CN106634275A - 一种超亲水/水下超疏油涂层材料及其制备方法 - Google Patents

一种超亲水/水下超疏油涂层材料及其制备方法 Download PDF

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CN106634275A
CN106634275A CN201611156887.9A CN201611156887A CN106634275A CN 106634275 A CN106634275 A CN 106634275A CN 201611156887 A CN201611156887 A CN 201611156887A CN 106634275 A CN106634275 A CN 106634275A
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周树学
顾云娇
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Abstract

本发明涉及一种超亲水/水下超疏油涂层材料及其制备方法。本发明涂层材料由底漆层和面漆层构成，其中底漆层主要由含羟基的丙烯酸树脂及其固化剂组成，面漆层由聚乙烯醇和纳米粒子组成，且底漆中的固化剂能与聚乙烯醇发生化学交联反应。具体制备步骤为：在基材表面涂覆底漆层；涂覆面漆层，在室温或低温下干燥预交联，使得底漆层和面漆层之间发生化学键合；将涂层在交联剂水溶液中浸泡处理一定时间；将涂层从交联剂水溶液中取出，室温干燥，或进行高温热处理使底漆层充分固化。由上述步骤得到的涂层材料具有梯度微纳结构的表面，超亲水和水下超疏油特性突出，且与基材结合力强，透明性好。该涂层材料可用作防雾涂层，亦可用作水下设施表面的自清洁防污涂层。

Description

一种超亲水/水下超疏油涂层材料及其制备方法
技术领域
本发明涉及化工新材料领域，涉及一种超亲水/水下超疏油涂层材料的组成及其制备方法。
背景技术
超亲水涂层是水滴在其表面接触角小于10゜的涂层，水在其表面极易铺展形成水膜，具有突出的防雾和自清洁特性。当其用于水下环境时，则表现出超疏油性能，因而也可以用作水下超疏油自洁涂层。目前，其中一类水下超疏油材料为含有亲水基团或两性离子基团的聚合物水凝胶，如聚乙二醇、聚乙烯醇、壳聚糖、海藻酸钙、甜菜碱类等，见中国专利CN104804116A和CN104861755A。这种水凝胶类材料透明性好、水下超疏油性能突出，但因其吸水率大，易溶胀变形从基材表面脱离，不宜直接用作涂层材料。另一类水下超疏油材料为表面具有微纳结构的材料，这种微纳结构的构建方法有电化学刻蚀、模板法、溶胶凝胶法、有机无机复合法等。如，中国专利CN105063738A报道了一种钛合金水下超疏油表面的制备方法，即在由NaCl和H2O2组成的中性电解液中，对钛合金片表面进行电化学刻蚀，获得具有微米级的凹坑和空腔结构，但电化学刻蚀法仅局限于金属基材。中国专利CN103524766A通过砂纸打磨制备透明或不透明聚合物微纳结构模板，而CN101220165以鱼鳞为天然模板，通过一次赋形，得到具有鱼鳞负结构的聚二甲基硅氧烷模板，在此基础上，将亲水聚合物或单体在交联时进行赋形，获得表面微纳结构，但上述模板法并不适合大面积制备水下超疏油表面。中国专利CN104610875A和CN105906219A主要通过硅氧前驱体的溶胶凝胶法制备了表面具有粗糙度结构的有机无机杂化涂层，产生水下超疏油性能。中国专利CN101704955A以壳聚糖的乙酸溶液和纳米二氧化硅的氢氧化钠溶液为原料，常温一步法制备了微纳粗糙结构表面，从而防止水下油污粘附。溶胶-凝胶法和纳米复合涂层法虽然能获得大面积的水下超疏油表面，但其微纳结构不仅存在于表面，同样也存在于涂层内部，导致涂层透明性低，力学性能不佳。另外，采用亲水聚合物作为成膜物质时，还存在涂层易剥落、耐水性差等问题。因此，高耐久性（高力学性能、高附着力、高耐水性）、高透明性的超亲水/水下超疏油涂层材料的制备仍亟待发展。
