Development of New Synthetic Method for Block Copolymers of Controlled Molecular Weights.

控制分子量嵌段共聚物新合成方法的开发。

• 批准号: 02453105
• 负责人: INOUE Shohei
• 金额: $ 3.71万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453105/
• 关键词: Metalloporphyrin; Aluminum Porphyrin; Block Copolymer; Living Polymer; Methacrylic Ester; Methyl Methacrylate; Epoxide; Lactone; ブロック共重合体; 金属ポルフィリン錯体

The present research is to develop a novel method for the synthesis of novel tailored block copolymers of controlled molecular weights.The results include the (1) synthesis of block copolymers of poly (methacrylic esters) polyethers and - polyesters of narrow molecular weight distributions, by the sequential living polymerizations of methacrylic esters and epoxides and lactones, respectively, with aluminum porphyrin initiators, (2) synthesis of block copolymers consisting polyethers and polythioethers by the photo-driven living polymerization of episulfides and epoxides with zinc N-substituted porphyrins, (3) development of high-speed living polymerization of methacrylic esters with aluminum porphyrins assisted by bulky Lewis acids such as methylaluminum 2, 6-disubstituted phenolates, (4) molecular design of highly active aluminum tetraphenylporphyrin initiators by introducing polar substituents such as chlorine and methoxy groups into all the ortho positions of the peripheral phenyl groups.

本研究旨在开发一种合成可控分子量的新型定制嵌段共聚物的新方法。研究结果包括（1）通过甲基丙烯酸酯、环氧化物和内酯分别与铝卟啉引发剂进行连续活性聚合，合成窄分子量分布的聚（甲基丙烯酸酯）聚醚和聚酯嵌段共聚物， (2)通过环硫化物和环氧化物与锌N-取代卟啉的光驱动活性聚合来合成由聚醚和聚硫醚组成的嵌段共聚物，(3)在大路易斯酸如甲基铝2, 6-二取代酚盐的辅助下开发甲基丙烯酸酯与铝卟啉的高速活性聚合， (4)通过在外围苯基的所有邻位引入氯、甲氧基等极性取代基，进行高活性四苯基卟啉铝引发剂的分子设计。

项目成果

Yasunori Hosokawa,Masakatsu Kuroki,Takuzo Aida,Shohei Inoue: "Controlled Synthesis of Poly(acrylic esters)by aluminum Porphyrin Initiators" Macromolecules. 24. 824-829 (1991)

Yasunori Hosokawa、Masakatsu Kuroki、Takuzo Aida、Shohei Inoue：“铝卟啉引发剂控制聚丙烯酸酯的合成”大分子。

Shohei Inoue,Takuzo Aida: "Hand Book of Polymer Syntheeis" Plenum, (1992)

Shohei Inoue、Takuzo Aida：“高分子合成手册”全会，（1992 年）

井上 祥平,相田 卓三,杉本 裕: "高分子機能材料シリ-ズ" 高分子学会(編) 共立出版, 37 (1991)

Shohei Inoue、Takuzo Aida、Yutaka Sugimoto：“高分子功能材料系列”，高分子科学学会（编辑），Kyoritsu Shuppan，37（1991）

Yoshihiko Watanabe,Takuzo Aida,Shohei Inoue: "First Example of Photoindued Copolymerizability Enhancement.Copolymerization of Epoxide and Episulfide Initiated with Zinc N-Substituted Porphyrin under Visible Light Irradiation." Macromolecules. 24. 3970-397

Yoshihiko Watanabe、Takuzo Aida、Shohei Inoue：“光致共聚性增强的第一个例子。在可见光照射下用锌 N-取代的卟啉引发环氧化物和环硫化物的共聚。”

Takuzo Aida, Ken-ichi Kawaguchi, and Shohei Inoue: ""Zinc N-Substituted Porphyrins as Novel Initiators for the Living and Immortal Polymerizations of Episulfides"" Macromolecules. 23. 3887-3892 (1990)

Takuzo Aida、Ken-ichi Kawaguchi 和 Shohei Inoue：“锌 N 取代卟啉作为环硫化物活性和永生聚合的新型引发剂”大分子。