CN114276733B - 一种透明无氟的超润滑防油涂层的制备方法 - Google Patents
一种透明无氟的超润滑防油涂层的制备方法 Download PDFInfo
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Abstract
本发明公开了一种透明无氟的超润滑防油涂层的制备方法，具体如下：将巯基化合物，苯乙烯共聚物，低表面能组分以及光引发剂溶解在有机溶剂中，搅拌均匀后，涂布于基底上，紫外灯固化，由此便获得透明无氟的超润滑防油涂层。对各种低表面张力的有机溶剂甚至高粘度液体如原油，蜂蜜等表现出优异的防黏附性能，具有优异的化学稳定性和机械耐久性，可以应用于玻璃，铝片，钢片，聚合物等多种基底，不受使用环境的限制，在空气，油，水环境下保持优异的防黏附性能，适用性广泛。且该方法能够使用喷涂，浸涂，旋涂等多种方式，简单易操作、反应条件可控、所制备的涂层透明无氟，成本低，可应用于多种场合。
Description
技术领域
本发明属于新型高分子功能材料、聚合物涂层领域，具体涉及一种透明无氟的超润滑防油涂层的制备方法。
背景技术
拒液表面在理论研究和实际应用如防污、无损运输、微流体、生物分析、液体收集、微反应器等领域都广受关注。尤其是防水表面发展迅速，能够实现对灰尘和水溶性污染物的快速去除。然而，由于油的表面张力较低，使得拒油表面的制备更为困难。因此，从含油废水中收集或分离油是一个巨大的挑战，特别是对于高粘度油。例如，原油一旦溢出，就会紧紧地粘在各种表面上，对基材造成严重污染，甚至可能使所有设备失效，造成巨大的经济损失。
目前存在三种主要的防止油粘附的策略。第一种是具有微纳米粗糙结构的超疏油或超双疏材料。通常这种表面都是通过使用含氟材料制备得来的。含氟原材料昂贵且无法降解，具有生物积累性，会对全球环境造成严重影响。此外，这种表面比较脆弱，化学稳定性和机械耐久性能差，难以同时满足超疏油性和透明性，进一步限制了其实际应用。第二种策略是通过制备超亲水/水下超疏油材料用于防止油的黏附，但它只能用于水下环境。第三种是受猪笼草启发，将润滑油注入多孔表面制备而成，具有防止水和各种具有极低表面能油类的黏附。为了锁住润滑液，需要制造具有多孔结构的基底，制备过程复杂且需要昂贵的设备。 而且，测试液滴与润滑液不能混溶，长期使用润滑液会逐渐挥发流失。因此，急需发展其他可持续的防油材料来清理溢油和收集粘稠油。
发明内容
为了解决上述问题，本发明制备了一种基于新型结构设计的“类液”固体超润滑苯乙烯共聚物涂层，用于防止油的黏附。具体来说就是利用这种新型的互穿聚合物网络结构中的柔性链段，使它们能够充当具有广泛表面张力的类液体状润滑层。由于发生化学交联，这些分子结构不会被接触的有机溶剂溶解或取代。在不加含氟硅烷情况下，现有技术中的苯乙烯共聚物涂料均只能得到防水性能，会被油污直接润湿，无法实现直接的防油性能。本发明在不添加其他微纳米颗粒作为无机填料的情况下，涂层能同时保持优异的韧性和机械强度，以及透明性。不仅能同时防止高表面张力和低表面张力液体的黏附，还能实现对高粘度液体的防黏附性能并保持优异的化学稳定性和机械耐久性。可以长期应用于玻璃，铝片，钢片，聚合物等多种基底，且可以克服使用环境的限制，在空气、水下、油下均能保持良好防粘附性能。该涂层不含氟，能够对各种低表面张力的有机溶剂甚至高粘度液体如原油，蜂蜜等表现出优异的防黏附性能。与商用氟化涂层相比，该涂层表现出更好的抗油粘附性和机械性能，有望在油气管道输送、微流控，防污自清洁、无损输送，液体收集，粘油回收，油水分离材料等领域得以广泛应用，具有较大的经济价值。
