Photomediated Controlled Radical Homopolymerization of Sulfonated α‐Olefins and Vinyl Ethers with Propagating Sulfonyl Radicals

Herein, we present the photomediated controlled radical homopolymerization of sulfonyl-functionalized α-olefin and vinyl ether monomers, yielding sequence-controlled polysulfones. This unique radical polymerization process is facilitated by sulfonyl radicals regulated through photoinduced electron transfer-controlled radical polymerization (PET-CRP). The resultant ternary sequence-controlled polysulfones exhibit notably enhanced thermal stability compared to conventional alternating binary polysulfones. This study presents the first demonstration of radical polymerization mediated by propagating heteroatom-centered radicals, regulated by PET-CRP. This photo-mediated controlled radical polymerization offers novel approaches for synthesizing polymers with precise main chain sequences, structures, and controlled molecular weights, presenting promising candidates for advanced polymeric materials.