CN114395822A - 一种物理与化学协同超疏水的水性聚氨酯膜的制备方法 - Google Patents
一种物理与化学协同超疏水的水性聚氨酯膜的制备方法 Download PDFInfo
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Abstract
一种物理与化学协同的超疏水水性聚氨酯膜的制备方法，属于水性聚氨酯的合成和改性技术领域。其过程先将共轭亚油酸用二氧化硒改性为双羟基油酸；然后以多元醇、多异氰酸酯、双羟基油酸、小分子扩链剂、催化剂、中和剂、封端剂、聚乙烯醇、水为原料制备水性聚氨酯乳液；将水性聚氨酯乳液通过静电纺丝方法制得表面具有超疏水微纳米结构的膜。由于引入双羟基油酸能在干燥固化时疏水基团迁移至表面，膜的基质材料因化学改性而提高了疏水性；通过静电纺丝方法使膜的表面具有疏水微纳米结构，增强了膜表面的物理疏水性。物理与化学协同的超疏水水性聚氨酯膜有超强的疏水性能，其水接触角能达到152°~156°，滚动角为4°~6°，耐摩性能优良。
Description
技术领域
本发明属于超疏水材料制造领域，尤其是涉及一种物理与化学协同超疏水的水性聚氨酯纤维膜的制备方法。
背景技术
近年来，超疏水材料在各领域中占据着越来越重要的位置，其也得到了研究者们越加广泛的研究。聚氨酯在一系列如隔热、隔音、耐磨、耐油、弹性等方面的优良性能是其它合成材料所达不到的所以其超疏水性正越来越为人们所需，有些超疏水聚氨酯的制备对于环境污染的考虑不周常使用一些对于环境和人体有危害的化学试剂如专利CN106750432B中使用含氟疏水聚氨酯以及如专利CN110527419A中大量所用有机溶剂等都会对人体和环境产生难以估量的危害。所以目前绝大部分技术人员都在关注聚氨酯溶剂的含量，无溶剂聚氨酯的研究与发展。水性聚氨酯作为以水为溶剂的一种聚氨酯，无毒无污染，然而由于水性聚氨酯在制备过程中大多需用亲水性扩链剂来使其在水中形成乳液，故其极易被水溶胀甚至溶解，对水性聚氨酯的应用范围产生了很大的影响，所以目前迫切需要水性聚氨酯材料实现超疏水，以填补行业内超疏水水性聚氨酯的空白。
目前超疏水材料的制备已有很多，困扰研究者们的一大难题便是其形成的微纳米结构易损，耐久性不足问题。很多研究者针对此问题进行了研究，专利CN107189656A公布了一种基于聚碳酸酯的耐磨超疏水涂层的制备方法，该方法首先在底部涂布一层聚碳酸酯胶水，再在胶水上涂布一层中间层用溶液，等其干燥后再在其表面涂布一层表面层溶液，待材料干燥后即得耐磨性超疏水涂层。该方法需要使用有毒的丙酮作为溶剂，并且操作复杂，需要涂覆多层，不利于实际应用。专利CN110041818A利用粘结剂粘结纳米多孔粉末从而形成表面的多孔微纳米结构，再利用低表面能的物质喷涂于其微纳米结构表面上，低表面能物质由侧链含氟单组分聚氨酯形成。该方法使用了含氟元素，且通过粉末粘结而成的多孔层状结构的均匀性值得商榷。水性聚氨酯的耐磨超疏水也有研究如专利CN110862756A利用疏水纳米二氧化硅与水性聚氨酯水溶液混合涂布于基材表面，起到耐磨超疏水的目的，但其疏水纳米二氧化硅不能在水中均匀分散，即使利用乙醇先行分散，但在水中混合时也不能保证分散均匀。静电纺丝法很好地解决了微纳米结构易损问题，因为静电纺丝方法不是只有表面一层为微纳米结构，表层磨损后里层结构同样具有微纳米结构，故而具备超强的耐久性，且其制备简单，膜表面微纳米结构分布均匀。
发明内容
本发明的目的在于提供一种环保且耐用的超疏水水性聚氨酯纤维膜的制备方法。解决了水性聚氨酯的耐水性差的问题，首次实现了水性聚氨酯在物理和化学双重改性的超疏水且耐久性好的水性聚氨酯膜的制备。
