title: Studies on the tosylation of cellulose in mixtures of ionic liquids and a co-solvent.
abstract: The tosylation of cellulose in ionic liquids (ILs) was studied. Due to the beneficial effect of different co-solvents, the reaction could be performed at 25°C without the need of heating (in order to reduce viscosity) or cooling (in order to prevent side reactions). The effects of reaction parameters, such as time, molar ratio, and type of base, on the degree of substitution (DS) with tosyl- and chloro-deoxy groups as well as on the molecular weight were evaluated. Products with a DStosyl≤1.14 and DSCl≤0.16 were obtained and characterized by means of NMR- and FT-IR spectroscopy in order to evaluate their purity and distribution of functional groups within the modified anhydroglucose unit (AGU). Tosylation of cellulose in mixtures of IL and a co-solvent was found to result in predominant substitution at the primary hydroxyl group. Size exclusion chromatography (SEC) revealed only a moderate degradation of the polymer backbone at a reaction time of 4-8h. Finally, the nucleophilic displacement (SN) of tosyl- and chloro-deoxy groups by azide as well as recycling of the ILs was studied.
authors.affiliation: Laboratory of Fibre and Cellulose Technology, Åbo Akademi University, Porthansgatan 3, FI-20500 Turku, Finland; Thuringian Institute for Textile and Plastics Research, Breitscheidstraße 97, D-07407 Rudolstadt, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Gericke
authors.affiliation: Thuringian Institute for Textile and Plastics Research, Breitscheidstraße 97, D-07407 Rudolstadt, Germany.
authors.forename: Jens
authors.initials: J
authors.lastname: Schaller
authors.affiliation: Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Centre of Excellence for Polysaccharide Research, Humboldtstraße 10, D-07743 Jena, Germany.
authors.forename: Tim
authors.initials: T
authors.lastname: Liebert
authors.affiliation: Laboratory of Fibre and Cellulose Technology, Åbo Akademi University, Porthansgatan 3, FI-20500 Turku, Finland.
authors.forename: Pedro
authors.initials: P
authors.lastname: Fardim
authors.affiliation: Thuringian Institute for Textile and Plastics Research, Breitscheidstraße 97, D-07407 Rudolstadt, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Meister
authors.affiliation: Laboratory of Fibre and Cellulose Technology, Åbo Akademi University, Porthansgatan 3, FI-20500 Turku, Finland; Thuringian Institute for Textile and Plastics Research, Breitscheidstraße 97, D-07407 Rudolstadt, Germany; Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Centre of Excellence for Polysaccharide Research, Humboldtstraße 10, D-07743 Jena, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Heinze
mesh_terms: D000081:Acetamides / Q000737:chemistry; D000498:Allyl Compounds / Q000737:chemistry*; D002482:Cellulose / Q000737:chemistry*; D002850:Chromatography, Gel; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D005021:Ethylamines / Q000737:chemistry; D007093:Imidazoles / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D018021:Lithium Chloride / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D010755:Organophosphates / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D014105:Tosyl Compounds / Q000737:chemistry*
chemical_list: C544334:1-allyl-3-methylimidazolium; C543070:1-ethyl-3-methyl imidazolium diethyl phosphate; D000081:Acetamides; D000498:Allyl Compounds; D005021:Ethylamines; D007093:Imidazoles; D052578:Ionic Liquids; D010755:Organophosphates; D011725:Pyridines; D012997:Solvents; D014105:Tosyl Compounds; C025506:4-toluenesulfonyl chloride; C502841:1-butyl-3-methylimidazolium chloride; D002482:Cellulose; D018021:Lithium Chloride; C013959:dimethylacetamide; C023666:pyridine; C016162:triethylamine; D004121:Dimethyl Sulfoxide