CN110791199B - 含氟有机聚硅氧烷自清洁涂料 - Google Patents
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Abstract
本发明涉及涂料领域,公开了一种含氟有机聚硅氧烷自清洁涂料,包括含氟硅氧烷前驱体5~50wt%,硅氧烷预聚体50~95 wt%;其制备方法如下:常温环境下,将含氟硅氧烷前驱体与硅氧烷预聚体混合搅拌,搅拌均匀后,在基底上喷涂成膜;置于含有氨水氛围的恒温恒湿环境中静置预设时间,得到含氟有机聚硅氧烷自清洁涂层。这种自清洁涂层疏水性强,自清洁效果好,耐磨性高,使用范围广等特点。该制备方法与现有的制备技术相比,本方法操作更为简便、无需溶剂,市场前景广阔。
Description
技术领域
本发明涉及涂料制备技术领域,特别涉及一种含氟有机聚硅氧烷超疏水自清洁涂料。
背景技术
超疏水自清洁涂层因其表面的灰尘、污物可以通过自然力如风,雨,重力等自行脱落的功效而受到广泛关注。目前,超疏水表面已经开发出很多种制备方法,如溶胶凝胶法、溶液浸渍法、化学蚀刻法、等离子体刻蚀法、电化学沉积法、阳极氧化法、模板法、静电纺丝法、高温热氧化法等。但在研发和应用的过程中仍存在一些问题,例如一个普遍的问题,超疏水自清洁涂层表面的粗糙结构很容易被磨损而使得超疏水性不能长期保持,因而缩短了使用寿命;其次,采用的制备方法通常比较复杂;此外,某些方法所用仪器特殊且昂贵,制备涂层所需的原料稀少或昂贵等,这些问题都限制了超疏水自清洁涂层的大规模生产和应用。因此,开发出制备简单、成本低、耐久性好、多功能化、智能化的超疏水自清洁涂层是未来的研究方向。
有机氟树脂是迄今为止发现的耐候性、耐久性最为优良的聚合物。但是随着人们对环保和节能意识的逐步提高,各国对VOC(挥发性有机化合物)含量的限制日益严格,以有机溶剂作为成膜介质的溶剂型含氟聚合物涂料和高温固化含氟聚合物涂料的应用受到了一定的限制。而无溶剂涂料具有安全无害、工艺清洁、技术先进、低能耗、低排放等特点,因而备受人们的青睐,其中含氟有机聚硅氧烷具备了有机硅聚合物和氟碳聚合物二者的优点,用它作涂料成膜物时既保留了有机硅聚合物良好的特性,又兼具了氟碳聚合物优良耐候性、耐沾污性、疏水疏油性、耐酸耐碱性等优点,正日益引起世界各国的极大关注,是今后涂料工业发展的一个重要方向。
发明内容
发明目的:针对现有技术中存在的问题,本发明提供一种含氟有机聚硅氧烷超疏水涂料,制备出的含氟有机聚硅氧烷超疏水涂层耐磨性好,使用时间长、使用效果好,制备过程无需使用任何溶剂,制备方法简单。
技术方案:本发明提供了一种含氟有机聚硅氧烷自清洁涂料,包括含氟硅氧烷前驱体5~50wt%,硅氧烷预聚体50~95 wt%。
优选地,所述含氟硅氧烷前驱体为以下任意一种:1H,1H,2H,2H-全氟葵基三乙氧基硅烷、1H,1H,2H,2H-全氟十二烷基三乙氧基硅烷、1H,1H,2H,2H-全氟十七烷三甲氧基硅烷。
优选地,所述硅氧烷预聚体为以下任意一种:聚(二甲氧基)硅烷PDMOS、聚(二乙氧基)硅烷POEOS。
本发明还提供了一种含氟有机聚硅氧烷自清洁涂料的制备方法,包括以下步骤:常温环境下,常温环境下,将质量百分比为5~50wt%的含氟硅氧烷前驱体与质量百分比为50~95 wt%的硅氧烷预聚体混合搅拌,搅拌均匀后,在基底上喷涂成膜;置于含有氨水氛围的恒温恒湿环境中静置预设时间,得到含氟有机聚硅氧烷自清洁涂层。
优选地,所述预设时间为6-48 h。优选时间为12-24 h。
优选地,所述氨水氛围中氨水的浓度为1-5%时,所述恒温恒湿环境的温度为50-80°C,湿度为40-80%;所述氨水氛围中氨水的浓度为5-25%时,所述恒温恒湿环境的温度为20-50°C,湿度为40-80%。
优选地,所述基底为玻璃、滤纸、硅片、铝合金、马口铁、聚碳酸酯或织布。
有益效果:本发明中将含氟硅烷前驱体与硅氧烷预聚体直接混合搅拌均匀后,喷涂到基底上得到有机硅液态涂层;然后置于氨水产生的碱性氛围中引发含氟硅烷和硅氧烷预聚体中的SiOCH2CH3或SiOCH3基团水解缩合反应,由于氟硅烷提供的低表面能特性,结合涂层表面的粗糙结构,使得所得的含氟有机聚硅氧烷具备了超疏水自清洁性能。与传统酸催化的硅氧烷水解缩合不同,碱催化硅氧烷的水解缩合反应,可以让涂层获得更高的聚合度(缩合度),从而进一步提升涂层的机械强度和疏水性能(Si-OH基团的减少)。
