The
unique phenomenon of crystalline domain formation in thermosetting
crystalline urea–formaldehyde (UF) resins at low formaldehyde-to-urea
(F/U) molar ratios is responsible for their poor adhesion as wood
adhesives. The crystalline domains are apparently formed by hydrogen
bonds between linear molecules in UF resins at low molar ratios. Clear
evidence for the formation of linear molecules and subsequent hydrogen
bonds in the UF resins using two-dimensional nuclear magnetic resonance
(2D NMR) spectroscopy is reported for the first time through our study.
One-dimensional and 2D NMR spectroscopies were used to compare the
short-range and long-range correlations between hydrogen, carbon,
and nitrogen atoms in UF resin polymers prepared with high and low
F/U molar ratios (1.6 and 1.0). Complete signal assignments for various
structural units and interconnections among UF resin species are reported.
The results revealed that the second addition of urea at the final
step of UF resin synthesis split several linkages, such as branched
methylene ether, oxymethylene (or acetal), branched hydroxymethyl
urea, or uron, resulting in linear molecular structures, and showed
the formation of hydrogen bonds in UF resins at the low molar ratio.