【作者】 李永海；

【导师】 蔡再生；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2010， 博士

【摘要】 溶胶-凝胶技术作为一种材料制备与改性技术,因具有高化学均匀性、制备工艺简单、制备材料纯度高以及易成形和改性等特点,现已成为纺织品功能整理的一个新的发展方向。硅溶胶作为溶胶-凝胶技术中使用最为广泛的一种胶体材料,因具有成膜性好、成膜牢度高、成膜易改性、成膜耐高温和耐化学试剂性佳及本身无毒且具有生物惰性等特点,现已作为一种优良的生态环保性材料广泛应用于纺织品的功能整理。利用硅溶胶的成膜性可以包覆任何功能性活性因子,并且可通过对溶胶进行物理或化学改性,改变成膜的结构和微孔尺寸大小及分布,调控功能活性因子的固定化程度,从而达到控制释放的目的,因此,可用来制备具有长效功能的纺织品,如芳香保健功能纺织品。由鉴于此,本文的研究目的是利用溶胶-凝胶技术,以正硅酸乙酯(TEOS)为硅前驱体,以Y-缩水甘油醚氧丙基三甲氧基硅烷(GPTMS)为改性剂,以乙醇为共溶剂,以盐酸为反应催化剂,以聚乙烯醇(PVA)为成膜促进剂,制备稳定、透明、均匀及成膜性良好且对整理织物物理机械性能影响小的生态环保型纳米硅溶胶载体。以具有镇静、安神之功效的熏衣草精油作为芳香保健功能活性因子,通过硅溶胶载体于织物表面的成膜性包覆芳香保健功能活性因子——熏衣草精油,制备具有长效芳香保健功能的纺织品,以期为纺织品芳香保健功能整理开辟一种新的工艺简单且更加环保的整理技术。因此,本文的主要研究内容和结果如下。首先,本文采用单因素试验,研究了加水量、共溶剂乙醇用量、催化剂盐酸用量、成膜促进剂PVA的用量、改性剂GPTMS的用量以及反应温度和时间对制备硅溶胶载体性质(粘度、凝胶时间和粒径)的影响,采用五因素四水平[L16(45)]的正交试验设计方案,优化了制备工艺,并通过SPM分析了改性剂对硅溶胶载体膜形态结构的影响。结果显示,反应物配比(以摩尔比表示)为n[TEOS]:n[H2O]:n[EtOH]:n[HCl]:n[GPTMS]=1:50:8:8×10-3:1, PVA浓度为0.2%,反应温度为25℃,反应时间为3h,能够制备出稳定、透明、均匀及成膜性良好且对整理织物物理机械性能影响小的纳米硅溶胶载体。SPM分析表明,改性硅溶胶载体较未改性硅溶胶载体,其成膜厚度更低,成膜更加均匀。其次,根据上述制备工艺,制备出包覆熏衣草精油的硅凝胶和改性硅凝胶,研究了两者在95%乙醇溶液中的释放性能且对释放曲线进行了动力学模型拟合,并通过TG、FTIR分析表征了两种功能凝胶。结果显示,不论是改性硅凝胶,还是未改性硅凝胶,作为一种包覆材料,对功能活性因子——熏衣草精油,都具有较好的缓释性,后者的缓释性较前者略好。改性剂GPTMS的添加降低了硅凝胶载体的缓释性,但没有改变硅凝胶包覆物的释放机理。硅凝胶包覆物的释放动力学模型较好地符合Higuchi动力学模型,这表明硅凝胶载体中活性因子的释放是通过凝胶网络扩散和凝胶孔道来实现的。TG分析进一步证实了改性剂的添加降低了硅凝胶的缓释功能。FTIR分析表明,包覆过程仅是一种物理行为,并不影响装载物的性质。再次,基于上述的研究结果,制备了装填熏衣草精油的硅溶胶整理液,用其整理棉织物,制备出具有长效芳香保健功能的纺织品,并研究了整理方法、焙烘条件、熏衣草精油/Si02质量比以及改性剂等因素对整理织物留香时间的影响,此外,也考察了改性剂对整理织物的耐水洗性及物理机械性能的影响,并利用TG、DSC、FTIR、SEM和SPM等分析手段表征了整理织物。结果显示,浸轧法整理织物的留香期较浸渍法长。焙烘条件对整理织物的留香时间具有较大影响,同时也对整理织物的芳香性具有一定的影响,合理的焙烘条件为焙烘温度120℃,焙烘时间1min。不同熏衣草精油/Si02质量比同样对整理织物的留香时间具有较大影响,较佳的质量比为1:2。改性剂的添加降低了整理织物的芳香缓释性,但改善了耐水洗性,同时降低了对整理织物物理机械性能的影响。与未处理样相比,整理织物的热分解性基本没有变化,而玻璃化转变温度升高,其中改性硅溶胶包覆物处理样较未改性的略低。SEM显示,整理织物表面形成了一层连续薄膜。SPM分析表明,改性硅溶胶包覆物处理样表面所成凝胶网状结构较疏松,而未改性硅溶胶包覆物处理样表面所成凝胶网状结构较紧密。最后,研究了酸催化的硅溶胶载体对处理棉织物的断裂强力、撕破强力、手感、芯吸效应、透湿性、放湿性等性能的影响。结果显示,硅溶胶处理棉织物,一定条件下可提高处理织物的断裂强力,尤其在较高的焙烘温度或较长的焙烘时间下,当然,温度应严格控制在棉纤维所能承受的温度范围内。不同工艺条件下,硅溶胶处理棉织物的撕破强力、芯吸效应、透湿性都有不同程度的下降,尤其在较高的焙烘温度、较长的焙烘时间或较高的硅溶胶浓度下,影响更明显,加入改性剂GPTMS可降低硅溶胶处理所带来的负面影响,且效果随用量的增加而增加。整理织物的手感都有不同程度的下降,尤其在较高的焙烘温度、较长的焙烘时间或较高的硅溶胶浓度下,影响更明显,加入改性剂GPTMS可降低对它的负面影响,且效果随用量的增加而增加。整理织物的放湿性都有不同程度的下降,尤其在较低的焙烘温度、较短的焙烘时间或较低的硅溶胶浓度下,影响更明显,改性剂GPTMS的加入效果并不明显。ATR-FTIR分析表明,硅溶胶载体处理对棉纤维的微观结构没有明显影响。更多还原

【Abstract】 As a kind of preparing and modifying technique of material, sol-gel technique has already become a new developing trend of functional finishing of textile due to its characteristics of highly chemical homogeneity, easily processing, high purity, easily shaping & modifying, nontoxicity and inertness to organism, etc. As a kind of colloidal material most widely used, it has been widely applied to functional finishing of textile as excellent eco-friendly finishing material. Any functional factors can be embedded into silica gel by forming film of sol, and to aim to control its release, we can change the structure of film and size & size distribution of its microhole to tailor the immobility of factors, by which textile with long-term functionality can thus be fabricated, such