在自然界中荷叶的超疏水现象中找灵感，荷叶的表面结构特征有两个，其一是特殊的微纳米结构；其二是表面有一层生物蜡状物质。水滴在荷叶表面由于表面张力的作用会形成球形水珠，一般尺寸较大，通常为毫米级，不能够进入微纳米结构形成的小气室中，即这些小气室可以对球形水珠起到物理支撑的作用。二者的相互协同作用，导致了荷叶的超疏水性能。
有益效果：
1.本发明采用完全采用水作为分散介质，制备过程中不使用任何有机溶剂、金属催化剂和乳化剂，利用对人体、环境无害的亚油酸进行疏水改性，符合绿色环保的理念。
2.采用原位聚合双羟基油酸的方式使水性聚氨酯具有疏水特性，为化学改性方法；通过静电纺丝方法使疏水改性水性聚氨酯纺为微纳米层级的丝线，使其具有超疏水的另一条件，此为物理方法。物理化学协同作用，使得水性聚氨酯疏水性进一步加强，成为超疏水膜。
3. 此方法解决了超疏水行业的亟待解决的难题：超疏水膜的耐久性问题，普通超疏水膜的微纳米结构容易遭到外界环境因素的破坏，使其疏水性下降甚至丧失。本发明由于纳米纤维膜有多层，即使表面被破坏里层也可继续承担提供微纳米结构的作用，确保超疏水性不失。
具体实施方式
实施例1
一种物理与化学协同超疏水的水性聚氨酯纤维膜，其制备工艺如下：
(1) 双羟基油酸的制备：
称取共轭亚油酸4.5g、二氧化硒1.5g在60℃下搅拌反应12h后，加水洗涤，收集有机溶剂层，即得双羟基油酸，分子式为C18H34O4，形态为淡黄色的油状物，保存备用；
(2)双羟基油酸改性水性聚氨酯乳液的制备：
a) 端异氰酸根的水性聚氨酯预聚体的制备
在装有搅拌器、温度计、冷凝管的四口烧瓶中，加入8.38ml异氟尔酮二异氰酸酯、15.52ml聚丙二醇2000，4滴二月桂酸二丁基锡，在机械搅拌及氮气保护下加热至70℃，反应至NCO含量为80.5%时停止反应，反应得端异氰酸根的水性聚氨酯预聚体；
b) 双羟基油酸改性水性聚氨酯乳液的制备，
在a)预聚体中加入计量步骤（1）所得双羟基油酸2ml和0.25ml 1，4-丁二醇后反应1h，加入0.9ml三乙胺中和1h，随后加入含有2ml乙二胺的64ml去离子水，高速搅拌30min，得双羟基油酸改性水性聚氨酯乳液；
(3) 水性聚氨酯膜的制备：
a) 纺丝原液的制备
将聚乙烯醇置于90℃水浴条件下,搅拌1.5h溶于蒸馏水中,控制得到15%质量分数的聚乙烯醇水溶液，然后用蒸馏水将b)水性聚氨酯的质量百分比控制为15%,聚乙烯醇与水性聚氨酯体积比为7:3,混合均匀并冷却至室即得到纺丝原液；
b)水性聚氨酯膜的制备
将步骤(3)中a)制得的纺丝原液加入到带有针头的注射器内，注射器装卡于精密注射泵上，注射泵流速设为0.5ml-1。针头与15kv高压电源相连，针头距接收位置20cm。利用一层铝箔收集纤维，铝箔接地。在室温环境下进行静电纺丝2h，制得超疏水的水性聚氨酯纤维膜。
性能表征：
(1)水接触角的测试：采用深圳触角测试仪DR-500，液滴体积为5μL，所得的接触角数据是基于样品表面 5 个不同点接触角的平均值测得该实例制备出来的纤维膜平均水接触角为154.2°。
(2)滚动角的测试：用微量注射器取 5ml 的去离子水滴落在水性聚氨酯纤维膜上，然后缓慢的倾斜样品台，当样品台倾斜到一定角落时，涂层上的水滴由于重力作用刚好向下滚落，此时样品表面与水平之间的夹角即为滚动角。经相同5次测试，该实例制备出来的纤维膜平均滚动角为 4°。
(3)抗摩擦性能测试：将1000目的砂纸放置在水性聚氨酯纤维膜上并使水性聚氨酯纤维膜与砂纸直接接触，在砂纸上面放置 50g 的砝码，然后匀速的拉动砂纸，保持涂纤维膜与砂纸的贴合，移动 20cm后测量水性聚氨酯纤维膜的接触角。此操作步骤重复三次，平均水接触角为153.4°。
