On the abnormal “forced hydration” behavior of P(MEA-co-OEGA) aqueous solutions during phase transition from infrared spectroscopic insights

Abstract

Turbidity, DLS and FTIR measurements in combination with the perturbation correlation moving window (PCMW) technique and 2D correlation spectroscopy (2Dcos) analysis have been utilized to investigate the LCST-type transition of a oligo ethylene glycol acrylate-based copolymer (POEGA) in aqueous solutions in this work. As demonstrated in turbidity and DLS curves, the macroscopic phase separation was sharp and slightly concentration dependent. Moreover, individual chemical groups along polymer chains also display abrupt changes in temperature-variable IR spectra. However, according to conventional IR analysis, the C–H groups present obvious dehydration, whereas CO and C–O–C groups exhibit anomalous “forced hydration” during the steep phase transition. From these analyses together with the PCMW and 2Dcos results, it has been confirmed that the hydrophobic interaction among polymer chains drove the chain collapse and dominated the phase transition. In addition, the unexpected enhanced hydration behavior of CO and C–O–C groups was induced by forced hydrogen bonding between polar groups along polymer chains and entrapped water molecules in the aggregates, which originated from the special chemical structure of POEGA.