CN107189656B - 一种基于聚碳酸酯的耐磨超疏水涂层的制备方法 - Google Patents

一种基于聚碳酸酯的耐磨超疏水涂层的制备方法 Download PDF

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CN107189656B
CN107189656B CN201710571725.XA CN201710571725A CN107189656B CN 107189656 B CN107189656 B CN 107189656B CN 201710571725 A CN201710571725 A CN 201710571725A CN 107189656 B CN107189656 B CN 107189656B
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王鹏
范孝良
孙博
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North China Electric Power University
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Abstract

本发明公开了一种基于聚碳酸酯的耐磨性超疏水涂层的制备方法。该方法首先将聚碳酸酯与消泡剂溶解在溶剂中制备得到中间层用溶液，再将疏水性氧化物纳米颗粒与低表面能材料溶解在丙酮溶液中制备得到表面层用溶液。施工过程中，首先在基底上涂布市售的聚碳酸酯胶水，然后在胶水上涂布中间层用溶液，待中间层用溶液干燥后在其上面进一步涂布表面层用溶液，干燥后即得到耐磨性超疏水涂层。本发明耐磨性超疏水涂层的制备方法通过利用聚碳酸酯与丙酮溶液之间的相互作用，巧妙地实现了嵌入式纳米结构与层级结构的有机结合，由此制备出来的超疏水涂层展现出优异的耐磨性。

