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Factors influencing chain transfer with monomer and with hydrogen in propene polymerization using MgCl2-supported Ziegler-Natta catalysts

机译:MgCl2负载的齐格勒-纳塔催化剂在丙烯聚合中影响单体与氢的链转移的因素

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Full Paper: C-13 and H-1 NMR analysis of polypropylene prepared using various MgCl2-supported catalysts at different polymerization temperatures at different hydrogen concentrations has revealed that chain transfer with monomer, yielding vinylidene-terminated chains, is essentially unaffected by hydrogen but is dependent on catalyst selectivity. Chain transfer with hydrogen and with monomer are therefore processes which operate independently of each other, but in bath cases, the incidence of chain transfer increases with decreasing catalyst (site) selectivity. Chain transfer with monomer takes place after primary insertion, while chain transfer with hydrogen takes place after either primary or secondary insertion. Chain initiation via a secondary insertion into a Ti-H species leads either to a 2,3-dimethylbutyl terminal unit, as has recently been observed in metallocene-catalyzed polymerizations, or to a further transfer reaction with hydrogen, generating traces of propane. [References: 23]
机译:全文:使用各种MgCl2负载的催化剂在不同的聚合温度和不同的氢浓度下制备的聚丙烯的C-13和H-1 NMR分析表明,与单体的链转移(产生亚乙烯基末端的链)基本上不受氢的影响,但取决于催化剂的选择性。因此,与氢和与单体的链转移是彼此独立地进行的过程,但是在浴槽情况下,链转移的发生率随着催化剂(位点)选择性的降低而增加。与单体的链转移发生在初次插入后,而与氢的链转移发生在初次或二次插入后。如最近在茂金属催化的聚合反应中所观察到的那样,通过二次插入Ti-H物种引发的链引发或者导致2,3-二甲基丁基末端单元,或者导致与氢的进一步转移反应,生成痕量丙烷。 [参考:23]

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