Development of Ring-Opening-Closing Alternating Copolymerization

开闭环交替共聚研究进展

• 批准号: 02650658
• 负责人: SHODA Shin-ichiro
• 金额: $ 1.28万
• 依托单位: Tohoku 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: 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/grant/KAKENHI-PROJECT-02650658/
• 关键词: Ring-Opening-Closing Alternating Copolymerization; Ring-Opening Monomer; Ring-Closing Monomer; Trivalent Phosphorus Compound; Muconic Acid; 2-Oxazoline; Acrylic Anhydride; N-Methyldiacrylamide; 機能性高分子; 酸化還元交互共重合; エチレンフェニルホスホナイト; グルタルアルデヒド

It has been found that the copolymerizations of cyclic phosphonites with muconic acid undergo the ring-opening-closing alternating copolymerization without initiator to give alternating copolymers.N-methyldi(meth)acrylamide reacted with cyclic phosphonites without added initiator to give 1 : 1 alternating copolymers. The first step of the reaction is formation of a zwitterion by a Michael-type addition of the phosphonite to acrylamide, followed by a ring-closing process via an intramolecular-type addition, the next step is the reaction between two genetic zwitterions in which the phosphonium ring is opening by nucleophilic attack of the anion from another zwitterion according to an Arbuzov type of ring-opening.

研究发现，环状亚膦酸酯与粘康酸的共聚在不添加引发剂的情况下进行开环交替共聚，得到交替共聚物。N-甲基二(甲基)丙烯酰胺与环状亚膦酸酯在不添加引发剂的情况下反应，得到1:1交替共聚物。反应的第一步是通过亚膦酸酯与丙烯酰胺的迈克尔型加成形成两性离子，然后通过分子内型加成进行闭环过程，下一步是两个遗传两性离子之间的反应，其中根据阿尔布佐夫型开环，通过来自另一个两性离子的阴离子的亲核攻击打开鏻环。

项目成果

S.Kobayashi: "RingーOpeningーClosing Alternating Copolymerization of 2ーPhenyIー1、3、2ーdioxaphospholane with Muconic Acid" Macromolecules. 23. 3541-3543 (1990)

S.Kobayashi：“2－PhenyI－1,3,2－二氧磷杂环戊烷与粘康酸的开环－闭环交替共聚” 23. 3541-3543 (1990)

Shiro Kobayashi: "RingーOpeningーClosing Alternating Copolymerization of Cyclic Phosphonites with Muconic Acid:Synthesis,Mechanism,and Kinetic Studies" Macromolecules.

小林史郎：“环状亚膦酸酯与粘康酸的开环交替共聚：合成、机理和动力学研究”大分子。