电活性苯并噁嗪分子设计、制备及结构与性能关系研究

Polybenzoxazine (PBa) is one of the few novel high-performance thermosetting resins successfully industrialized in the last three decades. Owing to advantages such as flexible characteristics of molecular design, lower cost, and specific properties, the resin has the potential to replace and surpass the conventional thermosetting resins in various applications. However, there has been an extreme shortage of functional PBa products restricting the applications of PBa to a limited extent. The current work focused on the potential demand for a high-performance electroactive thermosetting resin in aerospace and electronic fields. The conductive polyaniline has poor processability. Our focus was on moving from structure-to-property to take complementary advantages of the structural characteristics of π-π conjugation of aniline segment, flexible molecular design and the excellent comprehensive properties of PBa resin. The formulated high-performance PBa resin had fine processability and electroactivity. Additionally, we studied the structure-property relationship of the material and determined the specific structure of materials with optimum comprehensive properties. The proposed novel research concept for the development of high performance-function integrated modification of resins is well-supported by reliable data. The current study on high-performance electroactive PBa provides a solid experimental basis and theoretical foundation for property optimization of the materials employed in the field, increasing the prospects of their potential applications.

苯并噁嗪树脂（Polybenzoxazine，PBa）是近三十年来为数不多的成功实现产业化的新型高性能热固性树脂，其灵活的分子设计性、低成本及独特的性能优势使其在很多应用领域可替代并超越传统的热固性树脂。但功能型苯并噁嗪树脂产品匮乏，在一定程度上制约苯并噁嗪树脂在诸多领域的应用。本项目瞄准航天航空、电子电器等领域对高性能电活性热固型树脂潜在需求，针对导电聚苯胺加工性能差的问题，从结构决定性能理念出发，对苯胺链段π-π共轭结构特点与苯并噁嗪树脂灵活的分子设计性及优异综合性能进行优势互补，制备具有良好加工性能和电活性的高性能苯并噁嗪树脂，并研究该材料结构与性能关系，确定最佳综合性能时材料的具体结构，为树脂高性能-功能一体化改性提供新研究思路和可靠数据支撑。高性能电活性苯并噁嗪树脂的研究，将为这一领域材料性能优化提供坚实的实验依据和理论基础，该材料也具有十分广阔的潜在应用前景。

苯并噁嗪树脂（Polybenzoxazine，PBa）是近三十年来为数不多的成功实现产业化的新型高性能热固性树脂，其灵活的分子设计性、低成本及独特的性能优势使其在很多应用领域可替代并超越传统的热固性树脂。但功能型苯并噁嗪树脂产品匮乏，在一定程度上制约苯并噁嗪树脂在诸多领域的应用。树脂材料的精细化、多功能化和高性能化是科技和社会发展需求的必然。苯并噁嗪树脂的高性能-功能本征一体化，是苯并噁嗪发展的一大趋势，也是高端领域对苯并噁嗪树脂性能需求之一。项目研究对苯胺链段π-π共轭结构特点与苯并噁嗪树脂灵活的分子设计性及优异综合性能进行优势互补，制备出具有良好加工性能和电活性的高性能苯并噁嗪树脂材料，并研究了该材料结构与性能关系，确定最佳综合性能时材料的具体结构，为树脂材料高性能-功能一体化设计和制备提供新的研究思路和可靠数据支撑。经过本项目探索和研究，很好地完成了电活性苯并噁嗪分子设计、制备及性能研究。项目主要研究结果包括（1）成功制备出单官能团和双官能团系列电活性苯并噁嗪单体，基于非等温差式扫描量热（DSC）和原位红外（in-situ FTIR）分析确定单体固化反应动力学和固化过程，为单体固化和成型奠定理论基础；（2）电化学（CV）研究表明，项目制备的电活性苯并噁嗪单体和树脂在电场作用下均展现出良好的氧化还原可逆性，结合in-situ FTIR和CV测试结果探讨了单体和树脂电场作用的可逆氧化还原反应机理；（3）利用浸渍法成功制备出电活性苯并噁嗪树脂涂层，交流阻抗、塔菲尔曲线和拟合电路等分析结果表明，电活性苯并噁嗪树脂作为金属防腐涂层展现出良好的综合性能；（4）在电活性功能苯并噁嗪研究基础上，拓展出光活性苯并噁嗪和光-电活性苯并噁嗪。本项目研究为苯并噁嗪功能化开拓新思路。