CN106521927A - 一种超疏水织物及其制备方法 - Google Patents
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Abstract
本发明公开了一种超疏水织物及其制备方法。该制备方法首先将织物浸渍在植酸溶液中，使其表面附着植酸分子；将织物取出置于含金属离子的溶液中，利用植酸对金属离子的螯合作用，在织物表面反应并沉积不溶性螯合物颗粒；循环上述步骤多次，在织物上重复沉积植酸‐金属螯合物颗粒；利用低表面能物质对织物进行疏水化改性，制得超疏水织物。本发明得到表面与水的接触角大于150°，滚动角小于10°，具有良好的超疏水性质的织物。本发明制备过程简单高效、原料环保、成本低廉、极易推广。
Description
技术领域
本发明涉及织物疏水改性，特别是涉及一种超疏水织物及其制备方法，属于功能性纺织物制备领域。
背景技术
通常将与水的接触角大于150°的表面称为超疏水表面。荷叶表面即为一种十分常见的超疏水表面，它具有极为优异的疏水性和较小的滚动角，能够保持不被沾污的自清洁功能，即所谓的“荷叶效应”。这种类似于荷叶的超疏水表面由于具有自清洁、抗粘附、防污抑菌、防水等优良特性，已经引起了科研人员的广泛关注。因此，研究和开发实现超疏水的新途径，并将超疏水特性应用到各种材料表面，对于拓展超疏水新材料的应用和发展具有十分重要的意义。
随着超疏水材料的开发，柔性的超疏水表面如织物材料基质逐渐引起了研究者及工业界的关注。超疏水纺织品在工业生产、医疗、军用产品方面和日常生活中都体现出了重要的应用价值。传统的制备超疏水织物的方法大多存在处理过程复杂、原料昂贵，不可大面积生产和稳定性不好等缺点。
中国发明专利申请CN104562709A公开了一种在织物基底上采用聚多巴胺螯合氧化银颗粒构造粗糙度，再通过疏水改性获得超疏水织物的方法，但是该方法使用的聚多巴胺昂贵且合成过程复杂，不利于实际应用。
中国发明专利申请CN105544221A和中国发明专利申请CN105544187A公开了两种利用硅凝胶和聚二甲基硅氧烷覆盖纺织物表面构建超疏水织物的方法，但是该方法原料水解、静置时间过长，大大降低了制备效率，不利于工业生产。
发明内容
针对现有技术存在的缺陷，本发明目的主要是提供一种超疏水织物及其制备方法。本发明获得的织物表面与水的接触角大于150°，滚动角小于10°，具有良好的超疏水性质。
本发明所采用的原材料之一——植酸主要存在于植物的种子、根干和茎中，其中以豆科植物的种子、谷物的麸皮和胚芽中含量最高，其毒性比食盐更低，因此原料获取容易、成本低廉、绿色环保。同时，本发明制备过程极其简单高效、无需高温高压反应，容易推广。
本发明目的通过如下技术方案实现：
一种超疏水织物的制备方法，具有以下步骤：
1)将织物浸渍在植酸溶液中，使其表面附着植酸分子；
2)将织物取出置于含金属离子的溶液中，利用植酸对金属离子的螯合作用，在织物表面反应并沉积不溶性螯合物颗粒；
3)循环步骤1)和步骤2)多次，在织物上重复沉积植酸‐金属螯合物颗粒；
4)利用低表面能物质对织物进行疏水化改性，制得超疏水织物。
为进一步实现本发明目的，优选地，所述植酸溶液的浓度为0.005～0.1mol/L。
优选地，所述金属离子为正三价铁离子、正四价锆离子、正一价银离子、正三价铈离子和正四价锡离子中的至少一种。
优选地，所述金属离子浓度为0.002～2.0mol/L。
优选地，所述循环步骤1)和步骤2)的次数为2～15次。
优选地，所述的利用低表面能物质对织物进行疏水化改性的方法为：将沉积了植酸‐金属离子螯合物颗粒的织物浸入体积分数为0.5～6％的含低表面能物质的氯仿溶液中，在室温下处理2～30min，然后取出织物，在60～90℃下处理30～300min。
优选地，所述的低表面能物质为1H,1H,2H,2H‐全氟癸基三乙氧基硅烷、1H,1H,2H,2H‐全氟辛基三乙氧基硅烷、1H,1H,2H,2H‐全氟辛基三甲氧基硅烷、1H,1H,2H,2H‐全氟癸基三甲氧基硅烷、氯硅烷类以及硅氧烷类化合物中的至少一种。
一种上述的制备方法制备得到的超疏水织物：所述织物与水滴的静态接触角为大于150°，滚动角小于10°。
步骤1)所述的织物的原料为棉、麻、羊毛、丝绸、腈纶、尼龙和涤纶中的一种或多种的混纺织物。
本发明与现有技术相比，具有以下优点和技术效果：