本发明只需简单混合含氟硅氧烷前驱体和硅氧烷预聚体,无需使用其他挥发性溶剂,而且在没有酸或碱催化剂的情况下,此配方溶液比较稳定;涂层的制备过程中只需在碱性环境下静置6-48 h,因此具有简单高效、绿色环保等优点,并且可应用于不同材质的基底;本发明中的超疏水涂层在自清洁方面具有较大的应用前景。
本发明中的超疏水涂层中,聚硅氧烷主链机械强度高、耐磨性好,而且不易被紫外光和臭氧分解,具有很好的热稳定性、耐候能力,交联含氟有机聚硅氧烷后大幅度降低涂层表面的表面能,从而获得较好的自清洁性能,有效克服现有自清洁涂层耐磨性差,使用时间短、使用效果不佳的局面,制备方法操作简单、无需使用任何溶剂。
附图说明
图1为实施方式5中制备得到的含氟有机聚硅氧烷超疏水涂层的SEM照片;
图2为实施方式5中制备得到的含氟有机聚硅氧烷超疏水涂层的疏水性能与摩擦测试次数的关系图。
具体实施方式
下面结合附图对本发明进行详细的介绍。
实施方式1:
将1H,1H,2H,2H-全氟葵基三乙氧基硅烷0.05g与PDMOS 1g在磁力搅拌下搅拌混合均匀后,在基底上喷涂成膜,置于含有1%浓度的氨水氛围、80°C的恒温恒湿箱中反应48h(湿度为80%),得到含氟有机聚硅氧烷超疏水涂层,结果见表 1。
实施方式2:
将1H,1H,2H,2H-全氟十二烷基三乙氧基硅烷0.1g与PDMOS 1g磁力搅拌下搅拌混合均匀后,在基底上喷涂成膜,置于含有5%浓度的氨水氛围、60°C的恒温恒湿箱中反应48h(湿度为40%),得到含氟有机聚硅氧烷超疏水涂层,结果见表 1。
实施方式3:
将1H,1H,2H,2H-全氟十七烷三甲氧基硅烷0.3g与PDMOS 1g磁力搅拌下搅拌混合均匀,完全溶解后在基底上喷涂成膜,置于含有5%浓度的氨水氛围、50°C的恒温恒湿箱中反应12h(湿度为60%),得到含氟有机聚硅氧烷超疏水涂层,结果见表 1。
实施方式4:
将1H,1H,2H,2H-全氟十七烷三甲氧基硅烷0.5g与PDMOS 1g磁力搅拌下搅拌混合均匀后,在基底上喷涂成膜,置于含有25%浓度的氨水氛围、20°C的恒温恒湿箱中反应6h(湿度为80%),得到含氟有机聚硅氧烷超疏水涂层,结果见表 1。
实施方式5:
将1H,1H,2H,2H-全氟十二烷基三乙氧基硅烷1g与PDEOS 1g磁力搅拌下搅拌混合均匀后,在基底上喷涂成膜,置于含有25%浓度的氨水氛围、40°C的恒温恒湿箱中反应24h(湿度为60%),得到含氟有机聚硅氧烷超疏水涂层,结果见表 1和图1。
从图1中可以看出该涂层具有很好的耐磨性能,在5KPa压力下,砂盘摩擦涂层40次后,涂层还能保持超疏水性能。
实施方式6:
将1H,1H,2H,2H-全氟葵基三乙氧基硅烷0.7g与PDEOS 1g磁力搅拌下搅拌混合均匀后,在基底上喷涂成膜,置于含有25%浓度的氨水氛围、50°C的恒温恒湿箱中反应48h(湿度为40%),得到含氟有机聚硅氧烷超疏水涂层,结果见表 1。
表1含氟有机聚硅氧烷超疏水涂层水接触角测试结果
注:接触角测试采用德国 Krüss公司产 DSA25型全自动视频接触角测量仪,取平行测试三次的平均值。
表1表明,通过实施方式1至5中的方法制备出的含氟有机聚硅氧烷超疏水涂层均具有较高的超疏水性能,而且滚动角很小,表明涂层在自清洁涂料、防雾涂料等领域具有很大的应用前景。
上述实施方式只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰,都应涵盖在本发明的保护范围之内。
Claims (1)
1. 一种含氟有机聚硅氧烷自清洁涂料,其特征在于,由含氟硅氧烷前驱体5~50wt%和硅氧烷预聚体50~95 wt%组成;
所述含氟硅氧烷前驱体为以下任意一种:
1H,1H,2H,2H-全氟葵基三乙氧基硅烷、1H,1H,2H,2H-全氟十二烷基三乙氧基硅烷、1H,1H,2H,2H-全氟十七烷三甲氧基硅烷;
所述硅氧烷预聚体为以下任意一种:
聚(二甲氧基)硅烷PDMOS、聚(二乙氧基)硅烷POEOS。
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CN106893486A (zh) * | 2017-03-29 | 2017-06-27 | 广州健邦化学有限公司 | 一种防水、防油、防污处理剂及其制备方法 |
CN108384443A (zh) * | 2018-01-11 | 2018-08-10 | 淮阴工学院 | 有机/无机杂化超疏水涂料及其制备方法和应用 |
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