CN114957524B - 一种透明超亲水抗雾涂层用聚合物及其制备方法 - Google Patents
一种透明超亲水抗雾涂层用聚合物及其制备方法 Download PDFInfo
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Abstract
本发明属于抗雾涂层领域，具体涉及一种透明超亲水抗雾涂层用聚合物及其制备方法。本发明的目的在于针对现有技术中超亲水涂层制备过程繁琐、抗雾涂层结合力差以及抗雾性能快速衰减的缺陷。在不影响原有材料的透光性能的基础上，提供一种简便、高效的超亲水抗雾涂层的制备方法。制备所得到的抗雾涂层持久、透明且与基材有良好的结合，具有优异的抗雾性能。除此之外，所采用的原料来源广、成本低，且以乙醇为溶剂，安全无毒，有利于环境保护。
Description
技术领域
本发明属于抗雾涂层领域，具体涉及一种透明超亲水抗雾涂层用聚合物及其制备方法。
背景技术
透明光学材料因具有优异的光学性能而在日常生活中应用广泛，例如汽车挡风玻璃、眼镜和医疗/分析仪器透镜、太阳能电池板等。由于温度或湿度的变化，这些光学材料表面会起雾从而对仪器和设备的实际使用带来显著的不良影响。医疗设备护目镜是医护人员非常重要的个人防护装备之一，其使用过程中雾气的产生会严重影响医疗操作(Kumar A.,et al.Copper@ZIF-8 Core-Shell Nanowires for Reusable Antimicrobial FaceMasks.Advanced Functional Materials 2021 31,2008054)。因此，抑制透明基材上雾气的产生具有非常重要的意义。
研究表明，雾气是由于温度和湿度等环境条件的变化，从而使空气中的水蒸气冷却和凝结，在透明材料表面产生水滴形成的(Lee H.,et al.Zwitter-wettability andantifogging coatings with frost-resisting capabilities.ACS Nano 2013 7,2172-2185)。
通过对材料表面润湿性的调控，抗雾涂层的研究主要分为超亲水、超疏水和吸水抗雾涂层三种类型(Wohl C.J.，et al.Contamination Mitigating Polymeric Coatingsfor Extreme Environments Preface.Advances in Polymer Science 2019 284,V-VI)。
超疏水抗雾涂层主要依靠外部机械驱动使水滴从表面滚落而不凝结起雾，构建超疏水表面的要点在于纳米级表面粗糙度和低表面能的结合(Gao X.,et al.The dry-styleantifogging properties of mosquito compound eyes and artificial analoguesprepared by soft lithography.Advanced Materials 2007 19,2213-2217)。吸水抗雾涂层主要依靠内部的吸水性聚合物基体对水分进行吸收而实现抗雾，而外部覆盖的一层疏水层则可以起到有效防止涂层吸水后过度溶胀的作用(Shibraen M.,et al.Anti-foggingand anti-frosting behaviors of layer-by-layer assembled cellulose derivativethin film.Applied Surface Science 2016370,1-5)。超亲水抗雾涂层利用材料表面良好的润湿性，使凝结的水滴迅速铺开形成一层薄薄的水膜，从而有效减少对光线的散射而起到抗雾的作用(Liang B.,et al.Transparent and Scratch-Resistant AntifoggingCoatings with Rapid Self-Healing Capability.ACS Applied Materials&Interfaces2019 11,30300-30307)。超亲水涂层由于可以使用表面活性剂、无机纳米颗粒、水溶性高分子、有机/无机杂化材料、光催化剂等低成本的原料进行制备，因此有望实现工业化生产。
