CN115505325A - 一种用于光伏玻璃的自修复自清洁双重固化涂层及其制备方法 - Google Patents

一种用于光伏玻璃的自修复自清洁双重固化涂层及其制备方法 Download PDF

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CN115505325A
CN115505325A CN202210282920.1A CN202210282920A CN115505325A CN 115505325 A CN115505325 A CN 115505325A CN 202210282920 A CN202210282920 A CN 202210282920A CN 115505325 A CN115505325 A CN 115505325A
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康翼鸿
喻学锋
程文杰
何睿
吴列
甄亚枝
杨帆
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Wuhan Zhongke Advanced Material Technology Co Ltd
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Abstract

本发明提供一种用于光伏玻璃的自修复自清洁双重固化涂层及其制备方法，涂层包括5‑30份TiO2纳米颗粒、30‑70份光‑热双固化树脂和5‑50份包覆聚醚胺的微胶囊，所述光‑热双固化树脂具有超支化结构，分子链端含有可供紫外光固化的碳碳双键，以及含有与胺类化合物容易发生反应的环氧基，由此形成的涂层交联密度高，包有胺类化合物的微胶囊均匀分布在这种致密的交联网络中，在物理磨损或有机物污染后涂层表面能够通过常温热固化，实现受损表面的自修复，另外TiO2纳米颗粒的加入使该涂层在紫外光下集光催化性和超亲水性于一身，具有明显的抗污染性。

Description

一种用于光伏玻璃的自修复自清洁双重固化涂层及其制备 方法
技术领域
本发明属于光伏玻璃涂层技术领域，具体涉及一种用于光伏玻璃的自修复自清洁双重固化涂层及其制备方法。
背景技术
光伏组件安装在环境复杂的室外，组件表面容易积聚大量的灰尘，而且随着自然界的降雨少量灰尘形成顽固污渍难以去除，导致光伏组件表面受热不均，遮挡效应形成热斑，导致光伏组件使用寿命减短，发电效率下降等诸多问题。
微胶囊填充型自修复涂层是目前常见的自修复涂层，它现有技术中利用微胶囊对超疏水表面进行修复有几种，一种是将低表面能的物质包裹在微胶囊中，当涂层表面被破坏时包裹的氟硅烷等物质可以迁移到涂层表面进行修复；一种是将修复剂封装在微胶囊中，并将微胶囊和能使修复剂聚合的催化剂一起复合在聚合物材料中，当聚合物受到外界作用在其内部产生裂纹时，微胶囊在裂纹的作用下发生破裂，修复剂在虹吸作用下被释放并充满裂纹内部，再与基体材料中的催化剂反应引发聚合，从而对裂纹进行修复，使涂层的性能得到恢复。
但是微胶囊的引入通常会导致涂层性能下降。这是由于微胶囊大量分布于涂层内部，当涂层受到外界破坏时，由于微胶囊与树脂基体混合后的界面一般属于物理连接，会导致机体内微裂纹扩展到界面处便沿着界面的薄弱处绕过微胶囊扩展，导致微胶囊难以破裂，不能正常工作，所以微胶囊与基体树脂的界面结合的程度是影响复合材料的性能和自修复效率的关键因素。
发明内容
本发明的目的是针对现有技术的不足，本发明提供一种用于光伏玻璃的自修复自清洁双重固化涂层及其制备方法，包括包覆有聚醚胺的微胶囊、光-热双固化树脂和TiO2纳米颗粒，在物理磨损或有机物污染后表面能够通过常温热固化，实现受损表面的自修复；TiO2纳米颗粒的加入可以实现借助雨水去除灰尘颗粒，借助紫外光杀灭玻璃表面有机物和分解有机污染物。
为实现上述目的，本发明采用的技术方案如下：
本发明提供一种用于光伏玻璃的自修复自清洁双重固化涂层，其特征在于，包括5-30份TiO2纳米颗粒、30-70份光-热双固化树脂和5-50份包覆聚醚胺的微胶囊。
