Effect of α-substituents on molecular motion and wetting behaviors of poly(fluoroalkyl acrylate) thin films with short fluoroalkyl side chains

•Bulky α-substituent enhances water repellency of poly(fluoroalkyl acrylate).•The water and oil repellency was attributed to the low main chain mobility.•The water repellency was kept below the surface glass transition temperature.

The effect of α-substituent on the molecular motion and wetting behavior of poly{2-(perfluorobutyl)ethyl acrylate} [PFA-C4], poly{2-(perfluorobutyl)ethyl methacrylate} [PFMA-C4], poly{2-(perfluorobutyl)ethyl α-fluoroacrylate} [PFFA-C4], and poly{2-(perfluorobutyl)ethyl α-chloroacrylate} [PFClA-C4] films were characterized by dynamic contact angle measurement, lateral force microscopy (LFM), wide angle X-ray diffraction (WAXD), and X-ray photoelectron spectroscopy (XPS). WAXD of oriented PFClA-C4 fiber suggested the presence of rod-like chain due to the presence of bulky α-substituent. The glass transition temperature (Tg) of PFFA-C4 and PFClA-C4 were well above the room temperature. The water repellencies of PFFA-C4 and PFClA-C4 were as high as that of PFMA-C4 and their oil repellency of PFFA-C4 and PFClA-C4 was higher than the PFMA-C4. This result was originated from the low main chain mobility of PFFA-C4 and PFClA-C4 due to the presence of bulky α-substituents. The effect of molecular motion on water repellency was clarified by the results of temperature dependence studies of dynamic contact angle, LFM, and surface chemical composition measured by XPS.

Graphical abstractDownload high-res image (213KB)Download full-size image