结晶性嵌段共聚物活性自组装用于构筑功能化表面的研究

Surface functionalization is of remarkable significance in industry and routine life. Besides to many traditional methods, a diverse array of modern nanotechnologies has now been widely applied to modify material surfaces. Nevertheless, it is still challenging to construct various functional surface micro/nanostructures in a highly efficient and flexible way similar to that adopted by living beings. In this project, we develop an in situ living method to directly fabricate unique micro/nanostructures using crystallization-driven living self-assembly of crystalline-coil block copolymers, where cylindrical micelle seeds are firstly immobilized on material surface and subsequently initiate the living self-assembly of further added block copolymer unimers to form cylindrical micellar brushes. According to various demands, the chemical composition, distribution and density, length and segmented structures, self-assembly behavior, and 3D topological structures of these micellar brushes can be well tailored. Moreover, the micellar brushes can be further functionalized by post modification and complexation. This provides a controllable, tunable and multiplex approach for surface functionalization, which appears to be highly promising for future applications in the fields of functional materials, micro/nano-devices, biomedicines, etc.

表面功能化在工业界和日常生活中都具有十分重要的意义，除传统方法以外，各类先进纳米技术也被广泛地应用于材料表面的修饰，但是像生物体一样高效、灵巧地构筑各种微纳米表面功能结构仍是一项富有挑战的课题。本项目设计合成一系列结晶－无定形嵌段共聚物，将其所形成的柱状胶束种子牢固地负载到各种材料表面上，通过结晶诱导的活性自组装，使后续加入的嵌段共聚物在种子诱导下组装形成柱状胶束刷，从而直接在材料表面原位构筑特定的微纳米结构。根据不同需求，柱状胶束刷的化学组成、分布密度、尺寸与嵌段结构、聚集形态、三维拓扑结构等都可以灵活调节，并进行丰富多样的后修饰与复合。通过该项目的研究，力争使聚合物活性自组装成为一种可控、灵活、多元化的表面功能化方法，并进一步发挥其在功能材料、微纳米器件、生物医药等领域的应用潜力。

在材料表面构筑均一、功能化的纳米结构在诸多领域都有着非常重要的意义。本项目提供了一种简单高效的制备策略，将结晶性柱状胶束种子负载到宏观材料表面，诱导后续加入的嵌段聚合物结晶驱动自组装组装，从而在材料表面构筑形成柱状胶束刷。制备得到的柱状胶束刷的化学组成、分布密度、尺寸与嵌段结构等能够予以灵活、精准的调控。基于胶束刷的特征化学性质，可进一步实现丰富多样的后修饰，例如透过电解质化构建超亲水表面，而复合有各类无机纳米粒子的胶束刷能够应用于界面抗菌、催化等领域。此外，柱状胶束刷还能生长于二维超薄材料表面（如氧化石墨烯），其沉积组装制得的薄膜能够用于特定组分或粒子的高效分离。因此，本项目所发展的活性生长方法为材料表面功能化提供了一种高效、可控、灵活的策略