CN114753143B - 一种超疏水纺织品的制备方法 - Google Patents
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
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Abstract
本发明属于纺织技术领域，特别涉及一种超疏水纺织品的制备方法，该方法首先将纤维素纤维织物浸入含有阳离子表面活性剂的铜盐溶液中，然后在纤维素纤维织物表面原位沉积纳米氧化亚铜，再采用硬脂酸对其进行处理，获得超疏水纺织品。采用超声辅助原位沉积的方式，在织物表面固着氧化亚铜，从而在织物表面构筑粗糙表面。在氧化亚铜制备过程中，添加阳离子表面活性剂作为粒子稳定剂，避免纳米氧化亚铜的团聚；同时，阳离子表面活性剂可与阴离子硬脂酸静电结合，提高整理织物的疏水性和耐洗性。
Description
技术领域
本发明属于纺织技术领域，特别涉及一种超疏水纺织品的制备方法。
背景技术
超疏水表面对水具有排斥性，可让水滴在其表面无法铺展开，一直保持球形滚动状。由于超疏水材料表面具有防水、自清洁、避免生物污染作用的功能，在纺织、生物科技、传热等领域中有重要应用前景。现有的超疏水材料的表面大多模仿荷叶的结构设计，通过在材料表面构筑乳突状凸起表面，再涂覆低表面能材料来实现。目前，超疏水纺织品的制备大多是首先采用表面刻蚀、碱处理、表面沉积二氧化硅等，再采用低表面能的氟化物、有机硅聚合物整理获得，该方法工艺路线长，操作不方便。
发明内容
为克服现有技术的不足，本发明提供了一种超疏水纺织品的制备方法，该方法首先在纺织品表面原位沉积纳米氧化亚铜，然后采用硬脂酸对其进行处理，不仅工艺简单，所得织物疏水性好。
本发明提供的超疏水纺织品的制备方法，包括以下步骤：
(1)将铜盐溶于一缩二乙二醇中，配制0.1-0.3mol/L铜盐溶液，然后在上述溶液中加入阳离子表面活性剂和还原剂，搅拌至完全溶解；加入经退浆、煮练、漂白的纤维素纤维织物，搅拌5-10min使织物充分润湿；将超声探头(材质优选钛合金，直径20mm)，在一定功率下(具体方法为，将超声探头插入溶液中央，探头端部位于液面下1cm)，在设定功率下超声进行原位沉积纳米氧化亚铜，反应结束后将织物取出，用去离子水洗涤3-5次后，备用；
(2)将硬脂酸溶于无水乙醇溶液中，配制0.05-0.5mol/L的硬脂酸溶液；将经步骤(1)处理的纤维素纤维织物浸入硬脂酸溶液中，20-40min后取出，用去离子水洗涤3-5次后，40-60℃烘箱中烘干，即可。
进一步的，步骤(1)中所述的铜盐为一水醋酸铜、五水硫酸铜、二水氯化铜中的任意一种。
进一步的，步骤(1)中所述的阳离子表面活性剂为十二烷基二甲基苄基氯化铵、十六烷基二甲基苄基氯化铵、十八烷基二甲基苄基氯化铵、十二烷基三甲基溴化铵、十六烷基三甲基溴化铵、十八烷基三甲基溴化铵中的任意一种或多种，进一步的，其浓度为0.05％-0.5％。
进一步的，步骤(1)中所述的还原剂为葡萄糖或抗坏血酸，其浓度为5-15g/L。
进一步的，步骤(1)中所述的超声反应功率为300-800W，超声反应时间为5-15min。
本发明首先采用超声辅助方式在织物表面沉积氧化亚铜，在氧化亚铜制备过程中添加阳离子表面活性剂，不仅可使沉积到织物表面的氧化亚铜分散均匀，粒径小；而且附着在氧化亚铜表面的阳离子表面活性剂可通过静电作用与硬脂酸结合，提高织物的疏水性和耐洗牢度。
(1)本发明有益效果在于：采用超声辅助原位沉积的方式，在织物表面固着氧化亚铜，从而在织物表面构筑粗糙表面。
(2)在氧化亚铜制备过程中，添加阳离子表面活性剂作为粒子稳定剂，避免纳米氧化亚铜的团聚；同时，阳离子表面活性剂可与阴离子硬脂酸静电结合，提高整理织物的疏水性和耐洗性。
附图说明
图1为Cu2O(图中a)、实施例1所得织物(图中b)及未处理棉织物(图中c)的XRD图谱。
图2为未经处理棉织物(图中A1至A3)和实施例1所得织物(图中B1至B3)不同放大倍数的扫描电镜图。
图3为未处理过的棉织物(图中a)、只沉积氧化亚铜的棉织物(图中b)、实施例1所得织物(图中c)及只经过硬脂酸修饰的棉织物(图中d)的水接触角。
