Dual Stimuli-Responsive Comb Polymers from Modular N-Acylated Poly(aminoester)-Based Macromonomers

We report the synthesis of dual-responsive N-acylated poly(aminoester) (NPAE)-based comb polymers with varying molecular composition and monomer sequence via a combination of spontaneous zwitterionic copolymerization and redox-initiated reversible addition-fragmentation chain transfer (RRAFT) polymerization. NPAE macromonomers were synthesized from different nucleophilic (M-N), for example, 2-ethyl-2-oxazoline (EtOx) or 2-ethyl-2-oxazine (EtOz), and electrophilic monomers (M-E), for example, acrylic acid (AA) or 2-carboxyethyl acrylate (CEA), to tune the hydrophilicity and sequence of the systems. The latter was found to influence the thermal properties and stability of the respective comb polymers. Turbidity investigations in aqueous solution revealed a dual-responsive behavior of the comb polymers being responsive to both temperature and pH changes due to co-carboxylic end groups of the NPAE-based macromonomers. Additional methylene groups in the NPAE backbone rendered the corresponding systems more hydrophobic and, hence, decreased the cloud point temperatures and, at the same time, increased the pH values (at constant temperature) at which the polymer phase separates from the aqueous solution.