含氟两亲性树状聚合物刷负载纳米银杂化材料的构筑及二元协同防污行为

Protein and microorganisms absorption on the solid surface is a common but complex phenomenon. Nonspecific adsorption for protein and associated bioadhesion is one of the most significant limitations to biomedical implants, marine ship hulls, water purification and textile industry. Recently, tethering of functional polymer brushes to the material surfaces provides an environmentally benign approach to develop efficient antifouling coatings. The amphiphilic polymer brush containing both hydrophilic and hydrophobic components is capable of resisting biofouling and releasing of fouling organisms. However, the fabrication of amphiphilic polymer brush is a big challenge and the antifouling mechanism is still unclear. Moreover, amphiphilic polymer brush with multiple synergistic surface functionalities for marine antifouling is rare. This project focuses on the development of novel amphiphilic dendritic polymer brush/silver nanoparticles (AgNPs) nanohybrids for antifouling with multiple synergistic effects. First, a series of amphiphilic dendritic polymer brushes with different ratios of hydrophilic/hydrophobic components and different generation dendritic methacrylate macromonomers and the according nanohybrids will be prepared and fully characterized. Second, the morphology and phase-segregation behaviors of the amphiphilic dendritic polymer brushes and the according nanohybrids will be investigated carefully. Finally, the adsorption behaviors of proteins, bacteria and algae on the amphiphilic dendritic polymer brushes and the according nanohybrids will be studied and the antifouling mechanism will further be explored. This study will provide a new idea for the preparation of highly efficient antifouling coatings with multiple functions, and will be of high academic importance as well as industrial interest.

固体材料表面的生物污染在生物植入、生物传感器、水产养殖以及船舶等领域危害颇多。表面接枝聚合物刷是一种改善表面理化性质，防止蛋白质以及污损生物吸附的有效方法。但是传统的两亲聚合物刷合成困难、种类单一、难以功能化修饰且防污机理尚不清楚。本项目拟以两亲性树状聚合物刷为媒介，将两亲性树状聚合物刷微相分离形成的纳米级“模糊”界面和负载纳米银这两种不同防污机制有机统一起来，利用二元协同防污设计理念，从两亲性树状聚合刷以及两亲性树状聚合刷/纳米银杂化材料的设计合成（组分比例和代数效应），表面性能研究和二元协同防污机制探索三个层次入手，设计制备一系列新型的两亲性树状聚合物刷/纳米银复合材料，重点探索亲疏水组分比例和树状分子代数对微相分离和防污性能的影响规律，从分子层次阐明分子结构与性能之间的构效关系，进而揭示二元协同防污机制；为进一步设计其他新型的多重防污机制协同作用的多功能防污材料提供新思路和新方法。

固体材料表面的生物污染在生物植入、生物传感器、水产养殖以及船舶等领域危害颇多。解决生物污染问题最根本的方法是“钝化”材料表面，提高材料表面的抗污损生物黏附性能。表面修饰亲/疏水性功能基团是一种改善表面理化性质，防止蛋白质以及污损生物吸附的有效方法之一。.本项目针对传统的两亲聚合物刷合成困难、种类单一、难以功能化修饰且防污机理不清楚等关键问题，以多元协同防污为设计理念，将绿色高效抗菌纳米粒子的触杀机制、薄层水凝胶的抑制吸附机制和有机硅凝胶涂层的易脱除机制有机的结合起来，设计构筑了亲水性树枝状聚硫（砜）醚水凝胶/纳米银杂化材料、基于动态化学键交联的自修复硫醚水凝胶/纳米银杂化材料和两亲性有机硅聚合物水凝胶/纳米银杂化材料三大类新型防污材料体系；从杂化材料的设计合成、表面性能和协同防污机制三个层次进行了系统研究：建立了水凝胶的化学组成和纳米银的负载量、尺寸和微观形貌之间的构效关系，聚硫醚树枝状官能团的螯合作用以及水凝胶的包裹作用可以有效地稳定和调控纳米银，聚硫醚树枝状分子的引入可以有效的调控纳米银的缓释机制；阐明了了纳米银与两亲性机硅聚合物之间相容性和相分离行为之间的影响规律，随着纳米银含量增加亲/疏水区域之间界面变模糊，相容性变好，避免了宏观相分离，纳米银的引入可以有效诱导亲水性聚合物和疏水性有机硅聚合物形成的互穿网络（IPN）结构可以有效增强二者的相容性，利于形成微观相分离结构；初步揭示了杂化材料的协同防污机制，纳米银的引入极大了提高了杂化材料的抗菌和抗藻性能，杂化材料对E.coli的杀菌性能高达100%，静态环境下小球藻、舟形藻和三角褐指藻在杂化材料表面贴附量比有机硅弹性体分别降低了70%，94%和4%，水流剪切脱吸附试验表明，杂化材料对小球藻、舟形藻三角和褐指藻的脱除率分别为50%，99% 和85%，比有机硅弹性体提高了40%；实海挂板实验表明杂化材料可以有效的抑制水螅、海草和藤壶的附着，污损生物覆盖面积明显减少。