Design and Performance Research of Hyperbranched Polysiloxane-modified High-temperature-resistant Thermosetting Polyimide Adhesives

BO Lu-wei; XU Yang; XI Kai

doi:10.14028/j.cnki.1003-3726.2025.25.170

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Design and Performance Research of Hyperbranched Polysiloxane-modified High-temperature-resistant Thermosetting Polyimide Adhesives

更新时间：2025-09-23

- Design and Performance Research of Hyperbranched Polysiloxane-modified High-temperature-resistant Thermosetting Polyimide Adhesives
- Polymer Bulletin Vol. 38, Issue 10, Pages: 1490-1499(2025)
- 作者机构：
  
  高性能高分子材料与技术教育部重点实验室，南京大学化学化工学院，南京 210023
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.170
  CLC：
- Received：07 June 2025，
  
  Accepted：14 July 2025，
  
  Published Online：01 September 2025，
  
  Published：20 October 2025
- 稿件说明：
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薄禄薇, 徐阳, 袭锴. 超支化聚硅氧烷改性耐高温热固性聚酰亚胺胶黏剂的设计及其性能研究. 高分子通报, 2025, 38(10), 1490–1499.

Bo, L. W.; Xu, Y.; Xi, K. Design and performance research of hyperbranched polysiloxane-modified high-temperature-resistant thermosetting polyimide adhesives. Polym. Bull. (in Chinese), 2025, 38(10), 1490–1499.
薄禄薇, 徐阳, 袭锴. 超支化聚硅氧烷改性耐高温热固性聚酰亚胺胶黏剂的设计及其性能研究. 高分子通报, 2025, 38(10), 1490–1499. DOI： 10.14028/j.cnki.1003-3726.2025.25.170.

Bo, L. W.; Xu, Y.; Xi, K. Design and performance research of hyperbranched polysiloxane-modified high-temperature-resistant thermosetting polyimide adhesives. Polym. Bull. (in Chinese), 2025, 38(10), 1490–1499. DOI： 10.14028/j.cnki.1003-3726.2025.25.170.

摘要

基于氨基超支化聚硅氧烷(NH

-HPSi)优异的耐高温、高反应活性以及多反应活性位点等特点，通过原位聚合的方法制备了一系列NH

-HPSi改性炔基封端的热固性聚酰亚胺(PI)胶黏剂，系统研究了NH

-HPSi对改性PI胶黏剂粘接性能、热性能及热机械性能的影响。研究结果表明，经过NH

-HPSi改性后的PI胶黏剂粘接强度由10.3 MPa提升至13.8 MPa，400 ℃下的粘接强度由0.9 MPa提升至2.6 MPa，且经过400 ℃老化3 h后，其粘接强度为12.2 MPa，保持率达到86.6%；改性后PI胶黏剂的初始热分解温度由534.4 ℃最高提升至553.8 ℃。由于NH

-HPSi与炔基封端的PI形成了高度密集的双交联网络结构，这不仅显著提升了PI胶黏剂的耐高温性能和粘接性能，还为新型耐高温PI胶黏剂的制备提供了一种新的方法。

Abstract

Based on the excellent high-temperature resistance

high reactivity

and multiple reactive sites of amino-terminated hyperbranched polysiloxane (NH

-HPSi)

a series of modified acetylene-terminated thermosetting polyimide (PI) adhesives were prepared

via in situ

polymerization. The effects of NH

-HPSi on the bonding performance

thermal properties

and thermome

chanical properties of modified PI adhesives were systematically investigated. The results demonstrated that the shear strength of NH

-HPSi-modified PI adhesives increased from 10.3 MPa to 13.8 MPa

while the real-time shear strength at 400 ℃ improved from 0.9 MPa to 2.6 MPa. After aging at 400 ℃ for 3 h

the modified adhesive retained a shear strength of 12.2 MPa

with a retention rate of 86.6%. Moreover

the thermal stability of the modified PI adhesives was enhanced

with the thermal decomposition temperature increasing from 534.4 ℃ to a maximum of 553.8 ℃. This improvement is attributed to the formation of a highly dense dual-crosslinked network structure between NH

-HPSi and acetylene-terminated PI

which further enhances the high-temperature resistance and bonding performance of the PI adhesive. This study provides a novel approach for the preparation of advanced high-temperature-resistant PI adhesives.

