Preparation of High Performance Polyimide Based on Metal Coordination Bond

Chen Yang; Xiu-ting Li; Jie Dong; Xin Zhao; Jing-hua Gong; Qing-hua Zhang

doi:10.11777/j.issn1000-3304.2021.21336

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Preparation of High Performance Polyimide Based on Metal Coordination Bond

Research Article | 更新时间：2024-10-08

- Preparation of High Performance Polyimide Based on Metal Coordination Bond
- ACTA POLYMERICA SINICA Vol. 53, Issue 6, Pages: 663-672(2022)
- 作者机构：
  
  东华大学纤维材料改性国家重点实验室上海 201620
- 作者简介：
  
  Xiu-ting Li, E-mail: LiXiuting@dhu.edu.cn
  Jing-hua Gong, E-mail: gjh@dhu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2021.21336
  CLC：
- Published：20 June 2022，
  
  Published Online：18 March 2022，
  
  Received：03 November 2021，
  
  Accepted：31 December 2021
- 稿件说明：
移动端阅览
杨晨,李琇廷,董杰等.基于金属配位作用制备高性能聚酰亚胺[J].高分子学报,2022,53(06):663-672.

Yang Chen,Li Xiu-ting,Dong Jie,et al.Preparation of High Performance Polyimide Based on Metal Coordination Bond[J].ACTA POLYMERICA SINICA,2022,53(06):663-672.
杨晨,李琇廷,董杰等.基于金属配位作用制备高性能聚酰亚胺[J].高分子学报,2022,53(06):663-672. DOI： 10.11777/j.issn1000-3304.2021.21336.

Yang Chen,Li Xiu-ting,Dong Jie,et al.Preparation of High Performance Polyimide Based on Metal Coordination Bond[J].ACTA POLYMERICA SINICA,2022,53(06):663-672. DOI： 10.11777/j.issn1000-3304.2021.21336.

摘要

通过分子结构设计合成了含金属配位交联网络的可溶性聚酰亚胺，由于Cu

与聚酰亚胺侧链羧基之间的配位交联作用限制了聚酰亚胺分子链的运动，使材料的

得到显著提升. 同时，由于Cu

具有非球面对称的电子云结构，导致Cu

在与有机配体配位时存在额外的晶体场稳定能(CFSE)以及较强Jahn-Teller效应(JTE)，使配位键能够在有机溶剂中稳定存在，极大地提高了薄膜的抗溶剂性能，制备的聚酰亚胺膜在DMF、DMAc等强极性溶剂中室温下浸泡48 h后质量残留率仍可高达80%. 此外，在聚酰亚胺分子结构中引入金属离子配位作用使其力学性能明显提升，拉伸强度从93 MPa提高到128 MPa. 研究结果为开发高性能可溶性聚酰亚胺材料提供新途径.

Abstract

Soluble polyimide containing metal coordination crosslinking network was synthesized through molecular structure design. Based on the coordination crosslinking between Cu

and the lateral carboxyl group of polyimide

the mobility of polyimide chain in solid state was limited and the

of the material was significantly improved. The

of the original polyimide is about 320 ℃

while the

of coordination crosslinked polyimide PI-Cu50% can reach about 362 ℃. After coordination with Cu

the initial "push-pull" electronic mode of polyimide is destroyed

the existing state of electrons in the main chain was changed

and the fluorescence intensity of polyimide was weakened. Meanwhile

has an aspherical symmetrical electron cloud structure

resulting in additional crystal field stability energy (CFSE) and strong Jahn teller effect (JTE) when Cu

coordinates with organic ligands

so that the coordination bond can exist stably in organic solvents

After the introduction of copper chloride

crosslinking network based on Cu

coordination was formed in the molecular structure of polyimide which greatly improves the solvent corrosion resistance of the films. The original polyimide film can be completely dissolved after soaking in strong polar solvents such as

‍

-dimethylformamide (DMF)

-methylacetamide (DMAc) and

-methylpyrrolidone (NMP) and standing at room temperature for two days

while the mass residue rate of the coordination crosslinked polyimide film PI-Cu50% can still be as high as 80% after soaking in strong polar solvents such as DMF and DMAc at room temperature for 48 h. Due to the decarboxylation crosslinking reaction of carboxy

l group at about 400 ℃

the

of polyimide containing carboxyl group is low

and the thermal stability of carboxyl group was significantly improved when coordinated with Cu

so the

of polyimide was improved. Moreover

the introduction of metal ion coordination into the polyimide molecular structure also improved its mechanical properties

and the tensile strength of film increased from 93 MPa to 128 MPa. This study provides a new way to develop high-performance soluble polyimide materials.

关键词

聚酰亚胺金属-配体配位交联聚合物抗溶剂腐蚀性机械性能

Keywords

PolyimideMetal ligand coordinationCrosslinked polymerSolvent resistanceMechanical property

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