Thermodynamic framework for switching the lower critical solution temperature of thermo-sensitive particle gels in aqueous solvent

Abstract Switching the lower critical solution temperatures (LCSTs) of thermo-sensitive particle gels including poly(N-isopropylacrylamide) (PNIPAM), poly(N-diethylacrylamide) (PNDEAM), and poly(N-vinylcaprolactam) (PNVCL) was investigated in various aqueous solvents. Three prepared particle gels represented a single LCST in a pure water solution near human body temperature. By adding a chaotropic co-solvent, such as dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), to given gels in aqueous solution, the degree of influence on change of LCST was significantly different due to the difference in chemical structures. LCSTs of polymer solutions were affected by changing solvent conditions from pure water to mixed solvents. The LCST behaviors of linear PNIPAM, PNDEAM, and PNVCL in water/DMF or DMSO were determined by thermo-optical analysis (TOA), which supported the switchability of LCSTs in hydrogel systems. We used the photon correlation spectroscopy (PCS) technique to measure the switched LCSTs of hydrogel particles in mixed solvent systems. The switched LCSTs of the investigated systems exhibited a non-linear trend by varying co-solvent contents. A molecular thermodynamic framework, a combination of the modified double lattice with chain length dependence (MDL-CL) model and the Flory-Rehner (F-R) model, was utilized to describe and correlate the liquid-liquid equilibrium (LLE) and thermosensitive swelling behaviors between linear and cross-linked polymer solutions. With the addition of chaotropic co-solvents, a non-linear trend for phase behaviors of the three polymers was described after taking into account temperature and composition dependence on the association fraction ( η i j ) between the species. We assumed the donor-acceptor concept and competitive hydrogen bonding between polymer/water and water/co-solvent. The association fraction for the secondary lattice model was modified from an arbitrarily determined value to a physically meaningful value. Accordingly, the phase equilibrium of the amphiphilic polymers influenced by the structure-breaker characteristics of the co-solute was properly implemented in both experimental and modeling aspects.