1)本发明所得的超疏水织物具有较好的超疏水性。
2)本发明所得的超疏水织物稳定性良好，经过UV光长时间照射或着采用砂纸摩擦后，织物与水表面的接触角仍然大于140°，保持了较好的疏水性。
3)本发明超疏水织物制备过程中不需要使用强酸性、强碱性试剂，所使用材料获取容易、成本低廉、绿色环保，易操作，不需要特殊的设备仪器。
4)本发明的超疏水织物制备方法不受织物基材种类限制，对本领域公知的织物如棉、麻、羊毛、丝绸、腈纶、尼龙、涤纶及其混纺织物等都适应。
附图说明
图1是本发明实施例1制备的超疏水织物的扫描电子显微镜照片。
图2为本发明实施例1制备的超疏水织物的水接触角图。
具体实施方式
为更好地理解本发明，下面结合附图和实施例对本发明作进一步的说明，但本发明的实施方式不限如此。
实施例中采用接触角仪测量织物表面与水的接触角和滚动角。实施例中采用文献Phys.Chem.Chem.Phys.,2015,17,6451‐6457中报道的方法对织物进行机械耐磨性测试。
实施例1
本实施例采用的织物为棉纤维。首先将3×3cm2棉纤维浸渍在50ml含0.013mol/L植酸(70％水溶液，上海源叶生物科技有限公司)的水溶液中2min，使织物表面附着植酸分子，然后将织物取出置于20ml含0.01mol/L FeCl3的水溶液中，利用植酸对铁离子的螯合作用，在织物表面反应并沉积不溶性植酸‐铁螯合物颗粒；循环浸入上述植酸溶液和FeCl3溶液4次，在织物上重复沉积植酸‐铁螯合物颗粒；拿出棉纤维织物烘干，放入含20ml含2wt％聚二甲基硅氧烷和0.2wt％有机硅弹性体固化剂的氯仿溶液中浸泡2min，最后在80℃下烘干120min，即得到接触角为151.5°，滚动角为8°的超疏水棉纤维织物。
将获得的棉纤维织物在40W UV光下照射24h，其接触角依然大于150°；将织物置于1000目SiC砂纸上，用100g重物压其表面，并拖动600cm后，摩擦后的表面与水接触角依然大于140°。显示出了良好的疏水稳定性。
图1为本发明实施例1制备的超疏水织物的SEM图，从图1可以看出植酸‐铁螯合物颗粒均匀覆盖织物表面形成一定的粗糙度。
图2为本发明实施例1制备的超疏水织物的液滴接触角图，接触角为151.5°。
下面实施例所得超疏水织物的SEM图以及超疏水织物的液滴接触角图与图1和图2相似，不一一提供。
实施例2
本实施例采用的织物为棉纤维。首先将3×3cm2棉纤维浸渍在50ml含0.006mol/L植酸(70％水溶液，上海源叶生物科技有限公司)的水溶液中2min，使织物表面附着植酸分子，然后将织物取出置于20ml含0.02mol/L Ce(NO3)3的水溶液中，利用植酸对铈离子的螯合作用，在织物表面反应并沉积不溶性植酸‐铈螯合物颗粒；循环浸入上述植酸溶液和Ce(NO3)3溶液3次，在织物上重复沉积植酸‐铈螯合物颗粒；拿出棉纤维织物烘干，放入含20ml含1.5wt％1H,1H,2H,2H‐全氟辛基三乙氧基硅烷的氯仿溶液中浸泡10min，最后在90℃下烘干300min，即得到接触角为153°，滚动角为6°的超疏水棉纤维织物。
将获得的棉纤维织物在40W UV光下照射24h，其接触角依然大于150°；将织物置于600目SiC砂纸上，用100g重物压其表面，并拖动600cm后，摩擦后的表面与水接触角依然大于145°。显示出了良好的疏水稳定性。
实施例3
本实施例采用的织物为涤纶纤维。首先将3×3cm2涤纶纤维浸渍在50ml含0.02mol/L植酸(70％水溶液，上海源叶生物科技有限公司)的水溶液中2min，使织物表面附着植酸分子，然后将织物取出置于20ml含0.1mol/L AgNO3的水溶液中，利用植酸对银离子的螯合作用，在织物表面反应并沉积不溶性植酸‐银螯合物颗粒；循环浸入上述植酸溶液和AgNO3溶液10次，在织物上重复沉积植酸‐银螯合物颗粒；拿出涤纶纤维织物烘干，放入含20ml含1.5wt％聚二甲基硅氧烷和0.15wt％有机硅弹性体固化剂的氯仿溶液中浸泡20min，最后在80℃下烘干200min，即得到接触角为153°，滚动角为4.5°的超疏水涤纶纤维织物。
将获得的涤纶纤维织物在40W UV光下照射24h，其接触角依然大于150°；将织物置于1000目SiC砂纸上，用100g重物压其表面，并拖动600cm后，摩擦后的表面与水接触角依然大于140°。显示出了良好的疏水稳定性。
实施例4
