New insight into the kinetics of diisocyanate-alcohol reactions by high-performance liquid chromatography and mass spectrometry

Tibor Nagy, Borbála Antal, K. Czifrák, Ildikó Papp, J. Karger-Kocsis, M. Zsuga, S. Kéki

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12 Citations (Scopus)

Abstract

The uncatalyzed reactions of 2,4-TDI (2,4-toluenediisocyanate) and MDI (4,4′-diphenylmethane-diisocyanate) with alcohols including butan-1-ol, butan-2-ol, diethylene glycol monomethylether (DEGME) were studied by high-performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS). The reactions were carried out at different temperatures from 22°C to 75°C using high molar ratios of alcohols to diisocyanates. It was found that the first isocyanate group of the MDI reacts about 1.5 times faster with the alcohols than the second one. The relative reactivities of the isocyanate groups (para and ortho) of 2,4-TDI as a function of the temperature was also deduced. From the temperature dependence of the rate constants the apparent activation energies were determined. Furthermore, the dependence of the apparent rate constant on the concentration of alcohols was also investigated and a mechanism was proposed for the reaction of diisocyanates with alcohols.

Original languageEnglish
Article number42127
JournalJournal of Applied Polymer Science
Volume132
Issue number25
DOIs
Publication statusPublished - Jul 1 2015

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High performance liquid chromatography
Mass spectrometry
Alcohols
Kinetics
Toluene 2,4-Diisocyanate
Isocyanates
Rate constants
Electrospray ionization
Glycols
Temperature
Activation energy

Keywords

  • Addition polymerization
  • Kinetics
  • Polyurethanes

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Surfaces, Coatings and Films
  • Chemistry(all)

Cite this

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abstract = "The uncatalyzed reactions of 2,4-TDI (2,4-toluenediisocyanate) and MDI (4,4′-diphenylmethane-diisocyanate) with alcohols including butan-1-ol, butan-2-ol, diethylene glycol monomethylether (DEGME) were studied by high-performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS). The reactions were carried out at different temperatures from 22°C to 75°C using high molar ratios of alcohols to diisocyanates. It was found that the first isocyanate group of the MDI reacts about 1.5 times faster with the alcohols than the second one. The relative reactivities of the isocyanate groups (para and ortho) of 2,4-TDI as a function of the temperature was also deduced. From the temperature dependence of the rate constants the apparent activation energies were determined. Furthermore, the dependence of the apparent rate constant on the concentration of alcohols was also investigated and a mechanism was proposed for the reaction of diisocyanates with alcohols.",
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T1 - New insight into the kinetics of diisocyanate-alcohol reactions by high-performance liquid chromatography and mass spectrometry

AU - Nagy, Tibor

AU - Antal, Borbála

AU - Czifrák, K.

AU - Papp, Ildikó

AU - Karger-Kocsis, J.

AU - Zsuga, M.

AU - Kéki, S.

PY - 2015/7/1

Y1 - 2015/7/1

N2 - The uncatalyzed reactions of 2,4-TDI (2,4-toluenediisocyanate) and MDI (4,4′-diphenylmethane-diisocyanate) with alcohols including butan-1-ol, butan-2-ol, diethylene glycol monomethylether (DEGME) were studied by high-performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS). The reactions were carried out at different temperatures from 22°C to 75°C using high molar ratios of alcohols to diisocyanates. It was found that the first isocyanate group of the MDI reacts about 1.5 times faster with the alcohols than the second one. The relative reactivities of the isocyanate groups (para and ortho) of 2,4-TDI as a function of the temperature was also deduced. From the temperature dependence of the rate constants the apparent activation energies were determined. Furthermore, the dependence of the apparent rate constant on the concentration of alcohols was also investigated and a mechanism was proposed for the reaction of diisocyanates with alcohols.

AB - The uncatalyzed reactions of 2,4-TDI (2,4-toluenediisocyanate) and MDI (4,4′-diphenylmethane-diisocyanate) with alcohols including butan-1-ol, butan-2-ol, diethylene glycol monomethylether (DEGME) were studied by high-performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS). The reactions were carried out at different temperatures from 22°C to 75°C using high molar ratios of alcohols to diisocyanates. It was found that the first isocyanate group of the MDI reacts about 1.5 times faster with the alcohols than the second one. The relative reactivities of the isocyanate groups (para and ortho) of 2,4-TDI as a function of the temperature was also deduced. From the temperature dependence of the rate constants the apparent activation energies were determined. Furthermore, the dependence of the apparent rate constant on the concentration of alcohols was also investigated and a mechanism was proposed for the reaction of diisocyanates with alcohols.

KW - Addition polymerization

KW - Kinetics

KW - Polyurethanes

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