发明内容
本发明的目的在于提供一种高耐久性、透明性佳的超亲水/水下超疏油涂层材料及其制备方法。
本发明所述的超亲水/水下超疏油涂层由底漆层和面漆层构成。其中，底漆层主要由羟基丙烯酸树脂及其固化剂组成，起增强涂层与基材附着力作用；面漆层由聚乙烯醇和纳米粒子组成，起表面亲水或水下疏油功能；并且，底漆层中的固化剂能与面漆中的聚乙烯醇发生化学交联反应，从而促进底漆层与面漆层之间的附着力。
本发明提出的一种超亲水/水下超疏油涂层材料，由底漆层和面漆层构成，其中：底漆层由羟基丙烯酸树脂及其固化剂组成，面漆层由聚乙烯醇和纳米粒子组成，聚乙烯醇占50-96wt%，纳米粒子占4-50wt%；底漆层中的固化剂能与聚乙烯醇发生化学交联反应。
本发明中，所述底漆层中的羟基丙烯酸树脂为溶剂型或水性羟基丙烯酸树脂，其羟值为30-140mgKOH/g，固化剂为异氰酸酯三聚体或氨基树脂。
本发明中，所述聚乙烯醇的醇解度为70%-100%，重均分子量为1000-500000g/mol。
本发明中，所述纳米粒子为纳米SiO2、ZnO、TiO2、MgO或BaSO4等中的一种或几种的混合。
本发明中，所述纳米粒子粒径为10nm-200nm，表面基团为羟基、氨基或羧基中任一种。其表面基团可为未经改性时的羟基，也可通过化学接枝在表面引入氨基或羧基基团，强化纳米粒子表面的亲水特性。
本发明提出的一种超亲水/水下超疏油涂层材料的制备方法，具体步骤如下：
（１）在基材表面涂覆底漆层；底漆层由喷涂、浸涂和辊涂等方法施工，溶剂挥发后，再于室温或低温下干燥0.5-2小时；
（２）涂覆面漆层，在室温或低温下干燥预交联，使得底漆层和面漆层之间发生化学键合；面漆层由喷涂、浸涂、淋涂等方法施工，在室温或低温下处理0.5-2小时，形成双层结构涂层；
（３）将双层结构涂层在交联剂水溶液中浸泡处理；
（４）将双层结构涂层从交联剂水溶液中取出，室温干燥，或进行高温热处理使底漆层充分固化。
本发明中，步骤（３）中所述浸泡处理的时间为0.2-2小时，浸泡温度为室温。
本发明中，步骤（３）中所述交联剂水溶液为酸性含醛基类水溶液、硼酸溶液或柠檬酸水溶液等中任一种。
本发明中，所述的含醛基类化合物为甲醛、乙醛、戊二醛中的一种或多种的复配，醛化合物浓度为2-10wt%。
本发明中，所述酸性调节剂为醋酸、草酸、盐酸、硫酸或硼酸中的一种或几种，酸性醛基水溶液的pH值为0.5-4。
本发明中，步骤（４）中所述高温热处理温度为100-180°C，时间为1-15分钟。
本发明所述的底漆层中的羟基丙烯酸树脂为溶剂型或水性羟基丙烯酸树脂，其羟值范围为30-140mgKOH/g，固化剂为异氰酸酯三聚体或三聚氰胺树脂。具体而言，异氰酸酯固化剂有HDI三聚体、IPDI三聚体、TDI三聚体等，用量按NCO/OH比值1.1-1.5进行设计；氨基树脂体系为甲醚化三聚氰胺树脂、丁醚化三聚氰胺树脂中的一种或两种复合，用量按羟基丙烯酸树脂的10-50%设计。
本发明中，所述的聚乙烯醇的醇解度范围为70%-100%，重均分子量范围为1000-500000g/mol，使用时先配制成5-50wt%的水溶液。
本发明所述的底漆层是通过底漆涂覆干燥后形成，其中涂覆方法包括喷涂、浸涂、辊涂等，涂覆完成后，再在室温下或低温进行干燥，时间0.5-2小时，通过干燥完全或部分除去挥发性溶剂，并使涂层发生一定程度的交联，从而使得底漆层从液态转变为固态或类固态。
本发明所述的底漆为双组份体系，其中A组份为羟基丙烯酸树脂、润湿剂、消泡剂、溶剂等的组合物，B组份为固化剂；在涂覆前，将A组份和B组份按比例混合。
本发明面漆层由聚乙烯醇基纳米复合涂料涂覆干燥后获得，其中涂覆方法包括喷涂、浸涂、淋涂等，干燥条件为室温或低温0.5-2小时。
