Double thermoresponsive graft copolymers with different chain ends: feasible precursors for covalently crosslinked hydrogels.

The tailored synthesis of graft copolymers from acrylic and methacrylic monomers can be accomplished solely through photoiniferter reversible addition-fragmentation chain transfer (RAFT) polymerization. Samples with poly[oligo(ethylene glycol) methacrylate] (POEGMA) backbones synthesized under green light irradiation and poly(N-isopropylacrylamide) (PNIPAM) side chains growing under blue light irradiation are presented. As monitored by temperature-dependent dynamic light scattering (DLS) measurements and temperature-variable nuclear magnetic resonance (NMR) spectroscopy, the architecture of the graft copolymers allows unique two-step lower critical solution temperature (LCST) transitions in aqueous solutions. Meanwhile, different end-groups introduced by the corresponding RAFT agents affect the detailed thermoresponsive behavior remarkably. This RAFT strategy shows more advantages when the multiple trithiocarbonate groups are converted into thiol reactive pyridyl disulfide (PDS) groups via a facile post-polymerization modification. The PDS-terminated graft copolymer can then be regarded as a usable precursor for various applications, such as thermoresponsive hydrogels.

Nonionic UCST-LCST Diblock Copolymers with Tunable Thermoresponsiveness Synthesized via PhotoRAFT Polymerization.

Nonionic double thermoresponsive diblock copolymers with both upper critical solution temperature (UCST) and lower critical solution temperature (LCST) phase transitions are synthesized via eco-friendly photoiniferter reversible addition-fragmentation chain transfer polymerization. While the biocompatible random copolymer of di(ethylene glycol) methyl ether methacrylate and oligo(ethylene glycol) methacrylate accounts for the LCST transition, the block of polymethacrylamide from an easily accessible monomer with low health hazard is responsible for the UCST transition. Temperature-dependent dynamic light scattering measurements confirm the formation of micellar aggregates in water at the temperatures below UCST- and above LCST-type cloud points. Additionally, the temperature interval between UCST and LCST, where both blocks are dissolved, can be tailored by varying the comonomer ratio in the random copolymer block. With these unique advantages, the presented work introduces a new polymer system for the design of schizophrenic polymers.