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Industrial application of molecular computations on the dimerization of methylene diphenyl diisocyanate

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Abstract

In the polyurethane industry, the undesirable dimerization and oligomerization of methylene diphenyl diisocyanate (MDI) are unwanted and problematic phenomena. The relative ratios of these dimers and oligomers have a strong temperature dependence, and they can be formed below and above the melting point of MDI (316.15 K). All possible structures of the isomers and their dimers were optimized, and then their thermodynamic functions were calculated at the M06-2X/6-31(d,p) level of theory. The dimerization of isocyanate groups can result in four-, five-, and six-membered rings. The four-membered ring is the most stable one due to the aromatic electrons in π orbitals of the uretidione ring. The relative stability of the dimers is therefore influenced by the steric effects and the relative positions of isocyanate groups. The most stable dimer is the one which is formed from the reaction of the p,o- and o,p-MDI isomers due to their intrinsic interactions, which were classified, and their impact on dimer stability was discussed.

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Acknowledgements

The authors would like to thank Tamás Purzsa, Vice President of BorsodChem, for his helpful contributions. The authors acknowledge the opportunity provided by Wanhua-BorsodChem to conduct this study. This research was supported by the European Union and the Hungarian State, co-financed by the European Regional Development Fund in the framework of the GINOP-2.3.4-15-2016-00004 project, aimed to promote the cooperation between higher education and industry.

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Authors and Affiliations

  1. BorsodChem Ltd, Bolyai tér 1, 3700, Kazincbarcika, Hungary

    R. Zsanett Boros & László Farkas

  2. Faculty of Materials Science and Engineering, Institute of Chemistry, University of Miskolc, 3515, Miskolc-Egyetemváros, Hungary

    R. Zsanett Boros, Anita Rágyanszki, Imre G. Csizmadia, Béla Fiser & Béla Viskolcz

  3. Department of Chemistry, University of Toronto, Toronto, M5S 3H6, Canada

    Anita Rágyanszki, Imre G. Csizmadia & Andrea Guljas

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  1. R. Zsanett Boros
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Correspondence to Béla Viskolcz.

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Boros, R.Z., Rágyanszki, A., Csizmadia, I.G. et al. Industrial application of molecular computations on the dimerization of methylene diphenyl diisocyanate. Reac Kinet Mech Cat 124, 1–14 (2018). https://doi.org/10.1007/s11144-018-1385-1

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  • DOI: https://doi.org/10.1007/s11144-018-1385-1

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