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 organization: Department of Chemistry
Helsinki Institute of Sustainability Science (HELSUS)
Synthesis and Analysis
Date: 2020-07
Language: eng
Number of pages: 18
Belongs to series: Cellulose
ISSN: 0969-0239
DOI: https://doi.org/10.1007/s10570-020-03044-6
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
Peer reviewed: Yes
Rights: cc_by
Usage restriction: openAccess
Self-archived version: publishedVersion


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