梳状聚合物/石墨烯复合相变材料及纤维结构与性能研究

In this project, taking comb-like polymer/graphene hybrid phase change materials and its fiber as an example, the effect of the composition and structural state of single/double side chains, the molecular weight and its distribution, the grafting degree and the polymer backbone on the structural ordering, crystallization ability and phase change behavior has been studied from the aspect of molecular architecture of comb-like polymeric phase change materials. The fine control on the molecular microstructure is well realized. By controlling the complexing and assembling process between comb-like polymeric phase change materials and the surface modified and functionalized graphene, the formed composite structures and their coordination behavior has been analyzed, and the enhanced conductivity and its mechanism also has been clarified. And, the thermophysics, cycle stability and the processing behavior of composites has been investigated from the viewpoint of the surface and interfacial structural state and the micro/nanostructual packing of phase change materials. The processing of comb-like polymer/graphene phase change and thermal storage fiber is explored. And, the confinement effect of the fiber stress and the graphene nanosheets on the aggregation, crystal ordering, phase change and thermal property of comb-like polymer has been deeply characterized. Furthermore, the correlation between the fiber structure-property and the microstructural ordering is also well proved. The basic thermomechanics feature and the relationship between the molecular chain structure, processability and the aggregation structural ordering for comb-like polymers has been clearly discovered. Through this project, the basic scientific problems and the practical application are well combined, and it provides a good direction for exploring the high-efficient thermal-storage phase change materials with a controlled molecular structure.

本项目以梳状聚合物/石墨烯复合相变材料及其纤维材料为研究对象，从梳状聚合物相变材料的分子设计层次出发，研究单分布或双分布长短侧链组成和结构、分子量及分布、接枝密度和主链结构等对结构有序、结晶能力和相变性能的影响，实现分子链微观结构的精准控制。通过表面修饰与构筑的石墨烯纳米片与梳状聚合物相变材料的可控复合与组装过程，分析二者复合结构及协同作用方式对强化传热本质及机理的影响，探索表面/界面结构和微纳结构调控对热物理性能、循环稳定性和复合物成型过程的影响。研究梳状聚合物/石墨烯相变储热纤维的成型加工过程，分析应力拉伸和石墨烯层状限域对梳状聚合物凝聚态结构、结晶有序行为、相转变和热性能的影响，建立纤维功能与微结构的定量关系，阐明梳状聚合物分子链结构-可加工性-聚集态有序结构之间的关系及热力学特征。本项目将基本科学问题与实际应用相结合，为高效结构化相变储热纤维的开发奠定基础。

基于相变能量转化与储存材料开发和纤维应用过程中的储放热不平衡和热循环效率低的行为，本项目针对梳状聚合物/石墨烯复合相变材料及纤维结构与性能进行研究。项目设计制备了多种不同聚合物主链结构、侧链长度的梳状聚合物相变材料，研究了梳状聚合物的微观分子结构、侧链结晶能力与相变热能的构效关系，分析了影响高热焓和高定型温度梳状聚合物相变材料的内外结构因素。采用共混方法制备了复合相变材料，研究了梳状聚合物与化学修饰石墨烯的界面作用及协同方式对相变热物理性能如热循环稳定性、导热系数、相变热效率的影响，分析了相变热性能和光热转换效率等导热储热性能增强的因素。制备了同轴和单组分结构梳状聚合物及石墨烯基复合相变纤维，并设计制备了不同热管理能力的相变织物，完善了影响纤维热传导性能和热循环效率的因素分析，强化了梳状聚合物微观分子链结构设计与宏观热性能的关联研究，为高效相变储热材料开发提供了指导，在纺织服装、农用薄膜和热疗制品开发应用方面奠定了良好基础。在相变储热纤维及相变织物开发的基础上，与相关企业开展合作，并进行了专利成果技术转让。在项目执行期间发表学术论文9篇，其中SCI论文8篇，获得天津市科技进步奖二等奖（第1）等科技奖励3项。申请国家发明专利4项，授权3项，转让1项；参加学术会议3次，培养博士4人、硕士5人，在读博士研究生1人、硕士研究生7人。