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Ethylene Polymerization Using Zirconocenes Supported on Pentafluorophenyl-Modified Solid Polymethylaluminoxane
Macromolecules ( IF 5.1 ) Pub Date : 2020-01-17 , DOI: 10.1021/acs.macromol.9b02146
Jessica V. Lamb 1 , Jean-Charles Buffet 1 , Zoë R. Turner 1 , Dermot O’Hare 1
Affiliation  

Three permethylindenyl zirconocenes have been supported on a hexane-insoluble form of polymethylaluminoxane modified with 40 wt % pentafluorophenol (sMAO(PFP)). The solid precatalysts were characterized by solid-state nuclear magnetic resonance spectroscopy, and their ethylene polymerization activity was studied. When supported on sMAO(PFP), Me2SB(Cp,I*)ZrX2 ({(η5-C9Me6)Me2Si(η5-C5H4)}ZrX2; X = Cl, CH2Ph, and Me) showed ethylene polymerization activities up to 25% higher than when supported on unmodified sMAO with the same [Al]0/[Zr]0 catalyst loading: activities of 6454 and 5144 kgPE molZr–1 h–1 bar–1 at 80 °C for Me2SB(Cp,I*)ZrCl2 supported on sMAO(PFP) and sMAO, respectively. The systems produced relatively low-molecular weight polyethylenes (Mw < 170 kg mol–1 at 80 °C) with minimal defects and branching. The polymers showed good flowability, although they displayed more aggregated morphologies than polyethylenes produced from unmodified sMAO. On increasing the solvent volume fivefold, the activity and polymer molecular weights approximately doubled.

中文翻译:

使用五氟苯基改性的固态聚甲基铝氧烷上的茂茂金属进行乙烯聚合

三种全甲基茚基锆茂化合物已负载在不溶于己烷的形式的聚甲基铝氧烷中,该聚甲基铝氧烷经40 wt%五氟苯酚(sMAO(PFP))改性。通过固态核磁共振光谱对固体预催化剂进行了表征,并研究了它们的乙烯聚合活性。当支撑在的sMAO(PFP),2 SB(CP,我*)ZRX 2 - ({(η 5 -C 96)Me 2的Si(η 5 -C 5 H ^ 4)} ZRX 2 ; X =氯, CH 2 Ph和Me)显示乙烯聚合活性比未修饰sMAO负载[Al] 0时高出25%。/ [Zr] 0催化剂负载量:负载在sMAO(PFP)和sMAO上的Me 2 SB(Cp,I *)ZrCl 2在80°C下的活性为6454和5144 kg PE mol Zr –1 h –1 bar –1,分别。该系统生产相对低分子量的聚乙烯(在80°C下M w <170 kg mol –1),且缺陷和分支最少。该聚合物显示出良好的流动性,尽管它们显示出比未改性的sMAO生产的聚乙烯更聚集的形态。在溶剂体积增加五倍时,活性和聚合物分子量大约增加一倍。
更新日期:2020-01-17
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