Copolymerization of Substituted Acetylenes with Cycloolefins

本课题研究了取代乙炔与环烯烃的共聚反应，其中包括新型聚合物的合成和聚合催化剂的开发。主要研究结果如下：1.降冰片烯与苯乙炔的共聚：在降冰片烯与苯乙炔以1：1的投料比进行共聚时，两种单体同时平稳地消耗。该共聚反应的主要产物是一种不溶于甲醇的聚合物，凝胶渗透色谱、2-D H-H-COSY核磁共振和紫外可见光谱表明它是一种共聚物。对位和间位取代苯乙炔与降冰片烯的共聚得到了无规共聚物，苯乙炔的反应活性随着环取代基给电子性的增加而增加。2.苯乙炔与环烯烃的共聚反应：以三环烯、苯并冰片二烯、环戊烯等为共聚单体，考察了苯乙炔的共聚反应。用二维核磁共振等方法证实了共聚物的形成，环烯烃的反应性可以用环应变、空间位阻、电子密度等来解释。3.高效共聚催化剂的开发：考察了多种催化剂对降冰片烯与1-氯-1-辛炔、1-氯-2-苯乙炔等含氯二取代乙炔的共聚反应的催化效果。最终，MoCl5-NbU4Sn型催化剂效果尤其明显。确定了共聚物的形成，并研究了其结构与反应活性的关系。

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.