Development of Stereospecific Cationic Polymerizationthrough Intramolecular Participation at Polymer-end

通过聚合物末端分子内参与的立体定向阳离子聚合的发展

• 批准号: 23655039
• 负责人: YAMAGO Shigeru
• 金额: $ 2.58万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Challenging Exploratory Research
• 财政年份: 2011
• 资助国家: 日本
• 起止时间: 2011 至 2012
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-23655039/
• 关键词: 立体規則性重合; 立体選択的反応; カチオン重合; ラジカル重合; 立体選択的重合; ルイス酸; カチオン反応; 分子内関与; ブロック共重合体

New monomers for the stereospecific cationic polymerization were designed and synthesized, and model reactions for the polymerization reaction were investigated. The monomer was designed to utilize intramolecular participation of the olefin-pendant group to the polymer-end cation, which would regulate the direction of an incoming monomer. The model reaction proceeded in good yield with >90% diastereoselectivity by an appropriate choice of the pendant group and Lewis acid used as an activator. The results suggest a new possibility for the control of stereoselectivity by using the polymer-end group, while the conventional method so far utilized steric effects of the penultimate group. The same concept was applied to the monomer design for the stereospecific radical polymerization, and a conditions for the extremely high (>99%) stereospecific radical polymerization was developed.

设计并合成了用于立体定向阳离子聚合的新单体，并研究了聚合反应的模型反应。该单体的设计是利用烯烃侧基对聚合物末端阳离子的分子内参与，从而调节进入单体的方向。通过适当选择侧基和用作活化剂的路易斯酸，模型反应以良好的产率进行，非对映选择性>90%。结果表明，使用聚合物端基控制立体选择性的新可能性，而迄今为止的常规方法利用倒数第二个基团的空间效应。同样的概念被应用于立体定向自由基聚合的单体设计，并开发了极高（>99%）立体定向自由基聚合的条件。

项目成果

有機テルル化合物を用いるリビングラジカル重合法 TERP の開発と応用

有机碲化合物活性自由基聚合法TERP的开发及应用

• 发表时间: 2013
• 作者: 山子茂

Highly Controlled Random and Alternating Copolymerization of (Meth)acrylates, Acrylonitrile, and (Meth)acrylamides with Vinyl Ethers by Organotellurium, Organostibine, and Organobismuthine Mediated Living Radical Polymerization Reactions

(甲基)丙烯酸酯、丙烯腈和(甲基)丙烯酰胺与乙烯基醚通过有机碲、有机锑和有机铋介导的活性自由基聚合反应进行高度受控的无规和交替共聚

• DOI: 10.1002/pola.26004
• 发表时间: 2012
• 期刊: J. Polym. Sci. Part A: Polym. Chem
• 作者: Mishima;E.; Yamago;S
• 通讯作者: S

触媒

催化剂

• 发表时间: 2004
• 作者: S.Shiraiwa;et. al.;H.Tomita;A.Komori;Y.Enokida et al.;金田 清臣
• 通讯作者: 金田 清臣