CN105925113B - 防水透气苯乙烯嵌段共聚物复合涂层材料及其制备和用途 - Google Patents
防水透气苯乙烯嵌段共聚物复合涂层材料及其制备和用途 Download PDFInfo
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Abstract
防水透气苯乙烯嵌段共聚物复合涂层材料及其制备和用途,涉及超疏水材料。所述防水透气苯乙烯嵌段共聚物复合涂层材料的嵌段共聚物选自苯乙烯‐丁二烯‐苯乙烯四臂星型三嵌段共聚物,纳米粒子选自气相二氧化硅。制备方法:在苯乙烯四臂星型三嵌段共聚物的良溶剂中加入气相二氧化硅并超声,得纳米粒子溶液,再加入苯乙烯四臂星型三嵌段共聚物,搅拌后即得防水透气苯乙烯嵌段共聚物复合涂层材料。所述防水透气苯乙烯嵌段共聚物复合涂层材料可作为织物的防水透气涂层材料。由于本发明的防水透气苯乙烯嵌段共聚物复合涂层材料具有微米‑纳米多级结构,并具有贯通孔道结构,同时具有优异的超疏水性,可用作为微滤膜应用。
Description
技术领域
本发明涉及超疏水材料,尤其是涉及一种防水透气苯乙烯嵌段共聚物复合涂层材料及其制备方法和用途。
背景技术
超疏水材料通常指的是其固体表面与水的接触角大于150°的材料。在自然界中,普遍存在着具有超疏水性能的生物材料,例如荷叶表面、昆虫角质层等。受到荷叶效应的启发,具有超疏水性能的材料引起了人们的广泛兴趣,超疏水性通常由材料表面的化学组成和表面粗糙度决定。由于超疏水材料独特的表面性能,使其可以广泛应用于防水、抗污、自清洁等领域,因此超疏水材料的发展得到了人们的广泛的关注并在现实生产生活中具有广阔的应用前景。
通过人们对自然界中超疏水现场的不断研究和探索,提高材料疏水性能主要通过两种方法:一种方案是利用疏水材料来构建表面粗糙结构;另一种方法是在粗糙表面上修饰低表面能的物质。X.Wang等(Adv.mater.2012,24,2409-2412)通过将二甲基硅氧烷和氟烷硅的纳米复合材料涂覆到纺织物上,得到具有优异耐久性的超疏水涂层材料。KripaK.Varanasi课题组(Nat.Mater.2013,12(4)315–320)发现镧系稀土元素氧化物具有疏水性,通过表面粗糙处理后,制备了不需要表面修饰的超疏水材料。除此之外,还有电纺丝法、溶胶-凝胶法、模板法、激光刻蚀法等。然而,现存制备超疏水材料的方法存在成本昂贵、反应条件苛刻等问题,难以进行大规模的工业化生产。因此,设计发明一种低成本、高效率制备具有优异性能的超疏水涂层材料是非常有必要的。
发明内容
本发明的目的在于针对现有超疏水涂层材料制备方法存在的问题,提供一种具有优异性能、低成本、易于生产的防水透气苯乙烯嵌段共聚物复合涂层材料及其制备方法和用途。
所述防水透气苯乙烯嵌段共聚物复合涂层材料的嵌段共聚物选自苯乙烯-丁二烯-苯乙烯四臂星型三嵌段共聚物,纳米粒子选自气相二氧化硅。
所述防水透气苯乙烯嵌段共聚物复合涂层具有微米-纳米结合的多级微观结构,涂层与水滴接触角大于150°,所述防水透气苯乙烯嵌段共聚物复合涂层具有优异的耐酸碱性和超疏水性能,经过酸碱处理后,其表面接触角仍能保持大于150°。