目前，超亲水抗雾表面可以通过表面物理改性(Domke M.,et al.Transparentlaser-structured glasses with superhydrophilic properties for anti-foggingapplications.Applied physics A:Materials science&processing 2019 125,675-685)、表面化学改性(Wei Z.,et al.Biodegradable poly(butylene succinate)nanofibrous membrane treated withoxygen plasma forsuperhydrophilicity.Surface and coatings technology 2020 381,125147)、涂层法(Zhang T.,et al.Highly transparent,healable,and durable anti-fogging coatingby combining hydrophilic pectin and tannic acid with poly(ethyleneterephthalate).Green chemistry 2019 21,5405-5413)来获得。根据制备超亲水涂层所使用的材料种类的不同，又可将其分为有机涂层、无机涂层以及有机无机杂化超亲水涂层。有机超亲水涂层由于具有众多亲水性基团，能够将表面雾滴快速铺展或在聚合物中形成水合分子，从而实现优异的抗雾性能。除此之外，相较于无机超亲水涂层，有机超亲水涂层与有机衬底(如PET)具有更好的兼容性。层层组装(LBL)(Cebeci F.C.,et al.Nanoporosity-driven superhydrophilicity:a means to create multifunctional antifoggingcoatings.Langmuir 2006 22,2856-2862)和在材料表面接枝聚合物刷(Ezzat M.,etal.Zwitterionic polymer brush coatings with excellent anti-fog and anti-frostproperties,RSC Advances 2016 6,61695-61702)是超亲水涂层制备中较为成熟的方法。
在超亲水涂层的制备方法中，一般物理吸附的涂层容易在清洗、摩擦以及使用过程中流失，与基材表面结合的并不牢固，因此防雾性能很快衰减，需要频繁涂覆。层层组装(LBL)和在材料表面接枝聚合物刷这两种制备方法具有良好的可控性，但制备过程繁琐。因此，开发简单、方便的技术制备具有持久防雾性能的涂层是十分必要的。
发明内容
为了解决上述技术问题，本发明提供一种透明超亲水抗雾涂层用聚合物，其结构通式如下：
其中，n选自1-5000中的任一自然数。
本发明还提供一种上述透明超亲水抗雾涂层用聚合物的制备方法，包括如下步骤：
S1：将化合物A和碱加入有机溶剂中，混合后加入2-溴异丁酰溴，反应后得到化合物B；所述化合物A与2-溴异丁酰溴的摩尔比为1：1-2；
所述化合物B((2-溴-2-甲基-N-(3-(三乙氧基硅基)丙基)丙酰胺))的结构式如下：
S2：将所述化合物B和N-乙烯基吡咯烷酮溶解于甲醇中，加入光引发剂，紫外光照反应，得到所述透明超亲水抗雾涂层用聚合物。
优选的，所述化合物A为(3-氨基丙基)三乙氧基硅烷，其结构式如下：
优选的，所述步骤S1中，反应的条件为0℃反应20-40min，再20-30℃反应3-5h。
优选的，所述碱为三乙胺、N,N-二异丙基乙胺、1,8-二氮杂二环[5.4.0]十一碳-7-烯或1,5,7-三氮杂二环[4.4.0]癸-5-烯；
优选的，所述有机溶剂为四氢呋喃或乙腈。
优选的，所述光引发剂为十羰基二锰，其结构式如下：
进一步地，所述光引发剂在使用时需要避光处理，且尽可能避免氧气对反应体系带来的干扰。
