含氟聚合物/SiO2杂化材料的制备及其涂膜疏水性能和粘接性能的研究

FPs/SiO2 nanohybrids made of fluorinated copolymers and SiO2 have been attracted much attention and have become the focus of high performance film materials. The surface chemical composition and micro/nano structured hierarchical morphology are the most key factors in dominating the surface properties for decreasing the energy and increasing the hierarchical morphology of surface. Two characteristics for FPs/SiO2 film in micro/nano hierarchical morphology (high roughness) and self-migration into top surface of fluorinated groups in copolymers (low surface free energy) have make it possible to obtain excellent water and oil repellence and the strong adhesion to the substrate. However, the coherence between hydrophobic and adhesive properties is the key point for FPs/SiO2 nanohybrids, and few of researches are reported so far. Therefore, this project aims to research the Synthesis, hydrophobic and adhesive properties of FPs/SiO2 nanohybrids. In this project, different FPs/SiO2 nanohybrids are structured and synthesized by ATRP/sol-gel and SI-ATRPATRP techniques; The relationship between the particles morphology and the chemical composition of film surface as well as surface energy is investigated; The regulatory function of self-assemble behavior and the disutribution of aggregated micelles to the micro/nano hierarchical morphology of film surface are studied; The relationship between the cross-section of film and the adhesion to the substrate is explored; Through these results, the regulation mechanism of surface chemical composition and micro/nano hierarchical morphology to the hydrophobic and adhesive properties is established. It is hoped that the results of this research could provide the scientific basis and technical support to the high-performance fluorinated polymer nanomaterials.

含氟聚合物(FPs)与纳米SiO2制备的FPs/SiO2纳米杂化材料已经成为高性能涂膜材料关注的焦点。FPs/SiO2涂膜表面伴有含氟官能团表面自迁移，以及主要粒子纳米级特征和自组装聚集体微米级特征，能够有效地降低表面自由能和增加表面粗糙度，从而赋予涂膜突出的疏水疏油性及对基体强的粘接性能。然而，如何在提高表面疏水性能的同时获得强的基体粘接性能是FPs/SiO2涂膜材料的关键所在。鉴于此，本项目采用ATRP/sol-gel 及SI-ATRP两种方法合成FPs/SiO2纳米杂化材料、研究FPs/SiO2化学组成及结构与表面化学组成 (表面能)的关系、研究FPs/SiO2自组装对表面微纳形貌 (粗糙度)的调控作用、探明膜层结构与粘接性能的关系，综合研究表面化学组成与微纳结构对表面疏水性能及粘接性能的调控作用，为FPs/SiO2纳米杂化材料高性能涂膜材料相关问题的研究提供科学依据和技术支持。

基于含氟聚合物(FPs)与纳米SiO2制备FPs/SiO2杂化粒子的纳米特征和自组装体的微米特征，结合提高表面疏水性能与获得强的基体粘接性能的关键研究，分别在FPs/SiO2杂化粒子的设计与合成、溶剂组装方式对FPs/SiO2复合纳米粒子聚集形态及粒径分布的影响、聚集体形貌和分布对SiO2/FPs膜表面微纳结构及粗糙度的影响、含氟官能团表面迁移及定向排列特性对表面能与疏水性能的调控、SiO2/FPs复合纳米粒子对膜表面化学组成与微纳结构及表面疏水性的调控作用、FPs/SiO2结构对复合纳米粒子热稳定性的影响、SiO2/FPs复合纳米粒子结构形态和粒径分布对粘接性能的影响、SiO2表面引发FPs的反应动力学等方面取得重大研究进展。.设计合成了4类SiO2纳米粒子表面引发含氟聚合物结构（grafting from）、3类聚合物模板组装生长纳米粒子SiO2（grafting to）、2类PDMS引发含氟聚合物、2类其它SiO2纳米粒子与PFs键合的FPs/SiO2；揭示了FPs/SiO2复合纳米粒子自组装构建表面微纳结构的规律，有机与无机有效化学结合，防止明显相分离，防止保护后期有机与无机各自发挥功能，突出了协同作用；揭示了微纳相结构有效提高硅基吸附性能与疏水性能，发现使用分散剂调控杂化粒子的聚集形态、微纳米结构、链段成膜表面竞争迁移程度、化学组成表面富集程度、成膜表面微纳米形貌、结构稳定性和润湿性等。揭示了SiO2-含氟聚合物协同效应机制及构效关系，无机成分限制有机链段运动，提高机械强度、热稳定性和机械拉伸模量，有机与无机结合方式对杂化材料性能具有调控作用。探明了FPs/SiO2膜表面化学组成及微纳结构对表面疏水性能的调控作用，建立了FPs/SiO2膜层分布对粘接性能的影响规律。揭示了嵌段结构和接枝引发比模板生长具有更高的稳定性。揭示了SiO2对杂化材料性能调控作用体现在有利于提高材料的耐热性能、耐水性能和程度不等的粘接性能。实现了项目的预期目标，解决了项目提出的关键科学问题。. 本项目执行过程中，共发表相关论文44篇，其中SCI收录期刊论文33篇，最高IF=13.3；出版著作2部，授权发明专利4项。共培养博士生5人，硕士生6人，其中1人获得博士生国家奖学金，在读博士生4人出国交流学习；完成培养外国人博士生2人。