催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (10): 1242-1246.DOI: 10.3724/SP.J.1088.2010.00425

• 研究论文 • 上一篇    下一篇

硼氢化稀土-二乙基锌-甘油三元体系催化环氧丙烷与 CO2 共聚反应

刘光烜, 郦聪, 陈丹, 倪旭峰, 江黎明, 沈之荃   

  1. 浙江大学高分子科学与工程学系, 高分子合成与功能构造教育部重点实验室, 浙江杭州 310027
  • 收稿日期:2010-10-25 出版日期:2010-10-25 发布日期:2014-03-04

Copolymerization of Propylene Oxide and CO2 Catalyzed by a Rare Earth Borohydride-Diethylzinc-Glycerine Ternary System

LIU Guangxuan, LI Cong, CHEN Dan, NI Xufeng, JIANG Liming*, SHEN Zhiquan   

  1. Key Laboratory of Macromolecular Synthesis and Functionalization, Ministry of Education, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2010-10-25 Online:2010-10-25 Published:2014-03-04

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摘要： 由硼氢化稀土、二乙基锌和甘油制备了三元体系 Ln(BH4)3•3THF-ZnEt2-Gly (甘油) 用于催化环氧丙烷 (PO) 与 CO2 共聚反应, 详细考察了催化剂组成、不同稀土元素和溶剂性质对聚合反应的影响. 通过正交试验优化的催化剂组成和聚合条件为: Y(BH4)3•3THF-ZnEt2-Gly (摩尔比 = 3:60:20) 催化剂, 乙二醇二甲醚溶剂, PO/Y 摩尔比 1000, [Y] = 6.67 mmol/L, p(CO2) = 3.0 MPa, 80oC, 6 h. 最高催化效率可达 4908 g /(mol•h); 碳酸酯含量为 95.7%, 数均分子量为 6.97x104.

关键词: 环氧丙烷, 二氧化碳, 共聚反应, 聚碳酸酯, 硼氢化稀土, 二乙基锌, 甘油, 正交试验

Abstract: A ternary catalytic system composed of rare earth borohydrides, diethylzinc, and glycerine has been developed and found to be effective for the copolymerization of propylene oxide (PO) with carbon dioxide. The effect of catalyst composition and reaction conditions on the copolymerization was examined through orthogonal experiments. With Y(BH4)3•3THF-ZnEt2-glycerine molar ratio of 3:60:20, the highest turnover frequency (TOF) of 4908 g/(mol•h was achieved at 80 oC and 3.0 MPa of CO2 using 1,2-dimethoxyethane as solvent. The poly(propylene carbonate) had a carbonate unit content of 95.7% and number-average molecular mass of 6.97x104.

Key words: propylene oxide, carbon dioxide, copolymerization, polycarbonate, rare earth borohydride, diethylzinc, glycerine, orthogonal design