高频低介电耐高温聚酰亚胺复合材料化学结构与性能

Chemical structure and properties of high frequency low dielectric high temperature resistant polyimide composites

摘要

针对高频5G通信与高超声速飞行器对低介电、耐高温及高力学强度聚酰亚胺复合材料的迫切应用需求，本工作提出酸酐构型调控的分子结构设计思路，基于含氟二胺4，4’-二氨基-2，2’-双三氟甲基联苯（TFMB）与不同构型的酸酐制备聚酰亚胺树脂及复合材料，系统研究酸酐单体构型对材料介电响应、热稳定性及弯曲强度的调控机制。结果表明：4，4’-（六氟异丙烯）二酞酸酐（6FDA）中的三氟甲基（―CF₃）通过降低表面能与摩尔极化率，降低复合材料在X波段（8.2～12.4 GHz）的介电常数和介电损耗；而3，3’,4，4’-二苯酮四甲酸二酐（BTDA）和3，3’,4，4’-联苯四甲酸二酐（s-BPDA）的对称刚性骨架则显著提升了材料热稳定性，使复合材料的玻璃化转变温度大于470 ℃；不同结构的酸酐共聚可以降低固化温度，同时赋予复合材料优异的高频低介电特性与良好的耐热性能。通过6FDA与BTDA共聚的构型互补策略，不仅实现了聚酰亚胺复合材料的高频低介电特性，还实现了固化温度降低24 ℃与弯曲强度提升至442.8 MPa的协同优化。

Abstract

To address the urgent demand for polyimide (PI) composites with low dielectric properties, high temperature resistance and high mechanical strength in 5G high-frequency communication and hypersonic vehicles, this study proposes a molecular structure design strategy based on anhydride configuration regulation. Polyimide resins and composites are prepared using fluorinated diamine 4, 4’-diamino-2, 2’-bis(trifluoromethyl) biphenyl (TFMB) and anhydrides with distinct configurations. The regulatory mechanisms of anhydride monomer configurations on the dielectric response, thermal stability and mechanical strength of materials are systematically investigated. The results show that ―CF₃ groups in 4, 4’-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) significantly reduce the dielectric constant and dielectric loss of composite materials in the X-band (8.2-12.4 GHz) by lowering the surface energy and molar polarizability. In contrast, the symmetric rigid frameworks of 3, 3’, 4, 4’-benzophenonetetracarboxylic dianhydride (BTDA) and 3, 3’, 4, 4’-biphenyltetracarboxylic dianhydride (s-BPDA) significantly enhance thermal stability, yielding a glass transition temperature (T_g) exceeding 470 ℃ for the composites. Copolymerization of structurally diverse anhydrides lowers curing temperature while imparting composites with excellent high-frequency low-dielectric properties and thermal resistance. Building on these findings, a configuration complementary strategy involving copolymerization of 6FDA and BTDA synergistically achieves high-frequency low-dielectric characteristics as well as collaborative optimization of a 24 ℃ reduction in curing temperature and an increased flexural strength of 442.8 MPa.

关键词

聚酰亚胺复合材料 / 构型互补策略 / 低介电 / 耐热性能 / 弯曲强度

Key words

PI composite / configuration complementary strategy / low dielectric / thermal resistance / flexural strength

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