as long-term fragrant and healthcare textile.In regard to this, the purposes of this paper are to prepare eco-friendly stable transparent homogeneous silica sol with good film-forming characteristic and little influence on the properties of treated fabric by sol-gel process using tetraethoxysilane (TEOS) as precursor, (y-glycidyloxypropyl)-trimethoxysilane (GPTMS) as modifier, ethanol as co-solvent, hydrochloric acid as catalyzer, poly (vinyl alcohol) (PVA) as film-forming accelerant and to fabricate long-term fragrant and healthcare textile by embedding lavender essence having calming and nerves-soothing effects into silica sol and forming film on the surface of fabric, and to try to develop a new finishing technique with simpler and more eco-friendly process for fragrant and healthcare functional finishing of textile. Thus, the main research contents and results of this paper are as follows:Firstly, in this paper, we investigated the influences of dosages of water, co-solvent (ethanol), catalyzer (hydrochloric acid), film-forming accelerant (PVA) & modifier (GPTMS) and reaction temperature & time on the properties of the obtained silica sol (viscosity, gelation time and size of colloidal particle) by single factor experimentation, and optimized the processes using orthogonal design [L)6(45)] and analyzed the influence of modifier on the morphology of silica film. The results show that stable transparent homogeneous silica sol with good film-forming characteristic and little influence on the properties of treated fabric can be obtained under the conditions that molar ratios of TEOS to H2O to Ethanol to HCl to GPTMS is 1:50:8: 8×10-3:1, concentration of PVA is 0.2% and reaction temperature & time are respectively 25℃and 3 h. The analysis of SPM indicates that modified silica film is thinner and more homogeneous than silica film not modified.Secondly, we prepared lavender-embedded silica and modified silica gel based on the processes above, and investigated the releasing properties of the two gels in 95% ethanol solution and made a kinetic model fitting, and also characterized the two gels by TG and FTIR. The results show that both silica gel and modified silica gel have slow-releasing effect on lavender essence inside and silica gel not modified is comparatively better. Adding modifier (GPTMS) will reduce the slow-releasing effect of silica gel, but will not change its releasing mechanism. The release mechanism of lavender-embedded silica gel accords with Higuchi model, which suggests that the release of functional factors inside is realized by diffusing through gel network and cavity. The analysis of TG testifies that the slow-releasing effect of modified silica gel reduced due to the addition of GPTMS, and the analysis of FTIR indicates that the embedding process is only physical mechanism, not influence the properties of substances loaded.Thirdly, long-term fragrant and healthcare textile was fabricated using the finishing solution containing lavender essence incorporated with silica sol or modified silica sol, and