Volume Phase Transition Mechanism of Poly[di(ethylene glycol)ethyl ether acrylate]-Based Microgels Involving a...

The microdynamic volume phase transition mechanism of poly[di(ethylene glycol)ethyl ether acrylate] (PDEGA)-based microgels with newly developed thermoresponsive polyionic liquid (PIL) (poly(tetrabutylphosphonium styrenesulfonate) P[P_4,4,4,4][SS]) moieties was studied by applying temperature-variable Fourier transform infrared (FTIR) spectroscopy in combination with two-dimensional correlation spectroscopy (2Dcos) and the perturbation correlation moving window (PCMW) technique. It can be found that the content of hydrophilic PIL moieties plays a significant role in the thermally induced phase transition behavior of microgel systems; namely, the microgels containing fewer PIL moieties present a sharp transition behavior and a gel-like state (10%, w/v) in water whereas the microgels with more PIL moieties undergo a slightly broad phase transition process and a flowable solution state. Herein, the C═O···D₂O-PIL hydrogen bonds as the interaction between PDEGA and P[P_4,4,4,4][SS] moieties result in a complete dehydration process for the microgels with fewer PIL moieties and the dehydrated behavior of SO₃^- groups acts as the driving force during the phase transition. As for the microgels with more PIL moieties, the whole transition process is dominated by the hydrophobic interaction of C-H groups. Even though the intermolecular hydrogen bonds (C═O···D₂O-PIL) appear as well, the more remarkable effect of the Coulombic repulsive force of PIL restrains the water molecules from breaking away, thus causing a gradual and incomplete dehydration process during heating.