DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex |
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| Authors: | Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang |
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| Affiliation: | 1. Department of Chemistry and Material Science, Langfang Teachers University, Langfang, China;2. College of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing, China;3. Joint Laboratory of Polymer Science and Materials, Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China |
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| Abstract: | DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 |
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| Keywords: | chain transfer mechanism copolymerization calculations hydrogen metallocene catalysts polypropylene functionalization |
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