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Degradation processes in the cellulose/N-methylmorpholine-N-oxide system studied by HPLC and ESR. Radical formation/recombination kinetics under UV photolysis at 77 K

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Abstract

Degradation processes of N-methylmorpholine-N-oxide monohydrate (NMMO), cellulose and cellulose/NMMO solutions were studied by high performance liquid chromatography (HPLC) and electron spin resonance (ESR) spectroscopy. Kinetics of radical accumulation processes under UV (λ = 248 nm) excimer laser flash photolysis was investigated by ESR at 77 K. Beside radical products of cellulose generated and stabilized at low temperature, radicals in NMMO and cellulose/NMMO solutions were studied for the first time in those systems and attributed to nitroxide type radicals ∼CH2–NO•–CH2∼ and/or ∼CH2–NO•–CH3∼ at the first and methyl •CH3 and formyl •CHO radicals at the second step of the photo-induced reaction. Kinetic study of radicals revealed that formation and recombination rates of radical reaction depend on cellulose concentration in cellulose/NMMO solutions and additional ingredients, e.g., Fe(II) and propyl gallate. HPLC measurements showed that the concentrations of ring degradation products, e.g., aminoethanol and acetaldehyde, are determined by the composition of the cellulose/NMMO solution. Results based on HPLC are mainly maintained by ESR that supports the assumption concerning a radical initiated ring-opening of NMMO.

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Acknowledgment

The authors wish to express their gratitude to one of the anonymous reviewers whose remarks greatly help to improve the article. Financial support by the German Federal Ministry for Education and Research (BMBF) under contract No. 94/02 is gratefully acknowledged.

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Authors and Affiliations

  1. Center for Micro and Nanotechnologies, Technical University of Ilmenau, Gustav-Kirchhoff-Str. 7, 98693, Ilmenau, Germany

    Alexander Konkin & Oliver Ambacher

  2. Centre of Excellence for Polysaccharide Research, Thuringian Institute for Textile and Plastics Research, Breitscheidstr. 97, 07407, Rudolstadt-Schwarza, Thuringia, Germany

    Frank Wendler, Frank Meister & Hans-Klaus Roth

  3. Physical department, Kazan State University, Kremljevskaja street 18, Kazan, Russia

    Albert Aganov

Authors
  1. Alexander Konkin
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  2. Frank Wendler
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  3. Frank Meister
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  4. Hans-Klaus Roth
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  5. Albert Aganov
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  6. Oliver Ambacher
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Correspondence to Frank Wendler.

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Konkin, A., Wendler, F., Meister, F. et al. Degradation processes in the cellulose/N-methylmorpholine-N-oxide system studied by HPLC and ESR. Radical formation/recombination kinetics under UV photolysis at 77 K. Cellulose 14, 457–468 (2007). https://doi.org/10.1007/s10570-007-9140-1

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