Preparation and Characterization of Polyimide Resins Containing In-chain and Terminal Alkynyl Crosslinking Sites

WANG Jin; LIU Jie; ZHONG Min; JIANG Qian; HUANG An-min; GAO Ji-ming

doi:10.14028/j.cnki.1003-3726.2025.25.095

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Preparation and Characterization of Polyimide Resins Containing In-chain and Terminal Alkynyl Crosslinking Sites

更新时间：2025-08-26

- Preparation and Characterization of Polyimide Resins Containing In-chain and Terminal Alkynyl Crosslinking Sites
- Polymer Bulletin Vol. 38, Issue 9, Pages: 1407-1415(2025)
- 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：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.095
  CLC：
- Received：31 March 2025，
  
  Accepted：09 June 2025，
  
  Published Online：17 July 2025，
  
  Published：20 September 2025
- 稿件说明：
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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：

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.

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references

Minegishi, R. ; Ogasawara, T. ; Aoki, T. ; Ishida, Y . Nonlinear stress-strain behavior of unidirectional carbon fiber/phenyl-ethynyl terminated KAPTON-type polyimide, TriA-X, composites at elevated temperatures . Adv. Compos. Mater. , 2021 , 30 ( 1 ), 24 – 38 .

包建文 . 耐高温树脂基复合材料及其应用 . 北京 : 航空工业出版社 , 2018 . 222 – 227 .

Hao, J. Y. ; Hu, A. J. ; Gao, S. Q. ; Ch Wang, X. ; Yang, S. Y . Processable polyimides with high glass transition temperature and high storage modulus retention at 400 ℃ . High Perform. Polym. , 2001 , 13 ( 3 ), 211 – 224 .

Kolesnikov, T. I. ; Orlova, A. M. ; Drozdov, F. V. ; Buzin, A. I. ; Cherkaev, G. V. ; Kechekyan, A. S. ; Dmitryakov, P. V. ; Belousov, S. I. ; Kuznetsov, A. A . New imide-based thermosets with propargyl ether groups for high temperature composite application . Polymer , 2022 , 254 , 125038 .

Soutis, C . Fibre reinforced composites in aircraft construction . Prog. Aerosp. Sci. , 2005 , 41 ( 2 ), 143 – 151 .

Zhou, D. R. ; Yuan, L. L. ; Hong, W. J. ; Zhang, H. Y. ; Hu, A. J. ; Yang, S. Y . Molecular design of interpenetrating fluorinated polyimide network with enhanced high performance for heat-resistant matrix . Polymer , 2019 , 173 , 66 – 79 .

Liu, Y. ; Xu, X. Z. ; Mo, S. ; Lan, B. W. ; Zhu, C. Z. ; Li, C. H. ; Xu, J. ; Fan, L . Long-term thermo-oxidative degradation modeling of a carbon fiber reinforced polyimide composite: Multistep degradation behaviors and kinetics . Chinese J. Polym. Sci. , 2020 , 38 ( 11 ), 1202 – 1213 .

Çakir, M. ; Akin, E . Characterization of carbon fiber-reinforced thermoplastic and thermosetting polyimide matrix composites manufactured by using various synthesized PI precursor resins . Compos. Part B Eng. , 2022 , 231 , 109559 .

Jordan, K. ; Iroh, J. O . Effect of isothermal aging on the imidization of PMR-15 . Polym. Eng. Sci. , 1996 , 36 ( 20 ), 2550 – 2555 .

Selladurai, M. ; Sarojadevi, M . Synthesis and properties of modified PMR-matrix resin type polyimide and composite with non-carcinogenic diamine . High Perform. Polym. , 2016 , 28 ( 2 ), 162 – 172 .

Yu, P. ; Wang, Y. ; Yu, J. R. ; Zhu, J. ; Hu, Z. M . Novel acetylene-terminated polyimide oligomers with excellent processability and high toughness of films . J. Appl. Polym. Sci. , 2015 , 132 ( 37 ), 42537 .

Zhou, H. ; Liu, F. ; Zhang, Y. S. ; Fan, W. F. ; Liu, J. F. ; Wang, Z. ; Zhao, T . Novel acetylene-terminated polyisoimides with excellent processability and properties comparison with corresponding polyimides . J. Appl. Polym. Sci. , 2011 , 122 ( 5 ), 3493 – 3503 .

Yokota, R. ; Yamamoto, S. ; Yano, S. ; Sawaguchi, T. ; Hasegawa, M. ; Yamaguchi, H. ; Ozawa, H. ; Sato, R . Molecular design of heat resistant polyimides having excellent processability and high glass transition temperature . High Perform. Polym. , 2001 , 13 ( 2 ), S61 – S72 .

Cano, R. J. ; Jensen, B. J . Effect of molecular weight on processing and adhesive properties of the phenylethynyl-terminated polyimide LARC TM -PETI-5 . J. Adhes. , 1997 , 60 ( 1-4 ), 113 – 123 .

Hergenrother, P. M. ; Connell, J. W. ; Smith, J. G . Phenylethynyl containing imide oligomers . Polymer , 2000 , 41 ( 13 ), 5073 – 5081 .

Zuo, H. J. ; Chen, J. S. ; Hu, A. J. ; Fan, L. ; Yang, S. Y . Meltable phenylethynyl-capped oligoimide resins derived from 1, 4-bis(4-amino-2-trifluoromethylphenoxy)benzene and 3, 4′-oxydianiline . Eur. Polym. J. , 2007 , 43 ( 9 ), 3892 – 3903 .

