Hydrophilic Poly(meth)acrylates by Controlled Radical Branching Polymerization: Hyperbranching and Fragmentation

Topology significantly impacts polymer properties and applications. Hyperbranched polymers (HBPs) synthesized via atom transfer radical polymerization (ATRP) using inimers typically exhibit broad molecular weight distributions and limited control over branching. Alternatively, copolymerization of inibramers (IB), such as α-chloro/bromo acrylates with vinyl monomers, yields HBPs with precise and uniform branching. Herein, we described the synthesis of hydrophilic HB polyacrylates in water by copolymerizing a water-soluble IB, oligo(ethylene oxide) methyl ether 2-bromoacrylate (OEOBA), with various hydrophilic acrylate comonomers. Visible-light-mediated controlled radical branching polymerization (CRBP) with dual catalysis using eosin Y (EY) and copper complexes resulted in HBPs with various molecular weights (M _n = 38 000 to 170 000) and degrees of branching (2%-24%). Furthermore, the optimized conditions enabled the successful application of the OEOBA to synthesize linear-hyperbranched block copolymers and hyperbranched polymer protein hybrids (HB-PPH), demonstrating its potential to advance the synthesis of complex macromolecular architecture under environmentally benign conditions. Copolymerization of hydrophilic methacrylate monomer, oligo(ethylene oxide) methyl ether methacrylate (OEOMA₅₀₀), and inibramer OEOBA was accompanied by fragmentation via β-carbon C-C bond scission and subsequent growth of polymer chains from the fragments. Furthermore, computational studies investigating the fragmentation depending on the IB and comonomer structure supported the experimental observations. This work expands the toolkit of water-soluble inibramers for CRBP and highlights the critical influence of the inibramer structure on reaction outcomes.