具体实施方式
下面结合具体的实施例，进一步详细地描述本发明。应理解，这些实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
实施例1
(1)将一水醋酸铜溶于一缩二乙二醇中，配制0.1mol/L醋酸铜溶液，然后在上述溶液中加入阳离子表面活性剂十二烷基二甲基苄基氯化铵，其浓度为0.05％；还原剂葡萄糖，其浓度为5g/L，搅拌至完全溶解；加入经退浆、煮练、漂白的纤维素纤维织物，搅拌5min使织物充分润湿；将钛合金超声探头(直径20mm)插入溶液中央，探头端部位于液面下1cm，在300W功率下，超声反应15min，将织物取出，用去离子水洗涤3次后，备用；
(2)将硬脂酸溶于无水乙醇溶液中，配制0.05mol/L的硬脂酸溶液；将经步骤(1)处理的纤维素纤维织物浸入硬脂酸溶液中，20min后取出，用去离子水洗涤3次后，40℃烘箱中烘干，即可。
比较例1-1(直接采用硬脂酸处理)
将硬脂酸溶于无水乙醇溶液中，配制0.05mol/L的硬脂酸溶液；将纤维素纤维织物浸入硬脂酸溶液中，20min后取出，用去离子水洗涤3次后，40℃烘箱中烘干，即可。
比较例1-2(未添加阳离子表面活性剂)
(1)将一水醋酸铜溶于一缩二乙二醇中，配制0.1mol/L醋酸铜溶液，然后在上述溶液中加入还原剂葡萄糖，其浓度为5g/L，搅拌至完全溶解；加入经退浆、煮练、漂白的纤维素纤维织物，搅拌5min使织物充分润湿；将钛合金超声探头(直径20mm)插入溶液中央，探头端部位于液面下1cm，在300W功率下，超声反应15min，将织物取出，用去离子水洗涤3次后，备用；
(2)将硬脂酸溶于无水乙醇溶液中，配制0.05mol/L的硬脂酸溶液；将经步骤(1)处理的纤维素纤维织物浸入硬脂酸溶液中，20min后取出，用去离子水洗涤3次后，40℃烘箱中烘干，即可。
实施例2
(1)将五水硫酸铜溶于一缩二乙二醇中，配制0.3mol/L硫酸铜溶液，然后在上述溶液中加入阳离子表面活性剂十六烷基三甲基溴化铵，其浓度为0.5％；还原剂抗坏血酸，其浓度为15g/L，搅拌至完全溶解；加入经退浆、煮练、漂白的纤维素纤维织物，搅拌10min使织物充分润湿；将钛合金超声探头(直径20mm)插入溶液中央，探头端部位于液面下1cm，在800W功率下，超声反应5min，将织物取出，用去离子水洗涤5次后，备用；
(2)将硬脂酸溶于无水乙醇溶液中，配制0.5mol/L的硬脂酸溶液；将经步骤(1)处理的纤维素纤维织物浸入硬脂酸溶液中，40min后取出，用去离子水洗涤5次后，60℃烘箱中烘干，即可。
实施例3
(1)将二水氯化铜溶于一缩二乙二醇中，配制0.2mol/L氯化铜溶液，然后在上述溶液中加入阳离子表面活性剂十八烷基二甲基苄基氯化铵，其浓度为0.25％；还原剂葡萄糖，其浓度为10g/L，搅拌至完全溶解；加入经退浆、煮练、漂白的纤维素纤维织物，搅拌8min使织物充分润湿；将钛合金超声探头(直径20mm)插入溶液中央，探头端部位于液面下1cm，在600W功率下，超声反应10min，将织物取出，用去离子水洗涤4次后，备用；
(2)将硬脂酸溶于无水乙醇溶液中，配制0.25mol/L的硬脂酸溶液；将经步骤(1)处理的纤维素纤维织物浸入硬脂酸溶液中，30min后取出，用去离子水洗涤4次后，50℃烘箱中烘干，即可。
实施例4
(1)将五水硫酸铜溶于一缩二乙二醇中，配制0.15mol/L硫酸铜溶液，然后在上述溶液中加入阳离子表面活性剂十二烷基三甲基溴化铵，其浓度为0.15％；还原剂抗坏血酸，其浓度为8g/L，搅拌至完全溶解；加入经退浆、煮练、漂白的纤维素纤维织物，搅拌6min使织物充分润湿；将钛合金超声探头(直径20mm)插入溶液中央，探头端部位于液面下1cm，在400W功率下，超声反应12min，将织物取出，用去离子水洗涤4次后，备用；
(2)将硬脂酸溶于无水乙醇溶液中，配制0.15mol/L的硬脂酸溶液；将经步骤(1)处理的纤维素纤维织物浸入硬脂酸溶液中，25min后取出，用去离子水洗涤4次后，45℃烘箱中烘干，即可。
