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

作　　者：李一凡 孙浩楠 闫宇 林琪芸 宁志鹏 陈令成 肖义[1] LI Yi-fan;SUN Hao-nan;YAN Yu;LIN Qi-yun;NING Zhi-peng;CHEN Ling-cheng;XIAO Yi(State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian Universityof Technology,Dalian 116024,China)

机构地区：[1]大连理工大学化工学院,精细化工国家重点实验室,大连116024

出　　处：《高分子通报》2024年第12期1768-1778,共11页Polymer Bulletin

基　　金：国家自然科学基金(基金号22174009);大连市科技创新基金(基金号2020JJ25CY014)。

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2614MPa和5010MPa,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(Tg)略有下降,但其热降解温度(Td5%)和统计耐热指数(Ts)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。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(Td5%)and statistical heat resistance index(Ts)were enhanced,although the glass transition temperature(Tg)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 

分 类 号：TQ320.1[化学工程—合成树脂塑料工业]