Co-Nonsolvency Effects for Surface-Initiated Poly(2-(methacryloyloxy)ethyl phosphorylcholine) Brushes in Alcohol/Water Mixtures

Surface-initiated atom transfer radical polymerization (SI-ATRP) has been used to grow brushes of poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) from silicon wafers using a polyelectrolytic macroinitiator on planar silicon wafers. Film thicknesses of up to 450 nm were possible within 21 h, and the effect of adding activator and deactivator species on the brush growth rate was studied. The solvation of PMPC brushes in mixed alcohol/water solvents was investigated using in situ ellipsometry. Co-nonsolvency (a re-entrant swelling transition) behavior was observed in water/ethanol binary mixtures; that is, the PMPC brushes were highly swollen in either pure ethanol or water but became deswollen at specific ethanol-rich solvent compositions. A similar effect was obtained with water/2-propanol mixtures, except that in this case pure 2-propanol was not a particularly good solvent for the PMPC chains. However, co-nonsolvency was not observed for water/methanol binary mixtures, since the brushes remained well swollen at all solvent compositions. This is consistent with prior reports of co-nonsolvency effects in both PMPC gels and linear PMPC chains. However, this is the first report of this phenomenon for PMPC brushes and one of the first examples of co-nonsolvency observed for any polymer brush system. A direct comparison of brush and gel swelling reveals an approximate power-law relationship between the equilibrium volumes of these two systems at various solvent compositions, which is interpreted by treating the brush layer as a surface-attached gel. We believe this to be the first quantitative comparison of brush and gel swelling using the same polymer under the same conditions. The kinetics of the PMPC brush response to adjustment of the alcohol/water composition is relatively fast, with the brush volume change occurring on time scales of less than 1 min as judged by in situ ellipsometry.