Abstract:

The syntheses of glycoluril and tetramethoxymethylglycoluril （TMMG） in a 500 mL batch reactor were investigated. Orthogonal experimental design method was used for process optimization. The results showed that the optimized conditions for synthesis of glycoluril were as follows: Under the conditions of the molar ratio of urea-to-glyoxal of 2.5∶1, pH of 1.2, reaction temperature of 60 ℃, and holding time of 3 h, the yield was 91.79% and the purity of product was 99% as confirmed by HPLC. For synthesis of TMMG, the optimized parameters were as follows: The molar ratio of methanol-to-precursor was 12∶1, the reaction temperature was 50 ℃, and the reaction time was 2 h, producing a yield of 86.54% and the purity of 99.92% as confirmed by HPLC. Macrokinetic analysis demonstrated that the reaction orders were 0.425 for urea and 1.637 for glyoxal in synthesis of glycoluril, indicative of an overall reaction order of 2.06 and activation energy of 87.446 kJ/mol. The synthesis of TMMG followed pseudo-first-order kinetics under methanol-excess conditions with an activation energy of 87.345 kJ/mol. The products were characterized by using ¹H NMR, FT-IR, melting point analysis and HPLC, which confirmed that the products met industrial specifications. This study could provide theoretical support for applications in daily chemicals and photoresist materials.

Key words: glycoluril, tetramethoxymethylglycoluril, kinetics, Arrhenius formula