本发明所涉及的聚乙烯醇基纳米复合涂料组成如下：聚乙烯醇2-20 wt%、纳米粒子2-10 wt%、水70-95 wt%、消泡剂、0-0.5 wt%。其制备过程如下：先将聚乙烯醇溶解在水中，配制成浓度为5-50wt%的水溶液，再加入消泡剂，而后在高速分散搅拌下，逐渐加入计量好的纳米粒子，搅拌转速500-2000rpm，纳米粒子全部加完后再剪切分散2小时，完成所需的纳米复合涂料的制备。
本发明所制备的底漆层/面漆层双层结构涂层进一步放入交联剂水溶液中处理，浸泡时间为0.2-2小时，浸泡温度为室温。涂层浸泡过程中，表层部分聚乙烯醇树脂溶于水中，增大表面颜基比，从而获得梯度微纳结构表面，同时，醛化合物扩散进入聚乙烯醇涂层中，使聚乙烯醇发生交联，提高了聚乙烯醇涂层的耐水性。
本发明所采用的交联剂水溶液为酸性含醛基类水溶液、硼酸溶液、柠檬酸水溶液中的一种。
本发明所采用的醛基水溶液由醛类化合物、酸性调节剂和水组成。其中醛类化合物为甲醛、乙醛、戊二醛中的一种或多种的复配，醛化合物浓度为2-10wt%。酸性调节剂为醋酸、草酸、盐酸、硫酸、硼酸中的一种或几种，加入酸性调节剂使得酸性醛基水溶液的pH值为0.5-4。
本发明所述的涂层在浸泡处理阶段结束后，将涂层放于室温干燥；若底漆为羟基丙烯酸树脂/氨基树脂体系，浸泡结束后干燥时需要高温处理，处理温度范围为100-180°C，时间为1-15分钟，以使底漆层固化完全，同时促进底漆层与面漆层之间的化学键合。
本发明提出的超亲水/水下超疏油涂层材料具有以下优点：（1）原料成本低廉，工艺适合大面积制备；（2）微纳结构仅局限于涂层表面，涂层力学性能佳；（3）涂层透明性高，且可通过面漆层的厚度调控，以满足不同场合的使用要求。（4）通过底漆层/面漆层双层结构设计，解决了涂层与不同基材的附着力问题，适用范围广。
本发明制备的超亲水/水下超疏油涂层可以应用于各种基材表面，包括金属、塑料、玻璃等基材表面，起到防雾、防污、自洁、水下防油等功能。
具体实施方式
下面通过实施例进一步说明本发明。
实施例1：
用50g热水溶解5g醇解度为88%的聚乙烯醇(PVA)1788，并向其中加入2.5g粒径为12nm的SiO2，制成PVA/SiO2/33%分散液。2g羟基丙烯酸树脂与0.2g完全甲醚化三聚氰胺溶解于5g乙酸丁酯中，并添加0.01g对甲苯磺酸。溶液用120 μm线棒辊涂于标准载玻片上。待溶剂充分挥发，涂膜失去流动性后，在其上用120 μm线棒涂覆一层PVA/SiO2/ 33%分散液。上层液膜常温下干燥后，将此未交联双层涂层置于70℃烘箱中处理0.5-5h。取出后冷却至室温，并放入5 vol%甲醛水溶液（硫酸调节pH至2）中浸渍固化0.1-3小时，淋洗，干燥。最后，将该双层涂层于120℃热处理0.1-0.5小时使底涂充分交联。涂膜性能见表1。
实施例2：
用50g热水溶解5g醇解度为98%的聚乙烯醇Mowiol 117，并向其中加入5.0g粒径为20nm的SiO2，并滴加0.02g消泡剂BYK021，制成PVA/SiO2/50%水分散液。2g羟基丙烯酸树脂与0.5g部分甲醚化三聚氰胺溶解于2g乙酸丁酯中，并添加0.01g对甲苯磺酸。溶液用30μm线棒辊涂于标准载玻片上。待溶剂充分挥发，涂膜失去流动性后，在其上喷涂一层PVA/SiO2/17%分散液。将此未交联双层涂层置于90℃烘箱中处理0.1-2小时。取出后冷却至室温，并放入2.5vol%戊二醛水溶液（盐酸调节pH至2）中浸渍0.1-3小时，淋洗，干燥。最后，将该双层涂层于140℃热处理0.1-0.5小时使底涂充分交联。涂膜性能见表1。
实施例3：
