CN111501201A - 一种超疏水裂片型超细纤维非织造布及其制备方法 - Google Patents

一种超疏水裂片型超细纤维非织造布及其制备方法 Download PDF

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CN111501201A
CN111501201A CN202010313773.0A CN202010313773A CN111501201A CN 111501201 A CN111501201 A CN 111501201A CN 202010313773 A CN202010313773 A CN 202010313773A CN 111501201 A CN111501201 A CN 111501201A
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superfine fiber
woven fabric
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马兴元
何远鑫
郑四龙
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Shaanxi University of Science and Technology
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Abstract

本发明公开了一种超疏水裂片型超细纤维非织造布及其制备方法，属于超疏水纺织品技术领域。本发明的制备方法，以裂片型超细纤维非织造布为基材制备超疏水织物，通过混合碱使得涤纶纤维表面产生纳米粗糙结构且在涤纶超细纤维上产生大量的羟基和羧基，之后用混合酸在尼龙纤维表面的改性引入羟基的同时能够构筑纳米粗糙结构，再利用异氰酸酯基团将低表面能的长链烷烃通过异氰酸酯和活性氢基团的反应活性共价接枝在涤纶纤维和尼龙纤维表面，得到性质稳定的超疏水裂片型超细纤维非织造布；本发明的制备方法过程简单，条件温和，没有利用氟类物质作为原料，经济环保。

