Copolymerization of Substituted Acetylenes with Cycloolefins

取代乙炔与环烯烃的共聚

• 批准号: 03650748
• 负责人: MASUDA Toshio
• 金额: $ 1.28万
• 依托单位: KYOTO 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: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03650748/
• 关键词: Metathesis Polymerization; Copolymerization; Substituted Acetylene; Phenylacetylene; Cycloolefin; Norbornene; Transition-Metal Catalyst; Tungsten Hexachloride; 五塩化モリブデン

The present project has dealt with the copolymerization of substituted acetylenes with cycloolefines, in which synthesis of novel polymers and exploitation of polymerization catalysts. The results are summarized as follows; 1. Copolymerization of Norbornene with Phenylacetylenes: In the copolymerization of norbornene with phenylacetylene at a 1:1 feed ratio, both monomers were consumed simultaneously and smoothly. The main product of this copolymerization was a methanol- insoluble polymer, which proved to be a copolymer according to gel permeation chromatography, 2-D H-H COSY NMR, and UV-visible spectroscopy. Copolymerization of para- and meta-substituted phenylacetylenes with norbornene provided random copolymers, and the reactivity of phenylacetylene increased with increasing electron-donating nature of ring- substituents. 2. Copolymerization of Phenylacetylene with Cycloolefins: Copolymerization of phenyl- acetylene was examined by using deltacyclene, benzonorbornadiene, cyclopentene, etc as comonomers. Copolymer formation was confirmed by 2-D NMR etc. The reactivity of cycloolefins was interpretable in terms of ring strain, steric hindrance, electron density, and so on. 3. Exploitation of Catalysts Effective in Copolymerization: Various catalysts were examined to find one that is effective in the copolymerization of norbornene with Cl-containing disubstituted acetylenes such as 1-chloro-1-octyne and 1-chloro-2-phenylacetylene. Eventually MoCl_5-nBu_4Sn turned out especially effective. Copolymer formation was confirmed, and the structure-reactivity relationship was studied.

本课题主要研究取代乙炔与环烯烃的共聚反应，包括新型聚合物的合成和聚合催化剂的开发。研究结果如下：1.降冰片烯与苯乙炔的共聚：在降冰片烯与苯乙炔以1：1进料比的共聚中，两种单体同时且平稳地消耗。该共聚的主要产物是不溶于甲醇的聚合物，根据凝胶渗透色谱、2-D H-H COSY NMR和紫外可见光谱证明其为共聚物。帕拉和间位取代的苯乙炔与异丙基苯的共聚提供了无规共聚物，并且苯乙炔的反应性随着环取代基的供电子性质的增加而增加。2.苯乙炔与环烯烃的共聚合：研究了以δ-环烯、苯并降冰片二烯、环戊烯等为共聚单体的苯乙炔共聚合。通过二维核磁共振等手段证实了共聚物的形成。环烯烃的反应性可以从环张力、空间位阻、电子密度等方面来解释。开发在共聚中有效的催化剂：对各种催化剂进行了研究，以找到一种在异丙基烯与含Cl的二取代乙炔如1-氯-1-辛炔和1-氯-2-苯乙炔的共聚中有效的催化剂。最终MoCl_5-nBu_4Sn证明是特别有效的。证实了共聚物的形成，并研究了结构-反应性关系。

项目成果

T. Masuda, T. Yoshida, H.Makio, M. Z. A. Rahman, and T. Higashimura: "Metathesis Copolymerization of Cycloalkenes with Substituted Acetylenes" J. Chem. Soc., Chem. Commun.,. 503-504 (1991)

T. Masuda、T. Yoshida、H.Makio、M. Z. A. Rahman 和 T. Higashimura：“环烯烃与取代乙炔的复分解共聚”J. Chem。

H.Makio: "Metathesis copolymerization of norbornene with phenylacetylene and its ring-substituted derivatives catalyzed by WCl6.Part2.Reactivity of mononers" Polymer.

H.Makio：“WCl6 催化的降冰片烯与苯乙炔及其环取代衍生物的复分解共聚。第 2 部分。单体的反应性”聚合物。

H.Makio: "Metathesis Copolymerization of norbornene with phenylacetylene and its ring-substituted derivatives catalyzed by WCl6.Part1.Product characterization" Polmer.

H.Makio：“WCl6 催化的降冰片烯与苯乙炔及其环取代衍生物的复分解共聚。第 1 部分。产品表征”Polmer。

T.Masuda: "Metathesis Copolymerisation of Cycloalkenes with Substituted Acetylenes" J.Chem.Soc.,Chem.Commun.503-504 (1991)

T.Masuda：“环烯烃与取代乙炔的复分解共聚”J.Chem.Soc.，Chem.Commun.503-504 (1991)

H. Makio, T. Masuda, and T. Higashimura: "Metathesis copolymerisation of norbornene with phenylacetylene and its ring-substituted derivatives catalyzed by WCl_6. Part 1. Product characterization" Polymer.

H. Makio、T. Masuda 和 T. Higashimura：“WCl_6 催化的降冰片烯与苯乙炔及其环取代衍生物的复分解共聚。第 1 部分：产品表征”聚合物。