CN108977030B - 一种氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备方法 - Google Patents
一种氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备方法 Download PDFInfo
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- CN108977030B CN108977030B CN201810831984.6A CN201810831984A CN108977030B CN 108977030 B CN108977030 B CN 108977030B CN 201810831984 A CN201810831984 A CN 201810831984A CN 108977030 B CN108977030 B CN 108977030B
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- nanotube
- waterborne polyurethane
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- halloysite
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Abstract
本发明提供一种氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备方法。该方法将硅烷修饰的埃络石纳米管引入水性聚氨酯乳液中，经喷涂形成具有微纳米粗糙结构的复合涂层后用氟硅烷对其进行表面修饰，获得氟化埃洛石纳米管/水性聚氨酯疏水涂层。本发明采用的埃络石纳米管是一种具有管状形态的天然纳米颗粒，原料易得、成本低廉，并具有独特的表面特性、高分散能力及良好的生物相容性等优点。采用喷涂法将埃洛石纳米管/水性聚氨酯复合涂料喷涂在基体表面，形成微纳米粗糙结构，容易操作、适合大面积涂层的制备，并且形成的涂层厚度比较均匀。采用表面修饰法，利用氟硅烷对涂层进行修饰，节省溶剂使用量，操作简单、快捷。
Description
技术领域
本发明涉及水性涂料制备技术领域，具体而言，尤其涉及一种氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的的制备方法。
背景技术
聚氨酯是一类分子链上含氨基甲酸酯结构的多功能聚合物，通常是由二元或多异氰酸酯与含两个及以上活泼氢的化合物通过逐步聚合反应而制得。将聚氨酯树脂溶解或分散于水中而形成的二元胶态体系即为水性聚氨酯(WPU)。
水性聚氨酯硬段与软段的结构和比例可以灵活调节，并且还具有不燃、气味小、不污染、节能、操作加工方便等优点，使水性聚氨酯在环保型涂料、油墨与胶粘剂等领域的应用越来越广泛。但同时由于聚氨酯分子链上引入了亲水基团，导致水性聚氨酯膜疏水性、耐溶剂性能变差，限制了它在防水防污领域的应用。
目前提高水性聚氨酯疏水性的方法主要有两种，一是构造具有微纳米结构的粗糙表面，让空气滞留在水的下层；二是用低表面能试剂进行表面修饰，从而降低表面能。疏水涂层的制备方法主要有刻蚀法、等离子处理法、溶胶-凝胶法、喷涂法。
刻蚀法是通过在材料的表面刻蚀出微米或纳米粗糙结构以制备超疏水材料表面的方法。黄子发等[湖南工业大学学报，2011,25(4):5-8.]采用化学刻蚀方法在铝合金基体上制备出超疏水表面，具体方案是用盐酸、草酸混合液对铝合金表面进行刻蚀，经高锰酸钾溶液浸润氧化后用硬脂酸修饰。刻蚀法的优点是精度高、可批量生产且技术较成熟。不足之处是加工速度慢、成本高且对加工环境要求较高。
