CN113201934B - 一种水性超疏水涂料及其制备方法和应用 - Google Patents
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Abstract
本发明属于水性防水涂料领域，具体涉及一种水性超疏水涂料及其制备方法和应用。所述水性超疏水涂料，用于经预处理产生层次结构粗糙度和反应性巯基的羊毛织物，包括疏水剂0.5‑5vol％、表面活性剂5‑25mM、氧化剂10‑25mM、催化剂1‑5mM，余量为水，所述疏水剂为巯基类疏水剂。本发明的水性超疏水涂料，简单环保，成本较低，对设备要求不高，表面疏水性能优异；疏水剂可乳化分散在水相中，避免了有机溶剂的使用；水性超疏水涂料的应用，无论是酶刻蚀、断裂二硫键产生巯基的还原剂、巯基类疏水剂和重建二硫键的氧化剂等都有很多替代品，代表了一系列的水性的超疏水涂料，通用性强。
Description
技术领域
本发明属于水性防水涂料领域，具体涉及一种水性超疏水涂料及其制备方法和应用。
背景技术
超疏水涂料因其优异的表面防护性能，在自清洁、防污、防腐等很多领域得到应用。超疏水涂料通常由较低的表面张力和层次结构粗糙度组成，但是疏水剂通常需要有机溶剂溶解，且疏水涂层包括颗粒，对基底材料粘附力弱，在使用过程中，涂层易脱落和加速流失，而失去表面的超疏水性。然而，表面接枝的牢固化学键合作用在功能性整理中显现除了独特的前景，同时随着国家对环保性的要求，水性涂料等也是国家大力主推的方向，因此，发展绿色环保的和性能优异的水性涂料是势在必行的。
发明内容
为解决上述技术问题，本发明提供了一种水性超疏水涂料及其制备方法和应用，该涂料避免了有机溶剂的使用，绿色环保，成本较低，对设备要求不高，表面疏水性能优异。
按照本发明的技术方案，所述水性超疏水涂料，用于经预处理产生层次结构粗糙度和反应性巯基的羊毛织物，包括疏水剂0.5-5vol％、表面活性剂5-25mM、氧化剂10-25mM、催化剂1-5mM，余量为水，所述疏水剂为巯基类疏水剂。
进一步的，所述疏水剂为十二烷基硫醇、十八烷基硫醇或二十四烷基硫醇。
进一步的，所述表面活性剂为十六烷基三甲基溴化铵，所述催化剂为溴化铜。
进一步的，所述氧化剂为氧气、臭氧、过氧化氢、碘单质、高碘酸钠或高锰酸钠，可以氧化巯基重建二硫键来引入新的功能性。
本发明还提过了上述水性超疏水涂料的制备方法，包括以下步骤：将疏水剂和表面活性剂加入去离子水中，机械搅拌形成均相溶液，然后加入催化剂和氧化剂，形成所述水性超疏水涂料。其中，巯基类的疏水剂可在表面活性剂作用下乳化分散在水相中，并在氧化剂的辅助下重建二硫键，实现羊毛表面的超疏水整理。整理工艺简单环保，对设备要求不高，具有较高的应用价值。
本发明的另一方面提供了一种水性超疏水涂料的应用，包括以下步骤：
(1)将羊毛织物浸于蛋白酶和还原剂的水相溶液中预处理，产生层次结构粗糙度和反应性巯基；
(2)将预处理的羊毛织物浸于如权利要求1-4任一所述水性超疏水涂料中处理，处理后经洗涤并烘干得到超疏水羊毛织物。
进一步的，所述步骤(1)中的蛋白酶为木瓜蛋白酶、碱性蛋白酶和胰蛋白酶中的至少一种，蛋白酶的浓度为2-25g L-1。
进一步的，所述步骤(1)中的还原剂为L-半胱氨酸或硼氢化钠，用于还原断裂羊毛织物表面二硫键形成大量的巯基，还原剂的浓度为10-50g L-1。
