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

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 (T_g) 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-C_4. 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.