Waterborne 2-component polyurethane coatings based on acrylic polyols with secondary alcohols

We report the effects of increasing the molecular weight of a secondary alcohol-based polyol in a two-component waterborne polyurethane (2 K-WB-PUR) formulation. The system consists of an acrylic polyol latex and a water-dispersible polyisocyanate (hmPIC, Basonat HW1000 from BASF). The polyols investigated incorporated hydroxypropyl methacrylate as a comonomer to introduce the secondary –OH groups, in contrast to typical polyols which have primary -OH groups. Three molecular weights of this polyol were prepared (Mn ≈ 5100, Р= 2.4; 10,300, Р= 2.7; or 12,900 g/mol, Р= 3.6) with a uniform Tg (∼20 °C) and hydrodynamic diameter (dh) ≈ 120 nm. The polyol and polyisocyanate were mixed with a molar NCO:OH ratio of 1.3:1. The particle size of the mixed dispersion was monitored by dynamic light scattering. The 5 K sample remained stable in dispersion over 7 days whereas the higher molecular weight formulations flocculated after 1 day. Fourier Transform Infrared (FTIR) measurements revealed that all NCO groups were consumed within 15–23 h for all dispersed samples. Fluorescence resonance energy transfer (FRET) experiments were carried out on samples in the dispersed state as well as on films formed from these dispersions. Very little molecular level mixing was observed in the dispersed phase for the samples. In the films, a large extent of mixing was observed in the 5 K sample whereas the extents of mixing for the higher molecular weight samples were reduced. The FTIR measurements recorded as the films formed showed that the NCO consumption in the 5 K film (t1/2 = 56 h) was comparable to an analogous 2 K-WB-PUR formulation based on a 5 K primary alcohol from a previous study. Surprisingly, the NCO consumption in the higher molecular weight samples was faster (t1/2 = 31, 32 h). We found that the composition of the resulting films formed from higher molecular weight polyols contained a greater relative ratio of polyurea to polyurethane.