纳米壳聚糖和纳米TiO_2-壳聚糖对真丝（绸）的改性研究
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摘要
本论文基于绿色化学和生态纺织品的理念,成功制备了两种纳米材料的分散体系:一是纳米天然有机高分子材料——纳米壳聚糖,二是制备天然有机高分子材料与纳米无机材料的复合物——纳米二氧化钛—壳聚糖。旨在充分利用其纳米材料的特性以及壳聚糖和二氧化钛本身所具有的优异性能,克服真丝的弱点。
纳米壳聚糖分散体系采用降解后的低分子量壳聚糖(粘均分子量为2.1×104),根据离子凝胶法的原理制备;纳米二氧化钛—壳聚糖分散体系以钛酸四丁酯为前驱体,先制成纳米二氧化钛溶胶,再将纳米二氧化钛溶胶均匀分散于低分子量壳聚糖的柠檬酸溶液中制成。本论文探索了纳米壳聚糖体系中各组分用量、pH值、制备温度等因素对纳米壳聚糖粒径分布的影响,确定了用于真丝改性处理的纳米壳聚糖和纳米二氧化钛—壳聚糖分散体系的制备工艺。采用激光粒度分析、透射电镜等现代分析手段,分析了纳米壳聚糖和纳米二氧化钛—壳聚糖中纳米粒子的形成机理和分布状态等,所制备的纳米壳聚糖粒径分布在15～30nm范围内,平均粒径为20.82nm,多分散指数为0.43;制备的纳米二氧化钛—壳聚糖中纳米粒子的平均粒径为36.71nm,多分散指数为0.46。
采用扫描电镜、傅利叶红外光谱、X射线衍射、热分析和X射线光电子能谱等现代分析手段,系统研究了经两种纳米材料处理前后蚕丝纤维的结构,发现处理后蚕丝纤维内部结构呈现β化趋势,结晶度和热稳定性均有一定程度的提高,处理后的蚕丝纤维通过柠檬酸与壳聚糖之间产生了共价交联作用。
经两种纳米材料处理后,柞蚕丝和桑蚕丝纤维的断裂强度和伸长率提高,杨氏模量、断裂功、弹性和急弹性增大;柞蚕丝和桑蚕丝织物对酸性染料的上染率和染色深度增加,活性染料的上染率、固色率和染色深度提高,高粱红天然染料媒染染色的深度增大;柞蚕丝和桑蚕丝织物的急、缓弹性折皱回复角有不同程度的提高,抗皱性能有所改善;柞蚕丝和桑蚕丝织物对大肠杆菌和金黄色葡萄球菌均有较高的抑菌性能,抑菌率超过85%。
本研究成功制备了纳米壳聚糖和纳米二氧化钛—壳聚糖,并将这两种纳米材料应用于真丝材料的改性,提高了柞蚕丝和桑蚕丝纤维的热稳定性和力学性能,实现了对柞蚕丝和桑蚕丝织物的抗皱、抗菌、提高染色性能的目标,为开发功能性真丝新材料提供了一条新的途径。
The two nano-materials dispersion system of natural organic macromolecular nano-chitosan and composite of nano-TiO2 and chitosan were prepared based on the idea of green chemistry and ecological textiles in this dissertation. The purpose of this work is to make full use of special properties of nano-particles, chitosan and TiO2 to overcome the weak point of silk fibers and fabrics.
Nano-chitosan dispersion system was prepared with low molecular weight chitosan (viscosity average molecular weight is 2.1×104) according to the mechanism of ionotropic gelation action, and nano-TiO2 and chitosan dispersion system was prepared with sol-gel method using tetrabutyl-titanate as a precursor, the precursor was first made into stable nano-TiO2 sol, and then the sol TiO2 was dispersed into acid solution of chitosan homogeneously. The factors that affected nano-particles sizes including usage of the contents in the system, pH value, preparation temperature were discussed, and the optimum preparation technology was determined. Then the formation mechanism and dispersed state of nano-chitosan and nano-TiO2/chitosan were analysized by means of modern analysis of the laser size detector and transmission electron microscope. The average diameter of the prepared low molecular nano-chitosan was 20.82nm, and the polydispersity index was 0.43. The average diameter of nano-TiO2 and chitosan was 36.71nm, and the polydispersity index was 0.46.
The structures of Bombyx mori (B. mori) silk and tussah silk fibers treated with nano-chitosan and nano TiO2-chitosan were studied systematically by Fourier transform infrared microspectroscopy ( FT-IR), X-ray diffraction (XRD), thermal analysis and X-ray photoelectron spectroscopy (XPS) analysis. It was found that the interior structure of the two treated silk fibers tended to formβ-structure, and the crystallinity and thermal stability increased at the same time. Furthermore, the covalent crosslinking reaction occurred among silk fiber, citric acid and chitosan.
The mechanical properties, dyeing properties, wrinkle-resistant perfo rmance and anti-bacteria performance of B. mori silk and tussah silk treated with the two nano-materials were tested. It was found that the breaking strength, breaking elongation, Youngs modulus, rupture work, elasticity and immediate-elasticity of the two silk fiber increased; the dyeing uptake and depth of acid dyes, the dyeing uptake fixation and depth of reactive dyes, the dyeing depth of sorghum red natural mordant dye improved; the wrinkle-resistant performance of immediate-elastic and delay-elastic crease recovery angle of the treated silk fabrics improved. The modification of the two silk fabrics gives high anti-bacteria properties to bacillus coli and staphylococcus aureus, the bacterial reductions were all more than 85%.
