CN107226920B - 一种光固化型超疏水复合膜的制备方法 - Google Patents
一种光固化型超疏水复合膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种光固化型超疏水弹性复合膜的制备方法,所述复合膜包括弹性基底和表面超疏水层,其制备步骤包括:(1)弹性基底的制备:将光引发剂、预聚物混合均匀,经紫外光照射,制成预固化弹性基底。(2)悬浊液的制备:将低表面能的聚合物、光引发剂、交联剂、微米和/或纳米疏水颗粒均匀分散在溶剂中,制成悬浊液。(3)超水疏复合膜的制备:将悬浊液涂覆在弹性基底上,然后经紫外光照射固化处理,获得具有超疏水特性的复合膜。依据本发明方法制得的超疏水性复合膜,弹性基底和超疏水层之间通过化学交联形成一体化,具有制备工艺简单、耐磨擦抗拉伸性好、涂层不易脱落、超疏水效果稳定等优点。
Description
技术领域
本发明涉及超疏水复合膜的制备领域,特别涉及一种光固化型超疏水弹性复合膜的制备方法。
背景技术
仿生超疏水涂层具有优异的自清洁、抗润湿、防水阻水等性能,可以用于建筑材料表面自清洁,织物和电路板表面防水,船体表面减阻等领域。超疏水涂层这些优越性能促使人们努力构建各种具有超疏水功能的涂层。
现阶段构建超疏水涂层主要方法有气相沉积法(CN102953105A)、模板法(CN103724639A)、表面刻蚀法(CN103409754A)、自组装法(CN105039953A)、浸涂法等,这些制备方法多数构建于硬质表面,少部分在弹性表面。硬质表面的超疏水涂层在外力作用(如拉伸)下很容易受到破坏,从而失去超疏水性能;而构建于弹性表面的超疏水涂层与基底间大多是物理作用,涂层和基底结合强度较小,在外力作用(如拉伸)下,特别是大形变下,涂层容易发生脱粘、粉化,最终导致超疏水涂层失效。并且这些制备方法有的需要使用贵重仪器(CN105779943A),有的需要高温加热处理(CN106318184A);这些缺点在一定程度上限制了超疏水涂层的应用。
紫外光固化技术具有常温快速固化、节约能源、绿色环保等优点,是当今材料制备技术领域的一个重要发展方向。目前,利用紫外线光固化反应制备超疏水复合膜技术还处于前沿领域,可查询的相关技术方案中(CN200610011418)主要通过反复临摹生物表面疏水结构,从而制备疏水结构模板,再经过紫外线光固化处理,将模板中的疏水结构转移到制得的聚合物中,从而制得呈单层结构的超疏水膜产物。上述制备方案不仅对现有疏水结构的生物材料具有高度依赖性,而且在模板制作中,需要对现有疏水结构进行多次临摹处理,制备工艺步骤复杂,对工艺的精确度要求高,制备工艺成本高,不利于在工业上的推广实施。
发明内容
针对上述不足,本发明目的在于利用先进的紫外光固化技术,提供了一种制备工艺简单、工艺成本低,并且涂层和基底之间通过化学键交联,从而具有良好的抗涂层脱落性以及抗拉伸性的弹性超疏水复合膜制备方法。
为了实现上述发明目的,本发明提供以下技术方案:
一种光固化型超疏水复合膜的制备方法,所述复合膜主要由弹性基底和表面超疏水涂层组成,该制备方法主要包括如下步骤:
步骤(1):预固化弹性基底的制备,将预聚物和光引发剂按一定比例均匀混合,经短时间的紫外光照射预固化处理,制成预固化的弹性基底。所述预聚物是指能够在紫外线作用下产生自由基型聚合作用的光固化材料。
步骤(2):悬浊液的制备,将聚合物、光引发剂、交联剂、疏水性颗粒均匀分散在溶剂中,制成悬浊液。所述聚合物是低表面能且含碳碳双键的聚合物。
步骤(3):复合膜的制得,将步骤(2)中制得的悬浊液均匀涂覆在预固化弹性基底上,然后经紫外光照射固化,制得具有超疏水性能的弹性复合膜。
依据上述制备方案,步骤(1)中作为预聚物,在紫外线照射预固化处理过程中,被光引发剂中自由基激发,发生自身聚合反应从而形成具有良好弹性性能的基体材料。并且由于氧阻聚的存在,使得制备的弹性基体材料表面还残留了大量未反应的活性基团(-C=C),这些残留双键可以作为化学交联点,与其他物质发生交联反应。步骤(2)中配制的悬浊液作为步骤(3)中紫外光固化反应原液,用作超疏水涂层的制备,以及弹性基体与弹性基体的化学交联反应。