Copolymerization of Substituted Acetylenes with Cycloolefins

取代乙炔与环烯烃的共聚

基本信息

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

项目摘要

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.

本项目涉及取代的乙酰烯与旋风的共聚，其中新型聚合物的合成和聚合催化剂的剥削。结果总结如下； 1。与苯乙烯的共生共聚：在诺本烯与苯乙烯共聚时，以1：1的饲料比共聚时，同时且平稳地消耗了两个单体。该共聚物的主要产物是甲醇不溶的聚合物，根据凝胶渗透色谱法，2-D H-H-H舒适的NMR和UV-可见光谱法，该聚合物被证明是共聚物。与悬烯烯二取代的苯乙烯和元取代的苯乙烯共聚物提供了随机共聚物，并且苯乙烯的反应性随着环替代物的电子含量增长而增加。 2。苯乙烯与环霉素的共聚：通过使用二苯乙烯，苯甲酸苯二苯，环戊烯等作为共生体检查苯基 - 乙炔的共聚。共聚物形成通过2-D NMR等证实。Cycloolefins的反应性可以用环应变，空间障碍，电子密度等来解释。 3。对有效共聚的催化剂的剥削：检查了各种催化剂，以发现一种可有效的氯烯烯与含有克链蛋白的脱取二取代的乙酰基乙烯的共聚作用，例如1-氯-1- oc- 1- octyne和1-氯-2-氯乙烯。最终MOCL_5-NBU_4SN最有效。确认共聚物形成，并研究了结构反应关系。