用50g热水溶解5g醇解度为88%的聚乙烯醇1788，并向其中加入3.5g粒径为20nm的ZnO，制成PVA/ZnO/41%分散液。2g羟基丙烯酸树脂与0.2g完全甲醚化三聚氰胺溶解于5g乙酸丁酯中，并添加0.01g对甲苯磺酸。溶液用120 μm线棒辊涂于标准载玻片上。待溶剂充分挥发，涂膜失去流动性后，在其上用120 μm线棒涂覆一层PVA/ZnO/41%分散液。上层液膜常温下干燥后，将此未交联双层涂层置于70℃烘箱中处理0.5-5h。取出后冷却至室温，并放入5 vol%甲醛水溶液（硫酸调节pH至2）中浸渍固化0.1-3小时，淋洗，干燥。最后，将该双层涂层于120℃热处理0.1-0.5 小时使底涂充分交联。涂膜性能见表1。
比较例1：
用100g热水溶解5g醇解度为98-99%的聚乙烯醇，并向其中加入1.0g粒径为50nm的二氧化硅。制成PVA/SiO2/17%水分散液。向其中加入5%的戊二醛水溶液（50%）和10% 0.2M 盐酸，制成可固化PVA/SiO2/17%面漆浆料。2g羟基丙烯酸树脂与0.1g部分甲醚化三聚氰胺溶解于5g乙酸丁酯中，并添加0.01g对甲苯磺酸。溶液用80μm线棒辊涂于标准载玻片上。待溶剂充分挥发，涂膜失去流动性后，在其上喷涂一层可固化PVA/SiO2/17%面漆浆料。待上层干燥交联后，将此未交联双层涂层置于130℃烘箱中处理0.1-2小时，使底涂充分交联。
比较例2：
用50g热水溶解5g醇解度为98%的聚乙烯醇Mowiol 117，并向其中加入1.7g粒径为20nm的二氧化硅，制成PVA/SiO2/25%水分散液，将其直接用120μm线棒辊涂于铝板上。放入2.5vol%戊二醛水溶液（盐酸调节pH至2）中浸渍0.1-3小时，淋洗，干燥。涂膜性能见表1。
表1. 不同制备方法获得的涂层性能。

Claims (11)

1.一种超亲水/水下超疏油涂层材料，其特征在于由底漆层和面漆层构成，其中：底漆层由羟基丙烯酸树脂及其固化剂组成，面漆层由聚乙烯醇和纳米粒子组成，聚乙烯醇占50-96wt%，纳米粒子占4-50wt%；底漆层中的固化剂能与聚乙烯醇发生化学交联反应。
2.根据权利要求1所述的超亲水/水下超疏油涂层材料，其特征在于所述底漆层中的羟基丙烯酸树脂为溶剂型或水性羟基丙烯酸树脂，其羟值为30-140mgKOH/g，固化剂为异氰酸酯三聚体或氨基树脂。
3.根据权利要求1所述的超亲水/水下超疏油涂层材料，其特征在于所述聚乙烯醇的醇解度为70%-100%，重均分子量为1000-500000g/mol。
4.根据权利要求1所述的超亲水/水下超疏油涂层材料，其特征在于所述纳米粒子为纳米SiO2、ZnO、TiO2、MgO或BaSO4中的一种或几种的混合。
5.根据权利要求1所述的超亲水/水下超疏油涂层材料，其特征在于所述纳米粒子粒径为10nm-200nm，表面基团为羟基、氨基或羧基中任一种。
6.一种如权利要求１所述的超亲水/水下超疏油涂层材料的制备方法，其特征在于具体步骤如下：
（１）在基材表面涂覆底漆层；底漆层由喷涂、浸涂和辊涂等方法施工，溶剂挥发后，再于室温或低温下干燥0.5-2小时；
（２）涂覆面漆层，在室温或低温下干燥预交联，使得底漆层和面漆层之间发生化学键合；面漆层由喷涂、浸涂、淋涂等方法施工，在室温或低温下处理0.5-2小时，形成双层结构涂层；
（３）将双层结构涂层在交联剂水溶液中浸泡处理；
（４）将双层结构涂层从交联剂水溶液中取出，室温干燥，或进行高温热处理使底漆层充分固化。
7.根据权利要求６所述的制备方法，其特征在于步骤（３）中所述浸泡处理的时间为0.2-2小时，浸泡温度为室温。
8.根据权利要求６所述的制备方法，其特征在于步骤（３）中所述交联剂水溶液为酸性含醛基类水溶液、硼酸溶液或柠檬酸水溶液等中任一种。
9.根据权利要求８所述的制备方法，其特征在于所述的含醛基类化合物为甲醛、乙醛、戊二醛中的一种或多种的复配，醛化合物浓度为2-10wt%。
10.根据权利要求８所述的制备方法，其特征在于所述酸性调节剂为醋酸、草酸、盐酸、硫酸或硼酸中的一种或几种，酸性醛基水溶液的pH值为0.5-4。
