期刊
CELLULOSE
卷 27, 期 10, 页码 5545-5562出版社
SPRINGER
DOI: 10.1007/s10570-020-03044-6
关键词
Mercerization; Cellulose acetate; TEMPO oxidation; Ionic liquid; Pulp reactivity
资金
- University of Helsinki
- UPM-Kymmene
- Finnish Academy [311255, 310481]
- Helsinki University Central Hospital
- Academy of Finland (AKA) [310481, 310481] Funding Source: Academy of Finland (AKA)
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.
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