所述防水透气苯乙烯嵌段共聚物复合涂层材料的制备方法如下:
在苯乙烯四臂星型三嵌段共聚物的良溶剂中加入气相二氧化硅并超声,得纳米粒子溶液,再加入苯乙烯四臂星型三嵌段共聚物,搅拌后即得防水透气苯乙烯嵌段共聚物复合涂层材料。
所述苯乙烯嵌段共聚物可选自苯乙烯-丁二烯-苯乙烯四臂星型三嵌段共聚物。
所述苯乙烯四臂星型三嵌段共聚物的良溶剂可采用四氢呋喃。
所述苯乙烯四臂星型三嵌段共聚物的质量浓度为30mg/ml。
所述超声的时间可为1h。
所述纳米粒子溶液浓度为2~8mg/ml。
用制得的防水透气苯乙烯嵌段共聚物复合涂层材料在嵌段共聚物的非溶剂气氛中对不同基体表面进行喷涂,由蒸汽诱导相分离过程在基体上形成防水透气苯乙烯嵌段共聚物复合涂层。
苯乙烯四臂星型三嵌段共聚物与纳米粒子的混合溶液的挥发,在苯乙烯四臂星型三嵌段共聚物的非溶剂(乙醇)气氛中进行。
所述防水透气苯乙烯嵌段共聚物复合涂层材料可作为织物的防水透气涂层材料。
由于本发明的防水透气苯乙烯嵌段共聚物复合涂层材料具有微米-纳米多级结构,并具有贯通孔道结构,同时具有优异的超疏水性,可用作为微滤膜应用。
所述防水透气苯乙烯嵌段共聚物复合涂层材料具有优异的透气性能,经喷涂在织物表面后,在赋予织物表面超疏水性能的同时保证织物的透气性能基本不受影响。
所述防水透气苯乙烯嵌段共聚物复合涂层材料经加热处理后表现出优异的耐磨性能。
与现有的制备超疏水材料的方法相比,本发明采用一步法制备防水透气苯乙烯嵌段共聚物复合涂层材料,操作工艺简单,原材料成本低,产品性能优异,重现性好,无需昂贵的实验设备,也无需复杂的化学处理过程,具有非常好的大规模工业生产前景。所制得的防水透气苯乙烯嵌段共聚物复合涂层材料具有微米-纳米结合的多级微观结构,与水滴接触角大于150°,具有超疏水性能。同时具有优异的耐酸碱性、透气性和耐磨性,在防水透气涂层和微滤膜方面有着广阔的前景。
附图说明
图1为本发明实施例1制备的防水透气苯乙烯嵌段共聚物复合涂层材料的表面形貌扫描电镜图。在图1中,a是在自然环境下进行喷涂的苯乙烯四臂星型三嵌段共聚物的表面形貌,b是通过蒸汽诱导相分离法进行喷涂的苯乙烯四臂星型三嵌段共聚物的表面形貌,c-f为溶液中纳米粒子含量分别为2mg/ml、4mg/ml、6mg/ml、8mg/ml的苯乙烯四臂星型三嵌段共聚物和纳米粒子的混合溶液通过蒸汽诱导相分离法喷涂得到的薄膜的表面形貌电镜图,标尺为50μm。
图2为对应图1表面形貌的扫描电镜放大图,标尺为1μm。
图3为本发明实施例1制备的不同纳米粒子含量的防水透气苯乙烯嵌段共聚物复合涂层材料的接触角,横坐标为不同纳米粒子含量(mg/ml),纵坐标为平均接触角大小(°)。
图4为本发明实施例2防水透气苯乙烯嵌段共聚物复合涂层材料分别经过酸碱处理后的接触角大小。横坐标为不同纳米粒子含量(mg/ml),纵坐标为平均接触角大小(°)。
