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 (MN), for example, 2-ethyl-2-oxazoline (EtOx) or 2-ethyl-2-oxazine (EtOz), and electrophilic monomers (ME), 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 ω-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.

N-Acylated poly(aminoester) (NPAE) macromonomers were synthesised via spontaneous copolymerisation of 2-oxazolines and acrylic acid. Inherent quantitative introduction of α-vinyl end-groups was observed, which enabled the preparation of a series of well-defined NPAE comb polymers through redox-initiated RAFT polymerisation. Investigations of the thermal properties of the comb polymers revealed similarities to poly(2-oxazoline) based systems.

N-Acylated poly(aminoester) (NPAE) macromonomers were synthesised via spontaneous copolymerisation of 2-oxazolines and acrylic acid. Inherent quantitative introduction of α-vinyl end-groups was observed, which enabled the preparation of a series of well-defined NPAE comb polymers through redox-initiated RAFT polymerisation. Investigations of the thermal properties of the comb polymers revealed similarities to poly(2-oxazoline) based systems.