为了实现上述目的，本发明采用如下技术方案：
一种透明无氟的超润滑防油涂层的制备方法，包括以下步骤：
（1）将巯基化合物，苯乙烯共聚物，低表面能组分以及光引发剂溶解在有机溶剂中，搅拌均匀后，得到混合溶液，静置待用。
（2）将步骤（1）的混合溶液涂于清洗好的干净基底上。
（3）将步骤（2）中的涂层放于紫外灯下光照固化，取出即得到透明无氟的类液固体超润滑防油涂层。
进一步地，步骤（1）中所述的混合溶液中，巯基化合物，苯乙烯共聚物，低表面能组分三者的浓度分别为1-10wt%，1-30wt%，1-15wt%。
进一步地，步骤（1）中所述的苯乙烯共聚物赋予涂层优异的柔性，使涂层具有良好的韧性，能够应用于卷曲的基底。
进一步地，步骤（1）中所述的巯基化合物为季戊四醇四-3-巯基丙酸酯。利用其与苯乙烯共聚物在紫外灯照射下发生反应，其作用主要是用于提高化学交联程度，参与构造互穿聚合物网络结构，从而获得防高黏度液体黏附性能，提高涂层的硬度。
进一步地，步骤（1）中所述的低表面能组分为无氟的含硅具有低表面能的化合物。
进一步地，步骤（1）中所述的低表面能组分为羟基硅油。羟基硅油分子间会发生物理交联，形成氢键，与苯乙烯共聚物和巯基化合物生成的化学交联缠绕在一起，形成互穿聚合物网络结构，赋予涂层优异的防油性能和防黏附性能。
进一步地，步骤（1）中所述的光引发剂为自由基引发剂安息香二甲醚。
进一步地，步骤（1）中所述的有机溶剂为脂肪烃、芳香烃、饱和醇、饱和酮，具体包括氯仿、甲苯、环己烷、四氢呋喃中的一种。
进一步地，步骤（2）中采用滴涂、旋涂、喷涂或提拉浸涂的方法将混合溶液涂于基底上。
本发明中使用的苯乙烯共聚物赋予涂层优异的柔性，使涂层具有良好的韧性，能够应用于卷曲的基底；使用的巯基化合物为季戊四醇四-3-巯基丙酸酯。利用其与苯乙烯共聚物在紫外灯照射下发生反应，其作用主要是用于提高化学交联程度，参与构造互穿聚合物网络结构，从而获得防高黏度液体黏附性能，提高涂层的硬度；使用的低表面能组分为羟基硅油，羟基硅油分子间会发生物理交联，形成氢键，与苯乙烯共聚物和巯基化合物生成的化学交联缠绕在一起，形成互穿聚合物网络结构，赋予涂层优异的防油性能和防黏附性能。
本发明的优点是：
（1）可以使用喷涂，浸涂，旋涂等多种方式，工艺简单，操作方便，成本低。
（2）所制备的涂层透明无氟，可杜绝目前防油涂层体系中使用含氟物质造成的成本高，无法降解，具有生物积累性的问题。
（3）可以应用于玻璃，铝片，钢片，聚合物等多种基底，不受使用环境的限制，可以在空气，油，水环境下应用。
（4）涂层对各种低表面张力的有机溶剂甚至高粘度液体如原油，蜂蜜等表现出优异的防黏附性能。
（5）该涂层在各种基底上均具有良好的结合力。
（6）该涂层具有优异的化学，机械稳定性和耐久性。
附图说明
图1显示了各种液体在涂层涂敷的玻璃上的滑动；
图2显示了原油和煤油在所制备的涂层与商用含氟涂层上滑动图；
图3显示涂层放置在户外经过30天的风吹日晒雨淋后，乙醇在该表面的滑动角和接触角变化图；