Description

一种超疏水裂片型超细纤维非织造布及其制备方法
技术领域
本发明属于超疏水纺织品技术领域，尤其是一种超疏水裂片型超细纤维非织造布及其制备方法。
背景技术
超疏水表面主要为水滴在该表面形成大于150°的接触角且滚动角小于10°。超疏水表面由于自身优异的自清洁能力以及良好的疏水性具有很广阔的使用价值，进而被广泛地应用在油水分离、防冰、金属防腐等多个领域。
在纺织品上制备超疏水表面，可以提高纺织品的应用价值，提升纺织品的档次和附加值，具有超疏水表面的纺织品在工业、军用产品方面有着重要的应用，在日常生活中的同样应用十分广泛，如“防水服、雨伞、防水帐篷、广告布料等”。在不改变或者少改变织物原有的白度、强度的前提下，增加其使用价值，扩大在工业和日常生活中的应用，具有较大的实际意义。
目前，超疏水表面使用原料昂贵、制备工艺复杂，超疏水表面耐用性不佳，或者大量使用有机氟等低表面能物质来修饰超疏水表面，因而限制了其在工业生产中的广泛应用。氟类化合物普遍具有很高的稳定性，能够经受很强的热、光、氧、化学作用、微生物作用和高等脊椎生物的代谢作用而不降解，会随着食物链的传递而在生物机体内富集和放大至很高的浓度，对生物体具有很大的危害和潜在的致癌性。
发明内容
本发明的目的在于克服现有的超疏水表面制备方法使用有机氟作原料的缺点，提供一种超疏水裂片型超细纤维非织造布及其制备方法。
为达到上述目的，本发明采用以下技术方案予以实现：
一种超疏水裂片型超细纤维非织造布的制备方法，包括以下步骤：
1)将裂片型超细纤维非织造布进行清洗，洗去纺丝助剂；
所述裂片型超细纤维非织造布由裂片型纤维经针刺法或水刺法制成，所述裂片型纤维由尼龙纤维和涤纶纤维构成；
其中，尼龙纤维的质量百分数为30％～70％，剩余为涤纶纤维；
2)对裂片型超细纤维非织造布进行碱减量处理，得到的非织造布内的涤纶超细纤维上暴露出大量的羟基和羧基；
3)对裂片型超细纤维非织造布进行羟基化反应，得到羟基化的尼龙超细纤维；
4)在超细纤维非织造布上的羟基和羧基上接枝端异氰酸酯基团；
5)将具有活性氢的长链烷烃通过异氰酸酯和活性氢基团的反应接枝在纤维表面，得到超疏水裂片型超细纤维非织造布；
所述具有活性氢的长链烷烃为十六胺、十七胺、十八胺或十八酸。
进一步的，步骤1)中进行清洗所用的溶剂为丙酮或乙醇；
清洗温度为30～60℃，清洗时间为30～100min。
进一步的，步骤2)中进行碱减量处理所用的碱溶液为强碱和耐碱型助剂的混合溶液；
在混合溶液中，强碱的浓度为5～500g/L，耐碱型助剂的浓度为0～10g/L；
耐碱型助剂为十二烷基二甲基苄基氯化铵、乙二胺或尿素。
进一步的，步骤2)中采用浸渍法或浸扎蒸汽法进行碱减量处理；
其中，浸渍法的处理温度为60～100℃，处理时间为30～300min；
浸扎蒸汽法的处理温度为100～150℃，处理时间为1～120min。
进一步的，步骤3)的具体操作为：
将超细纤维非织造布置于甲醛和中强酸的混合溶液中，在30-100℃反应3-30h；
在混合溶液中，中强酸的质量百分数为1％～20％，甲醛的质量百分数为3％～30％。
进一步的，步骤4)的具体操作为：
将步骤3)得到的超细纤维非织造布置于异氰酸酯基团的供体中，在25～100℃进行反应，反应时间为1～20h；
其中，异氰酸酯基团的供体为二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯或六亚甲基二异氰酸酯三聚体。
进一步的，步骤5)的具体操作为：
将步骤4)得到的超细纤维非织造布置于具有活性氢的长链烷烃的溶液中，在20～120℃的温度下进行反应，反应时间为1～10h；
具有活性氢的长链烷烃的溶液的溶剂为乙醇、甲苯、乙醚、氯仿或四氯化碳。
一种超疏水裂片型超细纤维非织造布，根据本发明的制备方法制备得到。
与现有技术相比，本发明具有以下有益效果：
本发明的超疏水裂片型超细纤维非织造布的制备方法，以裂片型超细纤维非织造布为基材制备超疏水织物，在制造过程中机械法开纤，不需要通过减量溶去多余组分得到超细纤维非织造布，制备过程环保；通过混合碱使得涤纶纤维表面产生纳米粗糙结构且在涤纶超细纤维上产生大量的羟基和羧基，之后用混合酸在尼龙纤维表面的改性引入羟基的同时能够构筑纳米粗糙结构，再利用异氰酸酯基团将低表面能的长链烷烃通过异氰酸酯和活性氢基团的反应活性共价接枝在涤纶纤维和尼龙纤维表面，得到性质稳定的超疏水裂片型超细纤维非织造布；本发明的制备方法过程简单，条件温和，没有利用氟类物质作为原料，经济环保。
本发明制备的超疏水裂片型超细纤维非织造布，表面覆盖了长链烷烃类的低表面能物质，具有超疏水性，经耐磨测试50次、沸水水煮2h、家庭洗涤100次、有机溶剂浸泡24h、酸性溶液浸泡24h、碱性溶液浸泡24h后均能保持超疏水性质，能够应用于多种使用条件下。
附图说明
图1为实施例1的不同放大倍数下的裂片型超细纤维非织造布的SEM图，其中，图1(a)为高放大倍数的SEM图，图1(b)为低放大倍数的SEM图；
图2为实施例1的步骤3)得到的裂片型超细纤维非织造布的SEM图；
图3为实施例1得到的超疏水裂片型超细纤维非织造布的SEM图；
图4为实施例1的超疏水裂片型超细纤维非织造布磨损后的SEM图；
图5为实施例1的超疏水裂片型超细纤维非织造布的静态接触角；
图6为实施例1的超疏水裂片型超细纤维非织造布磨损后的疏水性测试图。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
需要说明的是，本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
本发明以裂片型超细纤维非织造布为基材，通过碱减量工艺使得涤纶纤维表面粗糙化，随后在尼龙纤维上引入羟基同时使得纤维表面粗糙化，形成一定的微纳米粗糙结构；再利用异氰酸酯较高的反应活性将低表面能物质通过共价键接枝到纤维表面，在裂片型超细纤维的微纳粗糙结构上覆盖了低表面能物质，从而制造了具有持久超疏水性能的非织造布，本发明的制备方法制备过程简单，条件温和。经检测，本发明的超疏水非织造布，表面静态接触角大于150°，滚动角小于10°，经过耐磨测试50次(45KPa压重，摩擦行程20cm,300目砂纸)、沸水水煮2h、家庭洗涤100次、有机溶剂浸泡24h、PH(1～14)的溶液中浸泡24h后均能保持超疏水状态，可满足多种使用条件下对超疏水织物的要求。