本实施例采用的织物为腈纶纤维。首先将3×3cm2腈纶纤维浸渍在50ml含0.05mol/L植酸(70％水溶液，上海源叶生物科技有限公司)的水溶液中2min，使织物表面附着植酸分子，然后将织物取出置于20ml含0.2mol/L SnCl4的水溶液中，利用植酸对锡离子的螯合作用，在织物表面反应并沉积不溶性植酸‐锡螯合物颗粒；循环浸入上述植酸溶液和SnCl4溶液2次，在织物上重复沉积植酸‐锡螯合物颗粒；拿出腈纶纤维织物烘干，放入含1.0wt％1H,1H,2H,2H‐全氟癸基三乙氧基硅烷的氯仿溶液中浸泡10min，最后在90℃下烘干240min，即得到接触角为152°，滚动角为5°的超疏水腈纶纤维织物。
将获得的腈纶纤维织物在40W UV光下照射24h，其接触角依然大于150°；将织物置于2000目SiC砂纸上，用100g重物压其表面，并拖动600cm后，摩擦后的表面与水接触角依然大于145°。显示出了良好的疏水稳定性。
实施例5
本实施例采用的织物为麻纤维。首先将3×3cm2麻纤维浸渍在50ml含0.005mol/L植酸(70％水溶液，上海源叶生物科技有限公司)的水溶液中2min，使织物表面附着植酸分子，然后将织物取出置于20ml含0.015mol/L ZrCl4的水溶液中，利用植酸对锆离子的螯合作用，在织物表面反应并沉积不溶性植酸‐锆螯合物颗粒；循环浸入上述植酸溶液和ZrCl4溶液6次，在织物上重复沉积植酸‐锆螯合物颗粒；拿出麻纤维织物烘干，放入含20ml含2.5wt％三氟丙基甲基二氯硅烷的氯仿溶液中浸泡20min，最后在70℃下烘干280min，即得到接触角为150.5°，滚动角为7°的超疏水麻纤维织物。
将获得的麻纤维织物在40W UV光下照射24h，其接触角依然大于150°；将织物置于800目SiC砂纸上，用100g重物压其表面，并拖动600cm后，摩擦后的表面与水接触角依然大于140°。显示出了良好的疏水稳定性。
本发明所采用的主要原材料中植酸主要存在于植物的种子、根干和茎中，其中以豆科植物的种子、谷物的麸皮和胚芽中含量最高，其毒性比食盐更低，因此原料获取容易、成本低廉、绿色环保。本发明不需要使用强酸性、强碱性试剂，本发明制备过程极其简单高效、无需高温高压反应，不需要特殊的设备仪器，除了使得织物具有很好的超疏水性外，对织物的机械性能没有实质影响，对多种织物适用，不影响织物的用途。本发明制备的超疏水织物可广泛应用于工业生产、医疗、军用及日常生活等诸多领域。
Claims (8)
1.一种超疏水织物的制备方法，其特征在于具有以下步骤：
1)将织物浸渍在植酸溶液中，使其表面附着植酸分子；
2)将织物取出置于含金属离子的溶液中，利用植酸对金属离子的螯合作用，在织物表面反应并沉积不溶性螯合物颗粒；
3)循环步骤1)和步骤2)多次，在织物上重复沉积植酸‐金属螯合物颗粒；
4)利用低表面能物质对织物进行疏水化改性，制得超疏水织物。
2.根据权利要求1所述的制备方法，其特征在于：所述植酸溶液的浓度为0.005～0.1mol/L。
3.根据权利要求1所述的制备方法，其特征在于：所述金属离子为正三价铁离子、正四价锆离子、正一价银离子、正三价铈离子和正四价锡离子中的至少一种。
4.根据权利要求1所述的制备方法，其特征在于：所述金属离子浓度为0.002～2.0mol/L。
5.根据权利要求1所述的制备方法，其特征在于：所述循环步骤1)和步骤2)的次数为2～15次。
6.根据权利要求1所述的制备方法，其特征在于：所述的利用低表面能物质对织物进行疏水化改性的方法为：将沉积了植酸‐金属离子螯合物颗粒的织物浸入体积分数为0.5～6％的含低表面能物质的氯仿溶液中，在室温下处理2～30min，然后取出织物，在60～90℃下处理30～300min。
7.根据权利要求1所述的制备方法，其特征在于：所述的低表面能物质为1H,1H,2H,2H‐全氟癸基三乙氧基硅烷、1H,1H,2H,2H‐全氟辛基三乙氧基硅烷、1H,1H,2H,2H‐全氟辛基三甲氧基硅烷、1H,1H,2H,2H‐全氟癸基三甲氧基硅烷、氯硅烷类以及硅氧烷类化合物中的至少一种。
8.一种权利要求1～7任意一项所述的制备方法制备得到的超疏水织物，其特征在于：所述织物与水滴的静态接触角为大于150°，滚动角小于10°。
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