有机次膦酸-过渡金属配合物在环氧树脂中潜伏固化行为及阻燃应用研究

Facing on the practical problem of both storage and transportation of the epoxy resin before application, as well as the flame retardance and smoke suppression requirements of the cured materials, in this project, based on the molecular design and structural optimization, a series of aryl-phosphinates and diphenyl dithiophosphinates complexes with potential latent curing activity and flame-retardant property will be firstly synthesized. Then, according to the comprehensive properties of the cured epoxy resins, including mechanical, thermal, electrical properties and flame retardance, different complexes will be screened out to meet the application prospects. The latent curing behavior of different curing agents will be systematically investigated, and the mechanism of latent curing will be analyzed. The mode of action of the latent curing behavior will be established and verified accordingly. At last, depending on the investigation of pyrolysis procedure and combustion behavior of the cured epoxy resins, activities of the metal cation on decomposition, flame retardance, and smoke suppression will be extrapolated, relationships between “complex structures” and “latent curing behavior”, and between “chemical environment and metal cation species” and “mechanisms for flame retardance and smoke suppression” will be therefore established. .The development of the project can obtain a variety of promising flame-retardant and latent curing agent for epoxy resin, which can further enrich the existing catalytic flame-retardant theory, and broaden the design-synthesis strategy for the flame retardants. Therefore, the project exhibits both scientific significance and application prospects.

针对环氧树脂施工前的储存运输问题及固化后的阻燃抑烟诉求，本项目首先通过结构设计及性能筛选，设计并制备多种兼具潜伏固化行为和阻燃性能的芳基次膦酸、芳基二硫代次膦酸金属配合物，以之固化环氧树脂而后测试所得树脂固化物的力学性能、热性能、电性能及阻燃性能等，据此优选出多种性能突出、有应用前景的环氧树脂用阻燃潜伏固化剂；其次分析不同结构固化剂的潜伏固化行为，揭示其作用机理，建立并验证一种科学、便捷的潜伏固化行为评价模型；最后研究各树脂固化物裂解及燃烧行为，推导出其热分解历程，推断出不同金属离子对聚合物热分解、燃烧及抑烟的作用机理，建立起“配合物结构”—“潜伏固化行为”和“阻燃元素化学环境、金属离子种类”—“树脂固化物阻燃性能及抑烟机制”之间的构效关系。项目的开展可以获取多种有应用前景的环氧树脂用潜伏型阻燃固化剂，充实现有催化阻燃理论，拓宽阻燃剂的结构设计思路。因此，本项目兼具科学意义和应用前景。

本项目通过结构设计及性能筛选，设计并制备多种兼具潜伏固化行为和阻燃性能的含磷金属配合物，以之固化环氧树脂而后测试所得树脂固化物的力学性能、热性能、电性能及阻燃性能等，据此优选出多种性能突出、有应用前景的三种环氧树脂用阻燃潜伏固化剂：二苯基膦酸金属配合物、二苯氧基磷酸金属配合物和二苯基硫代膦酸金属配合物；其次分析不同结构固化剂的潜伏固化行为，揭示其作用机理，建立并验证一种科学、便捷的潜伏固化行为评价模型；最后研究各树脂固化物裂解及燃烧行为，推导出其热分解历程，推断出不同金属离子对聚合物热分解、燃烧及抑烟的作用机理，建立起“配合物结构”—“潜伏固化行为”和“阻燃元素化学环境、金属离子种类”—“树脂固化物阻燃性能及抑烟机制”间的构效关系。最终详细评价了二苯基膦酸钴固化环氧树脂的耐热和介电性能。本项目的开展过程中，共发表SCI论文9篇，其中IF≥5的6篇；申请发明专利2项，授权1项（ZL201710136394.7），培养博、硕士研究生共3人。为制备综合性能优良的阻燃环氧树脂打下理论基础，同时为开发其它阻燃材料提供了一种新的思路。