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

ABSTRACT 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.