Aluminum-catalyzed Copolymerization of Cyclic Phosphoesters with Ethylene Oxide

QU Tian-tian; SUN Han-yang; ZHANG Chun-yang; GUO Fang

doi:10.14028/j.cnki.1003-3726.2024.23.131

您当前的位置：

首页 >

文章列表页 >

Aluminum-catalyzed Copolymerization of Cyclic Phosphoesters with Ethylene Oxide

更新时间：2024-01-11

- Aluminum-catalyzed Copolymerization of Cyclic Phosphoesters with Ethylene Oxide
- Polymer Bulletin Vol. 37, Issue 1, Pages: 73-79(2024)
- 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：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2024.23.131
  CLC：
- Published：20 January 2024，
  
  Received：10 April 2023，
  
  Accepted：03 May 2023
- 稿件说明：
扫描看全文
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

-Bu

Al/H

/DBU催化环氧乙烷(EO)与环状磷酸酯(包括2-甲氧基-2-氧代-1

2-二氧磷杂环戊烷(EMP)、2-乙氧基-2-氧代-1

2-二氧磷杂环戊烷(EEP)和2-异丙氧基-2-氧代-1

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，

-Bu

Al/H

/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(

=1.9×10

~4.1×10

)、窄分布(

=1.83~2.10)的聚合物，改变单体与

-Bu

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

2-dioxapho-spholane(EMP)

2-ethoxy-2-oxo-1

2-dioxaphospholane (EEP) and 2-isopropoxy-2-oxo-1

2-dioxapho-spholane (IPP)) with ethylene oxide (EO) by

-Bu

Al/H

/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

-Bu

Al/H

/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 (

=1.9×10

−4.1×10

) and narrow molecular weight distribution (

=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

references

Penczek, S.; Libiszowski, J. Polymerization of 2-methoxy-2-oxo-1,3,2-dioxaphospholane. kinetics and polymer microstructure. Makromol. Chem., 1988, 189(8), 1765–1785.

Bian, J.; Zhang, M. Z.; He, J. L.; Ni, P. H. Prepara-tion and self-assembly of double hydrophilic poly-(ethylethylene phosphate)-block-poly[2-(succinyloxy)ethyl methacrylate]diblock copolymers for drug delivery. React. Funct. Polym., 2013, 73(3), 579–587.

Wu, Q. H.; Wang, C. A.; Zhang, D.; Song, X. M.; Verpoort, F.; Zhang, G. L. Synthesis and micellization of amphiphilic biodegradable methoxypolyethylene glycol/poly(D,L-lactide)/polyphosphate block copolymer. React. Funct. Polym., 2011, 71(9), 980–984.

Yuan, Y. Y.; Wang, J. Temperature-induced mor-phological change of ABC 3-miktoarm star terpolymer assemblies in aqueous solution. Colloids Surf. B, 2011, 85(1), 81–85.

Wu, J.; Liu, X. Q.; Wang, Y. C.; Wang, J. Template-free synthesis of biodegradable nanogels with tunable sizes as potential carriers for drug delivery. J. Mater. Chem., 2009, 19(42), 7856–7863.

Wang, Y. C.; Tang, L. Y.; Li, Y.; Wang, J. Ther-moresponsive block copolymers of poly(ethylene glycol) and polyphosphoester: thermo-induced self-assembly, biocompatibility, and hydrolytic degradation. Biomacromolecules, 2009, 10(1), 66–73.

Zhang, S. Y.; Zou, J.; Zhang, F. W.; Elsabahy, M.; Felder, S. E.; Zhu, J. H.; Pochan, D. J.; Wooley, K. L. Rapid and versatile construction of diverse and functional nanostructures derived from a polyphosphoester-based biomimetic block copolymer system. J. Am. Chem. Soc., 2012, 134(44), 18467–18474.

Müller, L. K.; Steinbach, T.; Wurm, F. R. Multifunctional poly(phosphoester)s with two orthogonal protective groups. RSC Adv., 2015, 5(53), 42881–42888.