依据本发明方法步骤(3),将步骤(2)配制的悬浊液均匀涂覆在步骤(1)中制备的预固化弹性基体表面后,在紫外线照射和光引发剂的作用下,悬浊液中的低表面能且含碳碳双键聚合物同时发生如下两个光固化聚合反应:一是作为超疏水涂层的聚合主体,通过化学交联反应聚合形成固态的膜状结构,悬浊液中的纳米级和/或微米级疏水颗粒均匀分散在聚合物固态膜状结构中,从而形成超疏水涂层膜;二是与弹性基体表面残留的化学双键,在交联剂的作用下发生聚合反应,形成涂层膜与弹性基体材料之间的化学交联聚合,从而实现超疏水涂层和弹性基体之间在微观分子结构上的一体化,增强了超疏水涂层与弹性基体之间的结合力,使得依据本发明方法制备的超疏水复合膜具有较强的涂层抗脱落性和机械稳定性。并且,相比现有的物理性喷涂方式而言,由于本发明所述的光固型超疏水弹性复合膜的制备方法中,超疏水涂层膜的自身形成和涂层膜与弹性基体材料之间的结合,是在紫外线光固化作用下通过分子化学键之间的交联反应同步完成,使得超疏水涂层与基体材料之间的结合更加完整和均匀,其超疏水效果也更为稳定。
进一步,所述步骤(1)中制备预固化弹性基底中的预聚物,是指能够在紫外线作用下产生自由基型聚合作用的光固化材料。
所述预聚物是具有碳碳双键的低聚物。优选地,所述预聚物是至少部分结构单元中含有碳碳双键的低聚物。
进一步,所述预聚物是低聚物。所述预聚物的聚合度优选为50-5000,进一步预聚物的聚合度为50-3000,再一步将预聚物的聚合度优选为50-1000。
更优选地,所述预聚物具体是指单官能团或双官能团的丙烯酸酯类化合物,更优选如聚氨酯丙烯酸酯、环氧丙烯酸酯、聚醚丙烯酸酯、有机硅改性丙烯酸酯等中的一种或几种。丙烯酸酯类化合物具有挥发性低、污染小、粘度低、流平性好的特点,是紫外线光固化反应中最常用的自由基型光固化预先材料,也是本发明中优选的自由基型光固化预聚物材料。
所述步骤(1)中制备预固化弹性基底中的光引发剂是指2-羟基-2-甲基-1-苯基丙酮(1173)、1-羟基环己基苯基甲酮(184)、2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮(907)中的一种或几种。上述光引发剂在紫外线的照射作用下,先释放出自由基,再通过自由基激发预聚物的交联聚合反应。
进一步,所述步骤(1)中制备预固化弹性基底中光引发剂的含量为0.5-5%(Wt),预聚物的含量为95-99.5%(Wt),光引发剂和预聚物按一定配比称量后,经搅拌,超声后混合均匀。其中,光引发剂含量直接影响预聚物光固化反应的快慢,从而影响最终产物超疏水弹性复合膜的疏水稳定性和抗拉伸性。若光引发剂的含量过高,预聚物光固化反应过快,则反应过程中产生的氧阻聚作用小,使得步骤(1)中制备的弹性基体表面残留的化学活性双键少,进而减少步骤(3)中弹性基体与超疏水涂层之间的化学交联结合,从而降低超疏水涂层的抗脱落性能,影响其疏水性能的稳定性。但若光引发剂的含量过低,则会降低步骤(1)的反应速度并使氧阻聚作用过大,降低预聚物之间的聚合度,从而影响复合膜基体的弹性和抗拉伸性能。所以将光引发剂和预聚物含量控制在上述范围时,最终制得的超疏水弹性复合膜的抗拉伸性以及疏水稳定性能效果最佳。
进一步,所述步骤(1)中对预聚物进行预固化的紫外曝光量为50<Hv<1000mJ/cm2。控制紫外线的曝光量主要在于合理控制预聚物的光固化反应速度,从而实现对制备产物超疏水弹性复合膜的疏水涂层抗脱落性和抗拉性能的控制。原理同上述光引发剂含量对复合膜性能影响分析相同。
进一步,所述步骤(2)中所述聚合物具有低表面能特性,含有大量碳碳双键,且具有良好的弹性。优选采用聚丁二烯、聚异丁烯、硅橡胶、有机硅改性丙烯酸酯或氟化聚氨酯丙烯酸酯。
进一步,所述步骤(2)中光引发剂是指2-羟基-2-甲基-1-苯基丙酮(1173)、1-羟基环己基苯基甲酮(184)、2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮(907)中的一种或几种。
进一步,步骤(2)中所述交联剂是巯基交联剂,具体是指含有巯基的聚合物。优选采用巯基有机硅聚合物作为交联剂。将含有巯基的聚合物作为交联剂使用,一方面巯基作为交联基团,可以实现用于制备超疏水涂层的含碳碳双键的低表面能聚合物之间的网状式交联聚合,以及弹性基体表面残留的活性基团与超疏水涂层中的碳碳双键之间的化学交联聚合;另一方面,巯基具有抑制氧阻聚的效果,加入巯基可以抑制步骤(3)中发生的紫外光固化反应中的氧阻聚作用,从而提高碳碳双键之间的聚合度,减少残留活性双键的存在,使得最终固化制得的超疏水复合膜具有良好的稳定性。
进一步,所述步骤(2)中疏水微米和/或纳米颗粒是指经过疏水改性处理的二氧化硅、二氧化钛、碳酸钙颗粒中的一种或者几种。一般市售的疏水性微米或/和纳米颗粒就可以满足本发明制备方法要求。