图5为本发明实施例3所制备的基底为PET纤维织物的防水透气苯乙烯嵌段共聚物复合涂层材料透气性大小比较。编号1为涂覆上密封胶的PET纤维织物,编号2为未做处理的PET纤维织物,编号3~7分别为利用蒸汽诱导相分离法喷涂在PET基底上的不同纳米粒子含量的防水透气苯乙烯嵌段共聚物复合涂层材料(纳米粒子含量依次为0mg/ml、2mg/ml、4mg/ml、6mg/ml、8mg/ml)。横坐标为编号,纵坐标为单位面积的水蒸气透过量(L/m2)。
图6为本发明实施例4经过热处理的防水透气苯乙烯嵌段共聚物复合涂层材料的耐磨性能比较,其中横坐标为摩擦循环次数,纵坐标为平均接触角大小(°)。
具体实施方式
以下结合实施例和附图对本发明进一步的说明。
实施例1
向15ml四氢呋喃溶剂中加入不同含量的气相二氧化硅,剧烈超声1h后形成均匀溶液,再向其中加入450mg苯乙烯四臂星型三嵌段共聚物,剧烈搅拌24h后形成均匀溶液备用。将玻璃托盘盛满乙醇溶液后并放入手套箱中,后将手套箱密封24h,待乙醇挥发使得乙醇蒸汽充满整个手套箱。将备用溶液加入到气动喷枪中去,在密闭的手套箱中对玻璃基板表面进行喷涂,控制喷涂高度为10cm,控制喷涂面积为7.5cm×7.5cm,在喷涂过程中随着四氢呋喃挥发造成溶液表面温度降低,对嵌段共聚物是非溶剂的乙醇蒸汽在溶液表面冷凝,发生蒸汽诱导相分离过程,待溶剂完全挥发后既可制得表面白色超疏水苯乙烯嵌段共聚物纳米复合涂层材料。同时将30mg/ml的苯乙烯四臂星型三嵌段共聚物溶液在室外自然环境下进行喷涂作为对照试验。将薄膜喷铂后在电镜下观察。
实施例1制备的防水透气苯乙烯嵌段共聚物复合涂层材料表面形貌的扫描电镜图参见图1,防水透气苯乙烯嵌段共聚物复合涂层材料表面形貌结构放大扫描电镜图见图2,实施例1制备的防水透气苯乙烯嵌段共聚物复合涂层材料表面与5μl水滴的平均接触角大小见图3,可见防水透气苯乙烯嵌段共聚物复合涂层材料与水滴的接触角大于150°,具有超疏水性能,同时随着纳米粒子浓度的增大,制得的涂层的表面粗糙度进一步增大,超疏水性能得到提升。
实施例2
将实施例1中所制备的防水透气苯乙烯嵌段共聚物复合涂层材料分别在pH=1的H2SO4和pH=14的NaOH溶液中浸泡12h,取出后在去离子水中反复洗涤,除去表面残留的酸碱。在自然环境下干燥24h后测试其表面与5μl水滴的平均接触角大小,见图4。发现经过酸碱处理后,防水透气苯乙烯嵌段共聚物复合涂层材料仍能保持表面接触角大于150°,仍具有超疏水性能,说明本发明制备的防水透气苯乙烯嵌段共聚物复合涂层材料具有优异的耐酸碱性能。
实施例3
向15ml四氢呋喃溶剂中加入不同含量的气相二氧化硅,剧烈超声1h后形成均匀溶液,再向其中加入450mg苯乙烯四臂星型三嵌段共聚物,剧烈搅拌24h后形成均匀溶液备用。将玻璃托盘盛满乙醇溶液后并放入手套箱中,后将手套箱密封24h,待乙醇挥发使得乙醇蒸汽充满整个手套箱。将备用溶液加入到气动喷枪中去,在密闭的手套箱中对PET纤维织物基体表面进行喷涂,控制喷涂高度为10cm,控制喷涂面积为7.5cm×7.5cm,在喷涂过程中随着四氢呋喃挥发造成溶液表面温度降低,对嵌段共聚物是非溶剂的乙醇蒸汽在溶液表面冷凝,发生蒸汽诱导相分离过程,待四氢呋喃完全挥发后既可制得表面白色的防水透气苯乙烯嵌段共聚物复合涂层材料。