酚羟基取代的螺芴-呫吨型聚酰亚胺改性氰酸酯树脂固化体系的研究

李一凡; 孙浩楠; 闫宇; 林琪芸; 宁志鹏; 陈令成; 肖义

doi:10.14028/j.cnki.1003-3726.2024.24.196

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酚羟基取代的螺芴-呫吨型聚酰亚胺改性氰酸酯树脂固化体系的研究

研究论文 | 更新时间：2024-12-12

- 酚羟基取代的螺芴-呫吨型聚酰亚胺改性氰酸酯树脂固化体系的研究
- Study on the Curing System of Phenolic Hydroxyl-substituted Spirofluorene-xanthene-type Polyimide-modified Cyanate Ester Resin
- 高分子通报 2024年37卷第12期页码：1768-1778
- 作者机构：
  
  大连理工大学化工学院，精细化工国家重点实验室，大连 116024
- 作者简介：
  
  *陈令成，E-mail: lcchen@dlut.edu.cn；肖义，E-mail: xiaoyi@dlut.edu.cn
  *陈令成，E-mail: lcchen@dlut.edu.cn；肖义，E-mail: xiaoyi@dlut.edu.cn
- 基金信息：
  
  国家自然科学基金(22174009);大连市科技创新基金(2020JJ25CY014)
- DOI：10.14028/j.cnki.1003-3726.2024.24.196
  中图分类号：
- 纸质出版日期：2024-12-20，
  
  网络出版日期：2024-09-24，
  
  收稿日期：2024-07-05，
  
  录用日期：2024-09-01
- 稿件说明：
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李一凡,孙浩楠,闫宇,林琪芸,宁志鹏,陈令成,肖义. 酚羟基取代的螺芴-呫吨型聚酰亚胺改性氰酸酯树脂固化体系的研究. 高分子通报, 2024, 37(12), 1768–1778

Li, Y. F.; Sun, H. N.; Yan, Y.; Lin, Q. Y.; Ning, Z. P.; Chen, L. C.; Xiao. Y. Study on the curing system of phenolic hydroxyl-substituted spirofluorene-xanthene-type polyimide-modified cyanate ester resin. Polym. Bull. (in Chinese), 2024, 37(12), 1768–1778
李一凡,孙浩楠,闫宇,林琪芸,宁志鹏,陈令成,肖义. 酚羟基取代的螺芴-呫吨型聚酰亚胺改性氰酸酯树脂固化体系的研究. 高分子通报, 2024, 37(12), 1768–1778 DOI： 10.14028/j.cnki.1003-3726.2024.24.196.

Li, Y. F.; Sun, H. N.; Yan, Y.; Lin, Q. Y.; Ning, Z. P.; Chen, L. C.; Xiao. Y. Study on the curing system of phenolic hydroxyl-substituted spirofluorene-xanthene-type polyimide-modified cyanate ester resin. Polym. Bull. (in Chinese), 2024, 37(12), 1768–1778 DOI： 10.14028/j.cnki.1003-3726.2024.24.196.

摘要

氰酸酯树脂(cyanate ester resin

CE)具有优异的机械性能、良好的热稳定性和极小的尺寸收缩率，广泛用于电子封装等领域。本文利用合成的酚羟基取代的螺芴-呫吨型全刚性聚酰亚胺(PI-OH)对双酚A型氰酸酯树脂(bisphenol A cyanate ester

BADCy)进行改性。研究发现，PI-OH侧链上的酚羟基可以显著降低BADCy的固化温度，与未改性树脂相比，固化放热峰值温度降低了约142 ℃。室温下，PI-OH(10%)/BADCy的储能模量和杨氏模量分别为2614 MPa和5010 MPa，与纯BADCy相比，分别提高了34%和10.2%。此外，PI-OH(8%)/BADCy的拉伸强度和拉伸模量分别提高了63.9%和128.4%，虽然玻璃化转变温度(

)略有下降，但其热降解温度(

d5%

)和统计耐热指数(

)均得到提升。同时，由于PI-OH侧链含有大量疏水性的三氟甲基基团，PI-OH(10%)/BADCy体系的吸水率仅为0.73%，降低了47.9%。这一进展对于降低BADCy树脂的固化温度、制备具有良好热稳定性和机械性能的氰酸酯树脂材料具有重要意义。

Abstract

Cyanate ester resins (CE)

which have excellent mechanical properties

good thermal stability and very small dimensional shrinkage

are widely used in electronic packaging and other fields. In this study

the synthesized phenolic hydroxyl-substituted spirofluorene-xanthene-type fully rigid polyimide (PI-OH) was used to modify bisphenol A-type cyanate ester resin (BADCy). It was found that the phenolic hydroxyl groups on the side chain of PI-OH could significantly reduce the curing temperature of BADCy

and the peak exothermic temperature of curing was reduced by about 142 ℃ compared with that of the unmodified resin. At room temperature

the energy storage modulus and Young’s modulus of PI-OH(10%)/BADCy were 2614 MPa and 5010 MPa

respectively

which were increased by 34% and 10.2%

respectively

compared with those of pure BADCy. In addition

the tensile strength and tensile modulus of PI-OH(8%)/BADCy were increased by 63.9% and 128.4%

respectively

and its thermal degradation temperature (

d5%

) and statistical heat resistance index (

) were enhanced

although the glass transition temperature (

) was slightly decreased. Meanwhile

the water absorption of the PI-OH(10%)/BADCy system was only 0.73%

which was reduced by 47.9%

due to the large number of hydrophobic trifluoromethyl groups in the side chain of PI-OH. This progress is of great importance for the production of low-temperature curable cyanate ester resin materials with good thermal stability and mechanical properties.

关键词

酚羟基聚酰亚胺双酚A型氰酸酯固化温度耐高温

Keywords

Phenol hydroxyl polyimideBisphenol A cyanate esterCuring temperatureHigh temperature resistance

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