分级固化低极性大体积马来酰亚胺-三嗪树脂及其玻璃纤维覆铜板的研究

朱琳艳; 张文广; 宗立率; 王锦艳; 蹇锡高

doi:10.11777/j.issn1000-3304.2026.26104

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分级固化低极性大体积马来酰亚胺-三嗪树脂及其玻璃纤维覆铜板的研究

研究论文 | 更新时间：2026-07-24

- 分级固化低极性大体积马来酰亚胺-三嗪树脂及其玻璃纤维覆铜板的研究
- Study on Low-polarity and Bulky Bismaleimide-Triazine Resin with Hierarchical Curing and Its Glass Fiber Reinforced Copper Clad Laminates
- 高分子学报 2026年57卷第8期页码：1786-1797
- 作者机构：
  
  1.大连理工大学化工学院，高分子材料系，大连 116024
  2.大连理工大学化工学院，先进高分子及复合材料教育部工程研究中心，大连 116024
- 作者简介：
  
  E-mail: zongls@dlut.edu.cn
  E-mail: jian4616@dlut.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣52273065);52273005┫
- DOI：10.11777/j.issn1000-3304.2026.26104
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7623
- 收稿：2026-04-03，
  
  录用：2026-05-13，
  
  网络首发：2026-07-10，
  
  纸质出版：2026-08-20
- 稿件说明：
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朱琳艳, 张文广, 宗立率, 王锦艳, 蹇锡高. 分级固化低极性大体积马来酰亚胺-三嗪树脂及其玻璃纤维覆铜板的研究. 高分子学报, 2026, 57(8), 1786-1797.

Zhu, L. Y.; Zhang, W. G.; Zong, L. S.; Wang, J. Y.; Jian, X. G. Study on low-polarity and bulky bismaleimide-triazine resin with hierarchical curing and its glass fiber reinforced copper clad laminates. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1786-1797.
朱琳艳, 张文广, 宗立率, 王锦艳, 蹇锡高. 分级固化低极性大体积马来酰亚胺-三嗪树脂及其玻璃纤维覆铜板的研究. 高分子学报, 2026, 57(8), 1786-1797. DOI： 10.11777/j.issn1000-3304.2026.26104. CSTR： 32057.14.GFZXB.2026.7623.

Zhu, L. Y.; Zhang, W. G.; Zong, L. S.; Wang, J. Y.; Jian, X. G. Study on low-polarity and bulky bismaleimide-triazine resin with hierarchical curing and its glass fiber reinforced copper clad laminates. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1786-1797. DOI： 10.11777/j.issn1000-3304.2026.26104. CSTR： 32057.14.GFZXB.2026.7623.

摘要

通过调控含三苯基均三嗪结构的双马来酰亚胺(PT-BMI)与多胺型马来酰亚胺(BMI950)2种不同结构马来酰亚胺的比例，与双环戊二烯型氰酸酯(DCPDCE)，在双叔丁基过氧异丙基苯(BIPB)的引发下，分级固化得到低极性大体积马来酰亚胺-三嗪(BPT-Bs)树脂体系. 研究表明，分级固化依次发生马来酰亚胺自由基自聚、氰酸酯与马来酰亚胺共聚以及氰酸酯自聚反应. PT-BMI与BMI950复配的BPT-Bs体系加工窗口拓展至89 ℃，黏度低至90 mPa·s，树脂失重5%温度超过398 ℃，具有较高的热稳定性. BPT-Bs树脂基经玻璃纤维布增强制成了覆铜板，该复合材料具有优异的综合性能：玻璃化转变温度超过280 ℃，

轴与

轴热膨胀系数最低为13.5和6.1 ppm·K

-1

，介电常数为3.74~4.08，介电损耗为0.0058~0.0090，弯曲强度高于521 MPa，弯曲模量超过31.1

GPa，覆铜板的剥离强度为0.57~0.76 N·mm

-1

. 该分级固化策略通过引入低极性大体积刚性共轭结构与致密互穿网络，平衡了树脂的加工性、耐热性、尺寸稳定性与高频介电性能，为高频IC基板用高性能覆铜板基材提供了新思路.

