Well-Defined Poly(sulfobetaine) Brushes Prepared by Surface-Initiated ATRP Using a Fluoroalcohol and Ionic Liquids as the Solvents

Surface-initiated atom transfer radical polymerization (ATRP) of 2-(<i>N</i>-2-methacryloyloxyethyl-<i>N</i>,<i>N</i>-dimethyl) ammonatoethanesulfonate) (MAES), 3-(<i>N</i>-2-methacryloyloxyethyl-<i>N</i>,<i>N</i>-dimethyl) ammonatopropanesulfonate) (MAPS), and 4-(<i>N</i>-2-methacryloyloxyethyl-<i>N</i>,<i>N</i>-dimethyl) ammonatobutanesulfonate) (MABS) was carried out in 2,2,2-trifluoroethanol (TFE) containing a small amount of 1-hexyl-3-methylimidazolium chloride at 60 °C to produce well-defined poly(sulfobetaine) brushes and the corresponding free polymers with predictable number-average molecular weight (<i>M</i><sub>n</sub>, 1 × 10<sup>4</sup> to 3 × 10<sup>5</sup> g mol<sup>−1</sup>) and narrow molecular weight distributions (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> < 1.2). A first-order kinetic plot for ATRP of MAPS revealed a linear relationship between the monomer conversion index (ln([M]<sub>0</sub>/[M])) and polymerization time. The polymerization rates decreased with increasing ionic liquid concentration. The <i>M</i><sub>n</sub> of poly(MAPS) increased in proportion to the conversion. The sequential polymerization of MAPS initiated with the chain ends of poly(MAPS) produced the postpolymer with quantitative efficiency. The thickness of the polymer brush was controllable from 5 to 100 nm based on the <i>M</i><sub>n</sub> of the polymer. The polymer brush was cleaved from the silicon substrate under the acidic condition to measure the molecular weight by size exclusion chromatography equipped with a multiangle light scattering detector (SEC-MALS). We have confirmed that the molecular weight distribution of polymer brush was also narrow (<i>M</i><sub>n</sub> = 150 000, <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> =1.26) as well as the corresponding free polymer. These results suggest the successful control of the polymerization of sulfobetaine-type methacrylates owing to the TFE and ionic liquids. In particular, the high affinity of TFE for the sulfobetaine monomers and polymers yielded a homogeneous polymerization media to improve surface-initiated polymerization generating the polymer brushes on the substrate surface as well as the free polymers formed in the solution. The effect on ATRP of the chemical structure of ionic liquids and ligands for copper catalyst was also investigated.