Cellulose phosphorylation comparison and analysis of phosphorate position on cellulose fibers

Fleur Rol; Cécile Sillard; Michel Bardet; Jayasubba Reddy Yarava; Lyndon Emsley; Corinne Gablin; Didier Léonard; Naceur Belgacem; Julien Bras

doi:10.1016/j.carbpol.2019.115294

Cellulose phosphorylation comparison and analysis of phosphorate position on cellulose fibers

Carbohydr Polym. 2020 Feb 1:229:115294. doi: 10.1016/j.carbpol.2019.115294. Epub 2019 Sep 7.

Authors

Fleur Rol¹, Cécile Sillard², Michel Bardet³, Jayasubba Reddy Yarava⁴, Lyndon Emsley⁵, Corinne Gablin⁶, Didier Léonard⁷, Naceur Belgacem⁸, Julien Bras⁹

Affiliations

¹ Univ. Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000, Grenoble, France. Electronic address: Fleur.rol@grenoble-inp.fr.
² Univ. Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000, Grenoble, France. Electronic address: Cecile.sillard@lgp2.grenoble-inp.fr.
³ Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland; Université Grenoble Alpes, CEA, INAC, MEM, Laboratoire de Résonance Magnétique, Grenoble, 38000, France. Electronic address: Michel.bardet@cea.fr.
⁴ Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland. Electronic address: yarava@fmp-berlin.de.
⁵ Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland. Electronic address: lyndon.emsley@epfl.ch.
⁶ Univ Lyon, CNRS, Université Claude Bernard Lyon 1, ENS de Lyon, Institut des Sciences Analytiques, UMR 5280, 5, rue de la Doua, F-69100, Villeurbanne, France. Electronic address: Corinne.gablin@isa-lyon.fr.
⁷ Univ Lyon, CNRS, Université Claude Bernard Lyon 1, ENS de Lyon, Institut des Sciences Analytiques, UMR 5280, 5, rue de la Doua, F-69100, Villeurbanne, France. Electronic address: Didier.leonard@isa-lyon.fr.
⁸ Univ. Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000, Grenoble, France. Electronic address: Naceur.belgacem@grenoble-inp.fr.
⁹ Univ. Grenoble Alpes, CNRS, Grenoble INP, LGP2, F-38000, Grenoble, France; Institut Universitaire de France (IUF), F-75000, Paris, France. Electronic address: Julien.bras@grenoble-inp.fr.

PMID: 31826473
DOI: 10.1016/j.carbpol.2019.115294

Abstract

Chemical modifications of cellulose fibers as pretreatment for cellulose nanofibrils (CNF) production have been investigated to improve the production process and the quality of obtained cellulosic nanomaterial. In this study, phosphorylation of cellulose fibers was done in anticipation of a future nanofibrillation. Different phosphate salts, namely NH₄H₂PO₄, (NH₄)₂HPO₄, Na₂HPO₄, NaH₂PO₄ and LiH₂PO₄ with different constants of solubility (Ks) were used to increase the efficiency of the modification. Phosphorylated cellulose pulps were analyzed using elemental analysis, solid-state ¹³C and ³¹P NMR, or conductimetric titration method. No effect of Ks was observed whereas a counterion effect was pointed out. The study also reported the effect of pH, cellulose consistency, temperature and urea content in phosphorylation efficiency. Finally, chemical functionalization and penetration of phosphorylation reagents in the cellulose fibers were evaluated using XPS, SEM-EDX, ToF-SIMS and solid-state NMR.

Keywords: Cellulose; NMR; Phosphorylation; ToF-SIMS.