Alternating copolymerizations of polar and nonpolar cyclic olefins by ring-opening metathesis polymerization
Alternating copolymerizations of polar and nonpolar cyclic olefins by ring-opening metathesis polymerization
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DOI：
10.1021/ma011394x
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发表时间：
2002-01-01
期刊：
影响因子：
5.5
通讯作者：
Coughlin, EB
中科院分区：
文献类型：
--
作者：
Ilker, MF;Coughlin, EB
报道了用RuCl2(=CHPh)(PCy3)(2)(1)及其单-1，3-二介咪唑烷-2-亚甲基衍生物(2)与一系列非极性环烯-环辛烯、环辛二烯、环戊烯和降冰片烯进行共聚反应的结果。用H-1、C-13和H-1-H-1 COSY核磁共振波谱对所得聚合物的微观结构进行了分析。在催化剂1的作用下，endo-N-ethyl-7-oxanorbornene-2，3-dicarboxylimide(endo-3)、exo、exo-7-氧-冰片烯-2，3-二甲基酯(exo-4)或exo-7-氧-冰片烯-2，3-二羧酸酐(exo-5)与环辛烯的共聚反应呈现出高度交替的结构。测定了endo-3、exo-5和环辛烯的均聚合速率，并与endo-3与环辛烯的均聚合速率进行了比较，发现聚合速率快于endo-3的均聚合，但慢于环辛烯的均聚合。观察到外显子-5与环辛烯的共聚速率大于任一单体的均聚合速率。催化剂2的使用导致了低水平的交替，有无规聚合的趋势。
The results from copolymerizations of polar 2,3-difunctionalized 7-oxanorbornene derivatives with a series of nonpolar cyclic olefins-cyclooctene, cyclooctadiene, cyclopentene, and norbornene-using catalysts RuCl2(=CHPh)(PCy3)(2) (1) and its mono- 1,3-dimesitylimidazolidine-2-ylidene derivative (2) are reported. The resulting polymer microstructures have been analyzed by H-1, C-13, and H-1-H-1 COSY NMR spectroscopies. Highly alternating structures were observed for the copolymerizations of endo-N-ethyl-7-oxanorbornene-2,3-dicarboxylimide (endo-3), exo,exo-7-oxanorbornene-2,3-dimethylester (exo-4), or exo-7-oxanorbornene-2,3-dicarboxylic anhydride (exo-5) with cyclooctene using catalyst 1. The rates of homopolymerizations of endo-3, exo-5, and cyclooctene were determined, Comparison with the rate of the copolymerization of endo-3 with cyclooctene reveals a rate faster than the homopolymerization of endo-3 but slower than the homopolymerization of cyclooctene. The rate of the copolymerization of exo-5 with cyclooctene was observed to be greater than the rate of homopolymerization of either monomer. The use of catalyst 2 resulted in lower levels of alternation with a tendency toward random polymerization.