等离子处理法是一类新型的表面处理方法，可对基材表面进行化学修饰从而赋予其特殊性能。Yung等[Carbon,2018,127,195-201.]利用气相沉积法得到排列整齐的碳纳米管阵列，采用两种等离子处理改变顶部表面的结构，用氧等离子处理后的表面具有超亲水性，用CF4等离子处理后的表面材料具有超疏水性。该方法的不足是可选择的基体材料有限，批量加工的质量难以保证。
溶胶-凝胶法是将化学前驱体在一定条件下进行水解-缩合反应生成溶胶，然后使溶剂挥发或热分解形成三维网状结构的凝胶。Zhai等[Journal of Applied PolymerScience,2013,128(3):1715-1724.]首先以APTES(γ-氨丙基三乙氧基硅烷)为封端剂对PU预聚体进行封端，然后加入不同含量的正硅酸乙酯水解缩合获得一系列的SiO2/PU乳液；并且随着硅含量的增加，涂膜表面的水接触角增加、耐水性提高。溶胶-凝胶法的可控性好，制备效率较高及合成方法无需加热等。缺点是前驱体价格昂贵、共溶剂有毒且污染环境，并且反应需要长达数天的时间。
喷涂法是通过喷枪，借助于压力，将涂料分散成均匀而微细的雾滴，涂布在物体表面的涂装方法。可分为空气喷涂、无空气喷涂、静电喷涂等。喷涂法因作业效率高，且手工作业及工业自动化生产都可使用，所以应用范围非常广泛。Yang等[New Journal ofChemistry,2011,35(3):576-580.]利用全氟辛酸和醋酸铜反应得到全氟辛烷铜，将反应生成物分散到乙醇中并喷涂于基板表面，得到超双疏涂层，该涂层对十六烷和十二烷的接触角均大于150°。
通常降低材料表面能的方法是引入低表面能的物质如有机硅、有机氟等。有机硅改性聚氨酯主要是利用带有反应型基团的聚硅氧烷和端异氰酸酯反应将具有低表面能的有机硅链段引入聚氨酯链段中。大部分的含氟聚氨酯是由双官能度的氟化聚醚为原料合成的，这种产物分子结构主链上含有氟原子，但是受分子主链的作用，较难迁移到表面，难以获得优良的疏水性能，且氟化聚醚价格普遍较高。
构建微纳米结构主要是通过形成或加入纳米颗粒实现。埃洛石纳米管(HAL)是纯天然的矿物质硅酸盐材料，储量丰富、价格低廉、原料来源广、提纯工艺简单。而且它拥有与碳纳米管(CNTs)一样完美的一维中空管状结构，并且埃洛石纳米管本身的缺陷结构较少，具备无机纳米粒子较高的理论强度和耐热性，将其应用于聚合物材料中可大幅提高材料的强度和耐热性、耐水性。而同样具有高强度的碳纳米管的制备工艺复杂、价格昂贵，限制了碳纳米管的广泛研究和应用。
发明内容
本发明的主要目的在于提供一种疏水性能好的氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备方法，以克服现有技术的不足，其具有工艺简单等特点。
本发明的又一目的在于提供前述氟化埃洛石纳米管/水性聚氨酯复合乳液作为疏水涂层的应用，该方法将硅烷修饰的埃络石纳米管引入水性聚氨酯中，喷涂在基体表面形成微纳米尺度的粗糙结构，再用氟硅烷进行表面修饰，用简单、快捷的方法制备了氟化埃洛石纳米管/水性聚氨酯疏水涂层，其工艺简单易于操作。
本发明公开的一种氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备方法，包括以下步骤：
S1、埃洛石纳米管的改性处理，