实施例1
一种超疏水裂片型超细纤维非织造布的制备方法，制备步骤如下：
1)将50％尼龙和50％涤纶含量的裂片型纤维经针刺法制成裂片型超细纤维非织造布，将裂片型超细纤维非织造布置于混合溶液中，在60℃处理200min，完成碱减量处理；
其中，在混合溶液中，氢氧化钠的浓度为5g/L，十二烷基二甲基苄基氯化铵的浓度为2g/L；
2)将完成碱减量处理的超细纤维非织造布置于混合溶液中，在30℃反应30h；
在混合溶液中，中强酸的质量百分数为3％，甲醛的质量百分数为3％；
3)将步骤2)得到的超细纤维非织造布置于二异氰酸酯中，在25℃进行反应，反应时间为20h；
4)将步骤3)得到的超细纤维非织造布置于具有活性氢的长链烷烃的溶液中，在20℃的温度下进行反应，反应时间10h，得到超疏水裂片型超细纤维非织造布；
具有活性氢的长链烷烃的溶液为十六胺的乙醇溶液。
参见图1，图1为实施例1的不同放大倍数下的裂片型超细纤维非织造布的SEM图，其中，图1(a)为高放大倍数的SEM图，图1(b)为低放大倍数的SEM图，从中可以看出裂片型超细纤维非织造布的纤维直径5μm左右；
图2为实施例1的步骤3)得到的裂片型超细纤维非织造布的SEM图，经过碱减量和羟基化的裂片型超细纤维非织造布，从图中可以看出，纤维表面变粗糙了；
参见图3，图3为实施例1得到的超疏水裂片型超细纤维非织造布的SEM图，从图中可以看出得到的超疏水裂片型超细纤维非织造布内的纤维更粗糙了，图5为实施例1的超疏水裂片型超细纤维非织造布的静态接触角，经测试，静态接触角161.7°，动态接触角3.2°；
参见图4和图6，图4和图6分别为实施例1的超疏水裂片型超细纤维非织造布磨损后的SEM图和疏水性测试图，结合两张图，经过耐磨测试后的截面图片，纤维表面的超疏水结构未被破坏，仍然具有超疏水性能。
实施例2
一种超疏水裂片型超细纤维非织造布的制备方法，制备步骤如下：
1)将30％尼龙和70％涤纶含量的裂片型纤维经针刺法制成裂片型超细纤维非织造布，将裂片型超细纤维非织造布置于混合溶液中，在100℃处理20min，完成碱减量处理；
在混合溶液中，氢氧化钠的浓度为50g/L，氢氧化钾的浓度为5g/L，乙二胺的浓度为10g/L；
2)将完成碱减量处理的超细纤维非织造布置于混合溶液中，在80℃反应15h；
在混合溶液中，中强酸的质量百分数为10％，甲醛的质量百分数为5％；
3)将步骤2)得到的超细纤维非织造布置于4,4'-二环己基甲烷二异氰酸酯中，在60℃进行反应，反应时间为10h；4)将步骤3)得到的超细纤维非织造布置于具有活性氢的长链烷烃的溶液中，在120℃的温度下进行反应，反应时间为1h，得到超疏水裂片型超细纤维非织造布；
具有活性氢的长链烷烃的溶液为十七胺的甲苯溶液。
实施例3
一种超疏水裂片型超细纤维非织造布的制备方法，制备步骤如下：
1)将40％尼龙和60％涤纶含量的裂片型纤维经针刺法或水刺法制成裂片型超细纤维非织造布布，将裂片型超细纤维非织造布置于混合溶液中，在80℃处理150min，完成碱减量处理；
其中，在混合溶液中，氢氧化钠的浓度为25g/L，氢氧化钾的浓度为10g/L，尿素的浓度为5g/L；
2)将完成碱减量处理的超细纤维非织造布置于混合溶液中，在30-100℃反应3-30h；
在混合溶液中，中强酸的质量百分数为20％，甲醛的质量百分数为15％；
3)将步骤2)得到的超细纤维非织造布置于4,4'-二环己基甲烷二异氰酸酯中，在60℃进行反应，反应时间为10h；
4)将步骤3)得到的超细纤维非织造布置于具有活性氢的长链烷烃的溶液中，在70℃的温度下进行反应，反应时间为6h，得到超疏水裂片型超细纤维非织造布；
具有活性氢的长链烷烃的溶液为十八胺的乙醚溶液。
实施例4
一种超疏水裂片型超细纤维非织造布的制备方法，制备步骤如下：
1)将70％尼龙和30％涤纶含量的裂片型纤维经水刺法制成裂片型超细纤维非织造布，将裂片型超细纤维非织造布置于混合溶液中，在90℃处理50min，完成碱减量处理；
其中，在混合溶液中，氢氧化钠的浓度为300g/L，氢氧化钾的浓度为100g/L，尿素的浓度为8g/L；
2)将完成碱减量处理的超细纤维非织造布置于混合溶液中，在100℃反应30h；
在混合溶液中，中强酸的质量百分数为1％，甲醛的质量百分数为30％；
3)将步骤2)得到的超细纤维非织造布置于六亚甲基二异氰酸酯中，在30℃进行反应，反应时间为10h；
4)将步骤3)得到的超细纤维非织造布置于具有活性氢的长链烷烃的溶液中，在60℃的温度下进行反应，反应时间为6h，得到超疏水裂片型超细纤维非织造布；
具有活性氢的长链烷烃的溶液为十八酸的氯仿溶液。
实施例5
一种超疏水裂片型超细纤维非织造布的制备方法，制备步骤如下：
1)将30％尼龙和70％涤纶含量的裂片型纤维经针刺法制成裂片型超细纤维非织造布，将裂片型超细纤维非织造布置于混合溶液中，在70℃处理90min，完成碱减量处理；
在混合溶液中，氢氧化钠的浓度为400g/L，氢氧化钾的浓度为15g/L，十二烷基二甲基苄基氯化铵的浓度为10g/L；
2)将完成碱减量处理的超细纤维非织造布置于混合溶液中，在50℃反应15h；
在混合溶液中，中强酸质量百分数为12％，甲醛的质量百分数为15％；
3)将步骤2)得到的超细纤维非织造布置于六亚甲基二异氰酸酯三聚体中，在50℃进行反应，反应时间为10h；
4)将步骤3)得到的超细纤维非织造布置于具有活性氢的长链烷烃的溶液中，在100℃的温度下进行反应，反应时间为5h，得到超疏水裂片型超细纤维非织造布；
具有活性氢的长链烷烃的溶液为十六胺的四氯化碳溶液。
以上内容仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明权利要求书的保护范围之内。