实施例2
一种物理与化学协同超疏水的水性聚氨酯纤维膜，其制备工艺如下：
(1) 双羟基油酸的制备：
称取共轭亚油酸4.5g、二氧化硒1.5g在60℃下搅拌反应12h后，加水洗涤，收集有机溶剂层，即得双羟基油酸，分子式为C18H34O4，形态为淡黄色的油状物，保存备用；
(2)双羟基油酸改性水性聚氨酯乳液的制备：
a) 端异氰酸根的水性聚氨酯预聚体的制备
在装有搅拌器、温度计、冷凝管的四口烧瓶中，加入8.7ml异氟尔酮二异氰酸酯、15.76ml脱水聚碳酸酯二元醇2000，4滴辛酸亚锡，在机械搅拌及氮气保护下加热至70℃，反应至NCO含量达75.2%时停止反应，反应得端异氰酸根的水性聚氨酯预聚体；
b) 双羟基油酸改性水性聚氨酯乳液的制备，
在a)预聚体中加入计量步骤（1）所得双羟基油酸1.75ml和0.25ml新戊二醇后反应1h，加入1.5ml三乙胺中和1h，随后加入含有1ml乙二胺的100ml去离子水，高速搅拌30min，得双羟基油酸改性水性聚氨酯乳液；
(3) 水性聚氨酯膜的制备：
a) 纺丝原液的制备
将聚乙烯醇在95℃水浴条件下，搅拌1小时溶解于蒸馏水中，制得质量百分比为15%的聚乙烯醇水溶液然后用蒸馏水将b)水性聚氨酯乳液稀释至质量百分比为15%，聚乙烯醇与水性聚氨酯体积比为7:3，混合均匀并冷却至室即得到纺丝原液；
b)水性聚氨酯膜的制备
将步骤(3)中a)制得的纺丝原液加入到带有针头的注射器内，注射器装卡于精密注射泵上，注射泵流速设为1ml-1。针头与20kv高压电源相连，针头距接收滚筒25cm。利用一层铝箔收集纤维，铝箔接地。在室温环境下进行静电纺丝1h，制得超疏水的水性聚氨酯纤维膜。
水性聚氨酯纤维膜的性能测试方法参照实例1，测得该实例制备出来的纤维膜平均水接触角为152..1°，平均滚动角为5.2°，三次砂纸摩擦后平均水接触角为151.4°。
实施例3
(1) 双羟基油酸的制备：
称取共轭亚油酸4.5g、二氧化硒1.5g在60℃下搅拌反应12h后，加水洗涤，收集有机溶剂层，即得双羟基油酸，分子式为C18H34O4，形态为淡黄色的油状物，保存备用；
(2)双羟基油酸改性水性聚氨酯乳液的制备：
a) 端异氰酸根的水性聚氨酯预聚体的制备
在装有搅拌器、温度计、冷凝管的四口烧瓶中，加入17ml甲苯二异氰酸酯、25g聚四氢呋喃醚二元醇2000，4滴二月桂酸二丁基锡，在机械搅拌及氮气保护下加热至70℃，反应至所测得的NCO含量达85.5%时停止反应，反应得端异氰酸根的水性聚氨酯预聚体；
b) 双羟基油酸改性水性聚氨酯乳液的制备
在a)预聚体中加入计量步骤（1）所得双羟基油酸2.5ml和0.5ml 1,4-丁二醇后反应1h，加入1.875ml三乙胺中和2h，随后加入含有1ml乙二胺的64ml去离子水，高速搅拌30min，得双羟基油酸改性水性聚氨酯乳液；
(3) 水性聚氨酯膜的制备：
a) 纺丝原液的制备
将聚乙烯醇在95℃水浴条件下，搅拌1小时溶解于蒸馏水中，制得质量百分比为15%的聚乙烯醇水溶液然后用蒸馏水将b)水性聚氨酯乳液稀释至质量百分比为15%，聚乙烯醇与水性聚氨酯体积比为7:3，混合均匀并冷却至室即得到纺丝原液；
b)水性聚氨酯膜的制备
将步骤(3)中a)制得的纺丝原液加入到带有针头的注射器内，注射器装卡于精密注射泵上，注射泵流速设为1ml-1。针头与15kv高压电源相连，针头距接收滚筒20cm。利用一层铝箔收集纤维，铝箔接地。在室温环境下进行静电纺丝2h，制得超疏水的水性聚氨酯纤维膜。
水性聚氨酯纤维膜的性能测试方法参照实例1，测得该实例制备出来的纤维膜平均水接触角为152.8°平均滚动角为4.5°，三次砂纸摩擦后平均水接触角为151.6°。
