Abstract:

Polybenzoxazine(PBZ) as a class of heterocyclic polymers are ranked as materials of superb thermal stability, extremely high tensile strength and good chemical resistance, which has been applied in many fields such as aerospace composites, blends and electronic circuit boards. In this paper, three routes and synthesis methods for preparing BZ monomer are reviewed, and the mechanism of cationic ring-opening polymerization (ROP) of benzoxazine (BZ) monomer without catalyst is summarized. Functionalized BZ monomers with containing addition-curable sites are categorized, and the influence of curable groups on the properties of PBZ is mainly discussed. Similarly, the structure, properties and research status of functionalised BZ with varying structural features but no additional polymerisable groups are investigated in detail. By molecular design, the monofunctional, difunctional and polymerisable group-substituted BZ is prepared, as well as high-molecular-weight PBZ and main-chain BZ novice materials. The research progress of BZ composites is introduced. The shortcomings of PBZ resin, such as high processing temperature and high brittleness of classical PBZ, and the reasons are pointed out. Finally, the development direction of benzoxazine resin in the preparation of green bio-based BZ, the modification of PBZ composite material and the synthesis of functional BZ with new structure are prospected.

Key words: thermoset resin, heterocycles, benzoxazine, molecular design, structure-property relationships

摘要：

聚苯并嗪树脂（PBZ）是一类杂环聚合物材料，具有优异的热稳定性、高的抗拉强度和良好的耐化学性，在航空复合材料、共混物和电子电路板等许多领域得到了应用。本文概述了制备苯并嗪（BZ）单体的三种路线及合成方法，总结了在无催化剂条件下BZ单体的阳离子开环聚合（ROP）机理；详细阐述了含可固化基团的功能化BZ单体的种类以及可固化基团对PBZ树脂性能的影响，同样也详细论述了不含可固化基团的功能化BZ单体的结构性能以及研究现状。通过分子设计，科研人员已制备出了单官能团取代、双官能团取代、可聚合官能团取代的BZ单体，以及高分子量主链的BZ和主链含有BZ单元的化合物材料；简述了PBZ复合材料的研究进展，指出了PBZ树脂存在加工温度高、经典的PBZ脆性大的缺点以及产生的原因，最后指出苯并嗪树脂的发展方向为制备绿色生物基BZ、PBZ复合材料的改性以及合成新结构的功能性BZ。

关键词: 热固性树脂, 杂环化合物, 苯并嗪, 分子设计, 结构与性能