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Tandem Action of SNS–Cr and CGC–Ti in Preparation of Ethylene–1‐Hexene Copolymers from Ethylene Feedstock
Authors:Song Guo  Hong Fan  Zhiyang Bu  Bo‐Geng Li  Shiping Zhu
Affiliation:1. State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, , Hangzhou, 310027 PR China;2. Department of Chemical Engineering, McMaster University, , Hamilton, Ontario, L8S 4L7 Canada
Abstract:Ethylene–1‐hexene copolymer materials, ranging from semicrystalline linear low‐density poly­ethylene (LLDPE) to completely amorphous polyethylenes (PEs), are prepared from ethylene alone in a single reactor by the tandem polymerization of bis(2‐dodecylsulfanyl‐ethyl)amine–CrCl3 (SNS–Cr) and (N‐tert‐butylamido) (tetramethylcyclopentadienyl)–titanium dichloride (CGC–Ti) at 75 °C and under atmospheric pressure. The polymerization activities are on the order of 105–106 g (mol Ti)?1 h?1. 1‐Hexene incorporation in the resulting copolymers can be adjusted by varying the Cr–Ti molar ratio and/or applying a short period of pre‐trimerization. Copolymers with high 1‐hexene incorporation up to 15 mol% are obtained. Few vinyl and vinylene chain ends are detected by 13C NMR, suggesting that 1‐hexene does not act as a chain‐transfer agent. Narrow molecular‐weight distributions with polydispersities from 1.9 to 2.6 are obtained, characteristic of a single‐active‐site nature of the catalyst system.
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Keywords:comonomer effect  copolymer composition  ethylene–  1‐hexene copolymerization  pre‐trimerization  tandem catalysts
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