Crystallinity reduction and enhancement in the chemical reactivity of cellulose by non-dissolving pre-treatment with tetrabutylphosphonium acetate

Daniel Rico del Cerro, Tetyana V. Koso, Tia Kakko, Alistair W.T. King, Ilkka Kilpeläinen

Research output: Contribution to journalArticleScientificpeer-review

22 Citations (Scopus)

Abstract

Herein, we demonstrate the activation of commercial chemical cellulose pulps towards chemical modification by a pre-treatment step with tetrabutylphosphonium acetate ([P4444][OAc]). A heterogeneous (non-dissolving) pre-treatment was applied allowing for a significant reduction in crystallinity, without concomitant formation of the thermodynamically stable cellulose II. An increase in chemical reactivity was demonstrated using two model reactions; (1) acetylation (organic swelling conditions), where high degrees of substitution (DS) were obtained without the need for a catalyst, and (2) 4-acetamido-TEMPO oxidation (aqueous swelling conditions), where significant degrees of oxidation (DO) were obtained, beyond those for the untreated pulps. In both tests a notable improvement in cellulose reactivity was observed. Regioselectivity of acetylation was assessed using 2D NMR for one low and one high DS sample. The low DS showed a small degree of acetylation of the 6-OH, whereas, the high DS from the pre-treated sample showed mainly mixtures of triacetate and diacetates. Important mechanistic information is attained for future development of aqueous and organic-based reactions involving this ionic liquid pre-treatment.

Original languageEnglish
Pages (from-to)5545-5562
Number of pages18
JournalCellulose
Volume27
Issue number10
DOIs
Publication statusPublished - 1 Jul 2020
MoE publication typeA1 Journal article-refereed

Keywords

  • Cellulose acetate
  • Ionic liquid
  • Mercerization
  • Pulp reactivity
  • TEMPO oxidation

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