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Review
. 2024 Feb 28;9(10):11168-11180.
doi: 10.1021/acsomega.3c10069. eCollection 2024 Mar 12.

How To Get Isocyanate?

Affiliations
Review

How To Get Isocyanate?

Zhuhua Guo et al. ACS Omega. .

Abstract

Isocyanate, a pivotal chemical intermediate to synthesize polyurethane with widespread applications in household appliances, automobiles, and construction, is predominantly produced via the phosgene process, which currently holds a paramount status in industrial isocyanate production. Nonetheless, concerns arise from the toxicity of phosgene and the corrosiveness of hydrogen chloride, posing safety hazards. The synthesis of isocyanate using nonphosgene methods represents a promising avenue for future development. This article primarily focuses on the nonphosgene approach, which involves the formation of carbamate through the reaction of nitro-amino compounds with carbon monoxide, dimethyl carbonate, and urea, among other reagents, subsequently leading to the thermal decomposition of carbamate to get isocyanate. This paper emphasizes the progress in catalyst development during the carbamate decomposition process. Single-component metal catalysts, particularly zinc, exhibit advantages such as high activity, cost-effectiveness, and compatibility with a wide range of substrates. Composite catalysts enhance isocyanate yield by introducing a second component to adjust the active metal composition. The central research direction aims to optimize catalyst adaptation to reaction conditions, including temperature, pressure, time, and solvent, to achieve high raw material conversion and product yield.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Isocyanate process production route.
Figure 2
Figure 2
Wanhua MDI production process.
Figure 3
Figure 3
Production of TDI by the gas phase phosgene method socyanate process production route.
Figure 4
Figure 4
Methanol cycle diagram.
Figure 5
Figure 5
Reaction mechanism of carbamate decomposition catalyzed by ZnO. Adapted with permission from Hyun, M.J.; Shin, M.; Kim, Y.J.; Suh, Y.-W. Phosgene-free decomposition of dimethylhexane-1,6-dicarbamate over ZnO. Res. Chem. Intermediat. 2016, 42 (1), 57–70. 10.1007/s11164-015-2224-x. Copyright 2016. Springer Link.
Figure 6
Figure 6
Green synthetic TDI process.
Figure 7
Figure 7
MPC reaction system.
Figure 8
Figure 8
(a) XRD patterns of ZnAlPO4 catalysts: (a) ZnAlPO4 (0.04); (b) ZnO; (c) ZnAlPO4 (0.05); and (d) ZnAlPO4 (0.15). (b)Effects of n(Zn)/n(Al) on HDI yield, byproduct selectivity, and HDC conversion. Adapted with permission from Sun, D.L.; Luo, J.Y.; Wen, R.Y.; Deng, J.R.; Chao, Z.S. Phosgene-free synthesis of hexamethylene-1,6-diisocyanate by the catalytic decomposition of dimethylhexane-1,6-dicarbamate over zinc-incorporated berlinite (ZnAlPO4). J. Hazard. Mater.2014, 266, 167–173. 10.1016/j.jhazmat.2013.12.022. Copyright 2014. Elsevier.
Figure 9
Figure 9
NH3-TPD profiles of bare ZSM-5 (a), 2Co/ZSM-5 (b), Zn-2Co/ZSM-5 (c), Zn–Co/ZSM-5 (d), 2Zn–Co/ZSM-5 (e), and 2Zn/ZSM-5 (f) catalysts. Adapted with permission from Ammar, M.; Cao, Y.; He, P.; Wang, L.G.; Chen, J.Q.; Li, H.Q. Zn–Co bimetallic supported ZSM-5 catalyst for phosgene-free synthesis of hexamethylene-1,6-diisocyanate by thermal decomposition of hexamethylene-1,6-dicarbamate. Chin. Chem. Lett.2017, 28 (7), 1583–1589. 10.1016/j.cclet.2017.03.015. Copyright 2017. Elsevier.
Figure 10
Figure 10
Possible reaction mechanism for the thermal decomposition of HDC to HDI over the Zn–Co/ZSM-5 catalyst. Adapted with permission from Cao, Y.; Chi, Y.; Muhammad, A.; He, P.; Wang, l.; Li, H. Nonphosgene synthesis of hexamethylene-1,6-diisocyanate from thermal decomposition of hexamethylene-1,6-dicarbamate over Zn–Co bimetallic supported ZSM-5 catalyst. Chin. J. Chem. Eng.2019, 27 (3), 549–555. 10.1016/j.cjche.2018.05.001. Copyright 2019. Elsevier.
Figure 11
Figure 11
(a) Thermogravimetric curves of different solvents. (b) Effects of ionic liquids on MHDC decomposition. Adapted with permission from Han, Y.; Liu, S.; Wang, P.; Deng, Y. Synthesis of isocyanate by thermal decomposition of carbamate in ionic liquid catalytic system. J. Mol. Catal. (China)2016, 30 (4), 297–306. 10.16084/j.cnki.issn1001-3555.2016.04.001. Copyright 2016. Cnki.
Figure 12
Figure 12
Carbamate decomposition reaction catalyzed by montmorillonite K-10. Adapted with permission from Pedro, U.; Marc, S.; Pilar, S.; Sergio, C.; Carmen, C.; Elena, F. A new and efficient catalytic method for synthesizing isocyanates from carbamates. Tetrahedron Lett.2002, 43 (9), 1673–1676. 10.1016/S0040-4039(02)00094-1. Copyright 2002. Elsevier.

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