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Chromophores in cellulosics, XVIII. Degradation of the cellulosic key chromophore 5,8-dihydroxy-[1,4]-naphthoquinone under conditions of chlorine dioxide pulp bleaching: a combined experimental and theoretical study

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Abstract

5,8-Dihydroxy-[1,4]-naphthoquinone (DHNQ) is one of the key chromophores occurring in all types of aged cellulosics. This study investigates the degradation of DHNQ by chlorine dioxide at moderately acidic (pH 3) conditions, corresponding to the conditions of industrial bleaching (“D stage”). The degradation involves three major pathways. As initial reaction, a hydrogen transfer from DHNQ to chlorine dioxide via a PCET mechanism occurs to form a radical DHNQ· and chlorous acid. DHNQ· is then attacked by water to give a pentahydroxynaphthalene radical PHN· that is stabilized by strong delocalization of the non-paired electron into its aromatic ring. PHN· immediately disproportionates to give the observable intermediate 1,2,4,5,8-pentahydroxynapththalene (I), which was comprehensively confirmed by NMR and MS (path A). In the presence of excess ClO2, I is immediately further oxidized into acetic acid, glycolic acid, oxalic acid and CO2 as the final, stable, and non-colored products (path C). In the absence of excess ClO2, elimination of water from I regenerates DHNQ (path B), so that at roughly equimolar DHNQ/ClO2 ratios ClO2 is fully consumed while a major part of DHNQ is recovered. To avoid such DHNQ “recycling” under ClO2 consumption—and to completely degrade DHNQ to colorless degradation products instead—ClO2 must be applied in at least fivefold molar excess relative to DHNQ.

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Acknowledgments

We performed quantum chemical calculations with the workstation in the Sakaki group, Fukui institute for fundamental chemistry at Kyoto University, Japan, and would like to thank for the access. The financial support of the Austrian Christian Doppler Research Society (CDG) through the CD-lab “Advanced cellulose chemistry and analytics” and the Austrian Research promotion Agency (FFG), project “Chromophores-II”, is gratefully acknowledged.

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Authors and Affiliations

  1. Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Shimogamo-hangi-cho 11-5, Sakyo-ku, Kyoto-shi, Kyoto, Japan

    Takashi Hosoya

  2. Division of Chemistry of Renewable Resources, Department of Chemistry, University of Natural Resources and Life Sciences, Muthgasse 18, 1190, Vienna, Austria

    Nele Sophie Zwirchmayr, Karl Michael Klinger, Antje Potthast & Thomas Rosenau

  3. Mondi Uncoated Fine & Kraft Paper GmbH, Marxergasse 4A, 1030, Vienna, Austria

    Heidemarie Reiter & Martin Spitzbart

  4. Evonik-Degussa, Rodenbacher Chaussee 4, 63457, Hanau-Wolfgang, Germany

    Thomas Dietz

  5. Zellstoff Pöls AG, Dr. Luigi-Angeli-Str. 9, 8761, Pöls, Austria

    Klaus Eibinger

  6. SAPPI Papier Holding GmbH, Brucker Str. 21, 8101, Gratkorn, Austria

    Wolfgang Kreiner, Arnulf Kai Mahler & Heribert Winter

  7. Lenzing AG, Werkstraße 2, 4860, Lenzing, Austria

    Thomas Röder

  8. USDA Forest Service, Southern Research Station, 521 Devall Dr, Auburn, AL, 36849, USA

    Thomas Elder

  9. Johan Gadolin Process Chemistry Centre, Åbo Akademi University, Porthansgatan 3, 20500, Åbo/Turku, Finland

    Thomas Rosenau

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  1. Takashi Hosoya
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Correspondence to Thomas Rosenau.

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Hosoya, T., Zwirchmayr, N.S., Klinger, K.M. et al. Chromophores in cellulosics, XVIII. Degradation of the cellulosic key chromophore 5,8-dihydroxy-[1,4]-naphthoquinone under conditions of chlorine dioxide pulp bleaching: a combined experimental and theoretical study. Cellulose 25, 4941–4954 (2018). https://doi.org/10.1007/s10570-018-1912-2

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