Associative properties of poly(ethylene glycol)-poly(vinyl acetate) comb-like graft copolymers in water

The self-assembly of amphiphilic graft copolymers is generally reported for polymer melts or polymers deposited onto surfaces, while a small number of cases deal with binary mixtures with water. We report on the associative properties of poly(ethylene glycol)-graft-poly(vinyl acetate) (PEG-g-PVAc) comb-like copolymers in water, demonstrating the existence of a percolative behaviour when increasing the PEG-g-PVAc content. Rheology, light- and small-angle X-ray scattering experiments, together with dissipative particle dynamics simulations, reveal a progressive transition from spherical polymer single-chain nanoparticles (SCNPs) towards hierarchically complex structures as the weight fraction of the polymer in water increases. The ability of PEG-g-PVAc to attain different nano- and microstructures is of great importance in numerous applications such as in the fields of cosmetics, detergency and drug delivery.