Soluble–Insoluble–Soluble Transitions of Thermoresponsive Cryptand-Containing Graft Copolymers

[Image: see text] Cryptand-containing alternative copolymers were first made from copolymerization of styrenic derivatives and maleic anhydride and then chemically modified in this work by grafting methoxy poly(ethylene glycol) (MPEG) onto the maleic functional groups. These graft copolymers show interesting multistep soluble–insoluble–soluble (S–I–S) transitions in acidic aqueous media at a cloud point (T(cp)) and a subsequent mixing temperature (T(mix)). Turbidity measurements and dynamic light scattering studies indicate that such complex transitions may be attributed to the entropic contribution associated with the dehydration and aggregation of the MPEG groups and then the enthalpic contribution associated with the hydrogen bonding between ethylene glycol and carboxylic acid groups. More importantly, the phase transition temperatures and insoluble temperature ranges are very sensitive to changes in subtle hydrophobic–hydrophilic balance of the copolymers, such as the variation of pH, the cryptand size, and the length of the MPEG graft. The understanding of the S–I–S transition in relation to the structure of the copolymers and the external conditions may be useful in the design of smart materials and sensors.