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Syndiotactic polymerization of styrene and copolymerization with ethylene catalyzed by chiral half-sandwich rare-earth metal dialkyl complexes

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Abstract

The syndiotactic polymerization of styrene (St) and the copolymerization of St with ethylene (E) were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes (Cpx*) as the catalysts. The complexes are Ln(CH2SiMe3)2(THF) (1−4: Ln = Sc (1), Ln = Lu (2), Ln = Y (3), Ln = Dy (4)) bearing chiral cyclopentadienyl ligand containing bulky cylcohexane derivatives in the presence of activator and AliBu3. For the St polymerization, a high activity up to 3.1 × 106 g of polymer molLn−1·h−1 and a high syndiotactic selectivity more than 99% were achieved. The resulting syndiotactic polystyrenes (sPSs) have the molecular weights (Mn) ranging from 3700 g·mol−1 to 6400 g·mol−1 and the molecular weight distributions (Mw/Mn) from 1.40 to 5.03. As for the copolymerization of St and E, the activity was up to 2.4 × 106 g of copolymer molSc−1·h−1·MPa−1, giving random St-E copolymers containing syndiotactic polystyrene sequences with different St content in the range of 15 mol%−58 mol%. These results demonstrate that the bulky cyclopentadienyl ligands of the chiral half-sandwich rare-earth metal complexes effectively inhibit the continued insertion of St monomers into the (co)polymer chain to some extent in comparison with the known half-sandwich rare-earth metal complexes.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Nos. 20974014, 21274012, 21322401 and 21774014) and the 111 project (No. B07012).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, China

    De-Qian Peng, Xin-Wen Yan, Shao-Wen Zhang & Xiao-Fang Li

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  1. De-Qian Peng
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  2. Xin-Wen Yan
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Correspondence to Shao-Wen Zhang or Xiao-Fang Li.

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Invited paper for special issue of “Metal-Catalyzed Polymerization”

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10118_2018_2060_MOESM1_ESM.pdf

Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes

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Peng, DQ., Yan, XW., Zhang, SW. et al. Syndiotactic polymerization of styrene and copolymerization with ethylene catalyzed by chiral half-sandwich rare-earth metal dialkyl complexes. Chin J Polym Sci 36, 222–230 (2018). https://doi.org/10.1007/s10118-018-2060-8

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