›› 2023, Vol. 37 ›› Issue (7): 22-26.

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基于大体积芴侧基热固性聚酰亚胺的合成及性能研究

贾子辰1,马辰俣1,汪毅1,汪贵梅1,彭万1,黄琦睿1,潘丽静2,韩敏2,胡一鸣2,宇平1   

  1. 1. 江苏海洋大学
    2. 常州杰铭新材料科技有限公司
  • 收稿日期:2023-03-10 修回日期:2023-03-22 出版日期:2023-07-26 发布日期:2023-07-26
  • 基金资助:
    江苏省先进功能材料调控技术重点实验室开放基金;江苏省高校大学生创新创业训练计划项目;企业技术开发合作项目

Preparation and properties of thermoset polyimide with bulky side groups of fluorene

  • Received:2023-03-10 Revised:2023-03-22 Online:2023-07-26 Published:2023-07-26

摘要: 在二元酐2,3,3',4'-二苯醚四甲酸二酐(a-ODPA)基础上,利用二元胺9,9-双(4-氨基苯基)芴(BAFL)共聚合成耐高温的苯乙炔苯酐封端的聚酰亚胺树脂,采用傅里叶变换红外光谱、差示扫描量热、热失重分析等方法,研究了其化学结构与溶解度、固化特性、耐热性能的关系及其影响机理。结果表明,该预聚体在有机溶剂中具有较高溶解度;玻璃化转变温度随着芴基引入而增加,提高了41 ℃,达到356 ℃;固化后的树脂具有高的热稳定性,氮气下,5 %热失重温度大于520 ℃,800 ℃的残炭率高达62 %,本研究进一步提升了热固性聚酰亚胺树脂的耐温等级,有望在海工装备、国防军工等领域得到较好应用。

关键词: 热固性聚酰亚胺, 苯乙炔苯酐, 芴基, 耐热性能

Abstract: In this paper, a type of high-temperature-resistant polyimide (PI) resins terminated with phenylethynyl groups was prepared by using 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride and 9,9-bis(4-aminophenyl) fluorene as raw materials. The relationships between the chemical structure of the as-prepared products and their solubility, curing properties, and heat resistance were investigated by using Fourier-transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis, and the relevant influencing mechanisms were studied. The results indicated that the oligomers had high solubility in organic solvents. The as-prepared PI resin samples exhibited a maximum glass transition temperature of 356 ℃, which increased by 41 oC with increasing the fluorenyl content. The cured PI resins presented a high thermal stability with a 5 wt% thermogravimetric temperature of above 520 ℃ in nitrogen, and their residual char yields were as high as 60 wt% at 800 ℃. The thermoset PI resins gained an improvement in temperature resistance and were expected to be applied in marine engineering equipments, national defense, military industry, and other fields.

Key words: thermoset polyimide, 4-phenylethynylphthalic anhydride, fluorenyl group, thermal resistance