Chen, C. H. ; Yokota, R. ; Hasegawa, M. ; Kochi, M. ; Horie, K. ; Hergenrother, P . Isomeric biphenyl polyimides. (I) Chemical structure-property relationships . High Perform. Polym. , 2005 , 17 ( 3 ), 317 – 333 .

Petkov, V. I. ; Pelcastre, L. ; Solano, C. ; Fernberg, P . The influence of ethynyl in-chain crosslinkers on the properties of 6FDA-based polyimides . Materials , 2022 , 16 ( 1 ), 169 .

Xu, X. Z. ; Liu, Y. ; Lan, B. W. ; Mo, S. ; Zhai, L. ; He, M. H. ; Fan, L . High thermally stable and melt processable polyimide resins based on phenylethynyl-terminated oligoimides containing siloxane structure . Materials , 2020 , 13 ( 17 ), 3742 .

Fernberg, P. ; Gong, G. ; Mannberg, P. ; Tsampas, S . Development of novel high T g polyimide-based composites. Part I: RTM processing properties . J. Compos. Mater. , 2018 , 52 ( 2 ), 253 – 260 .

Tsampas, S. ; Fernberg, P. ; Joffe, R . Development of novel high T g polyimide-based composites. Part Ⅱ: Mechanical characterisation . J. Compos. Mater. , 2018 , 52 ( 2 ), 261 – 274 .

钟敏 , 王进 , 刘杰 , 江乾 , 胡峰 , 杨海洋 , 黄安民 , 杨军 . 苯乙炔基封端型聚酰亚胺树脂及复合材料的制备与性能研究 . 高分子通报 , 2024 , 37 ( 8 ), 1108 – 1116 .

Shu, C. ; Wu, X. M. ; Zhong, M. ; Wang, S. B. ; Yan, D. Y. ; Huang, W . Synthesis and properties of polyimides from a diamine containing side diphenylphosphine oxide and trifluoromethyl groups . J. Polym. Res. , 2022 , 29 ( 9 ), 394 .

Li, K. D. ; Ding, J. H. ; Guo, Y. X. ; Wu, H. C. ; Wang, W. W. ; Ji, J. Q. ; Pei, Q. ; Gong, C. L. ; Ji, Z. Y. ; Wang, X. L . Direct ink writing of phenylethynyl end-capped oligoimide/SiO 2 to additively manufacture high-performance thermosetting polyimide composites . Polymers , 2022 , 14 ( 13 ), 2669 .

Zhang, X. W. ; Zhang, B. ; Liu, C. Z. ; Sun, M. M. ; Zhang, X. G. ; Li, J. H. ; Xue, G . Effect on the thermal resistance and thermal decomposition properties of thermally cross-linkable polyimide films obtained from a reactive acetylene . React. Funct. Polym. , 2021 , 167 , 104994 .

Hong, W. J. ; Yuan, L. L. ; Zhang, H. Y. ; Cui, C. ; Chen, W. ; Yang, S. Y . Phenylethynyl-terminated imide oligomers modified by reactive diluent for resin transfer molding application . Chinese J. Polym. Sci. , 2022 , 40 ( 1 ), 107 – 120 .

Meng, X. S. ; Wen, Y. ; Wang, X. W. ; Shen, D. L. ; Yan, J. L. ; Wang, Z . High performance imide oligomers and thermosets derived from 9, 9-bis (3, 4-dicarboxyphenyl)fluorene dianhydride . Polymer , 2023 , 281 , 126086 .

今井淑夫 , 横田力男 . 聚酰亚胺的基础和应用 . 东京 : NTS出版社 , 2002 . 187 – 188 .

Simone, C. D . Synthesis and characterization of novel phenylethynyl end-capped fluorinated polyimides . Doctoral Dissertations, University of Connecticut , 2002 .

Chen, Z. W. ; Wang, L. Q. ; Lin, J. P. ; Du, L . Thermal curing mechanism of acetylene-terminated polyimides: A combination of density functional theory computation and microkinetic analysis . Polymer , 2021 , 218 , 123529 .

Meng, X. S. ; Lu, G. W. ; Liu, X. J. ; Meng, Q. J. ; Shi, J. W. ; Yuan, H. ; Ke, H. J. ; Wang, X. W. ; Fan, W. F. ; Liu, J. F. ; Yan, J. L. ; Wang, Z . Highly soluble phenylethynyl-terminated imide oligomers and thermosetting polyimides based on 2, 2', 3, 3'-biphenyltetracarboxylic dianhydride . Chem. Res. Chin. Univ. , 2019 , 35 ( 3 ), 530 – 536 .

Shen, J. X. ; Lin, X. S. ; Liu, J. ; Li, X . Effects of cross-link density and distribution on static and dynamic properties of chemically cross-linked polymers . Macromolecules , 2019 , 52 ( 1 ), 121 – 134 .

丁孟贤 . 聚酰亚胺: 化学、结构与性能的关系及材料 . 北京 : 科学出版社 , 2006 . 150 – 151 .

夏纪宇 , 姜宁 , 吴凝宇 , 赵兴旺 , 刘雨萌 , 刘西炜 , 扈艳红 , 林嘉平 . 萘乙炔基封端的含硅聚酰亚胺的制备与性能 . 高分子学报 , 2023 , 54 ( 12 ), 1826 – 1835 .

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