11.根据权利要求６所述的制备方法，其特征在于步骤（４）中所述高温热处理温度为100-180°C，时间为1-15分钟。
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107497652A (zh) * 2017-09-11 2017-12-22 阜南县大自然工艺品有限公司 一种提升木制工艺品耐污性能的方法
CN109096860A (zh) * 2018-08-09 2018-12-28 西北大学 一种聚阳离子或聚两性离子水下超疏油涂层及其制备方法
CN109232946A (zh) * 2018-08-15 2019-01-18 杭州联通管业有限公司 一种抗污塑料排水管及其制备方法
CN109898397A (zh) * 2019-03-28 2019-06-18 西安西拓交通设施公司 一种道路划线方法
CN110026136A (zh) * 2019-05-17 2019-07-19 湖北大学 水下超疏油抗冻有机水凝胶及其制备方法、应用、涂层、油水分离网及其制备方法
CN110512423A (zh) * 2019-09-09 2019-11-29 苏州科技大学 超亲水/水下超疏油改性基底材料的制备方法
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103316507A (zh) * 2013-06-06 2013-09-25 华南理工大学 超亲水及水下超疏油的油水分离网膜及其制备方法和应用
CN104610875A (zh) * 2015-01-22 2015-05-13 泉州三欣新材料科技有限公司 具有超亲水及水下超疏油涂层及其制备方法和用途
CN105499092A (zh) * 2015-11-30 2016-04-20 东南大学 一种透明超双疏表面层及层层原位喷涂反应制备法
CN105948817A (zh) * 2016-04-18 2016-09-21 江苏大学 一种超亲水-水下超疏油复合膜涂层的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103316507A (zh) * 2013-06-06 2013-09-25 华南理工大学 超亲水及水下超疏油的油水分离网膜及其制备方法和应用
CN104610875A (zh) * 2015-01-22 2015-05-13 泉州三欣新材料科技有限公司 具有超亲水及水下超疏油涂层及其制备方法和用途
CN105499092A (zh) * 2015-11-30 2016-04-20 东南大学 一种透明超双疏表面层及层层原位喷涂反应制备法
CN105948817A (zh) * 2016-04-18 2016-09-21 江苏大学 一种超亲水-水下超疏油复合膜涂层的制备方法

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107497652A (zh) * 2017-09-11 2017-12-22 阜南县大自然工艺品有限公司 一种提升木制工艺品耐污性能的方法
CN109096860B (zh) * 2018-08-09 2021-01-26 西北大学 一种聚两性离子水下超疏油涂层及其制备方法
CN109096860A (zh) * 2018-08-09 2018-12-28 西北大学 一种聚阳离子或聚两性离子水下超疏油涂层及其制备方法
CN109232946A (zh) * 2018-08-15 2019-01-18 杭州联通管业有限公司 一种抗污塑料排水管及其制备方法
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