氧化环己烯连续进料下二氧化碳-环氧丙烷-氧化环己烯三元共聚物的合成

doi:10.3724/SP.J.1095.2014.40243

摘要/Abstract

摘要： 由于氧化环己烯（CHO）与二氧化碳的共聚反应速度比其与环氧丙烷（PO）快，这种竞聚率的差异导致一锅法所得的二氧化碳-环氧丙烷-氧化环己烯三元共聚物的组成难以稳定控制。为此本文在稀土三元催化剂下，采用氧化环己烯单体连续进料的方法合成了二氧化碳-环氧丙烷-氧化环己烯三元共聚物，催化效率可达575 g/(mol Zn h)。三元共聚物的玻璃化转变温度随CHO含量升高而增大，当CHO的摩尔投料比从0.19增加到0.59时，玻璃化温度从44.3 ℃提高到70.1 ℃。 CHO连续进料合成的三元共聚物的组成与投料比基本相近，且连续进料法所合成的三元共聚物只有一个玻璃化转变温度，而普通的一锅法所得的三元共聚物通常存在两个玻璃化转变温度，因此连续进料法是制备组成稳定的二氧化碳-环氧丙烷-氧化环己烯三元共聚物的有效方法。

关键词: 二氧化碳, 氧化环己烯, 环氧丙烷, 连续进料

Abstract: The copolymerization reaction rate of cyclohexene oxide(CHO) and carbon dioxide is faster than that of propylene oxide(PO) and carbon dioxide, which leads to the difficulty in controlling the composition of the CHO-PO-CO2 terpolymer from onepot synthesis. In this work, continuous feeding of CHO was used for the terpolymerization of CHO, PO and CO2 under a ternary rare earth metal coordination catalyst. Its catalytic activity can reach 575 g/(mol Zn h). Terpolymer PPCH100x(x is the molar farction of CHO in total oxides in comonomer feed) from the continuous process has only one glass transition temperature, while the terpolymer from one-pot synthesis has two glass transition temperatures. The glass transition temperature of PPCHx increases from 44.3 ℃ to 70.1 ℃ when the feed ratio of CHO increases from 0.19 to 0.59. It is encouraging to note that the composition of the terpolymer from continuous CHO feeding is similar to the feed ratio of comonomers, indicating that continuous feeding of comonomers is effective for controlling the composition of the terpolymer.

Key words: carbon dioxide, propylene oxide, cyclohexene oxide, continuous monomer feeding

中图分类号:

O633

张亚明, 高凤翔, 周庆海, 秦玉升, 王献红, 王佛松. 氧化环己烯连续进料下二氧化碳-环氧丙烷-氧化环己烯三元共聚物的合成[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.40243.

ZHANG Yaming, GAO Fengxiang, ZHOU Qinghai, QIN Yusheng, WANG Xianhong*, WANG Fosong. Terpolymerization of Carbon Dioxide-Propylene Oxide-Cyclohexene Oxide by Cyclohexene Oxide Continuous Feeding[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.40243.

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