| 摘要: |
| 受海葵刷状软毛和天然滑液关节微观结构的启发，将聚合物链的一端高密度地接枝到基底表面，形成“刷型”有序结构的聚合物膜，并通过合理的结构设计和调控化学组成，可以有效阻止蛋白质和微生物的吸附，已成为改善材料表界面性能和解决生物污损的有效策略之一。传统制备仿生聚合物刷的方法是表面引发自由基聚合，其聚合过程高度可控，获得的聚合物分子量分布窄，但存在操作步骤繁琐、需要严格无氧环境、成本高昂且难以实现大面积制备等缺点。近年来， 利用零价金属介导表面引发可控自由基聚合制备仿生聚合物刷逐渐受到广泛关注。这类方法避免了复杂冗长的除氧步骤， 能够在大气环境下直接实现功能性聚合物刷的大面积、高效制备。在介绍仿生聚合物刷特点的基础上，综述国内外表面引发聚合仿生聚合物刷的研究进展，重点对比和分析零价金属介导的表面引发可控自由基聚合的适用性及特点，并阐述仿生聚合物刷在海洋防污领域的研究进展，最后展望仿生聚合物刷在海洋防污领域的未来发展趋势，为海洋仿生防污材料的设计和制备提供参考。 |
| 关键词: 仿生 聚合物刷 表面引发可控自由基聚合 零价金属催化 海洋防污 |
| DOI：10.11933/j.issn.1007-9289.20240112001 |
| 分类号:TG156；TB114 |
| 基金项目:国家自然科学基金（52005491，52003279）；浙江省“尖兵”“领雁”研发攻关计划（2023C01089）；宁波市“3315”计划创新团队（2019-17-C）；宁波市公益性研究计划项目（2023S080） |
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| Research Progress on the Preparation of Biomimetic Polymer Brush for Marine Antifouling Applications |
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WU Daheng，WANG Jianing，ZHANG Tao
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Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences, Ningbo 315201 , China
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| Abstract: |
| Inspired by the soft bristles of sea anemones and the microstructure of natural synovial joints, a “brush like” ordered polymer film can be obtained by densely grafting of one end of the polymer chain can be grafted onto the substrate surface, and the adsorption of proteins and microorganisms can be effectively prevented through reasonable structural design and regulation of chemical composition. This is considered as an effective strategy for improving the surface and interface properties of materials, and inhibiting marine biofouling. The traditional method for preparing biomimetic polymer brushes is surface-initiated controlled radical polymerization, which is generally performed on substrates modified with a self-assembled monolayer of initiators, tethering polymer chains to the substrate, and thus endowing arbitrary surfaces with the desired placement of groups and targeted functions. However, this method requires cumbersome operation steps, strict oxygen exclusion, and high costs, making large-scale implementation difficult. To overcome these obstacles, a series of innovative and powerful techniques have been explored, triggered by various external stimuli, such as electrochemistry, the addition of a reducing agent, photochemistry, enzymes, microbial metabolism, and the use of zerovalent metals. In recent years, zero-valent metal-mediated surface-initiated controlled radical polymerization (SI-Mt0 CRP) has received widespread attention for the preparation of biomimetic polymer brushes. In the SI-Mt0 CRP setup, a metal(0) plate (Cu, Fe, Zn, or Sn) is placed proximately to an initiator-functionalized substrate to form a confined polymerization system, which considerably simplifies the synthesis of a wide range of polymer brushes with high grafting densities. This method avoids complex and lengthy deoxygenation steps and could efficiently prepare functional polymer brushes over large areas in ambient environments. In addition, SI-Mt0 CRP is well compatible with a range of emerging technologies, including “on water” reaction, galvanic replacement, lithography, and capillary microfluidics, which significantly broaden the universality of this technique. Because of these advantages, SI-Mt0 CRP has become a prevalent technique for preparing functional polymer brushes with excellent application potential in marine antifouling, surface lubrication, sensing platforms, and biomedical engineering. Thus, surface grafted polymer brushes fundamentally address shortcomings of traditional surface modification methods (such as physical adsorption and self-assembly) and can greatly improve the density of functional groups on the surface of solid materials, significantly enhancing the mechanical properties and chemical stability of the coatings. Moreover, heterografted polymer brushes can also effectively mitigate biofouling because compositional heterogeneities discourage thermodynamically favorable interactions between the foulant and the surface, leading to limited adsorption events. This article introduces the characteristics of biomimetic polymer brushes and reviews the research progress on surface-initiated polymerization of biomimetic polymer brushes, comparing and analyzing the applicability and characteristics of SI-Mt0 CRP catalyzed by zerovalent metals (e.g., Cu, Fe, Zn, and Sn). Further. the research progress on biomimetic polymer brushes in the field of marine antifouling is elaborated, and prospects are discussed, providing guidance for the design and preparation of biomimetic marine antifouling materials. |
| Key words: biomimetic polymer brushes surface-initiated controlled radical polymerization zerovalent metal catalysis marine antifouling |
