Distinct Cation–Anion Interactions in the UCST and LCST Behavior of Polyelectrolyte Complex Aqueous Solutions
Zhangxin Ye, Shengtong Sun, Peiyi Wu
Abstract
) of poly(styrenesulfonate) (PSS)/poly(diallyldimethylammonium) (PDADMA) PEC in the same saline solution, in addition to previously reported lower critical solution temperature (LCST), we experimentally observed the upper critical solution temperature (UCST)-type phase transition behavior of PSS/PDADMA PECs at a lower polymer concentration. As elucidated by temperature-dependent Raman spectroscopy and two-dimensional correlation analysis, at temperatures lower than UCST, more hydrophobic polyelectrolyte chains lead to a high proportion of contact ion pairs (CIPs), contributing to UCST-type solid-liquid phase transition; however, at higher concentrations of PEC, the less hydrophobic polyelectrolyte chains correspond to a higher proportion of solvent-separated ion pairs (SIPs), which enables the occurrence of LCST-type liquid-liquid phase transition. With the spectroscopic indicator of CIPs/SIPs peak ratio and monitoring the hydration state of polymer chains, the complex interplays of PSS/PDADMA PECs are hereby interpreted at the molecular level, which lays the mechanistic foundation for designing other thermoresponsive PEC assemblies.