Visible‐Light‐Enabled Organocatalyzed Controlled Alternating Terpolymerization of Perfluorinated Vinyl Ethers

Abstract

Polymerizations of perfluorinated vinyl ethers (PFVEs) providea ni mportant category of fluoropolymers that have received considerable interests in applications.Inthis work, we report the development of an organocatalyzed controlled radical alternating terpolymerization of PFVEs and vinyl ethers (VEs) under visible-light irradiation. This method not only enables the synthesis of ab road scope of fluorinated terpolymers of lowdispersities and high chain-end fidelity,f acilitating tuning the chemical compositions by rationally choosing the type and/or ratio of comonomers,b ut also allows temporal control of chain-growth, as well as the preparation of avariety of novel fluorinated blockcopolymers. To showcase the versatility of this method, fluorinated alternating terpolymers have been synthesized and customized to simultaneously displayav ariety of desirable properties for solid polymer electrolyte design, creating new opportunities in high-performance energy storage devices.

Facile Control of Molecular Weight Distribution via Droplet‐Flow Light‐Driven Reversible‐Deactivation Radical Polymerization†

“…High‐throughput RDRPs have attracted considerable interests in recent years, because it dramatically promotes material screening by providing necessary substances in massive numbers and in short times. [ 26,44‐45 ] Based on our continuous interests in fluoropolymers, [ 46‐51 ] we carried out high‐throughput flow copolymerization using DMA and TFEA as modal comonomers under visible‐light irradiation with a computer‐aided four‐pumps setup (pump 1 for DMA, CTA 2 and PC, pump 2 for TFEA, CTA 2 and PC, pump 3 for hexane, pump 4 for N 2 , Figure S23). The initial [DMA]/ [TFEA] ratio and V hex / V DMSO ratio were precisely manipulated through a program by altering flow parameters ( i.e ., flow rates).…”

Scalable, Green Chain Transfer Agent for Cationic RAFT Polymerizations

“…[ 9‐10 ] Since these initial reports, several other researchers have developed similar cationic RAFT systems controlled by an external stimulus. [ 11‐13 ]…”