Zhou Chengda, Zhang Zexi, Li Weiping, Chen Mao
Department of Macromolecular Science, State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai, 200433, China.
Division of Natural and Applied Sciences & Environmental Research Center, Duke Kunshan University, Suzhou, Kunshan, 215316, China.
Angew Chem Int Ed Engl. 2024 Jan 8;63(2):e202314483. doi: 10.1002/anie.202314483. Epub 2023 Dec 8.
Ultrahigh-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.
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的光有机催化氟代烷基马来酰亚胺与多种乙烯基共聚单体的可控自由基交替共聚反应，能够在高转化率下高效制备具有预定超高分子量和明确结构的氟化共聚物。通过扩展到可控三元共聚反应，证明了该方法的通用性，这使得能够方便地制备具有超高分子量和功能性侧基的氟化三元共聚物。所获得的共聚物表现出吸引人的物理性能，并在不同基材上作为涂层提供了热塑性、抗腐蚀和（超）疏水特性。分子模拟为涂层形态提供了深入了解，揭示了顶表面上的氟化物保护层，其极性基团连接到底部基材上，从而同时实现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层提供了思路。
