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

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Rico del Cerro , D , Koso , T V , Kakko , T , King , A W T & Kilpeläinen , I 2020 , ' Crystallinity reduction and enhancement in the chemical reactivity of cellulose by non-dissolving pre-treatment with tetrabutylphosphonium acetate ' , Cellulose , vol. 27 , no. 10 , pp. 5545-5562 . https://doi.org/10.1007/s10570-020-03044-6

Title: Crystallinity reduction and enhancement in the chemical reactivity of cellulose by non-dissolving pre-treatment with tetrabutylphosphonium acetate
Author: Rico del Cerro, Daniel; Koso, Tetyana V.; Kakko, Tia; King, Alistair W. T.; Kilpeläinen, Ilkka
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Helsinki Institute of Sustainability Science (HELSUS)
Date: 2020-07
Language: eng
Number of pages: 18
Belongs to series: Cellulose
ISSN: 0969-0239
URI: http://hdl.handle.net/10138/317322
Abstract: Herein, we demonstrate the activation of commercial chemical cellulose pulps towards chemical modification by a pre-treatment step with tetrabutylphosphonium acetate ([P-4444][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.
Subject: ACETYLATION
ACID
BIOPOLYMER
Cellulose acetate
DEEP EUTECTIC SOLVENTS
DISSOLUTION
ESTERS
FIBERS
IONIC LIQUIDS
Ionic liquid
Mercerization
Pulp reactivity
TEMPO
TEMPO oxidation
TRANSESTERIFICATION
116 Chemical sciences
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