可瓷化高分子合成与功能化进展

Recent Progress in Synthesis and Functionality of Ceramizable Polymers

可瓷化高分子是指在制备或使役过程中,能从有机交联网络转化为无机陶瓷并发挥独特功能的一类特种高分子,在特殊和极端环境下服役的材料结构中有重要应用.本文首先对含硼、锆、铪、铁等元素的可瓷化高分子设计与合成进行了详细介绍;然后对在高温、高压等极端条件应用的可瓷化高分子高性能化进行了总结,主要包括可瓷化高分子在耐高温抗氧化陶瓷、特种高温胶黏剂、耐电弧阻燃涂层中的应用;接着对航空航天用高温电磁波吸收材料、电磁屏蔽材料新应用驱动的可瓷化高分子多功能化进展做一综述.最后结合未来应用需求,对可瓷化高分子与增材制造、耐高温长寿命复合材料、超材料设计的融合和交叉做了初步展望.

The ceramizable polymers are a group of special functional polymers which can transform from organic cross-linked network to inorganic ceramics during pyrolysis or service under high temperature.This article reviews the latest research on ceramicizable polymers and their derived functional ceramics used under extreme and special environment and aerospace field.According to main elements contained in ceramicizable polymers,the design and synthesis of boron,zirconium,hafnium,iron-containing ceramic polymers are introduced in detail.The stoichiometric ratio,cross-linkable feature and linear,slightly cross-linked and hyperbranched topologies of ceramicizable polymers are key factors to the properties of pyrolyzed ceramics,including ceramic yield,mechanical property,high-temperature resistant and anti-oxidation performances.Due to their ceramicizable feature during pyrolysis or service,self-healing,and flame retardancy under high temperature or arc,the advanced ceramicizable polymers show remarkable application in high-temperature resistant and anti oxidation ceramics,high-temperature adhesives,arc breakdown resistance and flame retardant coatings mainly used in extreme conditions.Then the new developments in the multifunctionalization of ceramicizable polymers such as electromagnetic wave absorbing materials and electromagnetic interference shielding materials are presented.The introduction of transition metal into ceramicizable polymer is highly effective to tune dielectric and magnetic properties of their derived ceramics.The excellent electromagnetic wave absorption at 885℃with a low minimum reflection coefficient and a wide effective absorption bandwidth was achieved on iron-containing siliconboron carbonitride ceramics derived from the cross-linked network of hyperbranched polyborosilazane and 1,1'-bis(dimethylvinylsilyl)ferrocene.In addition,the perspective and further development of integration and intersection of ceramizable polymers are proposed,including but not limited to additive manufacturing,high-temperature self-healing and long-life composites,as well as metamaterials with potential in electromagnetic wave absorbing material at low frequency of 0.5-2 GHz.