原位交联聚合构筑聚砜基无机杂化微孔膜及其结构控制与性能研究

Polymer-based inorganic hybrid membranes often combine the advantages of both polymeric and inorganic membranes. This kind of membrane has been developed as a hot topic in the field of membrane technologies. In the project, cross-linked hybrid sols were synthesized via in situ cross-linked polymerization of triethoxyvinylsilane and a polymerizable hydrophilic organic monomer followed by hydrolysis and condensation reaction of alkoxysilane. Then polysulfone (PSf)-based inorganic hybrid membranes were prepared by non-solvent induced phase separation technology. As a result, PSf porous membranes will be filled and modified with hybrid polymers. In the hybrid membranes, inorganics were in situ synthesized, the aggregation issue of preformed inorganic nanomaterials can be overcome. The influence of the random copolymers structures and cross-linking processes on the nature of hybrid casting solutions will be studied. The influence of the casting solution on the structures and properties of the hybrid membranes will be discussed in-depth. The relationship between the casting solution and the hybrid membranes structures and properties will be established. We will to analysis and explain the effect of inorganic nanomaterials on the hybrid membranes in nature. The structures and performances of the hybrid membranes will be optimized by regulating the membranes forming process conditions. The project has important implications for the development of polymer-based inorganic hybrid membrane science and technology, and preparation technology of high-performance microporous membranes.

聚合物基无机杂化膜兼顾聚合物膜和无机膜的优势，是当前膜研究领域中最活跃的研究热点之一。本课题通过控制乙烯基三乙氧基硅烷和亲水性可聚合有机单体在聚砜（PSf）溶液中的原位聚合，随后乙氧基硅烷发生水解-缩合反应，生成适度交联的杂化铸膜液，再通过非溶剂诱导相分离法制备PSf基无机杂化微孔膜，实现对PSf膜杂化填充和原位交联改性的目的。杂化膜中无机纳米组分原位生成，解决无机纳米材料易团聚、难分散的问题。本课题考察无规共聚物结构与组成、交联条件与工艺对杂化铸膜液性质的影响规律；重点研究杂化铸膜液性质对膜结构与性能的影响规律，建立杂化铸膜液性质-膜结构-膜性能关系，揭示无机纳米组分对杂化膜结构与性能造成影响的本质原因和规律；调控制膜条件与工艺，优化杂化膜的结构与性能。本课题为丰富与发展聚合物基无机杂化膜科学理论、研发高性能杂化微孔膜方面提供理论依据和技术指导。

聚合物基无机杂化膜兼顾聚合物膜和无机膜的优势，是当前膜研究领域中最活跃的研究热点之一。但是无机纳米材料易团聚、难分散。本项目采用原位交联聚合法设计并可控制备了杂化制膜液，借助非溶剂诱导相分离法制备膜表面富集亲水链段的多孔杂化膜。取得了以下主要研究成果：. （1）采用原位交联聚合法可控制备聚砜/聚(丙烯酸-无规-乙烯基三乙氧基硅烷)(PSf/P(AA-r-VTES))和聚砜/聚(乙烯基吡咯烷酮-无规-乙烯基三乙氧基硅烷)(PSf/P(VP-r-VTES))杂化制膜液，探明了杂化制膜液物理/化学结构的可控演变规律。研究发现，随着功能单体浓度的增加，大分子聚集体增多、尺寸变大，导致杂化制膜液粘度显著增加。. （2）采用非溶剂诱导相分离(NIPS)，可控制备了杂化多孔膜，主要研究杂化制膜液物理/化学结构与多孔膜微观结构和分离性能之间的影响规律。研究发现，高粘度杂化制膜液促进多孔膜指状孔向海绵状孔演变；亲水性聚合物链在膜表面和孔壁的富集导致杂化膜亲水性明显提高，降低水分子透过阻力，提高水通量，同时抑制蛋白质、血小板的粘附与沉积，从而得到抗蛋白质污染和血液相容性显著提升的杂化多孔膜。. 本项目完成了预定的研究任务，实现了预期研究目标。研究结果为高性能聚合物基无机杂化膜的设计和可控制备提供必要的理论基础和指导。