核-壳-聚合物刷多功能阻燃添加剂及其应用基础研究

Based on the requirement of the integration of halogen-free flame retardant, electrical conduction, thermal conduction, hydrophobic properties for the flame retardant polymeric materials used in high-end electrical and electronic field, as well as the critical and common scientific problems of mutual restraint and barrier effect existed in the implement of multi-functional, we will design and assembly construct the flame retardant additive with core-shell-polymer brush structure and the integrated properties of flame retardant, electrical and thermal conduction. The common scientific and technical issues for achieving multi-functional will be solved, and the high-end multi-functional flame retardant polymeric composites will be successfully prepared and applied. The coating of flame retardants, the construction of surface polymer brush, and the assembly of nano-functional materials will be investigated and the novel multi-functional flame retardant additives will be prepared. The interpenetrating network structure of the outer polymer brush layer with electrical and thermal conductive function will be constructed in polymer matrix, meanwhile, the inner flame retardant will present synergistic effect with the outer shell materials. The properties and structure of multi-functional flame retardant additive will be researched, and the effect of its structure and components on the properties of polymeric composites will be deeply investigated, and the effect rule and relationship of dose-effect and structure-effect will be clarified. The distribution of outer functional polymer brush in polymer matrix, the integrity of the interpenetrating network structure and the forming rule will be investigated, and the mechanism of electrical and thermal conduction will be revealed. The theoretical basis will be provided for the development of great potential flame retardant polymeric materials used in high-end application field in the future.

基于高端电子电气领域阻燃聚合物材料对无卤阻燃与导电、导热、疏水等多功能一体化的需要，以及实现多功能化存在的相互制约和阻隔的关键共性科学问题，本项目拟通过结构设计，组装构建具有核-壳-聚合物刷的结构，兼具阻燃、导热及导电等性能于一体的阻燃添加剂，解决多功能化的共性科学技术问题，实现高端多功能阻燃聚合物复合材料的制备与应用。研究阻燃剂的包覆、表面聚合物刷的构建，以及纳米功能材料的组装，制备新型多功能阻燃添加剂，实现外层聚合物刷导电、导热功能层在聚合物中构筑互穿网结构，而内核阻燃剂与壳材料的阻燃协同。研究多功能阻燃添加剂的性能与结构，通过深入研究其结构及组分对材料的性能的影响，阐明其作用规律以及其量效及构效关系。研究聚合物刷功能层在聚合物中的分布形态、互穿网完整性等形成规律，揭示导热及导电的作用机制。研究该阻燃添加剂对材料的阻燃作用机理。为未来巨大潜在的阻燃材料高端市场的开发与应用奠定理论基础。

该项目针对高端电子电气、电子封装材料领域阻燃聚合物材料对阻燃、导热等多功能一体化的需要，以及实现多功能化存在相互制约的关键共性科学问题，本项目设计并制备了集阻燃、导热等功能于一体的聚合物添加剂，制备了综合性能优异的阻燃、导热聚合物材料。（1）以聚磷酸铵为核，在其表面接枝聚合物刷并将导热填料分散到聚合物刷中，制备了阻燃、导热添加剂。当添加量为9wt%，碳纳米管含量为1.8wt%时，材料的导热系数达到了1.02 W·m-1K-1，比单独添加相同碳纳米管的值高30.8%，材料通过UL-94 V-0级，氧指数为34.1%。将阻燃导热环氧树脂预聚体注入到辐射松，木材的导热系数为0.94 W·m-1K-1，力学性能得到明显增强，材料能实现离火自熄。（2）以金属锌有机咪唑框架化合物为原料，通过在氮气及空气条件下煅烧制备了树枝状及中空结构的氧化锌，表现了比商品氧化锌更高的导热效率。当添加量为10wt%时，填充树枝状氧化锌的环氧树脂材料的导热系数达到了1.10 W·m-1K-1，而添加商品氧化锌的材料导热系数仅为0.5 W·m-1K-1，中空结构的氧化锌也表现了优异的导热效率，材料的烟释放速率及总烟释放量都得到了有效降低。（3）通过高温氧刻蚀技术制备了氮化碳纳米片并组装到焦磷酸哌嗪等阻燃剂表面，获得阻燃导热填料。当填料的添加量为7wt%，其中氮化碳为1.5wt%时，材料的导热系数达到了1.14 W·m-1K-1，材料UL-94 V-0级，热释放、烟释放都得到了明显的降低。（4）通过模板法，将导热填料碳纳米管分散到纤维素气凝胶中并注入环氧树脂，当填料仅为0.35 vol%时，材料导热系数为0.93 W·m-1K-1，表现了很好的导热效率，同时材料的力学性能及玻璃化转变温度都得到了提高。通过该项目的研究，为制备多功能聚合物添加剂、综合性能优异的阻燃、导热聚合物材料奠定了理论基础，提供了实验依据。