Abstract

In this work

by adjusting the ratio of two maleimides with different structures

namely triphenyl-

-triazine-containing bismaleimide (PT-BMI) and polyamine-type maleimide (BMI950)

a series of bulky low-polarity maleimide-triazine (BPT-Bs) resin systems were fabricated

via

stepwise curing with dicyclopentadiene-type cyanate ester (DCPDCE) initiated by di-

tert

-butylperoxyisopropylbenzene (BIPB). The results revealed that the stepwise curing process sequentially underwwent radical self-polymerization of maleimide

copolymerization between cyanate ester and maleimide

and self-polymerization of cyanate ester. For the BPT-Bs systems modified with combined PT-BMI and BMI950

the processing window was broadened to 89 ℃ with a minimum viscosity as low as 90 mPa·s. The 5% weight loss temperature exceeded 398 ℃

demonstrating excellent thermal stability. Copper-clad laminates (CCLs) wer

e fabricated using glass fiber cloth-reinforced BPT-Bs resin composites. The as-prepared composites exhibited outstanding comprehensive performances: the glass transition temperature was higher than 280 ℃; the minimum coefficient of thermal expansion (CTE) along the

-axis and

-axis reached 13.5 and 6.1 ppm·K

-1

respectively; the dielectric constant ranged from 3.74 to 4.08

and the dielectric loss was in the range of 0.0058-0.0090. Moreover

the flexural strength was above 521 MPa

the flexural modulus exceeded 31.1 GPa

and the peeling strength of CCLs was between 0.57 and 0.76 N·mm

-1

.Through the construction of bulky low-polarity rigid conjugated structures and dense interpenetrating networks

this stepwise curing strategy effectively balanced the processability

heat resistance

dimensional stability and high-frequency dielectric properties of the resin. It provides a novel insight for the development of high-performance substrate materials of copper-clad laminates applied in high-frequency IC substrates.

关键词

Keywords

references

Wen Y. F. ; Chen C. ; Ye Y. S. ; Xue Z. G. ; Liu H. Y. ; Zhou X. P. ; Zhang Y. ; Li D. Q. ; Xie X. L. ; Mai Y. W. Advances on thermally conductive epoxy-based composites as electronic packaging underfill materials: a review . Adv. Mater. , 2022 , 34 ( 52 ), 2201023 . doi: 10.1002/adma.202270358 http://dx.doi.org/10.1002/adma.202270358

Hao Y. ; Xiang S. Y. ; Han G. Q. ; Zhang J. C. ; Ma X. H. ; Zhu Z. M. ; Guo X. X. ; Zhang Y. H. ; Han Y. N. ; Song Z. W. ; Liu Y. ; Yang L. ; Zhou H. ; Shi J. Y. ; Zhang W. ; Xu M. ; Zhao W. S. ; Pan B. ; Huang Y. Q. ; Liu Q. ; Cai Y. M. ; Zhu J. ; Ou X. ; You T. G. ; Wu H. Q. ; Gao B. ; Zhang Z. Y. ; Guo G. P. ; Chen Y. H. ; Liu Y. ; Chen X. F. ; Xue C. L. ; Wang X. J. ; Zhao L. X. ; Zou X. H. ; Yan L. S. ; Li M. Recent progress of integrated circuits and optoelectronic chips . Sci. China Inf. Sci. , 2021 , 64 ( 10 ), 201401 . doi: 10.1007/s11432-021-3235-7 http://dx.doi.org/10.1007/s11432-021-3235-7

陈忠红 ; 任英杰 ; 王亮 ; 陈佳 ; 周蓓 ; 刘国兵 ; 谢志敏 . IC封装载板用有机复合基板材料研究进展 . 第二十四届中国覆铜板技术研讨会. 中国浙江桐乡 , 2023 , 5 .

