A series of lacquer saps were prepared by prepolymerization under oxygen atmosphere. The prepolymerization process was investigated by GPC, UV-Vis, FT-IR, NMR, and microscope. The results showed that the polymerization of urushiol monomer was accelerated. The content of monomer in the lacquer sap swiftly decreased from 82.68% to 47.75% in 0.5 h. The mechanism of polymerization was complex and was involved in the coupling reaction of phenyl ring, the addition reaction of the unsaturated carbon-carbon double bond groups with urushiol hydroxyl groups, and other reactions that occurred on the side chains. In addition, the prepolymerization also improved significantly the drying property of lacquer film, especially at low relative humidity. At the same time, the sizes of the water drops in the lacquer saps significantly decreased with increasing the stirring time and the surface of lacquer film became smoother, which resulted in its excellent gloss (109–125). Due to the prepolymerization, the pencil hardness and the thermal stability of lacquer film were slightly improved as well.
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