AbstractUltrahigh‐molecular‐weight (UHMW) polymers with tailored structures are highly desirable for the outstanding properties. In this work, we developed a novel photoorganocatalyzed controlled radical alternating copolymerizations of fluoroalkyl maleimide and diverse vinyl comonomers, enabling efficient preparation of fluorinated copolymers of predetermined UHMWs and well‐defined structures at high conversions. Versatility of this method was demonstrated by expanding to controlled terpolymerization, which allows facial access toward fluorinated terpolymers of UHMWs and functional pendants. The obtained copolymers exhibited attractive physical properties and furnished thermoplastic, anticorrosive and (super)hydrophobic attributes as coatings on different substrates. Molecular simulations provided insights into the coating morphology, which unveiled a fluorous protective layer on the top surface with polar groups attached to the bottom substrate, resulting in good adhesion and hydrophobicity, simultaneously. This synthetic method and customized copolymers shed light on the design of high‐performance coatings by macromolecular engineering.

中文翻译：

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有机催化光控合成超高分子量含氟交替共聚物

摘要具有定制结构的超高分子量（UHMW）聚合物因其出色的性能而备受青睐。在这项工作中，我们开发了一种新型光有机催化受控自由基交替共聚氟烷基马来酰亚胺和多种乙烯基共聚单体，能够在高转化率下有效制备具有预定UHMW和明确结构的氟化共聚物。通过扩展到受控三元聚合，证明了该方法的多功能性，该方法允许面部接触 UHMW 的氟化三元共聚物和功能性垂饰。所得共聚物表现出有吸引力的物理性能，并在不同基材上作为涂层时具有热塑性、防腐和（超）疏水特性。分子模拟提供了对涂层形态的深入了解，它在顶部表面上形成了氟保护层，极性基团附着在底部基材上，同时产生了良好的附着力和疏水性。这种合成方法和定制的共聚物为通过高分子工程设计高性能涂料提供了线索。