Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization
Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization
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DOI：
10.1021/acs.macromol.5b02749
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发表时间：
2016-02
期刊：
影响因子：
5.5
通讯作者：
Nicole Schuster;Thomas Rünzi;S. Mecking
中科院分区：
文献类型：
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作者：
Nicole Schuster;Thomas Rünzi;S. Mecking
我们通过压力反应器研究（95 °C，3–20 bar）报告了 [{(o-MeOC6H4)2PC6H4SO3}PdMe(L)] 与乙烯共聚时各种极性乙烯基共聚单体和 1-烯烃的反应性，如马尔可夫统计中的 rE = 乙烯/k 共聚单体所定义。发现单体 β 乙烯基碳原子的 13C NMR 化学位移以及 Charton 和 Sterimol 参数分别是单体电子性质和空间需求的适当描述符。全面了解它们对单体反应性和插入区域选择性的影响。这还可以预测其他单体的反应性。
We report the reactivities of a comprehensive range of polar vinyl comonomers and 1-olefins in the copolymerization with ethylene by [{(o-MeOC6H4)2PC6H4SO3}PdMe(L)] from pressure reactor studies (95 °C, 3–20 bar), as defined by rE = kethylene/kcomonomer from Markov statistics. 13C NMR chemical shifts of the monomers’ β vinyl carbon atom and Charton and Sterimol parameters were found to be appropriate descriptors for the monomers’ electronic nature and steric demand, respectively. A comprehensive picture of their impact on monomer reactivity and also regioselectivity of insertion arises. This shall also allow for predictions of the reactivity of other monomers.