进一步,所述步骤(2)中溶剂是乙醇、丙酮、石油醚、环己烷、正己烷中的一种或几种。上述优选的有机溶剂能够对步骤(2)中用于制备的超疏水涂层的含碳碳双键的聚合物、交联剂、光引发剂这些有机化学物质起到较好的溶解作用,使得上述反应物能够从粘稠状变成稀溶液,增大物质之间的接触面积,提高反应速率和原料利用率。并且上述有机溶剂不会对疏水颗粒产出溶解作用,保证疏水颗粒的疏水性不受影响,但溶剂可以起到帮助疏水颗粒均匀分散在反应液中,使最终制得的涂层表面均匀分布疏水颗粒,从而获得具有稳定疏水性能的疏水涂层。
进一步,所述步骤(2)配制的悬浊液中聚合物含量为2-10wt%,微米和/或纳米颗含量为1-8wt%,光引发剂的含量为0.01-0.5wt%,交联剂的含量为0.04-1.5wt%,溶剂量为80-96.95wt%。悬浊液的总量是100wt%。
进一步,依据上述比例将一定配比的聚合物、微米和/或纳米颗粒、光引发剂、交联剂搅拌均匀,制成均匀悬浊液。优选采用超声分散,效果好,分散均匀。
进一步,所述步骤(3)中涂覆方式包括旋涂、浸涂、喷涂、淋涂、滚涂或刷涂;可以其中一种,可以是多种方式并用。将悬浊液均匀涂覆在经预固化处理的弹性基体表面,然后再进行紫外光曝光固化处理,从而实现复合膜表面的超疏水涂层的形成,以及同步进行的超疏水涂层与弹性基体之间的化学交联结合。
进一步,所述步骤(3)中对弹性基体与悬浊液进行的紫外线固化处理中紫外曝光量为1000<Hv<20000mJ/cm2。本步骤中通过输入较大能量的紫外线,从而加快涂层聚合形成和涂层与弹性基体化学交联聚合反应速度,减少上述光固反应中氧阻聚的作用,从而获得具有表面性能稳定的超疏水复合膜。
总体而言,本发明所述的制备方法技术方案的基本原理为:首先,步骤(1)中自由基型光固化材料作为预聚物,在紫外线照射预固化处理中,经过聚合反应形成具有良好弹性性能的基体材料;并且在预固化处理过程中,由于氧阻聚的存在,使该弹性基体表面残留大量活性基团(-C=C),这些残留的活性基团(-C=C)在步骤(3)中,与超疏水涂层中作为涂层聚合主体的低表面能且含碳碳双键的聚合物中的双键,在紫外光作用下,通过交联剂中巯基的连接作用形成化学交联,从而实现超疏水层与弹性基底两者在分子结构上的一体化结合,进而获得具有良好抗涂层脱落的超疏水弹性复合膜制备产物。并且本发明所述的超疏水复合膜制备方法步骤(3)中,通过紫外线固化处理步骤,同时实现超疏水涂层聚合形成以及涂层与弹性基体之间的化学交联聚合一体化,极大简化了超疏水复合膜的制备工艺,而且还能确保涂层与基体之间实现无缝式的一体化结合,从而实现制备产物复合膜整体疏水效果的稳定性。
由于巯基-乙烯基反应是Click反应中的一个重要反应,在紫外光固化过程中通过添加巯基化合物可以克服氧阻聚问题。所以本发明中优选将含有巯基的化合物作为交联剂,设计以丙烯酸酯类化合物自由基型预固化膜为复合膜基底,在其表面涂覆巯基-乙烯基反应型的超疏水涂层,最终实现超疏水涂层与基底之间的化学交联,从而制得在分子结构上实现一体化结合的超疏水弹性复合膜。
与现有技术相比,本发明的有益效果
1.本发明制备方法中,使用紫外光固化技术实现在常温下,快速制备具有超疏水特性的弹性复合膜,操作工艺简单;弥补了制备超疏水制备时需要加热固化、设备昂贵、工序复杂的不足。
2.相对其他超疏水涂层与基底是物理结合作用,本发明所述的制备方法通过超疏水涂层与基底间的化学交联,实现了超疏水层和基底在微观分子结构上的一体化,增强了涂层的抗脱离强度,从而使依照本方法制得的超疏水性弹性复合膜在拉伸状态下也能保持良好的疏水效果。
3.在本发明制备方法中,由于超疏水涂层的形成及涂层与基体材料之间的结合是在同一紫外线光固化反应下同时产生化学交联反应完成,从而实现涂层与基体间的整体结合,克服了现有物理性涂层喷涂方式出现的涂层脱粘和粉化以及涂层分布不均或呈块状分裂的问题,从而使依照本方法制得的超疏水性弹性复合膜的整体疏水性能更加稳定。
4.在本发明制备方法中,由优选丙烯酸酯类化合物通过紫外线光固化交联聚合形成的复合膜弹性基体具有良好的附着力,能够使依据本发明方法制备的疏水复合膜适用于不同基材表面,进一步扩大了疏水复合膜的可适用领域。
附图说明:
图1是实施1中制得的超疏水弹性复合膜在松弛状态下的照片;
图2是实施1中制得的超疏水弹性复合膜拉伸100%状态下的照片;
图3是实施1中制得的超疏水弹性摩擦前的超疏水表面的光学照片;
图4是实施1中制得的超疏水弹性摩擦后的超疏水表面的光学照片;
具体实施方式