称取一定质量的埃络石纳米管溶于乙醇水溶液中，超声振动30-45min，加入一定质量的氨水和3-氨丙基三甲氧基硅烷，常温搅拌24h-36h后离心分离，用无水乙醇和水各洗涤2-3次，离心分离后干燥，得到改性埃络石纳米管；
S2、埃洛石纳米管/水性聚氨酯复合乳液的制备，
将改性后的埃洛石纳米管、异氰酸酯和多元醇混合，在75℃-90℃下反应至NCO含量达到稳定状态，加入一定质量的2,2-二羟甲基丁酸、1,4-丁二醇和二月桂酸二丁基锡、丙酮，反应3-4h后，降低温度至40-50℃，加入一定质量的三乙胺中和25-30min，随后加入一定质量的去离子水，在1000-1200r/min的转数下搅拌乳化45-60min，减压蒸馏除去丙酮，得到埃洛石纳米管/水性聚氨酯复合乳液；
S3、埃洛石纳米管/水性聚氨酯复合涂层的制备，
将S2制备的所述氟化埃洛石纳米管/水性聚氨酯复合乳液用喷枪喷涂在清洗干净的基体表面，室温干燥，得到埃洛石纳米管/水性聚氨酯复合涂层；
S4、氟化埃洛石纳米管/水性聚氨酯疏水涂层的制备，
用喷枪将氟硅烷乙醇溶液喷涂在前述涂层表面，室温干燥，得到氟化埃洛石纳米管/水性聚氨酯复合疏水涂层。
进一步地，所述步骤S1中的乙醇水溶液、3-氨丙基三甲氧基硅烷、氨水和埃络石纳米管的质量比为100：10～20：5～10：0.5～2。
进一步地，所述步骤S2中的改性埃络石纳米管、异氰酸酯、多元醇、二月桂酸二丁基锡、丙酮、2,2-二羟甲基丁酸、1,4-丁二醇、三乙胺和去离子水的质量比为0.1～0.5∶5～10∶20～40∶0.1～0.5∶20～40∶0.7～1.5∶0.6～1.5∶0.4～0.8∶30～60。
进一步地，所述步骤S2中的的异氰酸酯可为甲苯二异氰酸酯(TDI)、或异佛尔酮二异氰酸酯(IPDI)、或二苯基甲烷二异氰酸酯(MDI)；所述多元醇可为聚醚多元醇、或聚碳酸酯二醇、或聚丙二醇。
进一步地，所述步骤S3中的氟硅烷可为十七氟癸基三甲氧基硅烷或十七氟癸基三乙氧基硅烷。
本发明还提供了一种由前述任一种方法制备的氟化埃洛石纳米管/水性聚氨酯复合疏水涂层。
较现有技术相比，本发明具有以下优点：
1、本发明用于构建微纳米尺度粗糙结构的埃络石纳米管是一种具有管状形态的天然纳米颗粒，原料易得、成本低廉，具有独特的表面特性，高分散能力及良好的生物相容性等优点。
2、采用喷涂法将埃洛石纳米管/水性聚氨酯复合涂料喷涂在基体表面，形成微纳米粗糙结构，该方法容易操作、适合大面积涂层的制备，并且形成的涂层厚度比较均匀。
3、采用表面修饰法，利用氟硅烷对涂层进行修饰，该方法节省溶剂的使用量，而且操作简单、快捷。
基于上述理由本发明可在水性涂料制备技术领域广泛推广。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图做以简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明埃络石纳米管的扫描电镜照片。
图2为本发明实施例1硅烷改性前后埃络石纳米管的红外光谱。
图3为本发明实施例2中氟化埃络石纳米管/水性聚氨酯复合涂层的红外光谱。
图4为本发明对比例1中水性聚氨酯涂层的红外光谱。
图5为本发明实施例及对比例的静态接触角测试结果。
具体实施方式
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
为使本发明实施例的目的、技术方案和优点更加清楚，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实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。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，都属于本发明保护的范围。
