Competitive polycondensation of model compound melamine-urea-formaldehyed (MUF) resin system by 13C NMR

Melamine-urea-formaldehyde (MUF) resin is an excellent adhesive in the field of wood adhesives, however the competition mechanism is questionable which affects the structure control and performance optimization of the resin. In this study, the competitive resin synthesis polycondensation reaction of MUF system under alkaline condition was studied based on the model compound 1,3-dihydroxymethyl urea (UF2) and melamine (M) system, and the competitive reaction mechanism in the system was deduced by 13C NMR quantitative analysis. The results show that the energy barrier of hydroxymethylation of melamine is lower than that of urea, and the priority of hydroxymethylation is lower; the addition of melamine results in a large amount of hydrolysis of UF2, and the formed free formaldehyde, resulting in hydroxymethylation of melamine; there is obvious polycondensation reaction in UF2+M system, mainly from the relationship between hydroxymethylurea and melamine or hydroxymethylmelamine. The type I bridge bond structure of polycondensation mainly comes from the reaction of UF2 and M, which is difficult to form the type II bridge bond. At low molar ratio, the formation of bridge bond is superior to that of ether bond. With the increase of molar ratio, the formation of ether bond shows advantages, but there is obvious competition between them. There may be competitive presence of the UF self-condensation products, melamine-formaldehyde (MF) self-condensation products and MUF co-condensed products after the polycondensation reaction.