RAFT-engineered polymeric surfactant: Exploring the self-assembly of homopolymers from poly(ethylene glycol) methyl ether methacrylate

Polymeric surfactants, valued for their ability to stabilize interfaces and tunable self-assembled structures, find extensive applications in personal care, drug delivery, pharmaceuticals, and industrial formulations. To develop an efficient polymeric surfactant, herein we investigate the synthesis and characterization of side-chain poly(ethylene glycol) (PEG)-based homopolymers (PPEGMAx), using reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of a hydrophobic tail-functionalized chain transfer agent (CTA), enabling precise control over molar mass and narrow dispersity (Đ). Structural confirmation and compositional analysis are performed using ¹H nuclear magnetic resonance (¹H NMR) spectroscopy. The amphiphilic nature and self-assembly behavior of the polymers are investigated through fluorescence spectroscopy, dynamic light scattering (DLS), and atomic force microscopy (AFM). The polymers show critical aggregation concentrations in the range 27–63 μg/mL in water, with sizes ranging from 40 to 80 nm. However, a suitable hydrophobic/hydrophilic balance in the polymer structure is necessary for the aggregation behavior to develop their potential as polymeric surfactants.