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

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外文摘要：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.

外文关键词：

Biobased monomerTerpenesOcimeneRare-earthsPolymerizationRegio/stereoselectivityElastomer

作者：

Qi-Yuan Wang、Li-Peng Sang、Zhen Zhang、Yang Jiang、Hui Tian、Xia Zhao、Xiang Guo、Shi-Hui Li

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作者单位：

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

Science and Technology on Aerospace Chemical Power Laboratory,Hubei Institute of Aerospace Chemotechonology,Xiangyang 441003,China

Shanxi Coal Chemical Industry Technology Research Institute,Xi'an 710000,China

Hubei Institute of Aerospace Chemotechonology,Xiangyang 441003,China

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基金：

open research fund program of Science and Technology on Aerospace Chemical Power LaboratoryNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of China

项目编号：

STACPL120221B03s2217505952073275U21A20279

出版年：

2024

DOI：

10.1007/s10118-023-3047-7

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

年,卷(期)：2024.42(2)

参考文献量57