新型铝配合物催化制备聚酯材料的研究

孟帅明; 冯孟昌; 周延川; 庞烜; 陈学思

doi:10.11777/j.issn.1000-3304.2024.0201

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新型铝配合物催化制备聚酯材料的研究

研究论文 | 更新时间：2024-11-20

- 新型铝配合物催化制备聚酯材料的研究
- Study on the Preparation of Polyester Catalyzed by the Novel Al Complexes
- 高分子学报 2024年页码：1-10
- 作者机构：
  
  1.中国科学院长春应用化学研究所中国科学院生态环境高分子材料重点实验室长春130022
  2.中国科学技术大学应用化学与工程学院合肥230026
- 作者简介：
  
  E-mail: xpang@ciac.ac.cn
  xschen@ciac.ac.cn
- 基金信息：
  
  国家自然科学基金基础科学中心项目(51988102);吉林省科技发展计划项目(20230101048JC)
- DOI：10.11777/j.issn.1000-3304.2024.0201
  中图分类号：
- CSTR：32057.14.GFZXB.2024.7294
- 网络出版日期：2024-11-07，
  
  收稿日期：2024-07-18，
  
  录用日期：2024-09-11
- 稿件说明：
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孟帅明, 冯孟昌, 周延川, 庞烜, 陈学思. 新型铝配合物催化制备聚酯材料的研究. 高分子学报, doi: 10.11777/j.issn.1000-3304.2024.0201

Meng, S. M.; Feng, M. C.; Zhou, Y. C.; Pang, X.; Chen, X. S. Study on the preparation of polyester catalyzed by the novel al complexes. Acta Polymerica Sinica, doi: 10.11777/j.issn.1000-3304.2024.0201
孟帅明, 冯孟昌, 周延川, 庞烜, 陈学思. 新型铝配合物催化制备聚酯材料的研究. 高分子学报, doi: 10.11777/j.issn.1000-3304.2024.0201 DOI： CSTR： 32057.14.GFZXB.2024.7294.

Meng, S. M.; Feng, M. C.; Zhou, Y. C.; Pang, X.; Chen, X. S. Study on the preparation of polyester catalyzed by the novel al complexes. Acta Polymerica Sinica, doi: 10.11777/j.issn.1000-3304.2024.0201 DOI： CSTR： 32057.14.GFZXB.2024.7294.

摘要

设计开发高效的催化体系用于可控制备高分子量聚酯材料，一直以来都是可降解高分子材料研发的重点. 本文报道了一种配体框架中含有Salen键和Catam键的新型不对称铝配合物. 这种特殊的配体结构可以促进中心金属对环酯单体(如

-己内酯(

-CL)和

-戊内酯(

-VL))的活化作用，赋予了铝配合物高活性催化环酯单体的能力，实现了高分子量聚酯材料的可控合成. 首先，考察比较了铝配合物结构和反应条件(温度、单体比例和单体结构)对催化聚合反应的影响规律. 在优化反应条件后，轴配位为苄氧基的铝配合物，可以在10 min内快速催化

-CL、

-VL及其混合单体的聚合反应，合成数均分子量高达175.7~443.8 kg·mol

-1

的聚酯材料. 进一步计算比较了混合单体比例和反应温度等条件对无规共聚酯材料的平均链段长度的影响，并详细表征了聚酯材料的组分结构与材料热学性能的关系.

Abstract

One major remaining challenge in development degradable polymer materials

is designing efficient catalytic systems for the controllable synthesis of high molecular weight polyesters. In this study

we reported the novel asymmetric Al complexes with a Salen bond and a Catam bond in the ligand framework. The specific ligand structure played an important role in the activation of the central metal atom to the cyclic ester monomers (

e.g.

-caprolactone (

-CL)

and

-valerolactone (

-VL)). The Al complexes exhibited excellent activity for the cyclic ester polymerizations

fabricating high molecular weight polyesters. Initially

the effects of aluminum complex structures and polymerization conditions (reaction temperatures

monomer ratios

and monomer structures) on catalytic polymerization were investigated systematically. After optimizing the reaction conditions

the asymmetric Al complex with a benzyl alkoxy as axial group

could controllably polymerize

-CL

-VL

and their mixed monomers

to polyesters with high number-average molecular weight (175.7-443.8 kg·mol

-1

) within 10 min. Furthermore

the relationship between chain structures (number-average sequence lengths of PCL and PVL) and reaction conditions (reaction temperatures and monomer ratios) was analyses. And the thermal properties of random polyesters were characterized in detail.

关键词

不对称铝配合物开环聚合反应环内酯高催化活性聚酯材料

Keywords

Asymmetric Al complexRing-opening polymerizationCyclic esterHigh catalytic activityPolyester

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新型铝配合物催化制备聚酯材料的研究