Urethane formation with an excess of isocyanate or alcohol: Experimental and Ab initio study

Wafaa Cheikh, Zsófia Borbála Rózsa, Christian Orlando Camacho López, Péter Mizsey, Béla Viskolcz, Milán Szori, Zsolt Fejes

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

A kinetic and mechanistic investigation of the alcoholysis of phenyl isocyanate using 1-propanol as the alcohol was undertaken. A molecular mechanism of urethane formation in both alcohol and isocyanate excess is explored using a combination of an accurate fourth generation Gaussian thermochemistry (G4MP2) with the Solvent Model Density (SMD) implicit solvent model. These mechanisms were analyzed from an energetic point of view. According to the newly proposed two-step mechanism for isocyanate excess, allophanate is an intermediate towards urethane formation via six-centered transition state (TS) with a reaction barrier of 62.6 kJ/mol in the THF model. In the next step, synchronous 1,3-H shift between the nitrogens of allophanate and the cleavage of the C-N bond resulted in the release of the isocyanate and the formation of a urethane bond via a low-lying TS with 49.0 kJ/mol energy relative to the reactants. Arrhenius activation energies of the stoichiometric, alcohol excess and the isocyanate excess reactions were experimentally determined by means of HPLC technique. The activation energies for both the alcohol (measured in our recent work) and the isocyanate excess reactions were lower compared to that of the stoichiometric ratio, in agreement with the theoretical calculations.

Original languageEnglish
Article number1543
JournalPolymers
Volume11
Issue number10
DOIs
Publication statusPublished - Oct 1 2019

Keywords

  • Ab initio
  • Allophanate
  • Isocyanate excess
  • Kinetics
  • Mechanism
  • Urethane formation

ASJC Scopus subject areas

  • Chemistry(all)
  • Polymers and Plastics

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