图1为埃络石纳米管的扫描电镜照片，可以看出它是中空的管状结构，表面光滑，两端有开口。每个纳米管的管长、管径都不同，管长为200～1000nm，内径为10～35nm，外径约为40～100nm，是一种具有空腔结构的天然纳米管。
本发明提供了一种氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备方法，包括以下步骤：
S1、埃洛石纳米管的改性处理，
称取一定质量的埃络石纳米管溶于75％乙醇水溶液中，超声振动30-45min，加入一定质量的氨水、3-氨丙基三甲氧基硅烷，常温搅拌24h-36h后离心分离，用无水乙醇和水各洗涤2-3次，离心分离后干燥，得到改性埃络石纳米管。
S2、埃洛石纳米管/水性聚氨酯复合乳液的制备，
将改性后的埃洛石纳米管、异氰酸酯和多元醇混合，在75℃-90℃下反应至NCO含量达到稳定状态。加入一定质量的2,2-二羟甲基丁酸、1,4-丁二醇和二月桂酸二丁基锡、丙酮，反应3-4h后，降低温度至40-50℃，加入一定质量的三乙胺中和25-30min，随后加入去离子水，在1000-1200r/min搅拌乳化45-60min，减压蒸馏除去丙酮，得到埃洛石纳米管/水性聚氨酯复合乳液。
S3、埃洛石纳米管/水性聚氨酯复合涂层的制备，
将S2制备的所述氟化埃洛石纳米管/水性聚氨酯复合乳液用喷枪喷涂在清洗干净的基体表面，室温干燥，得到埃洛石纳米管/水性聚氨酯复合涂层；
S4、氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备，
用喷枪将氟硅烷乙醇溶液喷涂在前述复合涂层表面，室温干燥，得到氟化埃洛石纳米管/水性聚氨酯疏水涂层。
所述步骤S1中的乙醇水溶液、3-氨丙基三甲氧基硅烷、氨水和埃络石纳米管的质量比为100：10～20：5～10：0.5～2。
所述步骤S2中的改性埃络石纳米管、异氰酸酯、多元醇、二月桂酸二丁基锡、丙酮、2,2-二羟甲基丁酸、1,4-丁二醇、三乙胺和去离子水的质量比为0.1～0.5∶5～10∶20～40∶0.1～0.5∶20～40∶0.7～1.5∶0.6～1.5∶0.4～0.8∶30～60。
所述步骤S2中的异氰酸酯可为甲苯二异氰酸酯(TDI)、或异佛尔酮二异氰酸酯(IPDI)、或二苯基甲烷二异氰酸酯(MDI)；所述多元醇可为聚醚多元醇、或聚碳酸酯二醇、或聚丙二醇。
所述氟硅烷为十七氟癸基三甲氧基硅烷，或十七氟癸基三乙氧基硅烷。
本发明还提供了一种由前述任一种方法制备的氟化埃洛石纳米管/水性聚氨酯疏水涂层。
图2为硅烷偶联剂改性前(HAL)后(APTMS-HAL)埃络石纳米管的红外光谱。可以发现，改性前后的埃洛石纳米管在3698cm-1和3617cm-1处均存在强烈的吸收峰，分别对应埃洛石纳米管内表面羟基与内部羟基的O-H伸缩振动；其它特征峰，如Si-O键在1095m-1与1030cm-1处伸缩振动，Si-O-Al键在540cm-1处弯曲振动，Si-O-Si键在458cm-1处弯曲振动均可见于两条曲线中。但改性后的埃洛石纳米管在2843cm-1和2917cm-1处出现新的振动峰，分别对应C-H键的对称与反对称伸缩振动峰，还发现在1473cm-1处有N-H特征峰，曲线中特有特征峰的出现表明埃洛石纳米管被成功改性。
实施例1
