为应对航空航天、高性能集成电路等领域未来发展所面临的极端应用环境, 本工作基于超支化聚硅氧烷结构高可设计性的特点开发了一类新型苯并噁嗪基超支化聚硅氧烷树脂, 其快速模塑成型特性填补了有机硅树脂在该应用领域的空白. 苯并噁嗪基团与超支化聚硅氧烷树脂的结合使其兼具了二者的优势, 高键能硅氧键的引入解决了传统有机树脂材料抗氧化、耐烧蚀性能不佳的问题, 而苯并噁嗪开环聚合则可以有效改善聚硅氧烷材料加工、机械性能差的缺陷. 对苯并噁嗪基超支化聚硅氧烷树脂性能测试结果表明其展示出优异的耐温性能、电性能和阻燃性, 相比现有树脂材料提升显著. 该研究为新型耐温快速成型材料、高性能封装材料开发提供了一种新思路.

The rapid development of aerospace and other fields has driven a revolution in electronic packaging materials, and in the development of integrated circuits, it is critical to develop electronic packaging materials with high reliability and performance to withstand more extreme operating environments. To this end, a new benzoxazine hyperbranched silicone resin based on the high designability characteristics of hyperbranched silicone structure was designed in this paper, and its rapid moulding characteristics can fill in the gaps of conventional silicone resins in this application. The combination of benzoxazine group and hyperbranched silicone resin can provide the advantages of both, and the introduction of silicon-oxygen bond with high bond energy can improve the oxidation- and ablation-resistance of traditional organic resin materials. The benzoxazine ring can effectively improve the processing performance and mechanical properties of silicone resin materials, thus solving the problems of traditional organic resin materials (e.g., poor oxidation- and ablation-resistance) and the organic silicon material (e.g., difficult to process and poor mechanical properties). Due to the low entanglement and the high intramolecular free volume of hyperbranched polysiloxane chain segments, the prepared benzoxazine hyperbranched polysiloxane resin has the characteristics of low viscosity. At the same time, its initial curing temperature was only 163 ℃, and the activation energy of curing was 93.25 kJ•mol⁻¹, so the curing activity was significantly improved, and the processing performance was greatly enhanced. Moreover, the introduction of silicon-oxygen bond and high cross-linked structure gives benzoxazine hyperbranched polysiloxane cured products excellent temperature-resistance and ablation-resistance performance. Its glass-transition temperature was more than 270 ℃, its 5% decomposition temperature was higher than 410 ℃, the residual carbon rate was more than 78% in 1000 ℃ nitrogen and more than 35% in oxygen, demonstrating significant improvement compared with the existing electronic packaging moulding compound substrates. In addition, it also shows good fire-resistance (not burning in open flame), water-resistance (water absorption rate<1%) and electrical insulation. This study provides a new idea for the development of new temperature-resistant rapid moulding materials and high-performance packaging materials.