Description

一种基于聚碳酸酯的耐磨超疏水涂层的制备方法
技术领域
本发明属于材料制备领域，特别涉及一种基于聚碳酸酯的超耐磨自清洁表面的制备方法。
背景技术
科学界将与水的接触角大于150°，滑动角小于10°的表面称之为超疏水表面。由于超疏水表面具有防水、自清洁、防腐蚀、防覆冰等特点，其在理论研究和工业应用中正得到越来越多的重视和关注。
制备超疏水表面往往需要同时满足适宜的粗糙度和低的表面自由能两个条件。基于这一理论，国内外的科学家们已通过压印法、激光烧灼法、溶胶凝胶法等多种方法和技术，制备出了超疏水表面。目前限制超疏水材料大规模应用的一个问题就是易破坏性，刀割或者砂纸打磨这些表面通常会失去超疏水性。文献(Science,2015,347:1132-1135)介绍了一种将氟硅烷改性后的二氧化钛纳米颗粒与喷胶相结合制备耐刀割超疏水涂层的方法，该文献提出的以喷胶为中间层黏结基底和二氧化钛纳米颗粒的方法，能够耐受100g重力作用下砂纸的40次打磨。中国专利CN105419450A公布了一种以半固化疏水性树脂黏结有机/无机杂化纳米涂料制备耐磨超疏水涂层的方法，该方法采用的疏水性树脂包括氟碳树脂、有机硅树脂或氟化改性聚氨酯、氟化改性环氧树脂，最高能够耐受100g重力作用下砂纸的70次打磨。除了用胶水粘接纳米颗粒的方法，分级结构是另一种制备耐磨超疏水涂层的方法。分级结构是一种在第一级微米凸起上引入第二级纳米凸起的结构，通过微米凸起对纳米凸起进行保护。文献(Advanced Function Materials，2008,18:3662-3669)通过在纺织物纤维上生成硅酮纳米毛的方法制备出了分级结构超疏水织物，制备出的样本能够耐受模拟皮肤接触的超长磨损。文献(Nanotechnology,2010,21:155705)通过对硅材料进行多次刻蚀的方法制备出了分级结构超疏水表面，制备出的材料能够耐受3.45kPa压力作用下砂纸的0.25m打磨。目前尚无数据显示有超疏水表面能够耐受500g(>5kPa)重力作用下砂纸的多次打磨。
发明内容
本发明是为了克服上述现有技术中超疏水表面耐磨性差，无法应用在高压力下的问题，提供了一种超耐磨自清洁超疏水表面的制备方法。
一种基于聚碳酸酯的耐磨超疏水涂层的制备方法，按照如下步骤进行：
(1)将10-30wt％的聚碳酸酯和0.1-0.5wt％的消泡剂(BYK 320)溶解在溶剂(四氢呋喃、苯或者甲苯)中，制备得到中间层用溶液备用；
(2)将1-3wt％低表面能材料放入丙酮中，磁力搅拌12小时，设置反应温度以使其充分溶解；再将4-6wt％疏水氧化物纳米颗粒加入低表面能材料丙酮溶液中充分混合，制成表面层用溶液备用；
(3)将市售的聚碳酸酯胶水涂布于基底上，等待2-3min后得到粘接层。
(4)将中间层用溶液涂布于粘接层上，等待1-2h，以使溶剂充分挥发,得到被聚碳酸酯胶水粘接的中间层。
(5)将表面层用溶液涂布于中间层上，等待2-4h，待表面层溶液中的丙酮完全挥发后，得到具有耐磨性的超疏水涂层。
所述低表面能材料为三甲基氯硅烷，六甲基二硅烷，十六烷基三甲氧基硅烷，硅烷耦合剂(KH550,KH560,KH590)，脂肪酸，硫醇中的一种或一种以上。
所述氧化物纳米颗粒为二氧化硅纳米颗粒、二氧化钛纳米颗粒或氧化锌纳米颗粒。
所述基底为金属，玻璃，橡胶，塑料，纸张，混凝土中的一种或一种以上。
与现有技术相比，本发明的特点在于本发明通过利用中间层与表面层用溶液之间的相互作用，巧妙地实现了嵌入式纳米结构与层级结构的有机结合，由此制备出来的超疏水涂层展现出优异的耐磨性。本发明的中间层的主要组成部分为聚碳酸酯，表面层用溶液的溶剂丙酮为聚碳酸酯的中性溶剂。当丙酮被用来溶解聚碳酸酯时，聚碳酸酯表面会出现微米级的粗糙度。表面层用溶液中还含有疏水性纳米颗粒，部分纳米颗粒会在丙酮溶解聚碳酸酯时进入聚碳酸酯中。随着丙酮的挥发，被溶解的聚碳酸酯再次固化，进入聚碳酸酯的纳米颗粒就嵌入到了聚碳酸酯中，形成嵌入式纳米结构。本发明具有耐磨性强、制备简单、成本低，使用方便的优点，适合大规模工业生产和日常应用。
附图说明
图1是耐磨性超疏水涂层的结构原理图。
图2是耐磨性超疏水涂层的实物图。
图3是耐磨性超疏水涂层的扫描电镜图。
图4是耐磨性超疏水涂层与水滴的接触角测试图。
图5是耐磨性超疏水涂层与水滴的滚动角测试图。
图6是耐磨性超疏水涂层经不同次数砂纸打磨后的接触角和滚动角。
图7是实施例4中制备得到表面的演示图。
图8是实施例5中制备得到的超疏水表面的演示图。
图9是实施例5中制备得到的超疏水表面被砂纸(500g压力)打磨一次后的演示图。
具体实施方式
下面结合附图，对本发明的具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。
实施例1
一种基于聚碳酸酯的耐磨超疏水涂层的制备方法，按照如下步骤进行：
(1)将20wt％的聚碳酸酯和0.2wt％的消泡剂(BYK 320)溶解在四氢呋喃中，制备得到中间层用溶液备用。
(2)将1wt％脂肪酸和1wt％三甲基氯硅烷放入丙酮中，磁力搅拌12小时，反应温度设置为50°以使其充分溶解；再将4wt％二氧化硅纳米颗粒加入丙酮溶液中充分混合，制成表面层用溶液备用；
(3)将市售的聚碳酸酯胶水涂布于基底上，等待3min后得到粘接层。
(4)将中间层用溶液涂布于粘接层上，等待2h，以使溶剂充分挥发,得到被聚碳酸酯胶水粘接的中间层。
(5)将表面层用溶液涂布于中间层上，等待4h，待表面层溶液中的丙酮完全挥发后，得到具有耐磨性的超疏水涂层。
该方法制备的透明超疏水涂层，如图1-6所示；图1是耐磨性超疏水涂层的结构原理图；图2是耐磨性超疏水涂层的实物图；图3是耐磨性超疏水涂层的实物图；图4为耐磨性超疏水涂层与水滴的接触角测试图；图5为是耐磨性超疏水涂层与水滴的滚动角测试图；选用玻璃作为基底测试耐磨性超疏水涂层的耐磨性，将涂覆于玻璃基底上超疏水涂层放置于80目砂纸上，在500g砝码的压力下，以15cm为一次打磨距离，图6是耐磨性超疏水涂层经不同次数砂纸打磨后的接触角和滚动角。
实施例2
一种基于聚碳酸酯的耐磨超疏水涂层的制备方法，按照如下步骤进行：
(1)将30wt％的聚碳酸酯和0.3wt％的消泡剂(BYK 320)溶解在甲苯中，制备得到中间层用溶液备用；
(2)将2wt％十六烷基三甲氧基硅烷放入丙酮中，磁力搅拌12小时，设置反应温度以使其充分溶解；再将5wt％二氧化钛纳米颗粒加入丙酮溶液中充分混合，制成表面层用溶液备用；
(3)将市售的聚碳酸酯胶水涂布于基底上，等待3min后得到粘接层。
(4)将中间层用溶液涂布于粘接层上，等待1h，以使溶剂充分挥发,得到被聚碳酸酯胶水粘接的中间层。
(5)将表面层用溶液涂布于中间层上，等待3h，待表面层溶液中的丙酮完全挥发后，得到具有耐磨性的超疏水涂层。
实施例3
一种基于聚碳酸酯的耐磨超疏水涂层的制备方法，按照如下步骤进行：
(1)将25wt％的聚碳酸酯和0.15wt％的消泡剂(BYK 320)溶解在苯中，制备得到中间层用溶液备用；
(2)将3wt％六甲基二硅烷放入丙酮中，磁力搅拌12小时，设置反应温度以使其充分溶解；再将6wt％氧化锌纳米颗粒加入丙酮溶液中充分混合，制成表面层用溶液备用；
(3)将市售的聚碳酸酯胶水涂布于基底上，等待3min后得到粘接层。
(4)将中间层用溶液涂布于粘接层上，等待2h，以使溶剂充分挥发,得到被聚碳酸酯胶水粘接的中间层。
(5)将表面层用溶液涂布于中间层上，等待3h，待表面层溶液中的丙酮完全挥发后，得到具有耐磨性的超疏水涂层
实施例4
一种表面的制备方法，按照如下步骤进行：
(1)将25wt％的聚碳酸酯和0.15wt％的消泡剂(BYK 320)溶解在苯中，制备得到中间层用溶液备用；
(2)将3wt％六甲基二硅烷放入四氢呋喃中，磁力搅拌12小时，设置反应温度以使其充分溶解；再将6wt％二氧化硅纳米颗粒加入丙酮溶液中充分混合，制成表面层用溶液备用；
(3)将市售的聚碳酸酯胶水涂布于塑料(PMMA)上，等待3min后得到粘接层。
(4)将中间层用溶液涂布于粘接层上，等待2h，以使溶剂充分挥发,得到被聚碳酸酯胶水粘接的中间层。
(5)将表面层用溶液涂布于中间层上，等待3h，待表面层溶液中的丙酮完全挥发后，得到具有耐磨性的超疏水涂层。
该方法制备的表面，如图7所示，由于四氢呋喃溶解聚碳酸酯的能力太强，纳米颗粒被完全嵌入到聚碳酸酯中，导致制备出的表面不具备超疏水性。
实施例5
一种超疏水表面的制备方法，按照如下步骤进行：
(1)将25wt％的聚碳酸酯和0.15wt％的消泡剂(BYK 320)溶解在苯中，制备得到中间层用溶液备用；
(2)将3wt％六甲基二硅烷放入四氢呋喃中，磁力搅拌12小时，设置反应温度以使其充分溶解；再将6wt％二氧化硅纳米颗粒加入乙醇溶液中充分混合，制成表面层用溶液备用；
(3)将市售的聚碳酸酯胶水涂布于塑料(PMMA)上，等待3min后得到粘接层。
(4)将中间层用溶液涂布于粘接层上，等待2h，以使溶剂充分挥发,得到被聚碳酸酯胶水粘接的中间层。
(5)将表面层用溶液涂布于中间层上，等待3h，待表面层溶液中的丙酮完全挥发后，得到具有耐磨性的超疏水涂层。
该方法制备的超疏水表面，如图8所示，由于乙醇无法溶解聚碳酸酯，纳米颗粒将简单地附着在聚碳酸酯中，导致制备出的表面耐磨性差，被砂纸打磨一次后就失去超疏水效果，如图9所示。
以上公开的仅为本发明的几个具体实施例，但是，本发明并非局限于此，任何本领域的技术人员能思之的变化都应落入本发明的保护范围。