进一步的，所述步骤(1)中的处理条件为50-70℃反应1-4小时。
进一步的，所述步骤(2)中的处理条件为震荡反应4-48小时，烘干温度为60-140℃，烘干时间为2-8h。
本发明的技术方案相比现有技术具有以下优点：
1、本发明的水性超疏水涂料，简单环保，成本较低，对设备要求不高，表面疏水性能优异；
2、疏水剂可乳化分散在水相中，避免了有机溶剂的使用；
3、本发明的水性超疏水涂料的应用，无论是酶刻蚀、断裂二硫键产生巯基的还原剂、巯基类疏水剂和重建二硫键的氧化剂等都有很多替代品，代表了一系列的水性的超疏水涂料，通用性强。
附图说明
图1为水性超疏水涂料形态的光学照片。
图2为水性超疏水涂料整理的羊毛织物的SEM微观图。
图3为羊毛织物表面疏水性能随巯基类疏水剂用量的变化图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例1
水性超疏水涂料的制备
将疏水剂十二烷基硫醇和表面活性剂十六烷基三甲基溴化铵加入去离子水中，机械搅拌(1000rpm)形成乳白均相溶液，然后加入催化剂溴化铜和氧化剂过氧化氢，形成含1vol％疏水剂、11mM表面活性剂、19mM氧化剂和5mM催化剂的水性超疏水涂料，其形态的光学照片如图1所示，显现出良好的分散性和稳定性。
实施例2
水性超疏水涂料的应用，包括以下步骤，
(1)羊毛织物酶刻蚀和巯基改性预处理
将羊毛织物浸入木瓜蛋白酶和L-半胱氨酸的水相溶液中，60℃反应1小时，经洗涤烘干得到预处理样品，其中木瓜蛋白酶的浓度为10g L-1，还原剂的浓度为25g L-1；
(2)整理工艺
将预处理样品浸入实施例1所得水性超疏水涂料中，震荡反应4小时，经洗涤和60℃烘干4h得到超疏水羊毛织物。
对实施例2所得功能产品采用如下的方法进行测试：
1、接触角测试
在室温条件下，采用光学接触角测量仪(Data Physics OCA 20)对基底材料羊毛织物表面的疏水性能进行测试，水滴为6μl，取不同位置的接触角值取其平均值。
2、样品微观结构表征
通过场发射冷场电镜(SEM)对超疏水羊毛织物微观结构进行表征。
3、折皱回复角测试
基于AATCC 66标准，使用Shirley折皱回复性能测试仪对羊毛织物整理前后的折皱性能进行比较。
结果显示：其水接触角约为160°。电镜图可以看出超疏水羊毛织物表面被疏水成分包裹，以及能看到酶刻蚀得到的粗糙表面(如图2所示)。
如图3所示，调整实施例1中疏水剂的浓度，将其整理到羊毛织物表面，显现良好的超疏水性，且随着疏水剂浓度的增加，表面疏水性先提高后下降，这是因为羊毛织物表面巯基以及巯基疏水剂自身也发生了二硫键交联，降低了到羊毛织物上的接枝水平。
如表1所示，相对比羊毛织物原样，经酶刻蚀以及还原断裂二硫键后的羊毛织物更易卷曲，其无论是经纬方向，折皱回复角都出现了一定程度的下降，经疏水化之后，重建的二硫键适当提高了羊毛织物的抗折皱性能，这可能归功于羊毛织物表面自身的二硫键重建，然而更多的二硫键被重建用于表面疏水剂接枝。
表1羊毛织物原样、刻蚀和二硫键还原断裂以及二硫键氧化重建超疏水化的折皱回复角
实施例3
水性超疏水涂料的制备
将疏水剂十八烷基硫醇和表面活性剂十六烷基三甲基溴化铵加入去离子水中，机械搅拌(1000rpm)形成乳白均相溶液，然后加入催化剂溴化铜和氧化剂碘单质，形成含0.5vol％疏水剂、5mM表面活性剂、10mM氧化剂和1mM催化剂的水性超疏水涂料。