本发明具体实施方案为:一种使用紫外光固化技术制备具有弹性的超疏水复合膜,包括以下步骤:(1)弹性基底的制备,将光引发剂、预聚物混合均匀,经短时间紫外光照射,制成预固化弹性基底。(2)悬浊液的制备,将低表面能且含碳碳双键聚合物、光引发剂、交联剂、微米和/或纳米颗粒按一定质量比均匀分散在溶剂中,制成悬浊液。(3)将悬浊液涂覆在弹性基底上,然后经紫外光照射固化,获得具有超疏水性能的弹性复合膜。
下面结合试验例及具体实施方式对本发明作进一步的详细描述。但不应将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明内容所实现的技术均属于本发明的范围。
实施例1
聚氨酯丙烯酸酯预聚物和光引发剂1173按质量比98:2称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将硅橡胶、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水纳米二氧化硅,搅拌后超声30min,制成悬浊液;此悬浊液中硅橡胶、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:5%,0.6%,0.05%,4%,90.35%。将悬浊液喷涂在预固化弹性基底上,紫外光照射30s,制得超疏水弹性复合膜。
实施例2
聚氨酯丙烯酸酯预聚物和光引发剂184按质量比95:5称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射20s,制得预固化弹性基底。将硅橡胶、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水纳米二氧化硅,搅拌后超声30min,制成悬浊液;此悬浊液中硅橡胶、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:5%,0.8%,0.05%,3.8%,90.35%。将悬浊液喷涂在预固化弹性基底上,紫外光照射50s,制得超疏水弹性复合膜。
实施例3
聚氨酯丙烯酸酯预聚物和光引发剂TPO按质量比97:3称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将硅橡胶、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水微米和纳米二氧化硅(1:1),搅拌后超声30min,制成悬浊液;此悬浊液中硅橡胶、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:7%,1.1%,0.2%,5.5%,86.2%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例4
聚氨酯丙烯酸酯预聚物和光引发剂1173按质量比99.5:0.5称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射2s,制得预固化弹性基底。将硅橡胶、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水纳米二氧化硅,搅拌后超声30min,制成悬浊液;此悬浊液中硅橡胶、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:2%,0.04%,0.01%,1%,96.95%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例5
聚氨酯丙烯酸酯预聚物和光引发剂1173按质量比96:4称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将硅橡胶、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水微米和纳米二氧化硅(1:1),搅拌后超声30min,制成悬浊液;此悬浊液中硅橡胶、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:10%,1.5%,0.5%,8%,80%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例6
