Fluoro-silsesquioxane-urethane hybrid for thin film applications

New fluoropolyurethane hybrids containing fluorinated polyhedral oligomeric silsesquioxane were synthesized for thin film applications using fluoro(13) disilanol isobutyl-POSS (FluoroPOSS) and a short chain fluorodiol and diisocyanate. The kinetics of the urethane reaction was monitored using Fourier transform infrared spectroscopy (FTIR) and the formation of urethane was confirmed using (29)Si Nuclear magnetic resonance spectroscopy (NMR). The effect of addition of FluoroPOSS either in the I step or II step of the two step polymerization reaction is evaluated using various spectroscopic, thermal, microscopic, and diffraction techniques. In general, the major shortcoming of the lack of flexibility of fluoropolyurethane from short chain diol and diisocyanate has been overcome by the use of tethered FluoroPOSS. X-ray photoelectron spectroscopy (XPS), atomic force microscpopy (AFM), and contact angle measurements on the hybrid thin films on silicon wafer demonstrate the migration of FluoroPOSS segment to the air-thin film interface when FluoroPOSS is used in I stage reaction, and it resides at the interface when used as a chain extender. However, in both cases, the formed thin film exhibits ultrahydrophobicity with water contact angle of approximately 107 degrees and low contact angle hysteresis and solvent resistance, which are preferable for protective thin film applications.