优选的，所述步骤S2中，所述紫外光照反应的温度为20-30℃，时间为1-3h；紫外光的作用距离为20cm。
优选的，紫外光照反应，使用乙醚作为沉淀剂，将沉淀离心、洗涤后获得目标聚合物。
优选的，所述N-乙烯基吡咯烷酮和化合物B的摩尔比为75-125：1。
本发明还提供一种透明超亲水抗雾涂层，包括上述透明超亲水抗雾涂层用聚合物。
本发明还提供一种上述透明超亲水抗雾涂层的制备方法，包括如下步骤：
(1)将所述透明超亲水抗雾涂层用聚合物溶于醇溶液中，得到涂料；
(2)将所述涂料涂覆于辐照后的PET基材表面，70-90℃烘干，得到所述透明超亲水抗雾涂层。
优选的，所述醇溶液中，溶剂为水，醇和溶剂的体积比10-20：1；所述醇为乙醇、甲醇和异丙醇中的一种或多种。
优选的，涂覆采用OPS-10线棒对所述预处理的PET基材表面进行涂布。
优选的，所述步骤(2)中，辐照的时间为3-10min。
本发明的目的在于针对现有技术中超亲水涂层制备过程繁琐、抗雾涂层结合力差以及抗雾性能快速衰减的缺陷。在不影响原有材料的透光性能的基础上，提供一种简便、高效的超亲水抗雾涂层的制备方法。制备所得到的抗雾涂层持久、透明且与基材有良好的结合，具有优异的抗雾性能。除此之外，所采用的原料来源广、成本低，且以乙醇为溶剂，安全无毒，有利于环境保护。
本发明的技术方案相比现有技术具有以下优点：
本发明中所制备的抗雾涂层内部的亲水性高分子端基含有的硅氧烷基团能够通过水解作用与基材表面的羟基牢固地结合，使其具有良好的耐久性。而涂层内部含有的酰胺键可以通过氢键相互连接形成交联网络，使制备的所述防雾涂层具有良好的亲水性和优异的抗雾性能。同时，聚合物涂层具有优异的光学性质，透光率良好，在透明的材料、器件和设备(如护目镜、浴室玻璃及镜子、车辆挡风玻璃及后视镜、太阳能电池板)的使用中具有一定的应用潜力。
附图说明
图1为实施例1中2-溴-2-甲基-N-(3-(三乙氧基硅基)丙基)丙酰胺的1HNMR谱图；
图2为实施例2中聚合物的1HNMR谱图；
图3为实施例2中聚合物的凝胶渗透色谱(GPC)流出曲线；
图4为实施例3中抗雾涂层的制备原理示意图；
图5为实施例4中涂层的傅里叶变换红外光谱图；
图6为实施例4中涂层的水接触角图；
图7为实施例4中涂层的透光率图；
图8为实施例5中改性前后PET薄膜的抗雾图片；
图9为本发明的抗雾机理示意图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例1
(2-溴-2-甲基-N-(3-(三乙氧基硅基)丙基)丙酰胺)的合成
量取式II所示的((3-氨基丙基)三乙氧基硅烷)1mL，用10mL无水四氢呋喃溶解，并加入0.96mL三乙胺，搅拌使溶液充分混合。随后在冰浴的条件下缓慢滴加0.5mL 2-溴异丁酰溴，并用氮气进行保护。滴加完成后先在冰浴下继续反应30min，之后转移至25℃条件下反应4h。反应结束后经后处理提纯得到式I所示化合物。对制得的式I所示化合物进行核磁检测(氢谱)，结果见图1，不同化学位移处所归属的质子峰与式I所示化合物的结构相符，产率为65％。
实施例2
聚合物-Si-O-PVP的制备
称取式I所示的(2-溴-2-甲基-N-(3-(三乙氧基硅基)丙基)丙酰胺)22mg、式Ⅳ所示的(N-乙烯基吡咯烷酮)1g(单体预先通过氧化铝柱除去阻聚剂)和式Ⅴ(十羰基二锰)2mg，溶解在3mL甲醇里，加入十羰基二锰后用铝箔纸对反应瓶做避光处理。通入15min氮气，并采用磁力搅拌使其充分溶解。之后转移至25℃水浴条件下紫外光照1h，光程为20cm，紫外灯功率为400W。反应结束后使用冰乙醚进行沉降，将所得沉淀离心、洗涤得到式Ⅲ所示化合物。对制得的式Ⅲ所示化合物进行核磁检测(氢谱)，结果见图2，不同化学位移处所归属的质子峰与式Ⅲ所示化合物的结构相符，转化率为20％；进行凝胶渗透色谱测试，结果见图3，数均分子量为7900g/mol。
实施例3
抗雾涂层的制备
