Surface and Bulk Collapse Transitions of Thermoresponsive Polymer Brushes

We elucidate the sequence of events occurring during the collapse transition of thermoresponsive copolymer brushes based on poly(di(ethyleneglycol) methyl ether methacrylate) chains (PMEO₂MA) grown by atom-transfer radical polymerization (ATRP). The collapse of the bulk of the brush is followed by quartz crystal microbalance measurements with dissipation monitoring (QCM-D), and the collapse of its outer surface is assessed by measuring equilibrium water contact angles in the captive bubble configuration. The bulk of the brush collapses over a broad temperature interval ( 25 °C), and the end of this process is signaled by a sharp first-order transition of the surface of the brush. These observations support theoretical predictions regarding the occurrence of a vertical phase separation during collapse, with surface properties of thermoresponsive brushes exhibiting a sharp variation at a temperature of T_br^surf. In contrast, the bulk properties of the brush vary smoothly, with a bulk transition T_br^bulk occurring on average 8 °C below T_br^surf and 5 °C below the lower critical solution temperature (LCST) of free chains in solution. These observations should also be valid for planar brushes of other neutral, water-soluble thermoresponsive polymers such as poly(N-isopropylacrylamide) (PNIPAM). We also propose a way to analyze more quantitatively the temperature dependence of the QCM-D response of thermoresponsive brushes and deliver a simple thermodynamic interpretation of equilibrium contact angles, which can be of use for other complex temperature-responsive solvophilic systems.