含主链和末端炔基交联位点聚酰亚胺树脂的制备与表征

王进; 刘杰; 钟敏; 江乾; 黄安民; 高纪明

doi:10.14028/j.cnki.1003-3726.2025.25.095

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含主链和末端炔基交联位点聚酰亚胺树脂的制备与表征

研究论文 | 更新时间：2025-08-26

- 含主链和末端炔基交联位点聚酰亚胺树脂的制备与表征
- Preparation and Characterization of Polyimide Resins Containing In-chain and Terminal Alkynyl Crosslinking Sites
- 高分子通报 2025年38卷第9期页码：1407-1415
- 作者机构：
  
  株洲时代新材料科技股份有限公司，株洲 412007
- 作者简介：
  
  wangjin@csrzic.com
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.095
  中图分类号：
- 收稿日期：2025-03-31，
  
  录用日期：2025-06-09，
  
  网络出版日期：2025-07-17，
  
  纸质出版日期：2025-09-20
- 稿件说明：
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王进, 刘杰, 钟敏, 江乾, 黄安民, 高纪明. 含主链和末端炔基交联位点聚酰亚胺树脂的制备与表征[J]. 高分子通报, 2025,38(9):1407-1415.

WANG Jin, LIU Jie, ZHONG Min, JIANG Qian, HUANG An-min, GAO Ji-ming. Preparation and Characterization of Polyimide Resins Containing In-chain and Terminal Alkynyl Crosslinking Sites[J]. Polymer bulletin, 2025, 38(9): 1407-1415.
王进, 刘杰, 钟敏, 江乾, 黄安民, 高纪明. 含主链和末端炔基交联位点聚酰亚胺树脂的制备与表征[J]. 高分子通报, 2025,38(9):1407-1415. DOI： 10.14028/j.cnki.1003-3726.2025.25.095.

WANG Jin, LIU Jie, ZHONG Min, JIANG Qian, HUANG An-min, GAO Ji-ming. Preparation and Characterization of Polyimide Resins Containing In-chain and Terminal Alkynyl Crosslinking Sites[J]. Polymer bulletin, 2025, 38(9): 1407-1415. DOI： 10.14028/j.cnki.1003-3726.2025.25.095.

摘要

以间苯二胺(

-PDA)和4

4′-(六氟异丙烯)二酞酸酐(6FDA)为二胺、二酐单体，4

4′-(乙炔-1

2-二基)二酞酸酐(EBPA)为主链交联剂，4‑苯基乙炔基邻苯二甲酸酐(PEPA)为封端剂，采用化学亚胺化法在

-甲基吡咯烷酮(NMP

)中合成了一系列重复单元数为2、具有不同含量主链交联活性位点的聚酰亚胺预聚体，并对其结构和性能进行了表征分析。结果表明，由于低分子量以及空间位阻和扭曲结构的贡献，所制备的聚酰亚胺预聚体在一定温度范围内具有良好的熔体流动性，并在330~340 ℃附近出现最低熔体黏度(5.04~6.80 Pa·s)；随着温度的升高，主链和末端炔基都将发生固化反应。经过370 ℃/2h固化处理的聚酰亚胺树脂具有高玻璃化转变温度(

=353~380 ℃)，并随着预聚体中主链交联活性位点含量的增加而逐渐升高；在经过380 ℃/1h后固化处理之后，含主链炔基的预聚体对应树脂的

出现了6~11 ℃的提高(高达391 ℃)。经过热固化处理的聚酰亚胺树脂具有优异的热稳定性，5%热失重温度介于538~546 ℃之间，10%热失重温度介于563~571 ℃之间，850 ℃时的残炭率超过59%。此外，通过对预聚体粉末洗涤工艺的探究，提供了一种可有效去除产物中残留有机杂质的方法。

Abstract

A series of polyimide prepolymers with number of repeat units of 2 and different contents of in-chain crosslinking active sites were synthesized in

-methyl pyrrolidone (NMP) by chemical imidization using

-phenylenediamine (

-PDA) and 4

4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) as the diamine and dianhydride monomers

and 4

4′-(ethyne-1

2-diyl) diphthalic anhydride (EBPA) as the main chain cross-linker in the presence of 4-phenylethynyl phthalic anhydride (PEPA) as the end-capping agent. The structures and properties of these prepolymers were characterized and analyzed. The results showed that the prepared polyimide prepolymers had good melt fluidity in a certain temperature range attributed to the low molecular weight

steric hindrance as well as twisted molecular structures

and the minimum melt viscosity (5.04–6.80 Pa·s) occurred at around 330–340 ℃. With the raise of temperature

both the in-chain and terminal alkynyl groups would undergo cure reactions. The polyimide resins cured at 370 ℃ for 2 h displayed high glass transition temperature (

=353–380 ℃)

which increased gradually as the rising of the contents of in-chain crosslinking active sites in prepolymers. After the post-cure at 380 ℃ for 1 h

the

of resins corresponding to prepolymers with in-chain alkynyl was improved by 6–11 ℃ (up to 391 ℃). The thermally cured polyimide resin

s had excellent heat stability with 5% weight-loss temperature of 538–546 ℃

10% weight-loss temperature of 563–571 ℃ and the char yields at 850 ℃ exceeding 59%. Moreover

an effective method to remove residual organic impurities from the product was provided by exploring the washing process of prepolymer powders.

关键词

Keywords

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