在装有冷凝管、搅拌器的三口烧瓶中，加入12.8g聚碳酸酯二醇(PCDL2000)及400mg改性后的埃络石纳米管，升高温度至85℃，待PCDL完全溶解并与埃络石纳米管均匀混合后，向烧瓶内加入5g异佛尔酮二异氰酸酯，持续搅拌、反应至NCO含量达到稳定值。加入0.7g的2,2-二羟甲基丁酸(DMBA)亲水扩链剂、0.54g的1,4-丁二醇小分子扩链剂和两滴二月桂酸二丁基锡催化剂，同时加入丙酮，反应至NCO含量达到稳定值后降低反应温度至50℃，加入0.47g三乙胺中和30min，随后加入去离子水，在1200r/min的转数下搅拌乳化1h，减压蒸馏除去丙酮，得到水性聚氨酯复合乳液。将其喷涂在清洗干净的基体表面，室温干燥，得到氟化埃洛石纳米管/水性聚氨酯复合涂层。再用喷枪将质量分数1％的氟硅烷乙醇溶液均匀喷涂在复合涂层表面，室温干燥，得到氟化埃洛石纳米管/水性聚氨酯复合疏水涂层。
对上述制备的氟化埃络石纳米管/水性聚氨酯复合疏水涂层进行表征。图3为氟化埃络石纳米管/水性聚氨酯复合疏水涂层的红外光谱，水接触角的测试结果如图5所示。由红外谱图可以看出，在2270cm-1处并未看到-NCO特征峰，说明-NCO全部参加反应，而且在3350cm-1、1730cm-1、1530cm-1、1245cm-1处均存在强烈吸收峰，分别代表氨基甲酸酯的N-H伸缩振动峰，C＝O伸缩振动峰、N-H变形振动峰及-NHCOO-中-C-O伸缩振动峰，2943cm-1处代表聚氨酯分子链中CH3和CH2伸缩振动峰，在1045cm-1处有明显的吸收峰，归属于Si-O的伸缩振动，898cm-1处为C-F的伸缩振动吸收峰，可见WPU薄膜表面羟基和低表面能氟硅烷通过共价键进行了偶联，将氟原子引到涂层表面。
实施例2
与实施例1不同的是，将改性后的埃络石纳米管400mg改为300mg，其他成分及过程均相同。
对比例1
在装有冷凝管、搅拌器的三口烧瓶中，加入12.8g聚碳酸酯二醇(PCDL2000)，升高温度至85℃，待PCDL完全溶解后，向烧瓶内加入5g异佛尔酮二异氰酸酯，持续搅拌，反应至NCO含量达到稳定值。加入0.7g的2,2-二羟甲基丁酸(DMBA)亲水扩链剂、0.54g的1,4-丁二醇小分子扩链剂、两滴二月桂酸二丁基锡催化剂、丙酮，反应至NCO含量达到稳定值后降低反应温度至50℃，加入0.47g的三乙胺中和30min，随后加入去离子水，在1200r/min的转数下搅拌乳化1h，减压蒸馏除去丙酮，得到水性聚氨酯乳液。将制好的乳液均匀喷涂在清洗干净的基体表面上，室温干燥，得到水性聚氨酯涂层。
对比例2
在装有冷凝管、搅拌器的三口烧瓶中，加入12.8g聚碳酸酯二醇(PCDL2000)及400mg改性后的埃络石纳米管，升高温度至85℃，待PCDL完全溶解并与埃络石纳米管混合均匀后，向烧瓶内加入5g异佛尔酮二异氰酸酯，持续搅拌，反应至NCO含量达到稳定值。加入0.7g的2,2-二羟甲基丁酸(DMBA)亲水扩链剂、0.54g的1,4-丁二醇小分子扩链剂、两滴二月桂酸二丁基锡催化剂、丙酮，反应至NCO含量达到稳定值后降低温度至50℃，加入0.47g三乙胺中和30min，随后加入去离子水，在1200r/min的转数下搅拌乳化1h，减压蒸馏除去丙酮，得到埃络石纳米管/水性聚氨酯复合乳液。将其喷涂在清洗干净的基体表面，室温干燥，得到埃络石纳米管/水性聚氨酯复合涂层。
对上述制备的水性聚氨酯涂层进行表征。图4为水性聚氨酯涂层的红外光谱，水接触角的测试结果如图5所示。由红外光谱图可以看出，在2270cm-1处并未看到-NCO特征峰，说明-NCO全部参加反应，而且在3350cm-1、1730cm-1、1530cm-1、1245cm-1处均存在强烈吸收峰，分别代表氨基甲酸酯的N-H伸缩振动峰，C＝O伸缩振动峰、N-H变形振动峰及-NHCOO-中-C-O伸缩振动峰，2943cm-1处代表聚氨酯分子链中CH3和CH2伸缩振动峰，证明形成了水性聚氨酯涂层。
