Mechanistic investigation and reaction kinetics of the low-pressure copolymerization of cyclohexene oxide and carbon dioxide catalyzed by a dizinc complex

Fabian Jutz, Antoine Buchard, Michael R. Kember, Siw Bodil Fredriksen, Charlotte K. Williams

Research output: Contribution to journalArticle

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Abstract

The reaction kinetics of the copolymerization of carbon dioxide and cyclohexene oxide to produce poly(cyclohexene carbonate), catalyzed by a dizinc acetate complex, is studied by in situ attenuated total reflectance infrared (ATR-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. A parameter study, including reactant and catalyst concentration and carbon dioxide pressure, reveals zero reaction order in carbon dioxide concentration, for pressures between 1 and 40 bar and temperatures up to 80 °C, and a first-order dependence on catalyst concentration and concentration of cyclohexene oxide. The activation energies for the formation of poly(cyclohexene carbonate) and the cyclic side product cyclohexene carbonate are calculated, by determining the rate coefficients over a temperature range between 65 and 90 °C and using Arrhenius plots, to be 96.8 ± 1.6 kJ mol–1 (23.1 kcal mol–1) and 137.5 ± 6.4 kJ mol–1 (32.9 kcal mol–1), respectively. Gel permeation chromatography (GPC), 1H NMR spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry are employed to study the poly(cyclohexene carbonate) produced, and reveal bimodal molecular weight distributions, with narrow polydispersity indices (≤1.2). In all cases, two molecular weight distributions are observed, the higher value being approximately double the molecular weight of the lower value; this finding is seemingly independent of copolymerization conversion or reaction parameters. The copolymer characterization data and additional experiments in which chain transfer agents are added to copolymerization experiments indicate that rapid chain transfer reactions occur and allow an explanation for the observed bimodal molecular weight distributions. The spectroscopic and kinetic analyses enable a mechanism to be proposed for both the copolymerization reaction and possible side reactions; a dinuclear copolymerization active site is implicated.
Original languageEnglish
Pages (from-to)17395-17405
Number of pages11
JournalJournal of the American Chemical Society
Volume133
Issue number43
DOIs
Publication statusPublished - 5 Oct 2011

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Carbon Dioxide
Reaction kinetics
Copolymerization
Carbon dioxide
Molecular Weight
Carbonates
Pressure
Molecular weight distribution
Oxides
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance spectroscopy
Conversion Disorder
Temperature
Nuclear magnetic resonance
Arrhenius plots
Catalysts
Gel Chromatography
Protons
Gel permeation chromatography
Polydispersity

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Mechanistic investigation and reaction kinetics of the low-pressure copolymerization of cyclohexene oxide and carbon dioxide catalyzed by a dizinc complex. / Jutz, Fabian; Buchard, Antoine; Kember, Michael R.; Fredriksen, Siw Bodil; Williams, Charlotte K.

In: Journal of the American Chemical Society, Vol. 133, No. 43, 05.10.2011, p. 17395-17405.

Research output: Contribution to journalArticle

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abstract = "The reaction kinetics of the copolymerization of carbon dioxide and cyclohexene oxide to produce poly(cyclohexene carbonate), catalyzed by a dizinc acetate complex, is studied by in situ attenuated total reflectance infrared (ATR-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. A parameter study, including reactant and catalyst concentration and carbon dioxide pressure, reveals zero reaction order in carbon dioxide concentration, for pressures between 1 and 40 bar and temperatures up to 80 °C, and a first-order dependence on catalyst concentration and concentration of cyclohexene oxide. The activation energies for the formation of poly(cyclohexene carbonate) and the cyclic side product cyclohexene carbonate are calculated, by determining the rate coefficients over a temperature range between 65 and 90 °C and using Arrhenius plots, to be 96.8 ± 1.6 kJ mol–1 (23.1 kcal mol–1) and 137.5 ± 6.4 kJ mol–1 (32.9 kcal mol–1), respectively. Gel permeation chromatography (GPC), 1H NMR spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry are employed to study the poly(cyclohexene carbonate) produced, and reveal bimodal molecular weight distributions, with narrow polydispersity indices (≤1.2). In all cases, two molecular weight distributions are observed, the higher value being approximately double the molecular weight of the lower value; this finding is seemingly independent of copolymerization conversion or reaction parameters. The copolymer characterization data and additional experiments in which chain transfer agents are added to copolymerization experiments indicate that rapid chain transfer reactions occur and allow an explanation for the observed bimodal molecular weight distributions. The spectroscopic and kinetic analyses enable a mechanism to be proposed for both the copolymerization reaction and possible side reactions; a dinuclear copolymerization active site is implicated.",
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T1 - Mechanistic investigation and reaction kinetics of the low-pressure copolymerization of cyclohexene oxide and carbon dioxide catalyzed by a dizinc complex

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AB - The reaction kinetics of the copolymerization of carbon dioxide and cyclohexene oxide to produce poly(cyclohexene carbonate), catalyzed by a dizinc acetate complex, is studied by in situ attenuated total reflectance infrared (ATR-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. A parameter study, including reactant and catalyst concentration and carbon dioxide pressure, reveals zero reaction order in carbon dioxide concentration, for pressures between 1 and 40 bar and temperatures up to 80 °C, and a first-order dependence on catalyst concentration and concentration of cyclohexene oxide. The activation energies for the formation of poly(cyclohexene carbonate) and the cyclic side product cyclohexene carbonate are calculated, by determining the rate coefficients over a temperature range between 65 and 90 °C and using Arrhenius plots, to be 96.8 ± 1.6 kJ mol–1 (23.1 kcal mol–1) and 137.5 ± 6.4 kJ mol–1 (32.9 kcal mol–1), respectively. Gel permeation chromatography (GPC), 1H NMR spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry are employed to study the poly(cyclohexene carbonate) produced, and reveal bimodal molecular weight distributions, with narrow polydispersity indices (≤1.2). In all cases, two molecular weight distributions are observed, the higher value being approximately double the molecular weight of the lower value; this finding is seemingly independent of copolymerization conversion or reaction parameters. The copolymer characterization data and additional experiments in which chain transfer agents are added to copolymerization experiments indicate that rapid chain transfer reactions occur and allow an explanation for the observed bimodal molecular weight distributions. The spectroscopic and kinetic analyses enable a mechanism to be proposed for both the copolymerization reaction and possible side reactions; a dinuclear copolymerization active site is implicated.

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