关键词

Keywords

references

凤鹏举 , 唐富强 , 李靖辉 , 王艳军 . 聚酰亚胺基耐高温胶粘剂的研究进展 . 中国胶粘剂 , 2024 , 33 ( 9 ), 9 – 16 .

Kavi Kerusiha, V. ; Swathi, V. ; Thayalan, K. ; Ahmed, S. ; Pitchan, M. K. ; Bhowmik, S. ; Epaarachchi, J. A . Durability of nano-reinforced polyimide adhesive bonding of titanium nitride deposited aluminium for aerospace applications . Mater. Res. Express , 2019 , 6 ( 9 ), 0965c7 .

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 ( 8 ), 1108 – 1116 .

时瑞鑫 , 吴霄 , 徐慧 , 蔡秀莲 , 于文芳 , 武明月 , 朱庆增 . 高性能聚酰亚胺胶粘剂的研究进展 . 中国胶粘剂 , 2023 , 32 ( 10 ), 53 – 59 .

王磊 , 张锡文 , 刘彩召 , 张斌 , 孙明明 , 张绪刚 . 二酐结构对热固型聚酰亚胺性能的影响 . 中国胶粘剂 , 2022 , 31 ( 4 ), 6 – 10 .

孙宏杰 , 杨士勇 , 范琳 . 耐高温聚酰亚胺胶黏剂的研究进展 . 宇航材料工艺 , 2007 , 37 ( 6 ), 1 – 6 .

Wang, D. Z. ; Zhao, L. W. ; Yang, H. D. ; Yue, C. E. ; Li, H. F. ; Xiao, W. B. ; Liu, C. W. ; Qu, C. Y . High temperature and toughened bismaleimide structural film adhesive for high performance CFRP bonding over 300 ℃ . Polym. Degrad. Stab. , 2022 , 204 , 110125 .

张斌 , 孙明明 , 李建 , 张绪刚 , 张密林 , 李坚辉 , 王磊 . 聚酰亚胺胶黏剂的粘接性能 . 航空学报 , 2008 , ( 3 ), 741 – 745 .

Xiang, Y. ; Lang, F. ; Liu, F. ; Wei, M. L. ; Li, D. X. ; You, Y. L . Structure and properties of polyimide/sericite composite adhesive prepared bypolyamide acid salt method . J. Adhes. Sci. Technol. , 2022 , 36 ( 5 ), 531 – 544 .

魏兆博 , 袭锴 . 苯并噁嗪基超支化聚硅氧烷树脂的设计及其应用研究 . 化学学报 , 2025 , 83 ( 3 ), 266 – 273 .

Lian, R. H. ; Lei, X. F. ; Chen, Y. H. ; Zhang, Q. Y . Hyperbranched-polysiloxane-based hyperbranched polyimide films with low dielectric permittivity and high mechanical and thermal properties . J. Appl. Polym. Sci. , 2019 , 136 ( 31 ), 47771 .

Dong, J. ; Yang, C. R. ; Cheng, Y. ; Wu, T. T. ; Zhao, X. ; Zhang, Q. H . Facile method for fabricating low dielectric constant polyimide fibers with hyperbranched polysiloxane . J. Mater. Chem. C , 2017 , 5 ( 11 ), 2818 – 2825 .

李治国 . 含磷氟聚硅氧烷阻燃剂的合成及其改性环氧树脂的研究 . 硕士学位论文 , 哈尔滨 : 哈尔滨工业大学 , 2022 .

袭锴 , 徐阳 . 一种氨基超支化硅氧烷及其改性聚酰亚胺气凝胶材料的制备方法 . 中国专利 , CN116253882A . 2023-09-15 .

Xu, Y. ; Bo, L. W. ; Wang, Y. D. ; Xu, H. C. ; Jiang, X. L. ; Wei, Z. B. ; Xi, K . Hybrid polyimide foams with hyperbranched organosilicon for high-temperature sound absorption . ACS Appl. Polym. Mater. , 2024 , 6 ( 22 ), 13979 – 13988 .

徐嫚 . 超支化聚硅氧烷改性PVDF膜的制备及其油水分离性能研究 . 硕士学位论文 , 镇江 : 江苏大学 , 2023 .

