabutadienes - Control of molecular weight and structure"Polymer Preprints, Japan. 51. 357 (2002)

Mikiharu Kamachi、Kentaro Matsuda、Akihito Hashidsume：“阿扎丁二烯的聚合 - 分子量和结构的控制”聚合物预印本，日本。

蒲池幹治, 道下岳史, 原田 明: "アザブタジエン誘導体の重合とポリマーの熱分解性"Polym. Prepr. Japan. 50,7. 1194-1194 (2001)

Mikiharu Kamachi、Takeshi Michishita、Akira Harada：“氮杂丁二烯衍生物的聚合和聚合物的热分解”Polym. 1194-1194 (2001)。

蒲池幹治, 松田健太朗, 橋爪章仁: "アザブタジエン誘導体の重合-分子量および構造制御の検討"Polymer Preprints. 51. 357-357 (2002)

Mikiharu Kamachi、Kentaro Matsuda、Akihito Hashizume：“氮杂丁二烯衍生物的聚合 - 分子量和结构控制的研究”聚合物预印本 51. 357-357 (2002)。