Copolymerization studies of vinyl chloride and vinyl acetate with ethylene using a transition-metal catalyst
Copolymerization studies of vinyl chloride and vinyl acetate with ethylene using a transition-metal catalyst
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DOI：
10.1021/ja0260061
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发表时间：
2002-07-31
影响因子：
15
通讯作者：
Goddard, WA
中科院分区：
文献类型：
--
作者：
Boone, HW;Athey, PS;Goddard, WA
自从乙烯的齐格勒-纳塔聚合出现以来，已经尝试将配位聚合扩展到具有极性官能团的商业上重要的单体。在这项研究中，我们研究了全氘代氯乙烯（VC）和全氘代乙酸乙烯酯（VA）与乙烯的共聚使用三齿二氯化铁（II）吡啶二亚胺金属催化剂。用GC/MS和~ 2 H NMR对所得乙烯齐聚物进行了表征。结果表明，VC每插入1/180个乙烯单体插入1次，VA每插入1/1350个乙烯单体插入1次。VC和VA表现为与乙烯的配位/插入聚合的共聚单体。然而，我们发现，插入任何单体导致终止增长链通过β-消除过程。氘原子仅位于每个单体的烯烃末端。
Since the advent of Ziegler−Natta polymerization of ethylene, attempts have been made to extend coordination polymerization to commercially important monomers with polar functionality. In this study we examined the copolymerization of perdeuterated vinyl chloride (VC) and perdeuterated vinyl acetate (VA) with ethylene using a tridentate Fe(II) dichloride pyridine diimine metal catalyst. The resulting ethylene oligomers were examined by GC/MS and2H NMR spectroscopy. It was shown that VC was inserted once for every ∼180 ethylene monomers and VA was inserted once for every ∼350 ethylene monomers. VC and VA behave as comonomers for coordination/insertion polymerizations with ethylene. However, we find that insertion with either monomer leads to termination of the growing chain via β-elimination processes. The deuterium atoms are exclusively located at the olefin terminus for each of the monomers.