The dispersion system of nano-chitosan and composite of nano-TiO2 and chitosan were prepared successfully. When applying the two nano-material system to B. mori silk and tussah silk fibers, the mechanical performances of the silk fibers improved, as well as thermal properties. And the aim of increasing the wrinkle-resistant performance, anti-bacteria performance and dyeing properties of B. mori silk and tussah silk fabrics were achieved. This paper offered a new for developing novel functional silk materials.
纳米壳聚糖分散体系采用降解后的低分子量壳聚糖(粘均分子量为2.1×104),根据离子凝胶法的原理制备;纳米二氧化钛—壳聚糖分散体系以钛酸四丁酯为前驱体,先制成纳米二氧化钛溶胶,再将纳米二氧化钛溶胶均匀分散于低分子量壳聚糖的柠檬酸溶液中制成。本论文探索了纳米壳聚糖体系中各组分用量、pH值、制备温度等因素对纳米壳聚糖粒径分布的影响,确定了用于真丝改性处理的纳米壳聚糖和纳米二氧化钛—壳聚糖分散体系的制备工艺。采用激光粒度分析、透射电镜等现代分析手段,分析了纳米壳聚糖和纳米二氧化钛—壳聚糖中纳米粒子的形成机理和分布状态等,所制备的纳米壳聚糖粒径分布在15～30nm范围内,平均粒径为20.82nm,多分散指数为0.43;制备的纳米二氧化钛—壳聚糖中纳米粒子的平均粒径为36.71nm,多分散指数为0.46。
采用扫描电镜、傅利叶红外光谱、X射线衍射、热分析和X射线光电子能谱等现代分析手段,系统研究了经两种纳米材料处理前后蚕丝纤维的结构,发现处理后蚕丝纤维内部结构呈现β化趋势,结晶度和热稳定性均有一定程度的提高,处理后的蚕丝纤维通过柠檬酸与壳聚糖之间产生了共价交联作用。
经两种纳米材料处理后,柞蚕丝和桑蚕丝纤维的断裂强度和伸长率提高,杨氏模量、断裂功、弹性和急弹性增大;柞蚕丝和桑蚕丝织物对酸性染料的上染率和染色深度增加,活性染料的上染率、固色率和染色深度提高,高粱红天然染料媒染染色的深度增大;柞蚕丝和桑蚕丝织物的急、缓弹性折皱回复角有不同程度的提高,抗皱性能有所改善;柞蚕丝和桑蚕丝织物对大肠杆菌和金黄色葡萄球菌均有较高的抑菌性能,抑菌率超过85%。
本研究成功制备了纳米壳聚糖和纳米二氧化钛—壳聚糖,并将这两种纳米材料应用于真丝材料的改性,提高了柞蚕丝和桑蚕丝纤维的热稳定性和力学性能,实现了对柞蚕丝和桑蚕丝织物的抗皱、抗菌、提高染色性能的目标,为开发功能性真丝新材料提供了一条新的途径。
The two nano-materials dispersion system of natural organic macromolecular nano-chitosan and composite of nano-TiO2 and chitosan were prepared based on the idea of green chemistry and ecological textiles in this dissertation. The purpose of this work is to make full use of special properties of nano-particles, chitosan and TiO2 to overcome the weak point of silk fibers and fabrics.
Nano-chitosan dispersion system was prepared with low molecular weight chitosan (viscosity average molecular weight is 2.1×104) according to the mechanism of ionotropic gelation action, and nano-TiO2 and chitosan dispersion system was prepared with sol-gel method using tetrabutyl-titanate as a precursor, the precursor was first made into stable nano-TiO2 sol, and then the sol TiO2 was dispersed into acid solution of chitosan homogeneously. The factors that affected nano-particles sizes including usage of the contents in the system, pH value, preparation temperature were discussed, and the optimum preparation technology was determined. Then the formation mechanism and dispersed state of nano-chitosan and nano-TiO2/chitosan were analysized by means of modern analysis of the laser size detector and transmission electron microscope. The average diameter of the prepared low molecular nano-chitosan was 20.82nm, and the polydispersity index was 0.43. The average diameter of nano-TiO2 and chitosan was 36.71nm, and the polydispersity index was 0.46.
The structures of Bombyx mori (B. mori) silk and tussah silk fibers treated with nano-chitosan and nano TiO2-chitosan were studied systematically by Fourier transform infrared microspectroscopy ( FT-IR), X-ray diffraction (XRD), thermal analysis and X-ray photoelectron spectroscopy (XPS) analysis. It was found that the interior structure of the two treated silk fibers tended to formβ-structure, and the crystallinity and thermal stability increased at the same time. Furthermore, the covalent crosslinking reaction occurred among silk fiber, citric acid and chitosan.
The mechanical properties, dyeing properties, wrinkle-resistant perfo rmance and anti-bacteria performance of B. mori silk and tussah silk treated with the two nano-materials were tested. It was found that the breaking strength, breaking elongation, Youngs modulus, rupture work, elasticity and immediate-elasticity of the two silk fiber increased; the dyeing uptake and depth of acid dyes, the dyeing uptake fixation and depth of reactive dyes, the dyeing depth of sorghum red natural mordant dye improved; the wrinkle-resistant performance of immediate-elastic and delay-elastic crease recovery angle of the treated silk fabrics improved. The modification of the two silk fabrics gives high anti-bacteria properties to bacillus coli and staphylococcus aureus, the bacterial reductions were all more than 85%.
The dispersion system of nano-chitosan and composite of nano-TiO2 and chitosan were prepared successfully. When applying the two nano-material system to B. mori silk and tussah silk fibers, the mechanical performances of the silk fibers improved, as well as thermal properties. And the aim of increasing the wrinkle-resistant performance, anti-bacteria performance and dyeing properties of B. mori silk and tussah silk fabrics were achieved. This paper offered a new for developing novel functional silk materials.
引文
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