CN105418837B - 一种相分离致多孔超疏水涂层材料的制备方法 - Google Patents
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Abstract
本发明公开了一种相分离致多孔超疏水涂层材料的制备方法。该方法采用甲基丙烯酸六氟丁酯(G02)和乙二醇二甲基丙烯酸酯(EDMA)为聚合单体,1,4‑丁二醇(BDO)和N‑甲基‑2‑吡咯烷酮(NMP)为共致孔剂,偶氮二异丁腈(AIBN)为引发剂,在玻璃基片上进行原位热引发自由基聚合,利用聚合过程中致孔剂导致的相分离在涂层表面及体相构建微/纳米二元粗糙结构,通过改变反应混合物组成来调节涂层的微观结构,从而制备出具有超疏水特性的多孔聚合物涂层。本方法不需要进行任何的涂饰等工艺操作,制备过程简单,成本低廉,所制备的超疏水涂层可望在自清洁、油水分离、流体减阻和金属防腐等领域获得广泛应用。
Description
技术领域
本发明涉及超疏水材料的制备领域,具体涉及了一种相分离致多孔超疏水涂层材料的制备方法。
背景技术
超疏水表面是指与水的静态接触角大于150°,滚动角小于10°的表面。当水滴与超疏水表面接触时,能很容易地滚落下来,同时,能将表面的灰尘污物带走。具有超疏水特性的表面在实际生活与生产中有广泛的应用前景,比如自清洁、油水分离、流体减阻和金属防腐等。超疏水是固体表面浸润性的一种表现,是由表面的化学组成和微观几何结构共同决定的,超疏水表面可以通过两种方法来制备:一种是在低表面能物质上构建精细的结构,另一种是在粗糙的表面上修饰低表面能的物质。目前,制备超疏水涂层的方法主要有相分离法、溶胶凝胶法、模板法、电化学沉积法、自组装法和气相沉积法等,尽管许多超疏水涂层的制备方法已趋于成熟,但大部分超疏水特性的产品制备过程较为繁琐、工艺条件苛刻、有些需要昂贵的低表面能物质或是所制备的超疏水表面耐久性、耐化学稳定性、耐磨性、耐高温性不足,限制了其在实际生活生产中的广泛应用。
Liang等(Junsheng Liang,Kuanyao Liu,Dazhi Wang,Applied SurfaceScience,2015,338,126)采用阳极氧化法,在Ti基片上构造出一定的粗糙度,此时Ti基片具有超亲水特性,接触角接近0°,之后用氟硅烷FAS修饰,接触角达160°。制备的超亲水/超疏水Ti基片具有良好的耐酸碱性以及稳定性。Liu等(Jianfeng Liu,Xinyan Xiao,YinlongShi,Applied Surface Science,2014,297,33)利用致孔剂导致的相分离作用,在玻璃基片上直接采用热引发自由基聚合形成具有一定厚度的涂层,然后将致孔剂移除,在聚合物内部构造出了微纳米粗糙结构。他们通过研究交联单体和致孔剂组分比例对涂层微观结构的影响,制备出接触角达159.5°超疏水涂层,所制备的聚合物超疏水涂层具有良好的耐酸碱性以及耐高温性。Hayase等(Gen Hayase,Kazuyoshi Kanamori,George Hasegawa,Angew.Chem.Int.Ed.2013,52,10788)采用溶胶凝胶法,以乙烯基三甲氧基硅烷(VTMS)和甲基乙烯基二甲氧基硅烷(VMDMS)为前驱体,采用酸碱两步水解缩合反应,制备出接触角达153°的超疏水气凝胶材料,具有海绵一样的柔韧性,在油水分离方面具有较大的应用前景。同时,他们利用硫醇烯链接反应,在富含乙烯基基团的凝胶表面接枝全氟烃基基团,制备出具有超双疏的特性的气凝胶。
发明内容
本发明提供了一种相分离致多孔超疏水涂层材料的制备方法。该法采用甲基丙烯酸六氟丁酯(G02)和乙二醇二甲基丙烯酸酯(EDMA)为聚合单体,1,4-丁二醇(BDO)和N-甲基-2-吡咯烷酮(NMP)为共致孔剂,偶氮二异丁腈(AIBN)为引发剂,在玻璃基片上进行原位热引发自由基聚合,利用在聚合过程致孔剂导致的相分离在涂层表面构筑微/纳米二元粗糙结构,通过改变反应混合物组成来调节涂层的微观结构,从而制备出一种具有超疏水特性的相分离致多孔超疏水涂层材料。本方法不需要进行任何的涂饰等工艺操作,制备过程简单,成本低廉,所制备的超疏水涂层可望在自清洁、油水分离、流体减阻和金属防腐等领域获得广泛应用。
