Temperature-responsive polymers and brushes with tunable onset of response

Temperature-responsive polymers are of high interest in the scientific field of stimuli responsive materials, in particular water soluble polymers with a response at $\sim$36.5$^{o}$C. However, difficulties in tailoring this T-response, as illustrated for example from studies of PNIPAM in numerous functionalized and copolymer forms, has hampered their proliferation. Here we present a systematic series of temperature-responsive polymers, which were designed, synthesized, and studied, and we show that we can tailor with high sensitivity their onset of T-response via the design of their monomer. Specifically, we demonstrate lower critical solution temperature (LCST) in water finely tuned between 5 and 70$^{o}$C, by controlling the hydrophilic/hydrophobic balance in the monomer (closely following predictions of phase behavior theories). In addition, we will also show that these polymers maintain their T-responsive characteristics when end-tethered to solid surfaces, over a wide range of grafting densities in combinatorial brushes. This approach allows for controlling contact angle, adhesion and tackiness as a function of temperature.