甲胺型苯并噁嗪改性环氧树脂的性能

Properties of Methylamine-Based Benzoxazine Modified Epoxy Resin

摘要

面向绝缘领域对耐高温、低介电树脂的需求，以脂环族环氧树脂（EP）为研究对象，基于苯并噁嗪与环氧树脂的共聚特性，利用双酚 A-甲胺型苯并噁嗪（BA）对 EP 进行改性。通过熔融共混-阶梯固化法制备了苯并噁嗪改性环氧树脂 (PEP/BA)，并以酸酐固化的环氧树脂 (PEP/aa)为对照样，借助差示扫描量热（DSC）、动态力学分析（DMA）和热重分析（TGA）对树脂的固化行为及热性能进行了研究，同时考察了树脂的介电性能、击穿强度、吸水率和弯曲性能。结果表明，BA 的加入使改性树脂的固化起始温度下降，苯并噁嗪先后发生开环自聚反应以及苯并噁嗪与环氧树脂的共聚反应，形成苯并噁嗪-环氧协同交联网络。随着 BA 含量的增加，改性树脂的玻璃化转变温度（T_g）升高，最高达到 249.6 ℃，介电常数最低可达到 2.75，击穿强度最高至 58.01 kV/mm，30 d 吸水率低至 1.42%，弯曲强度为 91.9 MPa，综合性能均优于 PEP/酸酐。此改性环氧树脂兼具优良的耐热性和介电性能，且成本可控，制备工艺简单，在绝缘领域具有广阔的应用前景。

Abstract

To meet the growing demand for high-temperature-resistant, low-dielectric-constant resins in electrical insulation applications, an alicyclic epoxy resin (EP) was selected as the matrix. Exploiting the copolymerization reactivity between benzoxazine and epoxy resin, a methylamine-based benzoxazine resin (BA) was used to modify EP. A series of PEP/BA were prepared via melt blending followed by stepwise curing. EP/anhydride was used as a reference. The curing behavior and thermal properties of the resins were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). In parallel, dielectric properties, breakdown strength, water absorption, and flexural properties were evaluated. Results show that the incorporation of BA decreases the onset curing temperature of the modified resins. The curing proceeds through sequential reactions: ring-opening self-polymerization of benzoxazine, followed by copolymerization between benzoxazine and epoxy, leading to a synergistic benzoxazine-epoxy cross-linked network. With increasing BA content, the glass transition temperature (T _g) increased and reached a maximum of 249.6 ℃, which is higher than that of neat epoxy resin. The dielectric constant decreased to a minimum of 2.75, the breakdown strength peaked at 58.01 kV/mm, the 30 d water absorption decreased to 1.42%, and the flexural strength reached 91.9 MPa. Overall, the properties of the PEP/BA are superior to those of PEP/anhydride. This modified epoxy resin combines excellent thermal stability and electrical insulation performance, offers controllable costs, and can be readily prepared, showing promising potential for insulation applications.

关键词

环氧树脂 / 苯并噁嗪 / 低介电常数 / 耐热性 / 绝缘

Key words

epoxy resin / benzoxazine / low dielectric constant / thermal resistance / insulation

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基金资助

国家自然科学基金(U24B2073)