本发明的目的可以通过以下方案来实现:
一种相分离致多孔超疏水涂层材料的制备方法,该制备方法选用甲基丙烯酸六氟丁酯(G02)和乙二醇二甲基丙烯酸酯(EDMA)为聚合单体,1,4-丁二醇(BDO)和N-甲基-2-吡咯烷酮(NMP)为共致孔剂,偶氮二异丁腈(AIBN)为引发剂,在玻璃基片上进行原位热引发自由基聚合反应,通过改变反应混合物组成,直接在玻璃基片上制备出相分离致多孔超疏水涂层材料,具体步骤如下:
1)依次称取甲基丙烯酸六氟丁酯、乙二醇二甲基丙烯酸酯、1,4-丁二醇和N-甲基-2-吡咯烷酮以及偶氮二异丁腈于25mL烧杯中;
2)将步骤1)的烧杯置于超声波清洗仪中超声处理10~40min,形成均匀透明的溶液;
3)取0.2~1.0mL步骤2)中的溶液注入预处理好的玻璃基片以及聚四氟乙烯板之间,得样品;
4)将步骤3)准备好的样品置于鼓风干燥箱中,设置温度为60~90℃,原位热引发自由基聚合反应15~30h,结束反应,并冷却至室温;
5)取步骤4)中反应结束后的玻璃基片和聚四氟乙烯板分开,将附有聚合物涂层的玻璃片浸没在甲醇中,自然晾干后,可获得相分离致多孔超疏水涂层材料。
进一步地,所述甲基丙烯酸六氟丁酯与乙二醇二甲基丙烯酸酯的质量比为40:60~65:35;所述1,4-丁二醇与N-甲基-2-吡咯烷酮的质量比为35:65~60:40;所述聚合单体总质量与共致孔剂总质量的比例为35:65~55:45;偶氮二异丁腈的用量为聚合单体总质量的1~4%。
进一步地,步骤2)所述超声处理过程是在室温25~30℃条件下进行。
进一步地,步骤3)中玻璃基片的预处理具体步骤为:将玻璃基片依次用蒸馏水、NaOH溶液、HCl溶液冲洗,干燥,然后采用γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷的乙醇溶液对玻璃基片接枝活性基团进行修饰,并采用丙酮冲洗,干燥备用。
进一步地,步骤4)所述的温度为60~80℃。
进一步地,步骤5)在甲醇中浸泡时间为10~30min。
本发明相对于现有技术具有如下优势:
(1)本发明采用原位热引发自由基聚合反应法,利用致孔剂在聚合过程中导致的相分离使涂层表面和体相均具有微/纳米二元粗糙度结构,即使表层被破坏,仍具有超疏水特性。本方法选择了含氟试剂,增强了聚合物的耐候性,抗氧化性等性能,并且操作可控,稳定性好。
(2)本方法直接在玻璃基片上制备出多孔聚合物超疏水涂层材料,不需要进行任何涂饰等工艺操作,制备过程简单,成本低廉,对基底材料没有限制,可广泛应用于各种基材,有利于超疏水涂层的工业化生产。
附图说明
图1为本发明实施例1中相分离致多孔超疏水涂层材料的SEM图;
图2为本发明实施例2中相分离致多孔超疏水涂层材料的接触角变化趋势图;
图3为本发明实施例3中相分离致多孔超疏水涂层材料表面的粘附性测试图。
具体实施方式
下面结合实例对本发明做进一步的描述,需要说明的是,实施例并不构成对本发明要求保护范围的限制。
实施例1
1)按照一定的质量比依次称取甲基丙烯酸六氟丁酯(G02),乙二醇二甲基丙烯酸酯(EDMA),1,4-丁二醇(BDO)和N-甲基-2-吡咯烷酮(NMP)(其中m(G02):m(EDMA)=50:50,m(G02+EDMA):m(BDO+NMP)=50:50,m(BDO):m(NMP)分别取35:65、40:60、45:55、50:50、60:40系列比例,m(G02+EDMA)+m(BDO+NMP)为6g),偶氮二异丁腈(AIBN)取2%(相对于聚合单体的总质量)于25mL烧杯中;
2)将步骤1)中的烧杯置于超声波清洗仪中超声处理30min,至形成均匀透明的溶液;
3)取0.2mL步骤2)中的溶液注入预处理好的玻璃基片以及聚四氟乙烯板之间,得样品;
4)将步骤3)准备好的样品置于鼓风干燥箱中,设置温度为80℃,热引发聚合反应20h,结束反应,并冷却至室温;
