Film Formation of Waterborne 2K Polyurethanes: Effect of Polyols Containing Different Carboxylic Acid Content

Abstract

While the interaction of NCO with carboxylic acids has been documented, a comprehensive knowledge of its effect on the film formation in a two-component waterborne polyurethane (2K-WPU) system is lacking. In this work, we synthesized a series of carboxyl-functional acrylic polyols (Mn ≈ 5000 g/mol, Đ ≈ 2.7, Tg ≈ 15 °C) of uniform diameter (120 nm) with varying amounts of methacrylic acid introduced into the latex. For 2K-WPU dispersions with a molar NCO/OH ratio of 1.3:1, we monitored particle size by dynamic light scattering and NCO consumption by FTIR. In the dispersion, we found that the particle size remained nearly constant, and the NCO was almost completely consumed after 2 days. Incorporating COOH in the polyol latex accelerated the consumption of NCO. We synthesized polyol samples labeled with donor and acceptor dyes for fluorescence resonance energy transfer (FRET) studies of polymer diffusion and molecular mixing. In films formed from the polyol latex in the absence of hmPIC, the COOH content of the polyols had no significant effect on the rate or extent of polymer diffusion. In contrast, in films formed from the 2K-WPU dispersions with a stoichiometric NCO/OH ratio (1.3:1), the extent of ET rapidly increased to the maximum value, showing that the full extent of molecular mixing of the two components can be accomplished in films. Thus, the hmPIC acts as a reactive plasticizer. In parallel experiments in which the hmPIC was labeled with the donor dye, we found evidence for partial mixing of the PIC and polyol in the dispersed state. We also showed that the rate of mixing of the hmPIC and the polyol in the films cast from these dispersions was accelerated by −COOH groups in the polyol.