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.

在本文中，我们演示了通过使用乙酸四丁基_phosph的预处理步骤将商业化学纤维素纸浆活化以进行化学改性的方法（[P ₄₄₄₄] [OAc]）。进行了异质（非溶解）预处理，可显着降低结晶度，而不会伴随形成热力学稳定的纤维素II。使用两个模型反应证明了化学反应性的提高；（1）乙酰化（有机溶胀条件），无需催化剂即可获得高取代度（DS），以及（2）4-氧化酰胺基-TEMPO氧化（水溶胀条件），其中氧化程度高（DO除了未处理的纸浆之外，还获得了）。在两种测试中，均观察到纤维素反应性的显着改善。使用2D NMR对一个低和一个高DS样品评估乙酰化的区域选择性。低DS显示6-OH的乙酰化程度较低，而 预处理样品的高DS值主要显示三乙酸酯和二乙酸酯的混合物。对于涉及这种离子液体预处理的水基和有机基反应的未来发展，可以获得重要的机械信息。