PAA-b-PPO-b-PAA triblock copolymers with enhanced phase separation and inverse order-to-order phase transition upon increasing temperature

Enhanced phase separation and inverse order-to-order phase transition with increasing temperature was observed for a series of poly (acrylic acid)- b -poly (propylene oxide)- b -poly (acrylic acid) triblock copolymers with various block lengths by temperature-variable synchrotron small-angle X-ray scattering (SAXS). This abnormal phase behavior was attributed to the change of hydrogen (H)-bonding interaction in block copolymers upon increasing temperature and theoretically explained from thermodynamic viewpoint. The temperature-dependent FTIR analysis revealed that increasing temperature led to the weakening of overall H-bonding interactions and the increase of free C O and C–O–C groups. The Flory-Huggins interaction parameter χ of PAA and PPO blocks was positive and increased with increasing temperature as determined from the SAXS profiles of disordered block copolymer. The thermodynamic calculation indicated that the increase of Δ H was larger than the decrease of – T Δ S with increasing temperature because of the relatively large value of χ , leading to the increase of overall Δ G mix and hence the enhanced phase separation at higher temperature.