图4显示了涂层在四种有机溶剂中浸泡72 h后的乙醇在涂层表面的接触角和滑动角变化图；
图5显示了涂层涂敷在铝片基底上，防原油性能展示；
图6显示了涂层经过超声处理长达20 h后，乙醇在涂层表面的接触角和滑动角变化图；
图7显示了墨水在裸片和涂层涂敷的玻璃片上的状态图，体现优异的防污性能；
图8显示了十六烷液滴在经过轻微磨损后的涂层表面滑动过程图；
图9显示了环路冲蚀实验的实物装置图；
图10显示了经过环路冲蚀实验，聚苯乙烯共聚物涂层和所制备涂层前后形貌变化；
图11显示了环己烷在苯乙烯共聚物涂层，对比例1涂层，对比例2涂层以及实施例4涂层表面的黏附行为；
图12显示了对比例1，对比例2和实施例4涂层铅笔硬度测试的硬度；
图13显示了实施例4和对比例1以及对比例2制备得到的涂层的电镜图；
图14显示了砂冲装置图；
图15显示了实施例4和对比例1以及对比例2制备得到的涂层经过60次砂冲后表面的形貌电镜图；
图16 中a显示了10μL浓盐酸液滴滴在倾斜的实施例4和对比例1以及对比例2制备得到的涂层表面后的滑动状态。b显示了50μL浓盐酸液滴滴在平放的实施例4和对比例1以及对比例2制备得到的涂层表面28 h后，不同涂层表面的状态。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
按表1比例配置涂层混合溶液
实施例1-4和对比例1-2中分别再加入光引发剂安息香二甲醚，占1wt%。其中实施例1中的苯乙烯共聚物为甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物，巯基化合物为季戊四醇四-3-巯基丙酸酯，有机溶剂为氯仿，占69wt%。实施例2中的苯乙烯共聚物为丙烯腈-丁二烯-苯乙烯共聚物，巯基化合物为季戊四醇四-3-巯基丙酸酯，有机溶剂为甲苯，占60wt%。实施例3中的苯乙烯共聚物为苯乙烯-异戊二烯共聚物，巯基化合物为季戊四醇四-3-巯基丙酸酯，有机溶剂为环己烷，占54wt%。实施例4中的苯乙烯共聚物为丙烯腈-异戊二烯-苯乙烯共聚物，巯基化合物为季戊四醇四-3-巯基丙酸酯，有机溶剂为四氢呋喃，占74wt%。对比例1和对比例2使用的苯乙烯共聚物均为丙烯腈-异戊二烯-苯乙烯共聚物，对比例1中有机溶剂为四氢呋喃，占76wt%。对比例2中使用的巯基化合物为季戊四醇四-3-巯基丙酸酯，有机溶剂为四氢呋喃，占75wt%。分别按表1中的比例混合苯乙烯共聚物、巯基化合物、低表面能组分，溶解在有机溶剂中，再加入光引发剂，然后采用旋涂的方法分别涂覆于基底表面，放于紫外灯（365 nm）下进行光固化成膜。
以下是针对各实施例和对比例涂层在不同基材上的特性进行检测的项目：
测试一：涂层对各种溶液的防黏附性
取涂覆有实施例2涂层的玻璃，在玻璃表面涂层上自左向右滴加不同的液体：白酒、人造汗液、红酒、蜂蜜、食用油。状态图如图1所示，各种溶液液滴均快速滑落包括高粘度的蜂蜜。从图1中可以看出，涂层对各类液体具有优异的防黏附性。
测试二：与商用含氟涂层性能对比
将原油和煤油分别滴在所涂覆有实施例1涂层的玻璃表面和商用含氟涂层的玻璃表面，观察其滑动状态。如图2所示，原油和煤油均能快速从实施例1涂层表面滑落，而润湿商用含氟涂层，表明本发明涂层优异的防黏附性。
测试三：户外耐久性