Claims (8)

1.一种超疏水裂片型超细纤维非织造布的制备方法，其特征在于，包括以下步骤：
1)将裂片型超细纤维非织造布进行清洗，洗去纺丝助剂；
所述裂片型超细纤维非织造布由裂片型纤维经针刺法或水刺法制成，所述裂片型纤维由尼龙纤维和涤纶纤维构成；
其中，尼龙纤维的质量百分数为30％～70％；
2)对裂片型超细纤维非织造布进行碱减量处理，得到的非织造布内的涤纶超细纤维上暴露出大量的羟基和羧基；
3)对裂片型超细纤维非织造布进行羟基化反应，得到羟基化的尼龙超细纤维；
4)在超细纤维非织造布上的羟基和羧基上接枝端异氰酸酯基团；
5)将具有活性氢的长链烷烃通过异氰酸酯和活性氢基团的反应接枝在纤维表面，得到超疏水裂片型超细纤维非织造布；
所述具有活性氢的长链烷烃为十六胺、十七胺、十八胺或十八酸。
2.根据权利要求1所述的超疏水裂片型超细纤维非织造布的制备方法，其特征在于，步骤1)中进行清洗所用的溶剂为丙酮或乙醇；
清洗温度为30～60℃，清洗时间为30～100min。
3.根据权利要求1所述的超疏水裂片型超细纤维非织造布的制备方法，其特征在于，步骤2)中进行碱减量处理所用的碱溶液为强碱和耐碱型助剂的混合溶液；
在混合溶液中，强碱的浓度为5～500g/L，耐碱型助剂的浓度为0～10g/L；
耐碱型助剂为十二烷基二甲基苄基氯化铵、乙二胺或尿素。
4.根据权利要求1所述的超疏水裂片型超细纤维非织造布的制备方法，其特征在于，步骤2)中采用浸渍法或浸扎蒸汽法进行碱减量处理；
其中，浸渍法的处理温度为60～100℃，处理时间为30～300min；
浸扎蒸汽法的处理温度为100～150℃，处理时间为1～120min。
5.根据权利要求1所述的超疏水裂片型超细纤维非织造布的制备方法，其特征在于，步骤3)的具体操作为：
将超细纤维非织造布置于甲醛和中强酸的混合溶液中，在30-100℃反应3-30h；
在混合溶液中，中强酸的质量百分数为1％～20％，甲醛的质量百分数为3％～30％。
6.根据权利要求1所述的超疏水裂片型超细纤维非织造布的制备方法，其特征在于，步骤4)的具体操作为：
将步骤3)得到的超细纤维非织造布置于异氰酸酯基团的供体中，在25～100℃进行反应，反应时间为1～20h；
其中，异氰酸酯基团的供体为二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯或六亚甲基二异氰酸酯三聚体。
7.根据权利要求1所述的超疏水裂片型超细纤维非织造布的制备方法，其特征在于，步骤5)的具体操作为：
将步骤4)得到的超细纤维非织造布置于具有活性氢的长链烷烃的溶液中，在20～120℃的温度下进行反应，反应时间为1～10h；
具有活性氢的长链烷烃的溶液的溶剂为乙醇、甲苯、乙醚、氯仿或四氯化碳。
8.一种超疏水裂片型超细纤维非织造布，其特征在于，根据权利要求1-7所述的制备方法制备得到。
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