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

Abstract

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.