Ambient temperature self-blowing mimosa tannin-based non-isocyanate polyurethane (NIPU) rigid foam was produced, based on a formulation of tannin-based non-isocyanate polyurethane (NIPU) resin. A citric acid and glutaraldehyde mixture served as a blowing agent used to provide foaming energy and cross-link the tannin-derived products to synthesize the NIPU foams. Series of tannin-based NIPU foams containing a different amount of citric acid and glutaraldehyde were prepared. The reaction mechanism of tannin-based NIPU foams were investigated by Fourier Trasform InfraRed (FT-IR), Matrix Assisted Laser Desorption Ionization (MALDI-TOF) mass spectrometry, and ¹³C Nuclear Magnetic Resonance (¹³C NMR). The results indicated that urethane linkages were formed. The Tannin-based NIPU foams morphology including physical and mechanical properties were characterized by mechanical compression, by scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). All the foams prepared showed a similar open-cell morphology. Nevertheless, the number of cell-wall pores decreased with increasing additions of glutaraldehyde, while bigger foam cells were obtained with increasing additions of citric acid. The compressive mechanical properties improved with the higher level of crosslinking at the higher amount of glutaraldehyde. Moreover, the TGA results showed that the tannin-based NIPU foams prepared had similar thermal stability, although one of them (T-Fs-7) presented the highest char production and residual matter, approaching 18.7% at 790 °C.

The structural changes during three-step synthesis of low-molar ratio urea–formaldehyde (UF) resin were tracked by quantitative ¹³C nuclear magnetic resonance (¹³C NMR) analysis and electrospray ionization-mass spectrometry (ESI–MS). Condensations that produced polymers were found to be linked by ether bonds in addition to hydroxymethylation reactions at the first alkaline stage with a formaldehyde to urea ratio of 2:1. Considerable formation of branched methylene linkages, with the highest content among all the condensed structures, was the key feature of the acidic stage. Notable changes were observed for the chemical structures and molecular masses of the resin components after the formaldehyde to urea molar ratio was lowered to 1.2 by adding post-urea at the final alkaline stage. Specifically, most of the branched hydroxymethyl groups on the polymers were cleaved, resulting in a significant decrease in the branching degree of the polymers. The performance degradation of the UF resin was attributed to this debranching effect and the production of components with low molecular masses. Based on the observations, the curing pattern of low molar ratio UF resin was postulated and branched polymeric formaldehyde catcher bearing urea-reactivity was proposed.