Concurrent ATRP and degenerative transfer enable controlled emulsion polymerizations in diverse surfactant systems

Herein, we report the concurrent Atom Transfer Radical Polymerization and Degenerative Transfer (ATRP/DT) of butyl methacrylate (BMA) in emulsions containing anionic, cationic, nonionic, and zwitterionic surfactants. Cyclic voltammetry confirmed the stability of the hydrophilic [Cu II TPMA] 2+ catalyst with these surfactants, and the ( K S u r f I I K S u r f I ) affinity constant was determined for the anionic and zwitterionic surfactants. Ionic surfactants (except sodium dodecylbenzene sulfonate) provide optimal polymerization control and the most stable latexes. ATRP/DT outperformed ATRP and RAFT when cocamidopropyl betaine, sodium cocoamphoacetate, Brij-98, and cetyltrimethylammonium bromide were used. To solve the partitioning of the chain transfer agent in emulsions, we introduce ATRP/DT in miniemulsion, which accelerates polymerization and improves control with anionic and zwitterionic surfactants with either the chain transfer agent or its disulfide precursor. The method yields poly(n-butyl methacrylate) (PBMA) with high conversions (up to 99 %), low dispersities ( Đ = 1.09–1.33), and preserved chain-end fidelity; PBMA prepared with cationic, nonionic, and zwitterionic surfactants exhibited living characteristics, extending the accessibility of well-defined polymers via aqueous emulsions to industrially relevant surfactant types. This work demonstrates that ATRP/DT is a versatile and unconventional strategy for polymerization in emulsions, providing access to polymers across various surfactant systems.