Synthesis, UV-curing Behavior and Surface Properties of New Fluorine-containing Aromatic Oxetane Monomers

摘要

In this paper, we combined high-end cationic UV-curable material with fluorinated chain obtaining a series of new fluorine-containing aromatic oxetane monomers via a mild nucleophilic substitution reaction. The structures and properties of monomers were characterized using ~1 H-NMR, ^(19) F-NMR, dynamic viscosity tests and differential scanning calorimetry(DSC). It was determined that all of the fluorinated monomers obtained had much lower viscosity and higher thermostability after the introduction of hexafluorobenzene. Then, UV-curable coatings were prepared using four fluorine-containing aromatic oxetane monomers(FOX1-4); the UV-curing kinetics, with three kinds of initiators, and properties of the cured films were evaluated using real-time Fourier transform infrared(FTIR) spectroscopy, water and diiodomethane contact angle tests, surface energy calculations and scanning electron microscopy(SEM). The FTIR spectroscopy results showed that the coatings possessed excellent conversion rate(> 99% with liquid initiator PAG-201 in 150 s), and as the fluorine content increased, the monomers exhibited decreased mobility with the increasing viscosity and worse solubility with fluorinated monomers, resulting in a lower conversion rate. Moreover, the coatings possessed favorable hydrophobic and oleophobic properties and low surface energies owing to the fluoride chains floating to the membrane-air interface, which was also confirmed by discrete concave structures in SEM images. These new kinds of monomers can replace traditional fluorinated cationic monomers applied to the fingerprint resistant, fouling resistant, scratch resistant and anti-aging coatings, adhesives or printing ink materials.