二氧化碳与环氧化物的三元共聚反应动力学过程控制

周庆海; 贾凡; 曹瀚; 刘顺杰; 王献红; 王佛松

doi:10.11777/j.issn1000-3304.2022.22097

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二氧化碳与环氧化物的三元共聚反应动力学过程控制

研究论文 | 更新时间：2024-10-08

- 二氧化碳与环氧化物的三元共聚反应动力学过程控制
  增强出版
- Kinetic Control of Carbon Dioxide and Epoxide Based Terpolymerization
- 高分子学报 2022年53卷第11期页码：1365-1371
- 作者机构：
  
  1.中国科学技术大学应用化学与工程学院合肥 230026
  2.中国科学院长春应用化学研究所中科院生态环境高分子材料重点实验室长春 130022
- 作者简介：
  
  E-mail: xhwang@ciac.ac.cn
- 基金信息：
  
  国家自然科学基金(基金号 51988102)
- DOI：10.11777/j.issn1000-3304.2022.22097
  中图分类号：
- 纸质出版日期：2022-11-20，
  
  网络出版日期：2022-07-25，
  
  收稿日期：2022-03-26，
  
  录用日期：2022-04-19
- 稿件说明：
移动端阅览
周庆海,贾凡,曹瀚等.二氧化碳与环氧化物的三元共聚反应动力学过程控制[J].高分子学报,2022,53(11):1365-1371.

Zhou Qing-hai,Jia Fan,Cao Han,et al.Kinetic Control of Carbon Dioxide and Epoxide Based Terpolymerization[J].ACTA POLYMERICA SINICA,2022,53(11):1365-1371.
周庆海,贾凡,曹瀚等.二氧化碳与环氧化物的三元共聚反应动力学过程控制[J].高分子学报,2022,53(11):1365-1371. DOI： 10.11777/j.issn1000-3304.2022.22097.

Zhou Qing-hai,Jia Fan,Cao Han,et al.Kinetic Control of Carbon Dioxide and Epoxide Based Terpolymerization[J].ACTA POLYMERICA SINICA,2022,53(11):1365-1371. DOI： 10.11777/j.issn1000-3304.2022.22097.

摘要

二氧化碳共聚物的分子结构调控有助于改善其物化性能，尤其是对深受低玻璃化温度困扰的二氧化碳(CO

)-环氧丙烷(PO)共聚物(PPC). 引入氧化环己烯(CHO)为第三单体进行三元共聚是提高PPC耐温性能的重要途径，但是三元共聚反应过程复杂，其动力学研究还处于探索阶段. 本文以均相的卟啉铝配合物为催化剂，利用Fineman-Ross方程和在线红外光谱研究CO

/PO/CHO的三元共聚反应. 实验发现较低共聚温度(60~70 ℃)下PO与CHO的单体竞聚率均小于1，因此通过调整单体投料比即可制备出无规共聚物，进而调整三元共聚物的热力学性能. 当共聚温度高于70 ℃时，CHO竞聚率大幅提高，更容易生成嵌段共聚物. 在线红外反应动力学研究表明，此催化体系70 ℃即使在极低黏度下依然可以快速引发聚合反应，但聚合温度提高后，环状碳酸酯生成量会大幅提升，可明显观察到聚合物的解拉链反应.

Abstract

The physicochemical properties of carbon dioxide (CO

)-based copolymer can be enhanced by the regulation of the chain structure

especially for the CO

/propylene oxide (PO) copolymer (PPC)

which is plagued by low glass transition temperature. Introducing cyclohexene oxide (CHO) as the third monomer in terpolymerization is an important way to improve the thermal property of PPC. However

the reaction process of such terpolymerization is complicated and its kinetics study is still in its infancy. Herein

the kinetic behaviour of terpolymerization of PO/CHO/CO

was thoroughly investigated by virtue of the Fineman-Ross equation and

in situ

FTIR study

in the presence of aluminum porphyrin complex formed homogeneous catalysis. Results showed that the monomeric reactivity ratios of both PO and CHO were smaller than 1 under a low temperature of 60-70 ℃. Through regulating the monomer feed ratios

the random terpolymer could be facilely achieved with tunable thermal and mechanical properties. The reactivity ratio of CHO boosted significantly at high temperatures

which is favorable for the formation of block copolymers. The

in situ

FTIR analysis demonstrated that the catalytic system could quickly initiate the polymerization even at very low viscosity at 70 ℃. With the increase of polymerization temperature

the production of cyclic carbonate will be greatly increased

and the chain unzipping reaction of pol

ymer can be obviously observed.

关键词

二氧化碳共聚合动力学竞聚率卟啉铝

Keywords

CO2 terpolymerizationKineticsReactivity ratioAluminum porphyrin

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