具体的，所述光-热双固化树脂是末端含有环氧基、硅氧烷以及碳碳双键的超支化树脂。
具体的，所述光-热双固化树脂由含有羟基的超支化树脂与酸酐、缩水甘油醚、硅烷偶联剂KH560以及羟基丙烯酸酯单体、二异氰酸酯进一步反应生成。
本发明还提供上述含有羟基的超支化树脂和光-热双固化树脂的制备方法，含有羟基的超支化树脂的制备过程如下：
1)二异氰酸酯与小分子多元醇反应得到支化的端NCO的预聚体，其中二异氰酸酯的异氰酸酯基(-NCO)和小分子多元醇的羟基(-OH)的摩尔比2:1；
2)支化的端NCO的预聚体与二元醇反应形成超支化树脂，其中支化的端NCO的预聚体的异氰酸酯基(-NCO)和二元醇的羟基(-OH)的摩尔比介于1:1-1:3之间。
进一步的，所述光-热双固化树脂的制备过程为：
1)将羟基丙烯酸酯单体与二异氰酸酯按照羟基(-OH)与异氰酸酯基(-NCO)摩尔比1：1反应得到部分封端的预聚体1；
2)将含有羟基的超支化树脂和步骤1)得到的预聚体1按照羟基(-OH)与异氰酸酯基(-NCO)摩尔比4：1-1：1混合反应，得到光固化树脂；
3)将步骤2)得到的光固化树脂按照羟基(-OH)与酸酐的摩尔比6：1-1：1混合反应，得到含羧基的光固化树脂；
4)将步骤3)得到的含羧基的光固化树脂按照羧基(-COOH)与缩水甘油醚、硅烷偶联剂KH560混合物的摩尔比1：1，以及质量份0.5％的三苯基磷催化剂混合后，在90-120℃反应3-6h，得到含环氧基的光-热双固化树脂，其中硅烷偶联剂KH560与缩水甘油醚的摩尔比为10：1～5：1。
具体的，所述的酸酐包括顺丁烯二酸酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酐中的至少一种；
具体的，所述的缩水甘油醚包括乙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、新戊二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、1,2-环己二醇二缩水甘油醚、异氰尿酸三缩水甘油酯中的至少一种。
优选地，所述二异氰酸酯包括异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、改性二苯基甲烷二异氰酸酯(液化MDI)中的一种或至少两种的组合；
所述的小分子多元醇包括季戊四醇、甘油、三羟甲基丙烷、三羟甲基乙烷中的至少一种；
所述羟基丙烯酸酯单体包括甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)、丙烯酸羟丙酯(HPA)、4-羟基丁基丙烯酸酯(4HBA)、季戊四醇三丙烯酸酯(PETA)中的至少一种。
进一步的，所述包覆聚醚胺的微胶囊的制备步骤为：
S1：将乳化剂、聚醚胺和引发剂混匀后乳化；
S2：升温，缓慢滴加甲基丙烯酸甲酯MMA，界面反应形成囊壁；
S3：冷却后过滤，滤饼用蒸馏水清洗，再过滤，干燥，得到PMMA包覆聚醚胺的微胶囊。
具体的，将十二烷基苯磺酸钠SDBS、聚醚胺T403(D2000、T5000)、偶氮二异丁腈混合均匀后在40-70℃、1000-3000rpm转速下乳化30-60min，然后升温至70-85℃，缓慢滴加甲基丙烯酸甲酯MMA，1-2h滴加完后保温2-4h。冷却后将反应液过滤，滤饼用蒸馏水清洗，再过滤，反复3次，然后45℃干燥12h，得到PMMA包覆聚醚胺的微胶囊。
其中，SDBS量是聚醚胺0.5-1.5％，偶氮二异丁腈量是MMA1％左右，MMA量是聚醚胺20-40％。
本发明还提供上述任一项用于光伏玻璃的自修复自清洁双重固化涂层的制备方法，先将包覆聚醚胺的微胶囊、TiO2纳米颗粒和溶剂混合，混合均匀后再加入光-热双固化树脂，根据需要添加涂料常用的分散剂、消泡剂及流平剂配制成水性纳米复合涂料，搅拌均匀后，涂覆在玻璃表面，干燥后UV光照后即得用于光伏玻璃的自修复自清洁双重固化涂层。
上述溶剂为无水乙醇，异丙醇，乙酸乙酯，乙酸丁酯，甲苯，二甲苯，丙酮，丁酮，环己酮，正丁醚中的一种或多种。