以上实例中用静态接触角(CA)表征水性聚氨酯涂层表面的润湿性，采用的水接触角测试方法如下：采用东莞市普赛特公司生产的PT-705B型接触角测试仪，用2μl去离子水，将水滴滴于涂层表面后进行测试，每个样品测试5个点，取平均值。
从图5可以看出，对比例1中水性聚氨酯涂层的水接触角为75°，表现出明显的亲水性；对比例2中埃络石纳米管改性的水性聚氨酯复合涂层的水接触角为98°，主要是因为埃络石纳米管在涂层表面形成微纳米结构，使接触角增大；实例1中经氟硅烷修饰后的复合涂层的水接触角为118°，实例2中复合涂层的水接触角为113°，涂层具有明显的疏水性，一方面是由于纳米粒子在涂层表面形成了可以捕捉空气的微纳米结构层，使滴液不能渗入涂层，从而提高了涂层表面的水接触角；另一方面，是由于水性聚氨酯涂层表面的羟基与低表面能的氟化硅烷偶联剂进行了偶联，将低表面能氟原子引入到涂层表面，疏水效果明显增强。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (5)
1.一种氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备方法，其特征在于，包括以下步骤：
S1、埃洛石纳米管的改性处理，
称取一定质量的埃络石纳米管溶于乙醇水溶液中，超声振动30-45min，加入一定质量的氨水和3-氨丙基三甲氧基硅烷，常温搅拌24h-36h后离心分离，用无水乙醇和水各洗涤2-3次，离心分离后干燥，得到改性埃络石纳米管, 乙醇水溶液、3-氨丙基三甲氧基硅烷、氨水和埃络石纳米管的质量比为100：10~20：5~10：0.5~2；
S2、埃洛石纳米管/水性聚氨酯复合乳液的制备，
将改性后的埃洛石纳米管、异氰酸酯和多元醇混合，在75℃-90℃下反应至NCO含量达到稳定状态，加入一定质量的2, 2-二羟甲基丁酸、1, 4-丁二醇和二月桂酸二丁基锡、丙酮，反应3-4h后，降低温度至40-50℃，加入一定质量的三乙胺中和25-30min，随后加入一定质量的去离子水，在1000-1200r/min的转数下搅拌乳化45-60min，减压蒸馏除去丙酮，得到埃洛石纳米管/水性聚氨酯复合乳液；
S3、埃洛石纳米管/水性聚氨酯复合涂层的制备，
将S2制备的所述氟化埃洛石纳米管/水性聚氨酯复合乳液用喷枪喷涂在清洗干净的基体表面，室温干燥，得到埃洛石纳米管/水性聚氨酯复合涂层；
S4、氟化埃洛石纳米管/水性聚氨酯复合疏水涂层的制备，
用喷枪将氟硅烷乙醇溶液喷涂在前述涂层表面，室温干燥，得到氟化埃洛石纳米管/水性聚氨酯复合疏水涂层。
2. 根据权利要求1所述的制备方法，其特征在于，所述步骤S2中的改性埃络石纳米管、异氰酸酯、多元醇、二月桂酸二丁基锡、丙酮、2, 2-二羟甲基丁酸、1, 4-丁二醇、三乙胺和去离子水的质量比为0.1～0.5∶5～10∶20～40∶0.1～0.5∶20～40∶0.7～1.5∶0.6～1.5∶0.4～0.8∶30～60。
3.根据权利要求2所述的制备方法，其特征在于，所述步骤S2中的异氰酸酯可为甲苯二异氰酸酯或异佛尔酮二异氰酸酯或二苯基甲烷二异氰酸酯；所述多元醇可为聚醚多元醇或聚碳酸酯二醇或聚丙二醇。
4.根据权利要求1所述的制备方法，其特征在于，所述步骤S4中的氟硅烷可为十七氟癸基三甲氧基硅烷或十七氟癸基三乙氧基硅烷。
5.由权利要求1-4中任一项所述方法制备的氟化埃洛石纳米管/水性聚氨酯复合疏水涂层。
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