机械活化甘蔗渣制备羧甲基纤维素及性能表征

    Preparation and characterization of carboxymethyl cellulose from mechanically activated bagasse cellulose

    • 摘要: 为进一步提高甘蔗渣的利用率,获得高取代度的羧甲基纤维素,该文采用自制搅拌磨对甘蔗渣进行机械活化预处理,以不同活化时间的甘蔗渣为原料,氯乙酸为醚化剂,氢氧化钠为催化剂制备羧甲基纤维素。以羧甲基纤维素的取代度为评价指标,分别探讨机械活化时间、固液比、氢氧化钠与氯乙酸摩尔比、反应时间、反应温度、水与底物比等因素对甘蔗渣羧甲基化反应的影响。并采用红外光谱(Fourier transform infrared spectroscopy,FTIR)、X-射线衍射(X-ray diffraction,XRD)、氢核磁共振谱(1HNMR spectroscopy,1HNMR)对甘蔗渣和羧甲基化产物表征。结果表明,机械活化对甘蔗渣羧甲基化反应具有明显的强化作用,经机械活化预处理后的甘蔗渣比原甘蔗渣更容易进行羧甲基化反应,取代度随着活化时间的延长先增大后减少。机械活化破坏了甘蔗渣中木素对纤维素的包裹作用,结晶结构受到破坏,降低纤维素的结晶度,醚化化试剂更容易渗透到甘蔗渣内部使纤维素发生羧甲基化反应,降低了对固液比、氢氧化钠/氯乙酸比、H2O/底物比、反应时间、反应温度的依赖性,提高了反应活性。在固液比为1∶18 g/mL,氢氧化钠/氯乙酸(摩尔比)为2∶1,H2O/底物比为1∶1 mL/g,75℃醚化2.0 h条件下,制得甘蔗渣羧甲基纤维素的取代度高达1.521,黏度为13 mPa·s。研究结果将为制备高取代度羧甲基纤维素提供依据和基础数据。

       

      Abstract: Abstract: Carboxymethyl cellulose (CMC) is a kind of anion and aliphatic and water-soluble cellulose ether. It has been widely used in food, medicine, detergent etc because it has good performance in thickening, dispersion and suspension and so on. It is vividly regarded as the "Monosodium glutamate" in industry. In recent years, the CMC demand is stably growing. Improving quality and developing special type of CMC for specific user are becoming the development directions of CMC. Sugarcane bagasse (SCB), a kind of waste in the process of sugar extraction, is abundant and low-cost lignocelullosic material. SCB is mainly composed of cellulose, hemicellulose and lignin. Cellulose forms microfibril by intramolecular and intermolecular hydrogen bond, and hemicellulose and lignin are filling and adhering agent among the microfibril. Because of the special structure of SCB, chemical agents are difficult to penetrate and diffuse in it, which limits its application. Therefore, it is necessary to pretreat SCB to remove lignin and hemicellulose, reducing cellulose's crystallinity. To utilize SCB and prepare CMC with high degree of substitution (DS), SCB was mechanically activated by a stirring-type ball mill. Using monochloroacetate (MCA) as etherifying agent and sodium hydroxide (NaOH) as catalyst, CMC was synthesized from SCB with different activation time. The effects of mechanical activation time, reaction time, reaction temperature, solid-liquid ratio, NaOH-MCA molar ratio and water content on carboxymethylation of SCB were investigated respectively by using the DS of CMC as evaluating parameter. The structure of CMC from SCB was characterized by using Fourier transform infrared spectroscopy (FTIR),X-ray diffraction (XRD) and 1HNMR spectroscopy (1HNMR). The results indicated that mechanical activation considerably enhanced the carboxymethylation of SCB, the mechanically activated SCB was easier for carboxymethylation than the original SCB, and the DS increased first and then decreased with activation time. The reasons were that mechanical activation broke the sealing of cellulose by lignin, destroyed the crystalline structure and decreased the crystallinity of cellulose, which made etherification reagent more easily penetrate into the SCB and could increase reactivity and decrease the dependence on solid-liquid ratio, ratio of NaOH/MCA, H2O/substrate, reaction time and reaction temperature. The DS and viscosity of CMC obtained were 1.521 and 13 mPa.s respectively through carboxymethylation under the conditions which were reaction time of 2.0 h, solid-liquid ratio (mass/volume) of 1:18 g/mL, NaOH-MCA molar ratio of 2:1, H2O/substrate (volume/mass) of 1:1 mL/g and reaction temperature of 75℃. The research results would provide the reference for the preparation of CMC with high DS.

       

    /

    返回文章
    返回