上述用于光伏玻璃的自修复自清洁双重固化涂层在物理磨损或有机物污染后表面能够通过常温热固化，实现受损表面的自修复。
上述用于光伏玻璃的自修复自清洁双重固化涂层借助雨水去除灰尘颗粒，借助紫外光杀灭玻璃表面有机物和分解有机污染物。
与现有技术相比，本发明具有如下突出效果：
本发明提供一种含有羟基的超支化树脂以及由该超支化树脂制备得到的光-热双固化树脂，该光-热双固化树脂具有超支化结构，分子链端含有无机硅氧烷链段，提供与无机基材良好的附着力，还含有可供紫外光固化的碳碳双键，以及含有与胺类化合物容易发生反应的环氧基，由于超支化分子链不易缠结，位于分子链端的双键被充分暴露，反应活性高，极大的提高了光固化反应程度，形成的涂层交联密度高，微胶囊均匀分布在这种致密的交联网络中，提高了与基体树脂的界面结合程度，在涂层发生裂纹时，微胶囊中的胺类化合物与光-热双固化树脂能及时的发生交联反应，使涂层的性能得到恢复，提升了自修复效率。另外，TiO2纳米颗粒的加入使该涂层在紫外光下集光催化性和超亲水性于一身，具有明显的抗污染性：：受到紫外光辐照后，纳米TiO2涂层受激发形成的超氧负离子和具有强氧化性的羟基自由基，能分解表面吸附的各类有机污染物；受紫外光激发形成羟基，羟基与水形成氢键而表现出超亲水性，这种特性使水能优先占据表面，污染物被多余的水带走，形成的亲水膜被风干。
附图说明
图1为光-热双固化树脂的制备过程。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1制备包覆聚醚胺的微胶囊
将0.2g十二烷基苯磺酸钠SDBS、20g聚醚胺T403(D2000、T5000)、0.04g偶氮二异丁腈混合均匀后在60℃、1000rpm转速下乳化30min，然后升温至75℃，缓慢滴加4g甲基丙烯酸甲酯MMA，2h滴加完后保温4h。冷却后将反应液过滤，滤饼用蒸馏水清洗，再过滤，反复3次，然后45℃干燥12h，得到PMMA包覆聚醚胺的微胶囊。
实施例2制备包覆碳聚醚胺的微胶囊
将0.3g十二烷基苯磺酸钠SDBS、20g聚醚胺T403(D2000、T5000)、0.08g偶氮二异丁腈混合均匀后在40℃、3000rpm转速下乳化50min，然后升温至70℃，缓慢滴加8g甲基丙烯酸甲酯MMA，1h滴加完后保温3h。冷却后将反应液过滤，滤饼用蒸馏水清洗，再过滤，反复3次，然后45℃干燥12h，得到PMMA包覆聚醚胺的微胶囊。
实施例3制备包覆聚醚胺的微胶囊
将0.3g十二烷基苯磺酸钠SDBS、60g聚醚胺T403(D2000、T5000)、0.12g偶氮二异丁腈混合均匀后在70℃、2000rpm转速下乳化60min，然后升温至85℃，缓慢滴加12g甲基丙烯酸甲酯MMA，2h滴加完后保温3h。冷却后将反应液过滤，滤饼用蒸馏水清洗，再过滤，反复3次，然后45℃干燥12h，得到PMMA包覆聚醚胺的微胶囊。
实施例4超支化树脂的制备
步骤1)250mL的三口烧瓶中加入44.46g(0.2mol)异佛尔酮二异氰酸酯和0.09g(0.1wt％)二月桂酸二丁基锡开启搅拌；另用50g异丙醇和100g乙酸乙酯将13.41g(0.1mol)三羟甲基丙烷混合溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至70℃反应直至混合物的异氰酸酯基(-NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，得到支化的端NCO的预聚体，如图1中的step1；
步骤2)如图1中的step2，然后加入1.52g(0.02mol)1,3-丙二醇和200g(0.2mol)聚丙二醇1000(N210)，继续反应直至异氰酸酯基(-NCO)的含量为零，得到超支化树脂，即图1中的(a)。
实施例5光-热双固化树脂的制备