实施例4
水性超疏水涂料的应用，包括以下步骤，
(1)羊毛织物酶刻蚀和巯基改性预处理
将羊毛织物浸入碱性蛋白酶和L-半胱氨酸的水相溶液中，50℃反应4小时，经洗涤烘干得到预处理样品，其中碱性蛋白酶的浓度为2g L-1，还原剂的浓度为10g L-1；
(2)整理工艺
将预处理样品浸入实施例3所得水性超疏水涂料中，震荡反应20小时，经洗涤和90℃烘干8h得到超疏水羊毛织物。
实施例5
水性超疏水涂料的制备
将疏水剂二十四烷基硫醇和表面活性剂十六烷基三甲基溴化铵加入去离子水中，机械搅拌(1000rpm)形成乳白均相溶液，然后加入催化剂溴化铜和氧化剂高碘酸钠，形成含5vol％疏水剂、25mM表面活性剂、25mM氧化剂和2.5mM催化剂的水性超疏水涂料。
实施例6
水性超疏水涂料的应用，包括以下步骤，
(1)羊毛织物酶刻蚀和巯基改性预处理
将羊毛织物浸入碱性蛋白酶、胰蛋白酶和L-半胱氨酸的水相溶液中，70℃反应2.5小时，经洗涤烘干得到预处理样品，其中碱性蛋白酶和胰蛋白酶的总浓度为25g L-1，还原剂的浓度为50g L-1；
(2)整理工艺
将预处理样品浸入实施例3所得水性超疏水涂料中，震荡反应48小时，经洗涤和140℃烘干2h得到超疏水羊毛织物。
实施例7-9
在实施例1的基础上，将氧化剂分别替换为氧气、臭氧和高锰酸钠。
实施例10
将实施例2中L-半胱氨酸替换为硼氢化钠。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (7)
1.一种水性超疏水涂料，其特征在于，用于经预处理产生层次结构粗糙度和反应性巯基的羊毛织物，包括疏水剂0.5-5 vol%、表面活性剂5-25 mM、氧化剂10-25 mM、催化剂1-5mM，余量为水；
所述疏水剂为十二烷基硫醇、十八烷基硫醇或二十四烷基硫醇；
所述表面活性剂为十六烷基三甲基溴化铵，所述催化剂为溴化铜；
所述氧化剂为氧气、臭氧、过氧化氢、碘单质、高碘酸钠或高锰酸钠。
2.如权利要求1所述的水性超疏水涂料的制备方法，其特征在于，包括以下步骤：将疏水剂和表面活性剂加入去离子水中，机械搅拌形成均相溶液，然后加入催化剂和氧化剂，形成所述水性超疏水涂料。
3.一种水性超疏水涂料的应用，其特征在于，包括以下步骤：
（1）将羊毛织物浸于蛋白酶和还原剂的水相溶液中预处理，产生层次结构粗糙度和反应性巯基；
（2）将预处理的羊毛织物浸于权利要求1所述水性超疏水涂料中处理，处理后经洗涤并烘干得到超疏水羊毛织物。
4.如权利要求3所述的水性超疏水涂料的应用，其特征在于，所述步骤（1）中的蛋白酶为木瓜蛋白酶、碱性蛋白酶和胰蛋白酶中的至少一种，蛋白酶的浓度为2-25 g L-1。
5.如权利要求3所述的水性超疏水涂料的应用，其特征在于，所述步骤（1）中的还原剂为L-半胱氨酸或硼氢化钠，还原剂的浓度为10-50g L-1。
6.如权利要求3所述的水性超疏水涂料的应用，其特征在于，所述步骤（1）中的处理条件为50-70oC 反应1-4小时。
7.如权利要求3所述的水性超疏水涂料的应用，其特征在于，所述步骤（2）中的处理条件为震荡反应4-48小时，烘干温度为60-140℃，烘干时间为2-8h。
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