Ionic liquid-mediated solvothermal synthesis of 4,4′-methylenediphenyl diisocyanate (MDI): an efficient and environment-friendly process

• Published in: New journal of chemistry 2018, Vol.42 (14), p.12243-12255
• Main Authors: Duan, C. W., You, J., Liu, B., Ma, J. L., Zhou, H. P., Zhang, H. B., Zhang, J.
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Catalytic activity; Chemical synthesis; Decomposition; Decomposition reactions; Diisocyanates; Imidazole; Ionic liquids; Ions; Methylene dianiline; Polyurethane resins; Solvents; Zinc acetate
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/C8NJ01175C

4,4′-Methylenediphenyl diisocyanate (4,4′-MDI) is an immensely important intermediate employed in the manufacturing of polyurethanes. Many synthetic routes have been developed over the decades for the synthesis of 4,4′-MDI compounds on a large scale; these compounds are highly toxic and hazardous in nature. In this study, an environment-friendly route is proposed for the synthesis of 4,4′-MDI using 4,4′-diaminodiphenylmethane and dimethyl carbonate (DMC) as starting materials, which are nontoxic in nature. The synthesis of ionic liquids (ILs) and their utilization in the decomposition reaction are systematically investigated. Imidazole-functionalized ionic liquids were prepared for the synthesis of 4,4′-MDI, and their thermal performances were evaluated by TGA. We found that in comparison with other imidazole-functionalized ionic liquids, 1-ethoxycarbonylmethyl-3-methylimidazolium tetrafluoroborate ([EAmim]BF 4 ) exhibited preferable thermal activity for the decomposition of 4,4′-methylenediphenyl dimethylcarbamate (4,4′-MDC). Moreover, these ILs were more effective when they were combined with zinc as a catalyst, which enhanced the decomposition of MDC. Under optimal conditions, the yield of MDI compared to that of Zn(OAc) 2 –[EAmim]BF 4 catalyst increased up to 96%. The mechanism of the enhanced performance of ionic liquids by catalytic activity of zinc acetate was also investigated.