A General Aqueous Silanization Protocol to Introduce Vinyl, Mercapto or Azido Functionalities onto Cellulose Fibers and Nanocelluloses.

The effective and straight-forward modification of nanostructured celluloses under aqueous conditions or as “never-dried” materials is challenging. We report a silanization protocol in water using catalytic amounts of hydrogen chloride and then sodium hydroxide in a two-step protocol. The acidic step hydrolyzes the alkoxysilane to obtain water-soluble silanols and the subsequent addition of catalytic amounts of NaOH induces a covalent reaction between cellulose surficial hydroxyl groups and the respective silanols. The developed protocol enables the incorporation of vinyl, thiol, and azido groups onto cellulose fibers and cellulose nanofibrils. In contrast to conventional methods, no curing or solvent-exchange is necessary, thereby the functionalized celluloses remain never-dried, and no agglomeration or hornification occurs in the process. The successful modification was proven by solid state NMR, ATR-IR, and EDX spectroscopy. In addition, the covalent nature of this bonding was shown by gel permeation chromatography of polyethylene glycol grafted nanofibrils. By varying the amount of silane agents or the reaction time, the silane loading could be tuned up to an amount of 1.2 mmol/g. Multifunctional materials were obtained either by prior carboxymethylation and subsequent silanization; or by simultaneously incorporating both vinyl and azido groups. The protocol reported here is an easy, general, and straight-forward avenue for introduction of anchor groups onto the surface of never-dried celluloses, ready for click chemistry post-modification, to obtain multifunctional cellulose substrates for high-value applications.