The benzoxazine resin (DBA-a) synthesized from raw materials of 2,2′-diallyl bisphenol A (DBA), aniline and paraformaldehyde has been well-commercialized, but a reduction in its polymerization temperature and improved comprehensive properties are highly challenging to satisfy the requirements of various composites. Here, we have developed three strategies for improving the performance of DBA-a resin: the first is the chemical modification, synthesizing a novel DBA-based bisbenzoxazine containing acetylene functionality (DBA-ac); the second is the physical blend of bismaleimide (DDM-BMI) and DBA-a, forming a homogenous copolymer; and the third is combining both chemical and physical methods, achieving the DBA-ac/DDM-BMI blend as a new precursor for high-performance thermosets. The newly obtained DBA-ac possesses the advantages of relatively lower polymerization temperature and good thermal stability during the polymerization process. In addition, the polymerization temperature of DBA-ac can be further lowered by blending with DDM-BMI via multiple polymerization mechanisms. Specifically, the resulting copolymeric thermoset derived from DBA-ac/DDM-BMI blend is found to show fascinating properties such as exceptionally low coefficient of thermal expansion (CTE of 37.1 ppm/^oC), high thermal stability (T_g of 370 °C), outstanding flame retardancy (THR of 17.6 KJg⁻¹), and low dielectric constant (2.86 at 1 MHz). The current study delivers readily approaches to enhance the performance of thermosetting resins via both chemical modification and physical blending.

以 2,2'-二烯丙基双酚 A (DBA)、苯胺和多聚甲醛为原料合成的苯并恶嗪树脂 (DBA-a) 已被很好地商业化，但其聚合温度的降低和综合性能的提高很难满足各种复合材料的要求。在这里，我们开发了三种提高 DBA-a 树脂性能的策略：第一个是化学改性，合成了一种新型的基于 DBA 的含乙炔官能团的双苯并恶嗪 (DBA-ac)；第二种是双马来酰亚胺（DDM-BMI）和DBA-a的物理共混，形成均质共聚物；第三是结合化学和物理方法，实现 DBA-ac/DDM-BMI 混合物作为高性能热固性塑料的新前体。新获得的DBA-ac具有聚合温度较低、聚合过程热稳定性好等优点。此外，与DDM-BMI共混可进一步降低DBA-ac的聚合温度通过多种聚合机制。具体而言，发现源自 DBA-ac/DDM-BMI 共混物的共聚热固性材料显示出迷人的特性，例如极低的热膨胀系数（CTE 为 37.1 ppm/ ^o C）、高热稳定性（T _g为 370 °C )、出色的阻燃性（THR 为 17.6 KJg ^-1）和低介电常数（2.86 at 1 MHz）。目前的研究提供了通过化学改性和物理共混来提高热固性树脂性能的简便方法。