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

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

机构地区：[1]State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun,130022,China [2]School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei,230026,China [3]Science and Technology on Aerospace Chemical Power Laboratory,Hubei Institute of Aerospace Chemotechonology,Xiangyang,441003,China [4]Shanxi Coal Chemical Industry Technology Research Institute,Xi’an,710000,China [5]Hubei Institute of Aerospace Chemotechonology,Xiangyang,441003,China

出　　处：《Chinese Journal of Polymer Science》2024年第2期223-229,I0008,共8页高分子科学（英文版）

基　　金：financially supported by the open research fund program of Science and Technology on Aerospace Chemical Power Laboratory (No. STACPL120221B03);the National Natural Science Foundation of China (Nos. s22175059,52073275 and U21A20279)。

摘　　要：Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, 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 T_(g)(from-20 ℃ to 79 ℃ and 74 ℃) and hydrophilicity.

关 键 词：Biobased monomer TERPENES OCIMENE RARE-EARTHS Polymerization Regio/stereoselectivity Elastomer 

分 类 号：TQ203.2[化学工程—有机化工]