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烷基磷酸铝催化环氧乙烷与环状磷酸酯共聚合的研究
Aluminum-catalyzed Copolymerization of Cyclic Phosphoesters with Ethylene Oxide
- 高分子通报 2024年37卷第1期 页码：73-79
- 作者机构：
大连理工大学化工学院 精细化工国家重点实验室，大连 116024
- 作者简介：
*郭方， E-mail: guofang@dlut.edu.cn
- 基金信息：
DOI：10.14028/j.cnki.1003-3726.2024.23.131
中图分类号：纸质出版日期：2024-01-20，
收稿日期：2023-04-10，
录用日期：2023-05-03
- 稿件说明：
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屈甜甜, 孙涵阳, 张春阳, 郭方. 烷基磷酸铝催化环氧乙烷与环状磷酸酯共聚合的研究. 高分子通报, 2024, 37(1), 73–79
Qu, T. T.; Sun, H. Y.; Zhang, C. Y.; Guo, F. Aluminum-catalyzed copolymerization of cyclic phosphoesters with ethylene oxide. Polym. Bull. (in Chinese), 2024, 37(1), 73–79
屈甜甜, 孙涵阳, 张春阳, 郭方. 烷基磷酸铝催化环氧乙烷与环状磷酸酯共聚合的研究. 高分子通报, 2024, 37(1), 73–79 DOI： 10.14028/j.cnki.1003-3726.2024.23.131.
Qu, T. T.; Sun, H. Y.; Zhang, C. Y.; Guo, F. Aluminum-catalyzed copolymerization of cyclic phosphoesters with ethylene oxide. Polym. Bull. (in Chinese), 2024, 37(1), 73–79 DOI： 10.14028/j.cnki.1003-3726.2024.23.131.
摘要
研究了烷基磷酸铝催化剂
i
-Bu
3
Al/H
3
PO
4
/DBU催化环氧乙烷(EO)与环状磷酸酯(包括2-甲氧基-2-氧代-1
3
2-二氧磷杂环戊烷(EMP)、2-乙氧基-2-氧代-1
3
2-二氧磷杂环戊烷(EEP)和2-异丙氧基-2-氧代-1
3
2-二氧磷杂环戊烷(IPP))共聚合的性能，通过共聚合动力学、核磁共振波谱(NMR)、凝胶渗透色谱(GPC)和差示扫描量热仪(DSC)对所得共聚物的微观结构和热性能进行分析。结果表明，
i
-Bu
3
Al/H
3
PO
4
/DBU催化剂在60 ℃甲苯溶剂中催化不同比例的环状磷酸酯与EO共聚合2 h可以高收率地获得共聚单体含量可控的EO-EMP、EO-EEP、EO-IPP三种共聚物。GPC分析表明共聚物均为高分子量(
M
n
=1.9×10
4
~4.1×10
4
)、窄分布(
M
w
/
M
n
=1.83~2.10)的聚合物，改变单体与
i
-Bu
3
Al比例可以调控聚合物的分子量。环状磷酸酯磷原子上取代基团如甲基、乙基、异丙基不影响EO环状磷酸酯开环共聚合活性和单体转化率，但影响共聚合动力学和共聚物序列结构，其中EO-EMP共聚为无规共聚合，而EO-EEP和EO-IPP共聚为梯度共聚合，通过改变环状磷酸酯磷原子上的取代基团可以实现共聚物的序列结构调控。
Abstract
The copolymerization of cyclic phosphoesters (including 2-methoxy-2-oxo-1
3
2-dioxapho-spholane(EMP)
2-ethoxy-2-oxo-1
3
2-dioxaphospholane (EEP) and 2-isopropoxy-2-oxo-1
3
2-dioxapho-spholane (IPP)) with ethylene oxide (EO) by
i
-Bu
3
Al/H
3
PO
4
/DBU has been examined. The microstructures
thermal properties and molecular weights of the obtained copolymers were characterized by nuclear magnetic resonance spectroscopy (NMR)
gel permeation chromatography (GPC) and differential scanning calorimeter (DSC) and copolymerization kinetics. The copolymerization of EO with EMP
EEP
IPP by
i
-Bu
3
Al/H
3
PO
4
/DBU has also been successfully achieved at 60 ℃ in 2 h to afford EO-EMP
EO-EEP
EO-IPP copolymers with controllable compositions in high yield by changing the feed ratio. The GPC analysis of copolymers showed that the copolymers possessed high molecular weight (
M
n
=1.9×10
4
−4.1×10
4
) and narrow molecular weight distribution (
M
w
/
M
n
=1.83−2.10). The alkoxy substituent group on the phosphorus atom of cyclic phosphoesters did not affect the copolymerization activity of EO with EMP
EEP and IPP
but affected the kinetic behaviours of the copolymerization and the sequence structure of the obtained copolymers. The EO-EMP copolymerization is random copolymerization
while EO-EEP and EO-IPP copolymerization are gradient copolymerization.
关键词
环状磷酸酯环氧乙烷共聚
Keywords
Cyclic phosphoestersEthylene oxideCopolymerization
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