聚氨酯丙烯酸酯预聚物和光引发剂184按质量分数比98:2称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射2s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水纳米碳酸钙,搅拌后超声30min,制成悬浊液;此悬浊液中聚异丁烯、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:5%,0.7%,0.08%,4.1%,90.12%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例7
聚氨酯丙烯酸酯预聚物和光引发剂907按质量比99:1称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水纳米二氧化硅,搅拌后超声30min,制成悬浊液;此悬浊液中聚异丁烯、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:6%,0.7%,0.07%,4.5%,88.73%。将悬浊液喷涂在预固化弹性基底上,紫外光照射50s,制得超疏水弹性复合膜。
实施例8
聚氨酯丙烯酸酯预聚物和光引发剂1173按质量比98:2称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射20s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水微米二氧化硅,搅拌后超声30min,制成悬浊液;此悬浊液中聚异丁烯、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:8%,0.8%,0.08%,7.3%,83.82%。将悬浊液喷涂在预固化弹性基底上,紫外光照射50s,制得超疏水弹性复合膜。
实施例9
聚氨酯丙烯酸酯预聚物和光引发剂1173按质量比98:2称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按一定质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水微米和纳米二氧化硅(1:1),搅拌后超声30min,制成悬浊液;此悬浊液中聚异丁烯、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:6%,0.6%,0.04%,4.1%,89.26%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例10
聚氨酯丙烯酸酯预聚物和光引发剂1173按质量比98:2称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水微米和纳米二氧化硅(1:1),搅拌后超声30min,制成悬浊液;此悬浊液中聚异丁烯、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:3%,0.4%,0.02%,2.2%,94.38%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例11
聚氨酯丙烯酸酯预聚物和光引发剂1173按质量比98:2称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水纳米碳酸钙硅,搅拌后超声30min,制成悬浊液;此悬浊液中聚异丁烯、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:6%,0.7%,0.05%,4.7%,88.55%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例12
聚氨酯丙烯酸酯预聚物和光引发剂907按质量比97:3称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按质量比称取,加入一定量的正己烷,搅拌溶解,制成溶液,然后加入一定量的疏水微米碳酸钙硅,搅拌后超声30min,制成悬浊液;此悬浊液中聚异丁烯、巯基有机硅、光引发剂、二氧化硅和正己烷的质量分数分别为:6%,0.8%,0.05%,4.4%,88.75%。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例13
