Preparation of carboxylated cellulose nanocrystals via one-pot tandem reactions
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摘要: 为了探究高效、简便的羧基化纳米纤维素晶体(CCN)制备工艺,以微晶纤维素(MCC)为原料,过硫酸铵为氧化剂,采用一锅法制备出羧基化纳米纤维素晶体。并运用响应面分析法对影响羧基化纳米纤维素得率的各因素及其相互之间的交互作用进行优化。再采用透射电镜、马尔文激光粒度仪、红外光谱、X射线衍射和热分析对样品的微观形貌、粒度分布、晶体特性、结构和热稳定性能进行了研究。结果表明:过硫酸铵浓度与时间、温度与时间之间的交互作用比过硫酸铵浓度与温度间的交互作用对羧基化纳米纤维素得率的影响显著。通过优化得到的制备工艺条件为时间204min、过硫酸铵浓度2mol/L、温度62℃,优化条件下制备的羧基化纳米纤维素得率为46.41%,与模型预测值(46.93%)吻合较好,表明建立的数学模型是有效的。CCN为直径10~30nm、长度50~200nm均匀分布的棒状,Z均粒径为96.92nm;在1731cm-1出现了羧基基团的CO特征峰,表明过硫酸铵分解产生的氧化剂H2O2选择性地把纤维素C6原子上的羟基氧化成了羧基;CCN属纤维素Ⅰ型,结晶度为78.35%;羧基化后的CCN热稳定性相对于MCC有较明显的降低。Abstract: In order to explore an effective and simple technology for the preparation of carboxylated cellulose nanocrystals (CCN), we prepared CCN with microcrystalline cellulose (MCC) as raw material and ammonium persulfate (APS) as oxidant via one-pot tandem reactions. The effects of time, ammonium persulfate mole, temperature and their interactions on the yield of carboxylated cellulose nanocrystals were optimized with response surface methodology. Morphology and the particle size distribution, crystallinity, structure and thermal properties of raw material and CCN were analyzed by transmission electron microscopy (TEM), laser particle analyzer, X-ray diffraction (XRD), fourier transformation infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The results showed that the interaction between time and temperature,time and ammonium persulfate mole was better than that of ammonium persulfate mole and temperature on the yield of CCN. With the optimization, when time, ammonium persulfate mole and temperature were 204min, 2mol/L and 62℃, the yield of CCN would reach 46.41% and accorded well with the theoretical prediction value of 46.93 %, indicating that the designed model was reliable. CCN presented a uniform distribution of rod-like shape with the diameter of 10 to 30nm and the length of 50 to 200nm, and the Z-average size of CCN was 96.92nm. The peak of C=O appeared at 1731cm-1, indicating that H2O2 produced by the decomposition of ammonium persulfate selectively oxidized the hydroxymethyl groups of C6 into carboxyl. CCN was characteristic of the cellulose I crystal form, with the crystallinity of 78.35%. CCN had a lower thermal stability than MCC.
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