Claims (8)
1.一种物理与化学协同超疏水的水性聚氨酯膜的制备方法，其特征在于，该方法包括以下步骤：
(1) 双羟基油酸的制备
用轭亚油酸与二氧化硒摩尔比为1:0.25~4比例下，共轭亚油酸0.5～2.0份、二氧化硒0.125~8份在25-60℃下搅拌反应12-48h后，加水洗涤，收集有机溶剂层，即得双羟基油酸，分子式为C18H34O4，形态为淡黄色的油状物，保存备用；
(2)双羟基油酸改性水性聚氨酯乳液的制备：
a) 端异氰酸根的水性聚氨酯预聚体的制备
在装有搅拌器、温度计、冷凝管的四口烧瓶中，加入多异氰酸酯8.0～20.0份、脱水多元醇2.0～6.0份，催化剂0.01~0.1份，在机械搅拌及氮气保护下加热至70~85℃，反应至所测得的NCO含量达到63%~87%时停止反应，反应得端异氰酸根的水性聚氨酯预聚体；
b) 双羟基油酸改性水性聚氨酯乳液的制备，
在a)预聚体中加入步骤（1）所得双羟基油酸2.5-6.5份和0.5~2.5份小分子扩链剂后反应1-2h，加入1.0~3.0份中和剂中和1-2h，随后加入含有1.0-3.0份多元胺类扩链剂的60~150份去离子水，高速搅拌0.5-1h，得双羟基油酸改性水性聚氨酯乳液；
(3) 水性聚氨酯膜的制备：
a) 纺丝原液的制备
将聚乙烯醇置于90~100℃水浴条件下,搅拌1~2h溶于蒸馏水中,控制得到15%质量分数的聚乙烯醇水溶液，然后用蒸馏水将b)水性聚氨酯的质量百分比控制为15%,聚乙烯醇与水性聚氨酯体积比为7:3,混合均匀并冷却至室即得到纺丝原液；
b)水性聚氨酯膜的制备
将步骤(3)中a)制得的纺丝原液加入到带有针头的注射器内,注射器装卡于精密注射泵上,注射泵流速设为0.5~1ml-1；针头与10-20kv高压电源相连,针头距接收位置15~30cm；利用一层铝箔收集纤维,铝箔接地；在室温环境下进行静电纺丝1~2h,制得超疏水的水性聚氨酯纤维膜。
2.一种物理与化学协同超疏水的水性聚氨酯膜的制备方法，其特征在于，双羟基油酸改性水性聚氨酯的化学反应过程如图所示：
3.根据权利要求1所述的一种物理与化学协同超疏水的水性聚氨酯纤维膜的制备方法,其特征在于,所述的多元醇为聚醚多元醇、聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇、聚烯烃多元醇、聚四氢吠喃醚多元醇、有机硅多元醇中的一种或二种以上的混合物。
4.根据权利要求1所述的物理与化学协同超疏水的水性聚氨酯纤维膜的制备方法,其特征在于,所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、四甲基甲苯二异氰酸酯、二苯甲烷二异氰酸酯、萘-1,5-二异氰酸酯、苯二亚甲基二异氰酸酯中的一种或多种。
5.根据权利要求1所述的物理与化学协同超疏水的水性聚氨酯纤维膜的制备方法，其特征在于，所述小分子扩链剂选自1，4-丁二醇、新戊二醇、二缩二乙二醇、和1，6-己二醇中的一种或多种。
6.根据权利要求1所述的物理与化学协同超疏水的水性聚氨酯纤维膜的制备方法，其特征在于，所述催化剂选自二月桂酸二丁基锡和辛酸亚锡中的一种或多种。
7.根据权利要求1所述的物理与化学协同超疏水的水性聚氨酯纤维膜的制备方法,其特征在于,所述中和剂选自三乙胺、N,N-二甲基乙醇胺、三乙醇胺、二乙醇胺和氨水中的一种或几种。
8.根据权利要求1所述的物理与化学协同超疏水的水性聚氨酯纤维膜的制备方法，其特征在于，所述的封端剂为乙二胺、己二酸二肼、水合肼、N，N-二羟基(二异丙基)苯胺中的一种或几种的组合。
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