Precise Synthesis of Ultra‐High‐Molecular‐Weight Fluoropolymers Enabled by Chain‐Transfer‐Agent Differentiation under Visible‐Light Irradiation

Abstract

Ultra‐high‐molecular‐weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible‐deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain‐transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible‐light irradiation. In situ chain‐end extensions from UHMW polymers facilitated the synthesis of well‐defined block copolymers, revealing the excellent chain‐end fidelity achieved by this method.

Fluorinated Bifunctional Solid Polymer Electrolyte Synthesized under Visible Light for Stable Lithium Deposition and Dendrite‐Free All‐Solid‐State Batteries

“…Photo‐CRPs have recently gained enormous attention in polymer synthesis for its ability to control polymerization process under mild conditions (Figure 1A). [ 37–40 ] Therefore, a visible light driven photo‐CRP was employed to obtain low molecular weight distribution of the SPE via an energy saving and green process. 4‐cyano‐4‐[[(dodecylthio)carbonothioyl]thio] pentanoic acid (CDTPA) was adopted as the chain transfer agent and diphenyl (2,4,6‐trimethylbenzoyl) phosphine oxide (TPO) was employed as the photoinitiator.…”

Light-intensity switch enabled nonsynchronous growth of fluorinated raspberry-like nanoparticles

“…As a result, a portion of PDMA-CTA would rst grow into uorinated polymers and lead to the generation of uorous particles via self-assembly. These particles would absorb PFS in solvent, subsequently provide uoropolymers with high molar masses due to the increased molar ratio of the monomer to growing chain, 42 and evolve into large particles during the relatively long-time polymerization. Meanwhile, the reaction between remaining PDMA-CTA and PFS dissolved in solvent would generate new uorous particles of small sizes, which would have time to further fuse with large ones (Fig.…”

“…[36][37][38][39] Motivated by the outstanding physicochemical properties of uoropolymers, 40,41 we have developed photo-RDRP of uorinated alkenes. 42,43 While the uorine-uorine (F-F) interaction has been adopted to generate various morphologies, [44][45][46][47] the preparation of uorinated RB particles remains unexploited. Recently, kinetic mediation by light intensity in photo-RDRP has been demonstrated by Boyer 24 and Miyake.…”

Recent Advances in Living Cationic Polymerization with Emerging Initiation/Controlling Systems

“…[ 48,51,66,67 ] As a “green” and low‐cost stimulus, light has been extensively investigated as an external trigger in CRP. [ 49,68–73 ] In contrast, living cationic photopolymerization has gained much less success due to the lack of effective initiating/controlling systems. [ 9 ] Recently, scientists have successfully combined the knowledge of photoinitiated cationic process and LCP to generate well‐defined polymers.…”