Iwasaki, Y.; Yamaguchi, E. Synthesis of well-defined thermoresponsive polyphosphoester macroinitiators using organocatalysts. Macromolecules, 2010, 43(6), 2664–2666.

Zhang, S. Y.; Li, A.; Zou, J.; Lin, L. Y.; Wooley, K. L. Facile synthesis of clickable, water-soluble, and degradable polyphosphoesters. ACS Macro Lett., 2012, 1(2), 328–333.

Zhai, X.; Huang, W.; Liu, J. Y.; Pang, Y.; Zhu, X. Y.; Zhou, Y. F.; Yan, D. Y. Micelles from amphiphilic block copolyphosphates for drug delivery. Macromol. Biosci., 2011, 11(11), 1603–1610.

Clément, B.; Grignard, B.; Koole, L.; Jérôme, C.; Lecomte, P. Metal-free strategies for the synthesis of functional and well-defined polyphosphoesters. Macromolecules, 2012, 45(11), 4476–4486.

Tee, H. T.; Zipp, R.; Koynov, K.; Tremel, W.; Wurm, F. R. Poly(methyl ethylene phosphate) hydrogels: degradable and cell-repellent alternatives to PEG-hydrogels. Eur. Polym. J., 2020, 141, 110075.

Guo, F.; Deng, M.; Li, F.; Chen, S. L. Aluminum-catalyzed statistical copolymerization of mono-, tri- and penta-fluorophenyl glycidyl ether with ethylene oxide and epichlorohydrin. Polym. Chem., 2021, 12(38), 5477–5484.

Deng, M.; Guo, F.; Li, Y.; Hou, Z. M. Synthesis of alkynyl-functionalized linear and star polyethers by aluminium-catalyzed copolymerization of glycidyl 3-butynyl ether with epichlorohydrin and ethylene oxide. Polym. Chem., 2019, 10(9), 1110–1118.

Deng, M.; Guo, F.; Liao, D. H.; Hou, Z. M.; Li, Y. Aluminium-catalyzed terpolymerization of furfuryl glycidyl ether with epichlorohydrin and ethylene oxide: Synthesis of thermoreversible polyepichlorohydrin elastomers with furan/maleimide covalent crosslinks. Polym. Chem., 2018, 9(1), 98–107.

李璠, 陈首龙, 董显文, 郭方. 羟基功能化聚环氧乙烷的可控合成. 高分子学报, 2022, 53(5), 482–487.

陈首龙. 烷基磷酸铝催化内酯与环氧烷烃共聚合的研究. 大连: 大连理工大学, 2022.

Wu, Q. H.; Zhou, D.; Kang, R. Y.; Tang, X. P.; Yang, Q.; Song, X. M.; Zhang, G. L. Synthesis and self-assembly of thermoresponsive amphiphilic biodegradable polypeptide/poly(ethyl ethylene phosphate) block copolymers. Chem. Asian J., 2014, 9(10), 2850–2858.

邓明. 环氧烷烃开环共聚合制备功能化聚醚的研究. 大连: 大连理工大学, 2020.

Views

193

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Iron Trichloride Initiated Ring Opening (co-)Polymerization of Cyclic Esters

Monte Carlo Simulation of Acrylonitrile/Itaconic Acid Copolymerization

Recent Progress on Poly (butylene succinate) : Synthesis, Copolymerization and Functionalization

Biodegradable Plastics Poly(butylene succinate) and its Copolymers : from Fundamental Research to Industrialization

Characterization and Copolymerization of Hemin and N-vinylpyrrolidone

Related Author

Xiao-yan LIU

Ying-zhe JI

Wen-Hua SUN

Fu-rong CAO

Rui WANG

Jia-hao GAO

Wen-juan ZHANG

Jin-xi DOU

Related Institution

Beijing Key Laboratory of Clothing Materials R&D and Assessment, School of Materials Science and Engineering, Beijing Institute of Fashion Technology

Key Laboratory of Engineering Plastics , Institute of Chemistry,Chinese Academy of Sciences

Advanced Material Laboratory, Fudan University

Sinopec Shanghai Petrochemical Company Limited

Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences (ICCAS)

⁰