Jiao Y. Z. ; Jiangjia H. ; Zhang S. L. ; Xia Z. Y. ; Li Z. Y. ; Hong Z. J. ; Zheng H. Y. ; Yang H. ; Zhang Q. L. Bismaleimide-triazine composites with superior prepolymer processability and integrated performance enabled by catalytic ZIF-8@SiO 2 nanofillers . J. Mater. Sci. Technol. , 2026 , 270 , 293 - 304 . doi: 10.1016/j.jmst.2026.01.047 http://dx.doi.org/10.1016/j.jmst.2026.01.047

肖思成 , 王晓蕾 , 李端怡 , 任茜 , 王振中 , 刘金刚 . 马来酰亚胺树脂在微电子封装领域中的研究与应用进展 . 热固性树脂 , 2025 , 40 ( 4 ), 61 - 68 .

Tang L. ; Zhang J. L. ; Tang Y. S. ; Kong J. ; Liu T. X. ; Gu J. W. Polymer matrix wave-transparent composites: a review . J. Mater. Sci. Technol. , 2021 , 75 , 225 - 251 . doi: 10.1016/j.jmst.2020.09.017 http://dx.doi.org/10.1016/j.jmst.2020.09.017

Wang H. ; Luo K. ; Li E. Z. ; Tang B. ; Yuan Y. Optimized dielectric performance in bismaleimide-triazine resin via a dual-modification strategy for high-frequency electronic packaging . J. Mater. Chem. C , 2025 , 13 ( 29 ), 14943 - 14952 . doi: 10.1039/d5tc01201e http://dx.doi.org/10.1039/d5tc01201e

Barton J. M. ; Hamerton I. ; Jones J. R. A study of the thermal and dynamic mechanical properties of functionalized aryl cyanate esters and their polymers . Polym. Int. , 1993 , 31 ( 1 ), 95 - 106 . doi: 10.1002/pi.4990310114 http://dx.doi.org/10.1002/pi.4990310114

Hong J. L. ; Wang C. K. ; Lin R. H. Cure kinetics of different molar ratios of 4,4′-bismaleimidodiphenylmethane and bisphenol A dicyanate . J. Appl. Polym. Sci. , 1994 , 53 ( 1 ), 105 - 112 . doi: 10.1002/app.1994.070530111 http://dx.doi.org/10.1002/app.1994.070530111

Reghunadhan Nair C. P. ; Francis T. ; Vijayan T. M. ; Krishnan K. Sequential interpenetrating polymer networks from bisphenol A based cyanate ester and bimaleimide: properties of the neat resin and composites . J. Appl. Polym. Sci. , 1999 , 74 ( 11 ), 2737 - 2746 . doi: 10.1002/(sici)1097-4628(19991209)74:11<2737::aid-app21>3.0.co;2-t http://dx.doi.org/10.1002/(sici)1097-4628(19991209)74:11<2737::aid-app21>3.0.co;2-t

Guo Y. ; Chen F. H. ; Han Y. ; Li Z. ; Liu X. ; Zhou H. ; Zhao T. High performance fluorinated Bismaleimide-Triazine resin with excellent dielectric properties . J. Polym. Res. , 2017 , 25 ( 2 ), 27 . doi: 10.1007/s10965-017-1407-0 http://dx.doi.org/10.1007/s10965-017-1407-0

Ma K. ; Chen G. F. ; Zhang Y. G. Thermal cross-link between 2,5-furandicarboxylic acid-based polyimides and bismaleimide via Diels-Alder reaction . J. Polym. Sci. , 2020 , 58 ( 20 ), 2951 - 2962 . doi: 10.1002/pol.20200538 http://dx.doi.org/10.1002/pol.20200538