由于制备的复合涂层具有相互贯通的多孔结构,因此可以利用其多孔结构测试其透气性。将制备的防水透气苯乙烯嵌段共聚物复合涂层材料用于密封装有10ml去离子水的瓶子,并分别用涂覆有气密性涂料的PET纤维织物和未处理的PET纤维织物作为对照组。在45℃下的烘箱中恒温干燥48h后取出,通过称体积法测试比较其单位面积的水蒸发量,见图5。结果表明水蒸气透过防水透气苯乙烯嵌段共聚物复合涂层材料的量与纯PET纤维基本相同,呈现出优异的透气性。而使用涂覆有气密性涂料的PET纤维织物,烘箱干燥后水基本没有损失。
实施例4
将实施例1中所制备的防水透气苯乙烯嵌段共聚物复合涂层材料放置于真空烘箱中,在110℃下加热1h后取出冷却到室温。将涂层一侧朝下,玻璃基板面一侧朝上放置在1500cc砂纸上,在玻璃基板上放置一个100g的砝码,在水平推动力作用下使得薄膜在砂纸上匀速移动10cm,再将涂层材料放置回起始位置,旋转90°后再在砂纸上重复移动10cm,此记为一个循环,每隔5个循环后测试涂层表面疏水角大小,见图6。结果表明,经过热处理后,防水透气苯乙烯嵌段共聚物复合涂层材料表现出优异的耐磨性能,在经过30次循环后仍能保持优秀的疏水性能。
防水透气苯乙烯嵌段共聚物纳米复合涂层材料及其制备方法和用途,涉及一种有机高分子材料和无机纳米粒子,通过将喷涂法和蒸汽诱导相分离法相结合的这种新型方式制备出具有高超疏水性的聚合物涂层材料。防水透气苯乙烯嵌段共聚物复合涂层材料的嵌段共聚物选自苯乙烯-丁二烯-苯乙烯四臂星型三嵌段共聚物,无机纳米粒子为气相二氧化硅(HMFS)。以苯乙烯嵌段共聚物的良溶剂溶解嵌段共聚物和纳米粒子,通过喷涂法在有机蒸汽中进行喷涂,由蒸汽诱导相分离过程形成最终涂层,得到具有微米-纳米结合的多级微观结构:涂层与水滴接触角大于150°,具有高超疏水性能。同时具有优异的耐酸碱性和透气性。通过进一步加热处理,防水透气苯乙烯嵌段共聚物复合涂层材料表现出优秀的耐磨性能。同时成本低廉,易于生产。
Claims (5)
1.防水透气苯乙烯嵌段共聚物复合涂层材料,其特征在于其嵌段共聚物选自苯乙烯-丁二烯-苯乙烯四臂星型三嵌段共聚物,纳米粒子选自气相二氧化硅;所述防水透气苯乙烯嵌段共聚物复合涂层材料由以下方法制备:
在苯乙烯四臂星型三嵌段共聚物的良溶剂中加入气相二氧化硅并超声,得纳米粒子溶液,再加入苯乙烯四臂星型三嵌段共聚物,搅拌后即得防水透气苯乙烯嵌段共聚物复合涂层材料;
所述苯乙烯四臂星型三嵌段共聚物的质量浓度为30mg/ml;
所述纳米粒子溶液浓度为2~8mg/ml。
2.如权利要求1所述防水透气苯乙烯嵌段共聚物复合涂层材料,其特征在于所述苯乙烯四臂星型三嵌段共聚物的良溶剂采用四氢呋喃。
3.如权利要求1所述防水透气苯乙烯嵌段共聚物复合涂层材料,其特征在于所述超声的时间为1h。
4.如权利要求1所述防水透气苯乙烯嵌段共聚物复合涂层材料作为织物的防水透气涂层材料。
5.如权利要求1所述防水透气苯乙烯嵌段共聚物复合涂层材料作为微滤膜。
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