Film Formation of High T_g Latex Using Hydroplasticization: Explanations from NMR Relaxometry

The film formation of acrylic latex dispersions, containing different amounts of carboxylic acid functional groups by the incorporation of methacrylic acid (MAA), was studied with GARField ¹H NMR at various relative humidities (RH). Polymer particles with glass-transition temperatures in the range from 26 to 50 °C formed films at room temperature because of hydroplasticization. It was found that with an increased drying rate due to lower RH, the evaporation flux of water was limited by the latex polymer. Only in the second stage of drying this phenomenon was more obvious with increasing MAA content. ¹H NMR relaxometry was used to study the change of hydrogen mobilities during film formation and hardening of the films. This showed that the drying rate itself had no impact on the hydrogen mobility in the latex films as measured via the T₂ relaxation time. Hydrogen mobilities of water and the mobile polymer phase only significantly decrease after most water has evaporated. This implies that the rigidity of the polymers increases with the evaporation of water that otherwise plasticizes the polymer through hydrogen bonding with the carboxylic acid groups. This hardening of the polymer phase is essential for applications in a coating. The hydrogen mobilities were affected by the MAA concentration. Densities of mobile hydrogens increase with increasing MAA content. This is expected if the mobile protons are contained in the MAA groups. The result thus confirms the role of carboxylic acid groups in hydrogen bonding and plasticization of the copolymers. Hydrogen mobilities, however, decrease with increasing MAA content, which is hypothesized to be caused by the formation of dimers of carboxylic acid groups that still hold water. They still enable short-range polymer hydrogen mobility due to hydroplasticization but limit long-range polymer mobility due to interaction between the carboxylic acid groups.