Highly Active Catalysts for Living Coordination Polymerization and Synthesis of Functional Polyolefins

用于活性配位聚合和功能聚烯烃合成的高活性催化剂

• 批准号: 62550666
• 负责人: DOI Yoshiharu
• 金额: $ 1.22万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550666/
• 关键词: Living Coordination Polymerization; Living Polypropylene; Highly Active Vanadiun-Catalysts; Functional Polyolefins; ブロックポリマー; リビングポリオレフィン; 高活性配位重合触媒; ポリプロピレンーポリ(メタクリル酸メチル)ブロック共重合体; リビングEPR

The structure of active center involving a living polypropylene chain has been studied by ^1H and ^<13>C NMR analysis. The majority of active centers is found to exist as secondary vanadium-carbon bond during the chain propagation. The living polypropylene end of vanadium-carbon bond reacts with some additives such as I_2 and CO to give terminally functionalized polypropylenes. In addition, this new type of living polypropylene has been applied to the synthesis of welldefined block copolymers of PP-EPR-PP, PP-PTHF, PP-PMMA, and PP-PS. The block copolymers of PP-EPR and PP-EPR-PP are prepared by the sequential coordination polymerization of propylene and ethylene. The PP-PTHF and PP-PMMA block copolymers are synthesized by the transformation of living polypropylene end to cationic or radical end which initiates the polymerization of THF or MMA. The block copolymer of PP-PTHF is prepared by the coupling reaction between iodineterminated polypropylene and living polystyrene anion.

通过 ^1H和 ^<13> c NMR分析研究了涉及活聚丙烯链的活性中心的结构。在链传播过程中，发现大多数活性中心作为次生钒碳键存在。钒碳键的活聚丙烯末端与某些添加剂（例如I_2和CO）反应，从而产生了暂停功能化的聚丙烯。另外，这种新型的活聚丙烯已应用于PP-EPR-PP，PP-PTHF，PP-PMMA和PP-PS的良好定义的块共聚物的合成。 PP-EPR和PP-EPR-PP的块共聚物是通过丙烯和乙烯的顺序配位聚合制备的。 PP-PTHF和PP-PMMA块共聚物是通过将活聚丙烯末端转化为阳离子或根部末端的，从而启动THF或MMA的聚合。 PP-PTHF的块共聚物是通过碘化聚丙烯和活聚苯乙烯阴离子之间的耦合反应来制备的。

项目成果

Yoshiharu Doi;Naoko Tokuhiro;Shigeo Suzuki;Kazuo Soga: Makromol. Chen., Ropid Commun.8. 285-290 (1987)

土居芳晴；德宏直子；铃木繁夫；曾我一夫：马克罗莫尔。

Yoshiharu Doi: "Synthesis and Characterization of Terminally Functionalized Polypropylenes" Makromol. Chem.188. 1273-1279 (1987)

Yoshiharu Doi：“末端官能化聚丙烯的合成和表征”Makromol。

Yoshiharu Doi: "Synthesis and Characterization of Living Copolymer of Ethylene and Propene" Makromol. Chem., Rapid Commun.8. 285-290 (1987)

Yoshiharu Doi：“乙烯和丙烯活性共聚物的合成和表征”Makromol。