Claims (5)

1.一种基于聚碳酸酯的耐磨超疏水涂层的制备方法，其特征在于，按照如下步骤进行：
(1)将10-30wt％的聚碳酸酯和0.1-0.5wt％的消泡剂溶解在溶剂中，制备得到中间层用溶液备用；
(2)将1-3wt％低表面能材料放入丙酮中，磁力搅拌12小时，设置反应温度以使其充分溶解；再将4-6wt％疏水氧化物纳米颗粒加入低表面能材料丙酮溶液中充分混合，制成表面层用溶液备用；
(3)将聚碳酸酯胶水涂布于基底上，等待2-3min后得到粘接层；
(4)将中间层用溶液涂布于粘接层上，等待1-2h，以使溶剂充分挥发,得到被聚碳酸酯胶水粘接的中间层；
(5)将表面层用溶液涂布于中间层上，等待2-4h，待表面层溶液中的丙酮完全挥发后，得到具有耐磨性的超疏水涂层；
所述低表面能材料为三甲基氯硅烷，六甲基二硅烷，十六烷基三甲氧基硅烷，硅烷耦合剂KH550，硅烷耦合剂KH560，硅烷耦合剂KH590，脂肪酸，硫醇中的一种或一种以上。
2.根据权利要求1所述的基于聚碳酸酯的耐磨超疏水涂层的制备方法，其特征在于，所述疏水氧化物纳米颗粒为二氧化硅纳米颗粒、二氧化钛纳米颗粒或氧化锌纳米颗粒。
3.根据权利要求1所述的基于聚碳酸酯的耐磨超疏水涂层的制备方法，其特征在于，所述基底为金属，玻璃，橡胶，塑料，纸张，混凝土中的一种或一种以上。
4.根据权利要求1所述的基于聚碳酸酯的耐磨性超疏水涂层的制备方法,其特征在于，所述消泡剂为BYK 320。
5.根据权利要求1所述的基于聚碳酸酯的耐磨超疏水涂层的制备方法,其特征在于，所述溶剂为四氢呋喃、苯或者甲苯。
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