Evolution of surface chemistry and physical properties during thin film polymerization of thermotropic liquid crystalline polymers

By applying a novel thin film polymerization technique, X-ray photoelectron spectroscopy (XPS), and the Lifshitz-van der Waals acid-base (LWAB) theory, we have determined the time evolution of surface chemistry and surface free energy during the polymerization of liquid crystalline poly(p-oxybenzoate/2,6- oxynaphthoate) at a molar ratio of 50/50. The surface free energy components of these main-chain liquid crystalline copolyesters were calculated from contact angle measurements using a Ramé-Hart goniometer and a three-liquid procedure (water, glycerol, and diiodomethane). The experimental data suggest that the Lewis base parameter (γ ^-) during thin film polymerization decreases rapidly with the progress of polymerization, while the Lewis acid parameter (γ ⁺) and the Lifshitz-van der Waals parameter (γ ^LW) are almost invariant. The surface roughness data measured by atomic force microscopy (AFM) suggested that the increase in water contact angle (or the decrease in y-) was not caused by the change in surface roughness, but by the change in surface chemistry, i.e. due to the reaction of acetoxy and carboxy groups to release acetic acid during the polymerization reaction. In addition, the XPS results coincide with our previous Fourier transform infrared spectroscopy results showing that the condensation polymerization is much faster in the beginning than in the later stages. Consequently, the decrease in y-in the early stages of the polymerization is well explained.