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Methylaluminoxane-activated neodymium chloride tributylphosphate catalyst for isoprene polymerization

Authors

  • Yanming Hu,

    Corresponding author
    1. State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, China
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  • Chunqing Zhang,

    1. State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, China
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  • Xianguang Liu,

    1. State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, China
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  • Keke Gao,

    1. State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, China
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  • Yuming Cao,

    1. State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, China
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  • Chunyu Zhang,

    1. Research Center of High Performance Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
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  • Xuequan Zhang

    1. Research Center of High Performance Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
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Abstract

The polymerization of isoprene was examined by using a novel binary catalyst system composed of neodymium chloride tributylphosphate (NdCl3·3TBP) and methylaluminoxane (MAO). The NdCl3·3TBP/MAO catalyst worked effectively in a low MAO level ([Al]/[Nd] = 50) to afford polymers with high molecular weight (Mn ∼105), narrow molecular weight distribution (Mw/Mn = 1.4–1.6), and high cis-1,4 stereoregularity (> 96%). The catalytic activity increased with an increasing [Al]/[Nd] ratio from 30 to 100 and polymerization temperature from 0 to 50°C, while the Mn of polymer decreased. The presence of free TBP resulted in low polymer yield. Polymerization solvent remarkably affected the polymerization behaviors; the polymerizations in aliphatic solvents (cyclohexane and hexane) gave polymer in higher yield than that in toluene. The Mw/Mn ratio of the producing polymer remained around 1.5 and the gel permeation chromatographic curve was always unimodal, indicating the presence of a single active site in the polymerization system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40153.

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