the influences of finishing method, baking conditions, mass ratio of lavender to SiO2 and modifier on fragrance retention time of the treated fabric were investigated, furthermore, the influence of modifier on washing fastness and mechanical properties of the treated fabric was also investigated, and the treated fabric was characterized by TG, DSC, FTIR, SEM and SPM. The results show that fragrance retention time of the fabric treated by dip-pad method is longer than that by immersion method. Baking conditions have remarkable influence on both fragrance retention time and aromaticity, the reasonable baking conditions are 120℃of baking temperature and 1 min of baking time. The mass ratio of lavender to SiO2 also has obvious influence on fragrance retention time and the optimized ratio is 1:2. Adding modifier reduced the slow-releasing effect of the treated fabric, but improved washing fastness and reduced the negative influence on the properties of the treated fabric. The heat-decomposing property of the treated fabric changed little compared with the untreated one. Glass transit temperature (Tg) of the treated fabric enhanced, and Tg of the fabric treated with modified silica sol is a little lower than that with silica sol not modified. SEM shows that the continuous silica film was formed on the surface of the treated fiber. The analysis of SPM indicates that the formed gel network from modified silica sol is looser than that from silica sol not modified.Lastly, the influences of treatment of acid-catalyzed silica sol derived from TEOS on the tensile strength, tear strength, hand, wicking effect and water vapor transmission & moisture desorption properties of the treated cotton fabric were investigated. The results show that treatment of silica sol on cotton fabric is favorable to the improvement of its tensile strength under certain conditions, especially at higher curing temperature or for longer curing time, certainly, the temperature must be strictly controlled in the range in which the fiber will not be damaged. The tear strength, wicking effect and water vapor transmission property of the treated cotton fabric all decreased at different levels, especially at higher curing temperature, or for longer curing time, or with higher silica content, whereas the addition of GPTMS can reduce the negative effect of the treatment on theirs, especially in a lower molar ratio of TEOS to GPTMS. The hand of the treated cotton fabric decreased, especially at higher curing temperature, or for longer curing time, or with higher silica content, whereas the addition of GPTMS can weaken the negative effect of the treatment on hand, especially in a lower molar ratio of TEOS to GPTMS. The moisture desorption property of the treated cotton fabric decreased, especially at lower curing temperature, or for shorter curing time, or with lower silica content, and the addition of GPTMS has not remarkable effect. The analysis of ATR-FTIR shows that the treatment of silica sol has not distinct influence on the microstructure of the treated fiber.更多还原