如图step3～5所示，步骤1)另取250mL三口烧瓶，向其加入11.11g(0.05mol)异佛尔酮二异氰酸酯和0.016g(0.1wt％)二月桂酸二丁基锡开启搅拌；另依次称取0.044g(0.262wt％)对羟基苯甲醚，0.088g(0.525wt％)2,6-二叔丁基-4-甲基苯酚以及5.8g(0.05mol)丙烯酸羟乙酯，充分混合至完全溶解，转移至恒压滴液漏斗中，在室温下缓慢滴加至上述三口烧瓶中(该反应剧烈放热，控制滴速避免局部过热)，滴完继续室温反应30min后，升温至70℃反应直至混合物的异氰酸酯基(-NCO)的含量达到理论值(通过盐酸二正丁胺法测定)，降温得到预聚体，即图1中的(b)；
步骤2)加入上述实施4中得到的超支化树脂继续反应直至异氰酸酯基(-NCO)的含量为零，得到光固化树脂，减压蒸馏脱除溶剂，干燥密封保存；
步骤3)将步骤2)得到的光固化树脂与3.92g(0.04mol)顺丁烯二酸酐混合后，40℃反应3h，得到含羧基的光固化树脂，即图1中的(c)；
步骤4)将步骤3)得到的含羧基的光固化树脂与6.09g(0.035mol)乙二醇二缩水甘油醚、1.18g(0.005mol)KH560，0.05g(0.5％)的三苯基磷催化剂混合后，在120℃反应6h，得到含环氧基的光-热双固化树脂，即图1中的(d)。
实施例6用于光伏玻璃的自修复自清洁双重固化涂层的制备
先将20份实施例1中的微胶囊、20份TiO2和100份无水乙醇混合，再加入60份光-热双固化树脂，再添加涂料常用的1份分散剂、0.5份消泡剂及0.5份流平剂配制成水性纳米复合涂料，搅拌均匀后，涂覆在玻璃表面，干燥后UV光照后即得用于光伏玻璃的自修复自清洁双重固化涂层。

Claims (9)

1.一种用于光伏玻璃的自修复自清洁双重固化涂层，其特征在于，包括5-30份TiO2纳米颗粒、30-70份光-热双固化树脂和5-50份包覆聚醚胺的微胶囊。
2.根据权利要求1所述用于光伏玻璃的自修复自清洁双重固化涂层，其特征在于，所述光-热双固化树脂是末端含有环氧基、硅氧烷以及碳碳双键的超支化树脂。
3.根据权利要求1所述用于光伏玻璃的自修复自清洁双重固化涂层，其特征在于，由含有羟基的超支化树脂与酸酐、缩水甘油醚、硅烷偶联剂以及羟基丙烯酸酯单体、二异氰酸酯进一步反应生成。
4.根据权利要求1所述用于光伏玻璃的自修复自清洁双重固化涂层，其特征在于，所述光-热双固化树脂的制备过程为：
1)将羟基丙烯酸酯单体与二异氰酸酯按照羟基(-OH)与异氰酸酯基(-NCO)摩尔比
1：1反应得到部分封端的预聚体1，60-80℃反应1-3h；
2)将含有羟基的超支化树脂和步骤1)得到的预聚体1按照羟基(-OH)与异氰酸酯基(-NCO)摩尔比4：1-1：1混合，70-90℃反应2-4h，得到光固化树脂；
3)将步骤2)得到的光固化树脂按照羟基(-OH)与酸酐的摩尔比6：1-1：1混合反应，40-70℃反应1-3h，得到含羧基的光固化树脂；
4)将步骤3)得到的含羧基的光固化树脂按照羧基(-COOH)与缩水甘油醚、硅烷偶联剂KH560混合物的摩尔比1：1，以及质量份0.5％的三苯基磷催化剂混合后，在90-120℃反应3-6h，得到含环氧基的光-热双固化树脂，其中硅烷偶联剂KH560与缩水甘油醚的摩尔比为10：1～5：1。
5.根据权利要求3所述用于光伏玻璃的自修复自清洁双重固化涂层，其特征在于，所述的酸酐包括顺丁烯二酸酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酐中的至少一种；所述的缩水甘油醚包括乙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、新戊二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、1,2-环己二醇二缩水甘油醚、异氰尿酸三缩水甘油酯中的至少一种。
6.根据权利要求1所述用于光伏玻璃的自修复自清洁双重固化涂层，其特征在于，所述包覆聚醚胺的微胶囊的制备步骤为：
S1：将乳化剂、聚醚胺和引发剂混匀后乳化；
S2：升温，缓慢滴加甲基丙烯酸甲酯MMA，界面反应形成囊壁；
S3：冷却后过滤，滤饼用蒸馏水清洗，再过滤，干燥，得到PMMA包覆聚醚胺的微胶囊。