5)取步骤4)中反应结束后的玻璃基片和聚四氟乙烯板分开,将附有聚合物涂层的玻璃片浸没在甲醇中20min,自然晾干后,可获得相分离致多孔超疏水涂层材料。由图1中SEM图(图1中的a,图1中的b中m(BDO):m(NMP)分别为40:60,60:40)可以看出,所制得涂层表面的孔径大小及生成物的聚合体大小随m(BDO):m(NMP)比值增加而增大。BDO含量较少时,共致孔剂极性较低,共致孔剂的溶剂化能力较强,反应物在溶剂中易溶解,相分离会出现的晚些,形成的微观结构比较精细,随BDO含量增高,共致孔剂极性增强,反应初期即发生相分离,形成的共聚物沉淀容易聚集在一起,形成较大平均孔径。
实施例2
1)按照一定的质量比依次称取一定量的甲基丙烯酸六氟丁酯(G02),乙二醇二甲基丙烯酸酯(EDMA),1,4-丁二醇(BDO)和N-甲基-2-吡咯烷酮(NMP)(其中m(BDO):(NMP)=40:60,m(G02+EDMA):m(BDO+NMP)=50:50,m(G02):m(EDMA)取40:60、45:55、55:45、60:40、65:35系列比例,m(G02+EDMA)+m(BDO+NMP)为6g),偶氮二异丁腈(AIBN)取2%(相对于聚合单体的总质量)于25mL烧杯中;
2)将步骤1)中的烧杯置于超声波清洗仪中超声处理30min,至形成均匀透明的溶液;
3)取0.2mL步骤2)中的溶液注入预处理好的玻璃基片以及聚四氟乙烯板之间,得样品;
4)将步骤3)准备好的样品置于鼓风干燥箱中,设置温度为80℃,热引发聚合反应20h,结束反应,并冷却至室温;
5)取步骤4)中反应结束后的玻璃基片和聚四氟乙烯板分开,将附有聚合物涂层的玻璃片浸没在甲醇中20min,自然晾干后,可获得多孔聚合物超疏水涂层材料。不同m(G02):m(EDMA)比对涂层接触角的影响结果如图2所示,随着m(G02):m(EDMA)比值的增加,涂层的静态水接触角先增大后又降低;当m(G02):m(EDMA)=60:40时,静态接触角达最大值157°。这是因为当m(G02):m(EDMA)比值较小时,相分离较晚出现,所形成的微观结构比较精细,涂层的粗糙度降低,疏水性能也随之降低;当m(G02):m(EDMA)比值较大时,相分离较早出现,形成的共聚物沉淀聚集较严重,也无法为涂层提供有利的粗糙结构。
实施例3
1)按照一定的质量比依次称取一定量的甲基丙烯酸六氟丁酯(G02)、乙二醇二甲基丙烯酸酯(EDMA)、1,4-丁二醇(BDO)和N-甲基-2-吡咯烷酮(NMP)(其中m(G02):m(EDMA)=60:40,m(BDO):m(NMP)=40:60,m(G02+EDMA):m(BDO+NMP)=45:55,m(G02+EDMA)+m(BDO+NMP)为6g),偶氮二异丁腈(AIBN)取2%(相对于聚合单体的总质量)于25mL烧杯中;
2)将步骤1)中的烧杯置于超声波清洗仪中超声处理30min,至形成均匀透明的溶液;
3)取0.2mL步骤2)中的溶液注入预处理好的玻璃基片以及聚四氟乙烯板之间,得样品;
4)将步骤3)准备好的样品置于鼓风干燥箱中,设置温度为80℃,热引发聚合反应20h,结束反应,并冷却至室温;
5)取步骤4)中反应结束后的玻璃基片和聚四氟乙烯板分开,将附有聚合物涂层的玻璃片浸没在甲醇中20min,自然晾干后,可获得多孔聚合物超疏水涂层材料。对超疏水涂层进行水滴的粘附性能测试,以说明涂层表面的非润湿性及超疏水性。将所制备的涂层放在接触角测定仪(JC2000C1,上海中晨数字技术设备有限公司)的样品台上,将样品台缓慢升高,使针尖上的水滴(6μL)完全接触涂层。将水滴接触、充分接触、即将离开和离开样品台的过程拍摄记录下来。多孔聚合物超疏水涂层材料表面的粘附性测试结果如图3,图3表明,水滴很难从针孔上掉落下来,说明水滴与超疏水涂层间的粘附力远低于针孔对水滴的吸附力,并且液滴在与涂层接触及充分接触的过程中,都保持圆球状,整个测试过程结束后,涂层表面没有水滴残留,说明所制涂层表面具有较好的疏水性。
实施例4
