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使用吡唑作为配体可极大地提高异丙醇钛对丙交酯开环聚合的催化活性:一种协同效应。

Use of pyrazoles as ligands greatly enhances the catalytic activity of titanium iso-propoxide for the ring-opening polymerization of l-lactide: a cooperation effect.

作者信息

Wang Tzu-Fang, Kosuru Someswara Rao, Yu Shu-Chun, Chang Yung-Chi, Lai Hsin-Yu, Chang Yu-Lun, Wu Kuo-Hui, Ding Shangwu, Chen Hsuan-Ying

机构信息

Department of Medicinal and Applied Chemistry, Drug Development and Value Creation Research Center, Kaohsiung Medical University Kaohsiung Taiwan 80708 Republic of China

Department of Chemistry, Graduate School of Science, The University of Tokyo Tokyo 113-0033 Japan.

出版信息

RSC Adv. 2020 Nov 9;10(67):40690-40696. doi: 10.1039/d0ra07824g.

Abstract

Using TiOPr with a pyrazole ligand for one-pot LA polymerization improved catalytic activity compared with using TiOPr only. At 60 °C, TiOPr with Pz exhibited a higher catalytic activity (approximately 3-fold) than TiOPr. At room temperature, TiOPr with Pz exhibited a higher catalytic activity (approximately 17-fold) than TiOPr. High molecular mass PLA ( = 51 100, and = 1.10) could be produced by using TiOPr with Pz in melt polymerization ([TiOPr] : [Pz] = 1000 : 1 : 1 at 100 °C, 240 min). The crystal structure of PzTiOPr revealed the cooperative activation between two Ti atoms during LA polymerization.

摘要

与仅使用异丙醇钛相比,使用带有吡唑配体的异丙醇钛进行一锅法丙交酯开环聚合可提高催化活性。在60℃下,带有吡唑的异丙醇钛比异丙醇钛表现出更高的催化活性(约3倍)。在室温下,带有吡唑的异丙醇钛比异丙醇钛表现出更高的催化活性(约17倍)。在熔融聚合中(100℃,240分钟,[异丙醇钛]∶[吡唑] = 1000∶1∶1),使用带有吡唑的异丙醇钛可制备高分子量聚乳酸( = 51 100, = 1.10)。吡唑异丙醇钛的晶体结构揭示了丙交酯聚合过程中两个钛原子之间的协同活化作用。

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