Wang Y. Q. ; Kou K. C. ; Wu G. L. ; Zhuo L. H. ; Li J. L. ; Zhang Y. The curing reaction of benzoxazine with bismaleimide/cyanate ester resin and the properties of the terpolymer . Polymer , 2015 , 77 , 354 - 360 . doi: 10.1016/j.polymer.2015.09.059 http://dx.doi.org/10.1016/j.polymer.2015.09.059

Yang J. ; Mao X. ; Du L. R. ; Wu B. ; Zhang F. F. ; Hu W. C. ; Tang X. Z. Thermally stabilized bismaleimide-triazine resin composites for 10-GHz level high-frequency application . High Perform. Polym. , 2018 , 30 ( 7 ), 833 - 839 . doi: 10.1177/0954008317732396 http://dx.doi.org/10.1177/0954008317732396

Li X. D. ; Liu X. Q. ; Hu X. Y. ; He R. ; Liu H. Y. A novel low-dielectric nanocomposite with hydrophobicity property: fluorinated MOFs modified bismaleimide-triazine resin . Mater. Today Commun. , 2021 , 29 , 102802 . doi: 10.1016/j.mtcomm.2021.102802 http://dx.doi.org/10.1016/j.mtcomm.2021.102802

Zhang X. ; Jin C. E. ; Wang F. ; Zhu Y. P. ; Ren Y. J. ; Wang L. ; Qi H. M. Copolymerization mechanism of bismaleimide and cyanate Ester resins: effect of naphthalene structures . React. Funct. Polym. , 2025 , 214 , 106282 . doi: 10.1016/j.reactfunctpolym.2025.106282 http://dx.doi.org/10.1016/j.reactfunctpolym.2025.106282

Yan H. Q. ; Wang H. Q. ; Cheng J. Interpenetrating polymer networks from the novel bismaleimide and cyanate containing naphthalene: cure and thermal characteristics . Eur. Polym. J. , 2009 , 45 ( 8 ), 2383 - 2390 . doi: 10.1016/j.eurpolymj.2009.04.031 http://dx.doi.org/10.1016/j.eurpolymj.2009.04.031

Liu X. Q. ; Chen W. D. ; Feng X. F. ; Xiang H. B. ; Tong L. F. ; Liu S. N. ; Liu X. B. Synergistic enhancement of thermal stability and dielectric performance of BT resin composites via difunct ional phthalonitrile monomers for high-frequency PCB substrates . Compos. Part B Eng. , 2026 , 309 , 113042 . doi: 10.1016/j.compositesb.2025.113042 http://dx.doi.org/10.1016/j.compositesb.2025.113042

Liu X. Q. ; Zhang S. ; Ye J. J. ; Wu M. ; Hou J. Y. ; Liu X. B. A highly-crosslinked phthalonitrile modified bismaleimide-triazine resin for PCB substrates: the synergistic effect on curing behavior and properties . Eur. Polym. J. , 2023 , 196 , 112243 . doi: 10.1016/j.eurpolymj.2023.112243 http://dx.doi.org/10.1016/j.eurpolymj.2023.112243

Wang W. X. ; Yang J. ; Li W. ; Yao Y. T. ; Yan Y. Q. ; Wang W. J. ; Wang N. ; Leng J. S. Synergistic water-driven shape memory performance and improving mechanism of grading photo-thermal curing shape memory composite . Mater. Des. , 2022 , 214 , 110397 . doi: 10.1016/j.matdes.2022.110397 http://dx.doi.org/10.1016/j.matdes.2022.110397

Xu M. Z. ; Jia K. ; Liu X. B. Self-cured phthalonitrile resin via multistage polymerization mediated by allyl and benzoxazine functional groups . High Perform. Polym. , 2016 , 28 ( 10 ), 1161 - 1171 . doi: 10.1177/0954008315620290 http://dx.doi.org/10.1177/0954008315620290

