Effects of cosolvent partitioning on conformational transitions and tethered chain flexibility in spherical polymer brushes†
In this work, based on the framework of preferential adsorption concept and analytical self-consistent field (SCF) theory, a model is proposed to investigate the reentrant transition experimentally observed from the thermoresponsive spherical brush in a series of aqueous alcohol solutions. The interaction between monomers is incorporated into the model. Conformational transitions of the spherical brush are quantitatively correlated to the physical parameters, including the number of adsorbed cosolvents which facilitates the solvent quality, the number of cosolvent bridges which drives the brush collapse, as well as their partition coefficients between the brush and the bulk solution. An analytical formula for the number of Kuhn segments per tethered chain is obtained based on the analytical SCF theory, which elucidates the flexibility of tethered chains in the intricate system of multicomponents involving the conformational transitions. Under the experimental conditions associated with the cosolvent–brush interaction, the variation of the monomer chemical potential with the monomer concentration indicates that the monomer distribution of the spherical brush remains continuous. The analysis based on the SFC theory also reveals that the distribution of adsorbed cosolvents is a positive parabola while the distribution of cosolvent bridges appears to be an exponential decay function, implying that the intervening space between tethered chains, rather than the number of adsorbed cosolvents, plays a crucial role in forming the cosolvent bridge. We demonstrate that the model formulated for the reentrant transition under weaker cosolvent–brush interactions provides guidelines for the one under stronger nanoparticle–brush interactions.