实施例5
使用德国Dataphysics公司生产的OCA40型视频接触角测量仪进行接触角测试，水量为5μL，当水滴与织物接触60s后读数。在同一样品不同位置测量8次，取平均值。
使用微量进样器控制水滴量为15μL，调整斜台的倾斜角度，并保持微量进样器针头至织物表面距离为1cm，水滴在织物上滚动距离为2cm。在同一样品不同位置测量10次，取能使至少5个水滴都完全滚落的最小倾斜角作为织物的滚动角。
耐洗性能测试按照GB/T 8629-2017《纺织品试验用家庭洗涤和干燥程序》在耐洗色牢度试验机中完成。洗涤、干燥结束后测试织物的接触角、滚动角及沾水性。
表1整理棉织物疏水性能
从表1可看出，本发明所得织物接触角均超过155°，滚动角均小于10°，具有优异的超疏水性，且具有优异的耐洗性。比较例1-1未沉积氧化亚铜，直接采用硬脂酸对织物进行处理，由于未在织物上构筑粗糙表面，因此，织物疏水性较差，且不耐水洗；比较例1-2在氧化亚铜制备过程中未添加阳离子表面活性剂，后面硬脂酸整理时，吸附在织物表面硬脂酸较少，且与织物结合弱，因此，所得织物疏水性、耐洗性均不及实施例1。
本发明首先利用纤维素纤维织物的毛细管作用，将Cu2+吸附到纤维内部，利用超声波振荡和声空穴作用，促进铜离子向纤维内部的扩散与渗透，再通过还原剂作用，在纤维内部原位沉积氧化亚铜，氧化亚铜除了与纤维上的含氧官能团作用外，纤维与纤维之间对氧化亚铜有机械包裹、缠绕作用，因此，其与纤维的结合更牢固。在氧化亚铜制备过程中，添加了阳离子表面活性剂，利用阳离子表面活性剂与阴离子硬脂酸之间的静电结合，进一步提高耐洗效果。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种超疏水纺织品的制备方法，其特征在于：包括如下步骤：首先将纤维素纤维织物浸入含有阳离子表面活性剂和还原剂的铜盐溶液中，然后在设定功率下超声在纤维素纤维织物表面原位沉积纳米氧化亚铜，再采用硬脂酸对其进行处理，获得超疏水纺织品，其中纳米氧化亚铜表面附着所述阳离子表面活性剂，且所述阳离子表面活性剂通过静电作用与硬脂酸结合；
铜盐溶液溶剂为一缩二乙二醇，铜盐浓度为0.1-0.3mol/L；
所述纤维织物为经退浆、煮练及漂白处理后的；
所述阳离子表面活性剂为十二烷基二甲基苄基氯化铵、十六烷基二甲基苄基氯化铵、十八烷基二甲基苄基氯化铵、十二烷基三甲基溴化铵、十六烷基三甲基溴化铵、十八烷基三甲基溴化铵中的任意一种或多种。
2.如权利要求1所述的超疏水纺织品的制备方法，其特征在于：所述方法的具体步骤为，
（1）将铜盐溶于一缩二乙二醇中，配制0.1-0.3mol/L铜盐溶液，然后在上述溶液中加入阳离子表面活性剂和还原剂，搅拌至完全溶解；加入经退浆、煮练及漂白的纤维素纤维织物，搅拌5-10min使织物充分润湿；插入超声探头，在设定功率下超声进行原位沉积纳米氧化亚铜，反应结束后将织物取出，用去离子水洗涤3-5次后，备用；
（2）将硬脂酸溶于无水乙醇溶液中，配制0.05-0.5 mol/L的硬脂酸溶液；将经步骤（1）处理的纤维素纤维织物浸入硬脂酸溶液中，20-40min后取出，用去离子水洗涤3-5次后，40-60℃烘箱中烘干，即可。
3.如权利要求2所述的超疏水纺织品的制备方法，其特征在于：步骤（1）中铜盐为一水醋酸铜、五水硫酸铜、二水氯化铜中的任意一种。
4.如权利要求2所述的超疏水纺织品的制备方法，其特征在于：步骤（1）中阳离子表面活性剂在铜盐溶液中的质量浓度为0.05%-0.5%。
5.如权利要求2所述的超疏水纺织品的制备方法，其特征在于：步骤（1）中所述的还原剂为葡萄糖或抗坏血酸，其浓度为5-15g/L。
6.如权利要求2所述的超疏水纺织品的制备方法，其特征在于：步骤（1）中超声反应功率为300-800W，超声反应时间为5-15min。
7.如权利要求2所述的超疏水纺织品的制备方法，其特征在于：步骤（1）中超声探头材质为钛合金，直径20mm，使用方法为将超声探头插入溶液中央，探头端部位于液面下1cm。
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