Song, J. H. ; Hong, S. M. ; Park, S. K. ; Kwon, H. K. ; Hwang, S. H. ; Oh, J. M. ; Koo, S. M. ; Lee, G. ; Park, C . Synthesis and characterization of hyperbranched thiol hardener and their curing behavior in thiol–epoxy . Macromol. Res. , 2025 , 33 ( 3 ), 367 – 375 .

Wang, S. J. ; Fan, X. D. ; Si, Q. F. ; Kong, J. ; Liu, Y. Y. ; Qiao, W. Q. ; Zhang, G. B . Preparation and characterization of a hyperbranched polyethoxysiloxane based anti-fouling coating . J. Appl. Polym. Sci. , 2006 , 102 ( 6 ), 5818 – 5824 .

Lei, X. F. ; Chen, Y. H. ; Qiao, M. T. ; Tian, L. D. ; Zhang, Q. Y . Hyperbranched polysiloxane (HBPSi)-based polyimide films with ultralow dielectric permittivity, desirable mechanical and thermal properties . J. Mater. Chem. C , 2016 , 4 ( 11 ), 2134 – 2146 .

Pang, Z. J. ; Sun, H. C. ; Guo, Y. ; Du, J. ; Li, L. ; Li, Q. Y. ; Yang, J. Z. ; Zhang, J. J. ; Wu, W. G. ; Yang, S . Research advances of porous polyimide-based composites with low dielectric constant . Polymers , 2023 , 15 ( 16 ), 3341 .

谢凯丽 . 功能聚硅氧烷的设计合成及其改性环氧树脂的研究 . 硕士学位论文 , 无锡 : 江南大学 , 2024 .

Birtane, H. ; Esmer, K. ; Madakbas, S. ; Kahraman, M. V . Structural and dielectric properties of POSS reinforced polyimide nanocomposites . J. Macromol. Sci. Part A , 2019 , 56 ( 3 ), 245 – 252 .

Li, X. T. ; Zhu, X. M. ; Dong, J. ; Zhao, X. ; Zhang, Q. H . Preparation of low-dielectric permittivity polyimide resins with high surface activity from chemically bonded hyperbranched polysiloxane . Chinese J. Polym. Sci. , 2021 , 39 ( 9 ), 1200 – 1210 .

Ge, Y. ; Zhang, X. Q. ; Dai, T. W. ; Wang, Y. ; Ling, Y. Q. ; Xu, Z. W. ; Heng, Z. G. ; Liang, M. ; Zou, H. W . Super-flexibility and high-temperature adhesion of epoxy structural adhesives endowed by homogeneous rigid-flexible crosslinking networks . Ind. Eng. Chem. Res. , 2022 , 61 ( 30 ), 10990 – 10998 .

吴迎霞 . 室温固化聚氨酯胶黏剂的研制 . 科学技术与工程 , 2006 , 6 ( 4 ), 496 – 499 .

杨彩娟 . 耐高温聚酰亚胺结构胶的合成及性能研究 . 硕士学位论文 , 长沙 : 中南大学 , 2013 .

Li, D. X. ; Yang, Y. S. ; Yang, C. J. ; Lai, D. W . Synthesis and characterization of a novel high-temperature structural adhesive based on MDA-BAPP-BTDA co-polyimide . J. Macromol. Sci. Part A , 2015 , 52 ( 7 ), 540 – 547 .

Ratta, V. ; Stancik, E. J. ; Ayambem, A. ; Pavatareddy, H. ; McGrath, J. E. ; Wilkes, G. L . A melt-processable semicrystalline polyimide structural adhesive based on 1,3-bis(4-aminophenoxy) benzene and 3,3',4,4'-biphenyltetracarboxylic dianhydride . Polymer , 1999 , 40 ( 7 ), 1889 – 1902 .

徐双双 , 常健 , 耿琼 , 王超 , 郭安儒 . 一种耐高温高韧性环氧胶粘剂性能研究 . 化学与粘合 , 2020 , 42 ( 2 ), 92 – 95 .

杨彩娟 , 李笃信 , 雷霆 . 耐高温聚酰亚胺结构胶改性研究进展 . 化工新型材料 , 2011 , 39 ( 10 ), 14 – 16 .

齐贵亮 , 王喜梅 , 张玉龙 . 耐高温有机胶粘剂的研究进展 . 粘接 , 2008 , 29 ( 11 ), 47 – 51 .

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