聚氨酯丙烯酸酯预聚物和光引发剂907按质量比98:2称取,经搅拌、超声(5min)混合均匀后,倒入四氟乙烯模具中,在223mW/cm2紫外灯下照射1s,制得预固化弹性基底。将聚异丁烯、巯基硅氧烷、光引发剂1173按质量比86:12:2称取,加入一定量的正己烷,搅拌溶解,制成6%(Wt)的溶液,然后加入一定量的疏水微米碳酸钙,碳酸钙含量为4.4%(Wt),搅拌后超声30min,制成悬浊液。将悬浊液喷涂在预固化弹性基底上,紫外光照射60s,制得超疏水弹性复合膜。
实施例14
聚氨酯丙烯采用与实施例12相同的工艺方法及参数进行超疏水弹性复合膜的制备,只是将聚氨酯丙烯酸酯预聚物用环氧丙烯酸酯替换。
实施例15
采用与实施例11相同的工艺方法及参数进行超疏水弹性复合膜的制备,只是将聚氨酯丙烯酸酯预聚物用聚醚丙烯酸酯替换。
实施例16
采用与实施例10相同的工艺方法及参数进行超疏水弹性复合膜的制备,只是将聚氨酯丙烯酸酯预聚物用有机硅改性丙烯酸酯替换。
实施例17
采用与实施例1相同的工艺方法及参数进行超疏水弹性复合膜的制备,只是将聚氨酯丙烯酸酯预聚物用有机硅改性丙烯酸酯替换。
测试例
对上述实施例1-12制备的超疏水复合膜,用德国克吕士公司生产的型号DSA-25接触角测试仪,分别测试其水接触角、将复合膜拉伸100%时的水接触角,从而对复合膜涂层表面的润湿性能进行测试,测试结果如附表1所示。
附表1
从上述测试结果可知,本发明方法实施例中制备的复合膜的接触角均大于150°,具备超疏水性能。并且在复合膜被拉伸形变100%情形下,其超疏水性能几乎不受影响,可见,依据本发明方法制备的复合膜具有良好机械稳定性,抗拉伸性强,超疏水性能稳定等特点。
Claims (9)
1.一种光固化型超疏水复合膜的制备方法,所述超疏水复合膜主要由弹性基底和疏水涂层组成,其特征在于,该制备方法主要包括如下步骤:
(1)弹性基底的制备:将光引发剂、预聚物混合均匀,然后经紫外光照射预固化处理,制成预固化的弹性基底;
所述预聚物是具有碳碳双键的低聚物;
(2)悬浊液的制备:将聚合物、光引发剂、交联剂、疏水颗粒均匀分散在溶剂中,制成悬浊液;
所述聚合物是低表面能且含碳碳双键的聚合物;
所述交联剂是巯基交联剂;
所述疏水颗粒是微米级和/或纳米级的疏水颗粒;
(3)将步骤2制备的悬浊液涂覆在步骤1制备的弹性基底表面,然后经紫外光照射固化处理,制得疏水复合膜。
2.根据权利要求1所述光固化型超疏水复合膜的制备方法,其特征在于,步骤(1)中所述的光引发剂,具体指:2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮中的一种或几种。
3.根据权利要求1所述光固化型超疏水复合膜的制备方法,其特征在于:步骤(1)中所述的预聚物,具体指聚氨酯丙烯酸酯、环氧丙烯酸酯、聚醚丙烯酸酯、有机硅改性丙烯酸酯中的一种或几种。
4.根据权利要求1-3中任一所述的光固化型超疏水复合膜的制备方法,其特征在于:所述步骤(1)中光引发剂的含量占比为0.5-5wt%,预聚物的含量占比为95-99.5wt%。
5.根据权利要求1所述光固化型超疏水复合膜的制备方法,其特征在于,步骤(2)中所述的聚合物,具体指聚丁二烯、聚异丁烯、硅橡胶、有机硅改性丙烯酸酯或氟化聚氨酯丙烯酸酯中的一种或几种。
6.根据权利要求1所述光固化型超疏水复合膜的制备方法,其特征在于,步骤(2)中所述的疏水颗粒是经过疏水改性处理的二氧化硅、二氧化钛、碳酸钙颗粒中的一种或者几种。
7.根据权利要求1所述光固化型超疏水复合膜的制备方法,其特征在于,步骤(2)中所述的溶剂是乙醇、丙酮、石油醚、环己烷、正己烷中的一种或几种。
8.根据权利要求1或5-7中任一所述的光固化型超疏水复合膜的制备方法,其特征在于,所述步骤(2)配制的悬浊液中:聚合物含量为2-10wt%,微米和/或纳米颗含量为1-8wt%,光引发剂的含量为0.01-0.5wt%,交联剂的含量为0.04-1.5wt%,溶剂量为80-96.95wt%。
9.根据权利要求1中所述的光固化型超疏水复合膜的制备方法,其特征在于,所述步骤(1)中紫外线照射预固化处理过程中,紫外线的曝光量控制在50<Hv<1000mJ/cm2范围内;所述步骤(3)中紫外线照射固化处理过程中,紫外线的曝光量控制在1000<Hv<20000mJ/cm2范围内。
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CN112708151B (zh) * | 2020-12-25 | 2023-03-17 | 宁波长阳科技股份有限公司 | 热塑性聚氨弹性体膜及其制备方法 |
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