1)按照一定的质量比依次称取一定量的甲基丙烯酸六氟丁酯(G02)、乙二醇二甲基丙烯酸酯(EDMA)、1,4-丁二醇(BDO)和N-甲基-2-吡咯烷酮(NMP)(其中m(G02):m(EDMA)=60:40,m(BDO):m(NMP)=40:60,m(G02+EDMA):m(BDO+NMP)=45:55,m(G02+EDMA)+m(BDO+NMP)为6g),偶氮二异丁腈(AIBN)取2%(相对于聚合单体的总质量)于25mL烧杯中;
2)将步骤1)中的烧杯置于超声波清洗仪中超声处理30min,至形成均匀透明的溶液;
3)取0.2mL步骤2)中的溶液注入预处理好的玻璃基片以及聚四氟乙烯板之间,得样品;
4)将步骤3)准备好的样品置于鼓风干燥箱中,设置温度为90℃,热引发聚合反应20h,结束反应,并冷却至室温;
5)取步骤4)中反应结束后的玻璃基片和聚四氟乙烯板分开,将附有聚合物涂层的玻璃片浸没在甲醇中20min,自然晾干后,可获得多孔聚合物超疏水涂层材料。测得接触角为130°。
实施例5
1)按照一定的质量比依次称取一定量的甲基丙烯酸六氟丁酯(G02)、乙二醇二甲基丙烯酸酯(EDMA)、1,4-丁二醇(BDO)和N-甲基-2-吡咯烷酮(NMP)(其中m(G02):m(EDMA)=60:40,m(BDO):m(NMP)=40:60,m(G02+EDMA):m(BDO+NMP)=45:55,m(G02+EDMA)+m(BDO+NMP)为6g),偶氮二异丁腈(AIBN)取2%(相对于聚合单体的总质量)于25mL烧杯中;
2)将步骤1)中的烧杯置于超声波清洗仪中超声处理30min,至形成均匀透明的溶液;
3)取0.2mL步骤2)中的溶液注入预处理好的玻璃基片以及聚四氟乙烯板之间,得样品;
4)将步骤3)准备好的样品置于鼓风干燥箱中,设置温度为80℃,热引发聚合反应15h,结束反应,并冷却至室温;
5)取步骤4)中反应结束后的玻璃基片和聚四氟乙烯板分开,将附有聚合物涂层的玻璃片浸没在甲醇中20min,自然晾干后,可获得多孔聚合物超疏水涂层材料。测得接触角为146°。
Claims (4)
1.一种相分离致多孔超疏水涂层材料的制备方法,其特征在于,该制备方法选用甲基丙烯酸六氟丁酯和乙二醇二甲基丙烯酸酯为聚合单体,1,4-丁二醇和N-甲基-2-吡咯烷酮为共致孔剂,偶氮二异丁腈为引发剂,在玻璃基片上进行原位热引发自由基聚合反应,通过改变反应混合物组成,直接在玻璃基片上制备出相分离致多孔超疏水涂层材料,具体步骤如下:
1)依次称取甲基丙烯酸六氟丁酯、乙二醇二甲基丙烯酸酯、1,4-丁二醇和N-甲基-2-吡咯烷酮以及偶氮二异丁腈于烧杯中;
2)将步骤1)的烧杯置于超声波清洗仪中超声处理10~40min,形成均匀透明的溶液;
3)取0.2~1.0mL步骤2)中的溶液注入预处理好的玻璃基片以及聚四氟乙烯板之间,得样品;
4)将步骤3)准备好的样品置于鼓风干燥箱中,设置温度为60~90℃,原位热引发自由基聚合反应15~30h,结束反应,并冷却至室温;
5)取步骤4)中反应结束后的玻璃基片和聚四氟乙烯板分开,将附有聚合物涂层的玻璃片浸没在甲醇中,自然晾干后,可获得相分离致多孔超疏水涂层材料;
所述甲基丙烯酸六氟丁酯与乙二醇二甲基丙烯酸酯的质量比为40:60~65:35;所述1,4-丁二醇与N-甲基-2-吡咯烷酮的质量比为35:65~60:40;所述聚合单体总质量与共致孔剂总质量的比例为35:65~55:45;偶氮二异丁腈的用量为聚合单体总质量的1~4%。
2.根据权利要求1所述的一种相分离致多孔超疏水涂层材料的制备方法,其特征在于,步骤2)所述超声处理过程是在室温25~30℃条件下进行。
3.根据权利要求1所述的一种相分离致多孔超疏水涂层材料的制备方法,其特征在于,步骤3)中玻璃基片的预处理具体步骤为:将玻璃基片依次用蒸馏水、NaOH溶液、HCl溶液冲洗,干燥,然后采用γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷的乙醇溶液对玻璃基片接枝活性基团进行修饰,并采用丙酮冲洗,干燥备用。
4.根据权利要求1所述的一种相分离致多孔超疏水涂层材料的制备方法,其特征在于,步骤5)在甲醇中浸泡时间为10~30min。
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