Reversible Patterning Cross-Linked, Humidity-Responsive Polymer Films with Programmatically and Accurately Controlled Deformation

A series of novel humidity-responsive and photosensitive polymer films (PCA–PAA–PEG) are prepared. These films can be patterning cross-linked by the photodimerization of coumarin pendant groups. The humidity-induced deformation can be well controlled by the pattern because of the different modulus and hydrophilicity between cross-linked and un-cross-linked segments. In addition, the pattern can be erased and the deformation direction can be changed programmatically by the de-cross-linking–re-cross-linking approach due to the reversible photodimerization of coumarin groups. The cross-linking degree also affects the humidity responsiveness of the film. The deformation of the gradient patterning cross-linked film can be more accurately controlled. Moreover, the length and width ratio (L/Ws/Wh) of the un-cross-linked segment to the cross-linked segment affects the deformation of the films as well. When L/Ws/Wh is 5/2/1 or 5/3/1, the deformation is controllable, and when L/Ws/Wh is 5/1/1 or 5/4/1, the deformation is random at the initial stage, but the whole film will bend along the short axis in the end.