通过低聚物偶联组装大规模制备高性能电纺聚苯纳米纤维

This project is proposed to explore the preparation of the phthalate-capped polyphenylene (PPP -phthalate) oligomer by using 4-chlorophthalic acid as a capping agent, 2-benzoyl-1,4-dichlorobenzene, 2,5-dichlorobenzoic acid, 2,5-dichloro-acetophenone and the like as monomers, nickel as the catalyst; the as-prepared PPP-phthalate oligomers would be used as the assembling units and 3,3',4,4'-biphenyltetramine as a coupling agent for exploring the formation of PPP-phthalate oligomer assembly nanofibers based on electrospinning technology. And the high temperature treatment of the electrospun assembly nanofibers will be used to convert the assembly joints from a weak interaction of the ammonium into a strong chemical bond of pyrrolone molecular structure, which would result in the formation of a type of heat-resistant, high strength, chemical-resistant polyphenyl nanofibers. The electrospun assembled polyphenyl nanofibers are a new class of ultrahigh performance polymer nanofibers, which will find broad uses in the fields like environmental engineering, new energy and advanced composite materials and so on. At the same time, the project will be not only to explore a novel technique for the preparation of the high-performance polyphenylene nanofibers, but also to create a new method of combining electrspinning and the molecular self-assemble technology for producing high-performance polymer nanofibers. The project should be important for expanding the electrospinning field.

本项目研究将以4-氯代邻苯二甲酸为封端剂、2-苯甲酰基-1,4-对二氯苯、2,5-二氯苯甲酸、2,5-二氯苯乙酮等为单体，镍为催化剂探索以邻苯二甲酸封端的聚苯类低聚物（PPP-phthalate）的合成；以四氨基联苯类物质为偶联剂、PPP-phthalate低聚物为组装单元及静电纺丝为技术手段，探索电纺组装聚苯类低聚物纳米纤维，并经高温处理使纤维中组装单元连接点上的銨盐弱相互作用转化为吡咙分子结构的强化学键连接，形成耐高温、高强度、抗腐蚀的电纺组装聚苯类物质纳米纤维。这种电纺组装的聚苯类物质纳米纤维是一类具有超高性能的新型聚合物纳米纤维，在未来环境工程领域、新能源领域和高端复合材料领域有潜在的广泛应用。同时, 本课题研究不仅是探索一种制备高性能聚苯类物质纳米纤维的技术，也是开创一种静电纺丝结合分子自组装形成聚合物纳米纤维的新方法，对拓展静电纺丝技术领域具有重要意义。

聚苯具有优异的耐高温性，耐化学腐蚀性、耐摩擦、耐辐射等特性，可用在恶劣环境下工作的化工设备、宇航设备、高速飞行的武器上。但高性能聚苯属于不熔、不溶或难溶聚合物，难于应用加工。本项目研究通过分子偶联组装和电纺技术相结合，成功地将羧酸官能基封端的、溶解性能良好的聚苯低聚物与四氨基联苯等偶联剂混合电纺组装形成聚苯类超分子纳米纤维，后经高温热处理使之转变为吡咙化学键合连接的电纺高分子量聚苯类物质的纳米纤维。这样制得的聚苯纳米纤维具有高耐温、高强度和耐强酸强碱等特性，有望在新能源领域、高端复合材料领域得到广泛应用。特别是，本项目研究也开创了一种由低聚物偶联组装制备高分子量聚合物材料的新方法，解决了一类难熔、难溶高性能聚合物材料应用加工的技术难题。通过该项目研究，本课题组发表了相关学术论文18篇、申请并授权专利11项；培养了博士毕业生2名、硕士毕业生4名。本项目研究已圆满完成了预期目标，所制备的聚苯纳米纤维多孔膜已用在碱性超级电容器中进行应用测试，各项性能指标大幅度领先现有超级电容器隔膜，有望得到深度开发和应用。