Cao Q. ; Li J. H. ; Qi Y. ; Zhang S. H. ; Wang J. Y. ; Wei Z. Y. ; Pang H. C. ; Jian X. G. ; Weng Z. H. Engineering double load-sharing network in thermosetting: much more than just toughening . Macromolecules , 2022 , 55 ( 21 ), 9502 - 9512 . doi: 10.1021/acs.macromol.2c01599 http://dx.doi.org/10.1021/acs.macromol.2c01599

Zhu L. Y. ; Zhang W. G. ; Wang J. M. ; Zhang Y. B. ; Liu R. Z. ; Lu Y. M. ; Zong L. S. ; Wang J. Y. ; Jian X. G. Hierarchical curing regulation and interpenetrating network construction of BT resin via multi-component a dditives: synergistic enhancement of dielectric properties and dimensional stability for high-frequency packaging . Compos. Sci. Technol. , 2026 , 283 , 111704 . doi: 10.1016/j.compscitech.2026.111704 http://dx.doi.org/10.1016/j.compscitech.2026.111704

Ding Z. C. ; Jiao J. J. ; Wang Y. H. ; Liu R. Z. ; Wang Q. ; Guo J. N. ; Wang S. Y. ; Zong L. S. ; Jian X. G. ; Wang J. Y. Synergistic improvement of toughness and thermal properties of phthalonitrile resin based on the multiple curing mechanism of amino-carborane . Compos. Part A Appl. Sci. Manuf. , 2025 , 194 , 108903 . doi: 10.1016/j.compositesa.2025.108903 http://dx.doi.org/10.1016/j.compositesa.2025.108903

Cao Z. B. ; Zhao X. G. ; Wang D. M. ; Chen C. H. ; Qu C. Y. ; Liu C. W. ; Hou X. ; Li L. L. ; Zhu G. Y. Polymerization of poly-(amic acid) ammonium salt in aqueous solution and its use in flexible printed circuit boards . Eur. Polym. J. , 2017 , 96 , 393 - 402 . doi: 10.1016/j.eurpolymj.2017.09.023 http://dx.doi.org/10.1016/j.eurpolymj.2017.09.023

Hwang H. J. ; Shieh J. Y. ; Li C. H. ; Wang C. S. Dielectric and thermal properties of polymer network based on bismaleimide resin and cyanate ester containing dicyclopentadiene or dipentene. III . J. Appl. Polym. Sci. , 2007 , 103 ( 3 ), 1942 - 1951 . doi: 10.1002/app.24951 http://dx.doi.org/10.1002/app.24951

Kim S. I. ; Kim D. J. ; Kim D. H. ; Jang D. M. ; Jang J. W. ; Lee S. Y. ; Kim H. S. Corrosion lifetime estimation of printed circuit board in marine atmosphere environment using multiphysics simulation . Int. J. Precis. Eng. Manuf. Green Technol. , 2023 , 10 ( 3 ), 789 - 805 . doi: 10.1007/s40684-022-00480-6 http://dx.doi.org/10.1007/s40684-022-00480-6

Bei R. X. ; Chen K. J. ; Liu Q. ; He Y. W. ; Li C. Y. ; Huang H. T. ; Guo Q. ; Chi Z. G. ; Xu J. R. ; Chen Z. Q. ; Liu S. W. ; Zhang Y. Relationship among the water adsorption, polymer structure, and high-frequency dissipation factor: precise analysis of water adsorption of low-dielectric constant polyimide films . Macromolecules , 2024 , 57 ( 5 ), 2142 - 2153 . doi: 10.1021/acs.macromol.4c00068 http://dx.doi.org/10.1021/acs.macromol.4c00068

Sawada R. ; Liu H. N. ; Yanagimoto S. ; Yanagimoto Y. ; Ando S. Extremely low humidity and frequency dependence of dielectric properties of highly fluorinated polyimides in the 10-330 GHz range . ACS Appl. Polym. Mater. , 2025 , 7 ( 21 ), 14371 - 14381 . doi: 10.1021/acsapm.5c02706 http://dx.doi.org/10.1021/acsapm.5c02706

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