7.一种如权利要求1～6任一项所述用于光伏玻璃的自修复自清洁双重固化涂层的制备方法，其特征在于，先将包覆聚醚胺的微胶囊、TiO2纳米颗粒和溶剂混合，混合均匀后再加入光-热双固化树脂，根据需要添加涂料常用的分散剂、消泡剂及流平剂配制成水性纳米复合涂料，搅拌均匀后，涂覆在光伏玻璃表面，干燥后UV光照后即得用于光伏玻璃的自修复自清洁双重固化涂层的制备方法。
8.根据权利要求7所述用于光伏玻璃的自修复自清洁双重固化涂层的制备方法，其特征在于，物理磨损或有机物污染后的涂层表面能够通过常温热固化，实现受损表面的自修复。
9.根据权利要求7所述用于光伏玻璃的自修复自清洁双重固化涂层的制备方法，其特征在于，借助雨水去除灰尘颗粒，借助紫外光杀灭玻璃表面有机物和分解有机污染物。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116445043A (zh) * 2023-04-21 2023-07-18 中山森柏雅新材料科技有限公司 一种光伏玻璃用的自清洁耐酸纳米防护涂层及其制备方法
CN116640521A (zh) * 2023-07-26 2023-08-25 苏州弘道新材料有限公司 一种长效自清洁透明背板及制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106752857A (zh) * 2016-11-28 2017-05-31 江南大学 一种双重固化丙烯酸酯超亲水防雾涂层的制备方法
CN113717366A (zh) * 2021-08-05 2021-11-30 韶关市合众化工有限公司 一种含硫二苯甲酮改性的超支化自引发光固化树脂
CN113717369A (zh) * 2021-08-05 2021-11-30 金色摇篮新材料股份公司 一种含双型光引发基团改性的超支化光固化树脂
CN113956710A (zh) * 2020-07-21 2022-01-21 杭州科望特种油墨有限公司 阳离子uv固化型玻璃油墨、采用其生产的产品及生产工艺
CN114085353A (zh) * 2021-12-31 2022-02-25 武汉中科先进技术研究院有限公司 一种光-热双重固化树脂及其制备方法
CN114181610A (zh) * 2021-12-31 2022-03-15 武汉中科先进技术研究院有限公司 一种微胶囊型自修复双重固化超疏水涂层及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106752857A (zh) * 2016-11-28 2017-05-31 江南大学 一种双重固化丙烯酸酯超亲水防雾涂层的制备方法
CN113956710A (zh) * 2020-07-21 2022-01-21 杭州科望特种油墨有限公司 阳离子uv固化型玻璃油墨、采用其生产的产品及生产工艺
CN113717366A (zh) * 2021-08-05 2021-11-30 韶关市合众化工有限公司 一种含硫二苯甲酮改性的超支化自引发光固化树脂
CN113717369A (zh) * 2021-08-05 2021-11-30 金色摇篮新材料股份公司 一种含双型光引发基团改性的超支化光固化树脂
CN114085353A (zh) * 2021-12-31 2022-02-25 武汉中科先进技术研究院有限公司 一种光-热双重固化树脂及其制备方法
CN114181610A (zh) * 2021-12-31 2022-03-15 武汉中科先进技术研究院有限公司 一种微胶囊型自修复双重固化超疏水涂层及其制备方法

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CN116640521A (zh) * 2023-07-26 2023-08-25 苏州弘道新材料有限公司 一种长效自清洁透明背板及制备方法
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Application publication date: 20221223