高分子科学(英文版)2024,Vol.42Issue(2) :223-229.DOI:10.1007/s10118-023-3047-7

Regio-and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

Qi-Yuan Wang Li-Peng Sang Zhen Zhang Yang Jiang Hui Tian Xia Zhao Xiang Guo Shi-Hui Li
高分子科学(英文版)2024,Vol.42Issue(2) :223-229.DOI:10.1007/s10118-023-3047-7

Regio-and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

Qi-Yuan Wang 1Li-Peng Sang 2Zhen Zhang 3Yang Jiang 1Hui Tian 1Xia Zhao 4Xiang Guo 2Shi-Hui Li1
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作者信息

  • 1. State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026,China
  • 2. Science and Technology on Aerospace Chemical Power Laboratory,Hubei Institute of Aerospace Chemotechonology,Xiangyang 441003,China
  • 3. State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;Shanxi Coal Chemical Industry Technology Research Institute,Xi'an 710000,China
  • 4. Hubei Institute of Aerospace Chemotechonology,Xiangyang 441003,China
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Abstract

Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex 1,β-diketiminate yttrium complex 2,bis(phosphino)carbazolide yttrium complex 3,half-sandwich benzyl fluorenyl scandium complex 4 and pyridyl-methylene-fluorenyl rare-metal complexes 5a-5c.Complexes 1,4 and 5a-5c show trans-1,2-regioselectivities and high activities,of which 5c exhibits excellent isoselectivity(mmmm>99%).Conversely,complexes 2 and 3 promote β-ocimene polymerization to produce isotactic cis-1,4-polyocimenes(cis-1,4>99%,mm>95%).Diblock copolymers cis-1,4-PIP-block-cis-1,4-POc and cis-1,4-PBD-block-cis-1,4-POc are obtained in one-pot reactions of β-ocimene with isoprene and butadiene using complex 3.Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced Tg(from-20 ℃ to 79 ℃ and 74 ℃)and hydrophilicity.

Key words

Biobased monomer/Terpenes/Ocimene/Rare-earths/Polymerization/Regio/stereoselectivity/Elastomer

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基金项目

open research fund program of Science and Technology on Aerospace Chemical Power Laboratory(STACPL120221B03)

National Natural Science Foundation of China(s22175059)

National Natural Science Foundation of China(52073275)

National Natural Science Foundation of China(U21A20279)

出版年

2024
高分子科学(英文版)
中国化学会 中国科学院化学研究所

高分子科学(英文版)

CSTPCD
影响因子:0.721
ISSN:0256-7679
参考文献量57
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