Stimuli-Responsive Films Based on N-Substituted Polyurethane with Different Alkyl Length

N-Alkyl-substituted polyurethanes with different alkyl chain lengths were prepared from the corresponding bromoalkane (1-bromooctane, 1-bromotetradecane, and 1-bromooctadecane) and polyurethane consisting of poly(propylene glycol) (PPG), 4,4′-diphenylmethane diisocyanate, and 1,4-butanediol. The synthesised materials were characterised by 1H NMR and FTIR spectroscopy and the degrees of substitution were discussed by changing the reaction conditions. Differential scanning calorimetry and X-ray diffraction were used to characterise the thermal properties and crystalline state. Microphase-separated nanostructures, with hard segments (nanofibre-like) embedded into amorphous PPG soft segments, are observed by atomic force microscopy and scanning electron microscopy. A reversible behaviour of the films was revealed by contact angle measurement. Stimuli-responsive films were realised by solvent vapour annealing and heat treatment, and exhibited a reversible switching in surface wettability with a remarkable change in the water contact angle of 21°.