Order-Order Transition in Statistical Copolymer Thin Film Induced by LCST-Type Behavior

In this paper, we describe the formation of an ordered structure in a copolymer thin film through hydration, which subsequently transitions to a different ordered structure upon dehydration. A statistical copolymer of poly(N-octadecyl acrylamide-stat-hydroxymethyl acrylamide) with a comonomer content ratio of 1:1, denoted as p(ODA50/HEAm50), was synthesized via free radical copolymerization. We prepared a thin film of this copolymer on a solid substrate and annealed it at 60 °C under humid conditions. This treatment formed a side-chain segregated lamellar (SCSegL) structure, in which the ODA and HEAm units are oriented perpendicularly to the polymer backbone and opposite each other. Increasing the annealing temperature to 90 °C led to a transition to a side-chain mixed lamellar (SCMixL) structure, where the ODA and HEAm units are also oriented perpendicularly to the polymer backbone but in both directions. The quartz crystal microbalance (QCM) data indicate that p(ODA50/HEAm50) exhibits LCST-like behavior with a transition temperature of approximately 50 °C. We conclude that the formation of the SCSegL structure at 60 °C is due to pronounced segregation between the water-adsorbed HEAm groups and the hydrophobic ODA. Conversely, dehydration at 90 °C reduces the segregation forces, forming the SCMixL structure, which exhibits lower strain. These results demonstrate that the p(ODA50/HEAm50) film undergoes an order-to-order transition driven by the hydration-dehydration process. Additionally, we found that changes in the lamellar structure significantly alter the swelling properties of the film.