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This study focuses on the competition reaction rules of a system containing resorcinol (as a tannin model compound) and dimethylol urea (as a urea–formaldehyde resin model compound) under various alkaline and acidic environments. The aim is to investigate the crosslinked modification mechanism of urea–formaldehyde resin with tannin adhesive. The study delves into the competitive relationship between self-condensation polymerization reactions and co-condensation polymerization reactions. It specifically highlights the conditions for the copolycondensation reaction of dimethylolurea and resorcinol and validates its rationality through an examination of the resorcinol–urea–formaldehyde system's reaction rules. The results show that (1) under strongly acidic conditions, the activity of carbocation intermediates produced by hydroxymethyl resorcinol for the resorcinol phenol ring is higher than the electrophilic reactivity of nitrogen atoms on hydroxymethyl urea, which is more beneficial for the resorcinol–formaldehyde self-polycondensation reaction, and the co-polycondensation structures do not play a dominant role. (2) Under weakly acidic conditions, the co-polycondensation structures are evidently advantageous over self-polycondensation structures, and the degree of the co-polycondensation reaction is positively correlated with pH below the neutral point of resorcinol. (3) Under alkaline conditions, the self-polycondensation between resorcinol and formaldehyde is dominant in the system. (4) The concentration of hydroxymethyl urea carbocation is the key factor to determine the degree of the co-polycondensation reaction. [ABSTRACT FROM AUTHOR]

Two types of urea–formaldehyde (UF) resin adhesives were synthesized with standard formaldehyde solution with 37% concentration and concentrated formaldehyde solution with 45% concentration. For 37% formaldehyde, 10% methanol was used as an inhibitor. For 45% formaldehyde, no more methanol was added. The chemical structure and changes during the resin preparation were analyzed. The performance of particleboards prepared with these resins was evaluated. The results indicated that the main difference between the concentrated formaldehyde and the standard formaldehyde was the higher content of methanol in the latter. Methanol affected the reaction during the preparation of UF resins and the final performance of the resins. Samples of the UF resin with standard formaldehyde taken at different stages during its preparation showed different contents of methylol groups, methylene ether bonds, uron structure, methylene bonds, and other groups compared to the resin prepared from concentrated formaldehyde. The performance concerning water resistance, mechanical performance, and formaldehyde emission of the particleboards prepared with the UF resin with concentrated formaldehyde was better than that with the resin with standard formaldehyde. [ABSTRACT FROM AUTHOR]

The urea-formaldehyde (UF) reaction under strong alkaline condition was investigated by using quantitative analysis of 13C NMR. The main reaction products were methylolureas and oligomers linked by ether bonds at the beginning stage. With the reaction undergoing, the methylene linkages began to be formed and become predominant at the end point. The conversion of linear methylene ether bond to methylene linkage was also observed. These features were also observed previously for the reaction under acidic condition. It was found that the cyclic ether structure (uron) is much more stable than the linear ether bond, and its stability is second only to the methylene linkages among all the condensed structures. The formaldehyde was consumed in fast Cannizarro reaction under strong alkaline condition, producing considerable amount of methanol, which is the main negative aspect of this condition. With the exception of the differences caused by Cannizarro reaction, the UF production reactions under alkaline and acidic conditions are similar. The pH did not change the thermodynamic nature of the involved reactions, but only changed the competitive relationships of different reactions in kinetics. [ABSTRACT FROM AUTHOR]

The characteristics of UF resin prepared with concentrated formaldehyde were studied in this paper. With the molar ratio F/U = 1.1, the UF resin prepared with concentrated formaldehyde showed better mechanical properties than that with formalin. The13C-NMR and FTIR results indicated that there were more methylene groups, ether groups and urons in a UF resin system prepared with concentrated formaldehyde than those in a normal UF resin. The differential scanning calorimetry and DMA results showed that the curing temperature of UF resin with concentrated formaldehyde was lower than that of a normal UF resin. UF resin with concentrated formaldehyde showed worse thermal stability and higher thermal decomposition temperature. [ABSTRACT FROM AUTHOR]