LCST Behavior of Symmetrical PNiPAm-<i>b</i>-PEtOx-<i>b</i>-PNiPAm Triblock Copolymers

Poly(N-isopropylacrylamide) (PNiPAm) and poly(2-ethyl-2-oxazoline) (PEtOx) represent two polymer types that are well-known for their lower critical solution temperature (LCST) behavior in aqueous media. To synthesize triblock copolymers containing both polymers, a crossover of two different polymerization methods was applied using a bifunctional initiator for the living cationic ring-opening polymerization (CROP) of EtOx. Quantitative end-functionalization with a trithiocarbonate resulted in a bifunctional PEtOx macro chain transfer agent (CTA). A series of well-defined PNiPAm-b-PEtOx-b-PNiPAm triblock copolymers were obtained by subsequent reversible addition–fragmentation chain transfer (RAFT) polymerization of NiPAm. The influence of the PNiPAm to PEtOx ratio on the thermoresponsive properties was intensively investigated via turbidimetry, dynamic light scattering, cryo transmission electron microscopy, and 1H NMR studies, revealing hydrogen bonds between both copolymer segments that strongly lower the phase separation temperature of aqueous solutions.