取实施例1涂层涂敷的玻璃放置在户外，经过30天的风吹日晒雨淋后，观察乙醇在该表面的滑动角和接触角变化图。由图3可得，涂层经过30天的户外放置，依旧能保持良好的有机溶剂防黏附性能，表明其优异的耐久性。
测试四：油性环境稳定性
取实施例3涂层涂敷的玻璃分别放于乙醇，甲苯，二氯甲烷，正己烷溶液中浸泡长达72 h，每隔8 h测一次乙醇在该表面的滑动角和接触角滞后。如图4所示，尽管经过72 h的有机溶液浸泡，涂层表面依旧具有优异的防油性能，表明其在油性环境优异的稳定性。
测试五：涂层防原油黏附性能
任取实施例4涂层涂敷的铝片基底固定在提拉浸渍机上浸入装满原油的烧杯中，铝片布满原油后，再拉来竖直放置。如图5所示，原油很快从涂敷有涂层的部分滑落，而紧紧黏附在未涂敷的部分，表明涂层能够防止高粘度油的黏附。
测试六：水下环境涂层结合力
任取实施例4涂层涂敷的玻璃片放置在装满水的烧杯中，进行水下环境的超声，观察经过不同时间乙醇在涂层表面的滑动角和接触角。如图6所示，涂层经过长达20 h的超声处理，其滑动角和接触角值较初始略有上升，但依旧保持优异防有机溶剂黏附性能，表明其在水下环境依然具有优异的结合力。
测试七：涂层防污性能
用毛笔蘸墨水分别在实施例1涂层涂敷的玻璃片与裸玻璃片上写字，如图7所示，涂层涂敷的玻璃片上几乎没有墨水印迹，而裸玻璃片上痕迹明显，表明本发明涂层优异的防污性能。
测试八：涂层的机械耐久性
用手术刀在实施例2涂层涂敷的玻璃片表面留下一道道的刮痕，再将十六烷液滴滴在经过刮伤的表面，观察其滑动行为。如图8所示，十六烷液滴依旧能够快速从受损的涂层表面滑落，表明其有优异的机械性。
测试九：冲蚀环路实验
将所制备的实施例4涂层和纯的苯乙烯共聚物涂层（丙烯腈-异戊二烯-苯乙烯共聚物）先后放置于环路管道的弯管中，进行环路沙子冲蚀实验（实验装置图如图9所示）。结果如图10所示，(a)-(b)分别为聚苯乙烯共聚物涂层冲蚀前后的表面形貌图，(c)-(d)分别为所制备的涂层冲蚀前后的形貌图。由图可知，聚苯乙烯共聚物涂层经沙子冲蚀后涂层，涂层完全被重碎裂，而所制备的涂层仅有轻微的划痕，表明经过物理和化学交联形成的共聚物互穿网络大大提高了涂层的耐磨耐冲击性能，赋予了涂层优异的机械性能。
测试十：不同涂层防油黏附性能对比
将10μL油红染色的环己烷分别滴在纯苯乙烯共聚物涂层（丙烯腈-异戊二烯-苯乙烯共聚物），对比例1涂层，对比例2涂层以及实施例4涂层表面，观察环己烷液滴滑动行为。由图可得，环己烷会完全润湿苯乙烯共聚物涂层，对比例1涂层和对比例2涂层，但是却可以从实施例4制备的涂层表面快速滑落，且没有任何残留，进一步表明充分交联结构赋予了涂层优异的防油黏附性能。
测试十一：不同涂层硬度测试
将对比例1，对比例2以及实施例4涂层进行铅笔硬度测试，由图12可得对比例1和对比例2表面硬度均为6B，而实施例4涂层表面的硬度为2H，硬度等级提高了9个等级，表明充分的物理和化学交联结构提高了涂层的硬度，赋予了较好的机械强度。
测试十二：不同涂层的表面形貌
分别测试纯苯乙烯共聚物涂层（丙烯腈-异戊二烯-苯乙烯共聚物），对比例1涂层，对比例2和实施例4涂层的表面形貌，如图13所示，（a）表明苯乙烯共聚物涂层的表面有细小的纹理，验证其表面是多相分离的结构，相比苯乙烯共聚物涂层，对比例1涂层表面形貌（b）变得更为光滑，而当苯乙烯共聚物涂层参与了化学交联反应后，对比例2涂层表面(c)出现了均匀的小孔结构，进一步测试实施例4涂层的表面形貌(d)，发现同时发生物理和化学交联反应，使涂层的形貌变为褶皱形，表明不同交联结构存在不同的表面形貌。
