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

Abstract 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 ΔH was larger than the decrease of –TΔS with increasing temperature because of the relatively large value of χ, leading to the increase of overall ΔGmix and hence the enhanced phase separation at higher temperature.