称取62mg所述式Ⅲ聚合物溶解在乙醇和水的混合溶剂中(水与乙醇的体积比为10：0.5)，得到具有一定粘度的涂料。基材PET先进行等离子体活化处理，辐照时间为5min，使表面产生大量的羟基。取少量涂料平铺于处理后的基材顶部，采用OPS-10线棒进行涂布，涂布后将基材置于80℃条件下烘干，得到抗雾涂层。涂层的制备原理示意图如图4所示。在水的作用下，端基硅氧烷基团会与基材表面的羟基通过水解作用而结合，从而将聚合物固定在材料表面。
实施例4
抗雾涂层的表征
针对超亲水抗雾涂层，采用傅里叶红外光谱仪对PET薄膜表面进行化学官能团测试分析(如图5所示)。改性后的PET表面在波数为1650cm-1出现了聚合物中羰基的吸收峰，在波数为3420cm-1出现了归属于羟基的伸缩振动峰，在波数为1500cm-1出现了硅氧烷基的吸收峰，在波数为2900cm-1出现了饱和碳链的吸收峰，表明涂层的化学组成符合预期。采用静态水接触角仪对PET薄膜表面润湿性进行分析(如图6所示)，改性后的PET薄膜的水接触角由改性前的80°左右下降至10°左右，呈现超亲水。采用紫外可见分光光度计对PET薄膜的透光率进行分析(如图7所示)，表面的透光率较未改性几乎没有变化，约为85％。
实施例5
抗雾涂层的抗雾性能
采用热蒸汽法对防雾性能进行了测试。具体操作为：将改性前后的PET薄膜和放置于盛有80℃热水的烧杯上方，静置30s，观察并采用相机拍摄基材起雾的情况(如图8所示)。改性后的PET表面没有雾气的生成，而未改性的PET表面起雾，这表明涂层的抗雾性能优异。
参照《GB/T9286.1998色漆和清漆漆膜的划格试验》对涂层进行界面粘结性能分析。具体操作为：将涂层改性后的PET放置在平台上，手持百格刀，使刀刃切割时垂直于样品平面。以20-50mm/s的速度在PET表面先划出10行等间隔横线，之后将PET旋转90°,再用百格刀在其表面划出10行等间隔与横线垂直的竖线，形成10×10的正方形网格。取透明胶带沿平行于网格线的方向粘在正方形网格上，使其黏结牢固，黏结牢固后揭开胶带一角，沿60°方向稳稳地撕下胶带。用放大镜观察PET基材网格的破损程度。按照国家标准GB1720-89(79)进行等级分析为0级，即涂层100％没有脱落，这表明涂层与基材具有良好的粘附作用。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (8)
1.一种透明超亲水抗雾涂层用聚合物，其特征在于，其结构通式如下：
；
其中，n选自1-5000中的任一自然数。
2.一种如权利要求1所述透明超亲水抗雾涂层用聚合物的制备方法，其特征在于，包括如下步骤：
S1：将化合物A和碱加入有机溶剂中，混合后加入2-溴异丁酰溴，反应后得到化合物B；所述化合物A与2-溴异丁酰溴的摩尔比为1：1-2；
所述化合物A为（3-氨基丙基）三乙氧基硅烷，其结构式如下：
；
所述化合物B的结构式如下：
；
S2：将所述化合物B和N-乙烯基吡咯烷酮溶解于甲醇中，加入光引发剂，紫外光照反应，得到所述透明超亲水抗雾涂层用聚合物；
所述步骤S1中，反应的条件为0-5 ℃反应20-40 min，再20-30 ℃反应3-5 h；所述光引发剂为十羰基二锰。
3.如权利要求2所述的制备方法，其特征在于，所述碱为三乙胺、N,N-二异丙基乙胺、1,8-二氮杂二环[5.4.0]十一碳-7-烯或1,5,7-三氮杂二环[4.4.0]癸-5-烯。
4.如权利要求2所述的制备方法，其特征在于，所述有机溶剂为四氢呋喃或乙腈。
5.如权利要求2所述的制备方法，其特征在于，所述步骤S2中，N-乙烯基吡咯烷酮和化合物B的摩尔比为75-125：1。
6.一种透明超亲水抗雾涂层，其特征在于，包括权利要求1所述透明超亲水抗雾涂层用聚合物。
7.一种如权利要求6所述透明超亲水抗雾涂层的制备方法，其特征在于，包括如下步骤：
（1）将所述透明超亲水抗雾涂层用聚合物溶于醇溶液中，得到涂料；
（2）将所述涂料涂覆于辐照后的PET基材表面，70-90 ℃烘干，得到所述透明超亲水抗雾涂层。
8.如权利要求7所述的制备方法，其特征在于，所述醇溶液中，溶剂为水，醇和溶剂的体积比10-20：1；所述醇为乙醇、甲醇和异丙醇中的一种或多种。
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