测试十三：不同涂层砂冲测试
将对比例1涂层，对比例2涂层以及实施例4涂层分别进行砂冲测试，测试装置如图14所示，将样品以45°倾斜角放置，40g 沙子从距离样品上方40 cm高度冲下，循环冲击60次后，观察不同样品表面形貌。由图15可得，对比例1和对比例2涂层表面均受到不同严重程度的损伤，与之相比，实施例4涂层表面形貌只受到轻微的磨损，表明实施例4涂层具有优异的机械性能。
测试十四：不同涂层的化学稳定性测试
采用铝片作为基底，得到不同的涂层。在对比例1涂层，对比例2涂层，实施例4涂层表面滴10μL的浓盐酸溶液，如图16中 a所示，盐酸液滴立马腐蚀对比例1和对比例2涂层，而会从实施例4表面滑落。进一步地，将50μL的盐酸液滴滴在上述涂层表面，28 h后观察不同涂层表面。由图16中 b可得，对比例1和对比例2涂层表面完全被破坏，而实施例4涂层依旧保持完好，表明实施例4涂层具有优异的化学耐腐蚀性。
因此，本发明所制备的超润滑防油涂层通过采用苯乙烯共聚物赋予涂层较好的韧性，便于应用于卷曲的基底，进一步通过结合化学交联和物理交联共同构建互穿聚合物网络结构，在没有微纳米颗粒作为无机填料的情况下，使涂层在保持良好韧性的同时能够获得优异的机械强度。这种新型互穿聚合物网络结构中具有柔性的大分子，拥有优异的流动性，能够充当类液体状的润滑层，从而防止高表面张力和低表面张力液体的黏附。更重要的是还能实现对高粘度液体的防黏附性能。此外，较高的物理和化学交联程度赋予了涂层优异的化学稳定性和机械耐久性，大大延长涂层的使用寿命。
应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，在不脱离本发明所述原理的前提下，还可以作出若干改进和润饰，其均应涵盖在本发明的权利要求范围当中。
Claims (4)
1.一种透明无氟的超润滑防油涂层的制备方法，其特征在于，所述方法包括如下步骤：
（1）将巯基化合物，苯乙烯共聚物，低表面能组分以及光引发剂溶解在有机溶剂中，搅拌均匀后，得到混合溶液；
（2）将步骤（1）的混合溶液涂于清洗好的干净基底上；
（3）将步骤（2）中涂覆的基底放于紫外灯下光照固化，取出即得到透明无氟的超润滑防油涂层；
步骤（1）所述混合溶液中巯基化合物、苯乙烯共聚物、低表面能组分三者的浓度分别1-10wt%，1-30wt%，1-15wt%；
所述苯乙烯共聚物含有丙烯腈、异戊二烯、丁二烯、丙烯酸丁酯、甲基丙烯酸甲酯中的多种物质且同时含有苯乙烯；
所述巯基化合物为季戊四醇四-3-巯基丙酸酯；
所述的低表面能组分为无氟的含硅具有低表面能的化合物，所述的含硅具有低表面能的化合物为羟基硅油；
所述的光引发剂为自由基引发剂安息香二甲醚。
2.根据权利要求1所述的方法，其特征在于，所述的有机溶剂为脂肪烃、芳香烃、饱和醇、饱和酮。
3.根据权利要求2所述的方法，其特征在于，所述的有机溶剂包括甲苯。
4.根据权利要求1所述的方法，其特征在于，步骤（2）中采用滴涂、旋涂、喷涂或提拉浸涂的方法将混合溶液涂于基底上。
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