CN108409911B - 一种超疏水性自清洁荧光涂层的制备方法 - Google Patents
一种超疏水性自清洁荧光涂层的制备方法 Download PDFInfo
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- CN108409911B CN108409911B CN201810053899.1A CN201810053899A CN108409911B CN 108409911 B CN108409911 B CN 108409911B CN 201810053899 A CN201810053899 A CN 201810053899A CN 108409911 B CN108409911 B CN 108409911B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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Abstract
本发明提供了一种超疏水性自清洁荧光涂层的制备方法,属于超疏水性荧光涂层技术领域。该制备方法包括:制备含氟的羧基聚合物粒子;将聚合物粒子在有机溶剂中分散,再与小分子配体和稀土化合物配位后进行涂布,得到超疏水荧光涂层。本发明制备微球粒径在微米级左右,能提供足够的粗糙度,含氟单体保证微球表面具有低表面能,所制备的超疏水荧光涂层接触角能达到150°以上,能应用于不同基体,具有自清洁的功能。且本发明所用方法简单,经济,可应用于工业生产。
Description
技术领域
本发明涉及超疏水性荧光涂层技术领域,具体涉及一种超疏水性自清洁荧光涂层的制备方法。
背景技术
超疏水涂层具有很高的接触角和很低的滚动角,而受到了人们的关注,目前超疏水涂层在抗冰、防腐蚀、油水分离等方面具有广泛的应用。
稀土高分子荧光材料由于其中的稀土离子具有独特的光学,电学,磁学等方面的特性,高分子具有良好的加工以及基质稳定性而受到了极大的关注。近些年来,关于稀土高分子材料的报道层出不穷,但稀土化合物为无机物,遇水不稳定,因此,若稀土高分子材料制具有超疏水性,则可以避免稀土离子的淬灭,还可以用于水下的环境且具有自清洁的效应。
目前的研究中,制备超疏水的涂层一般利用利用高分子和稀土化合物制备荧光材料主要有直接共混掺杂法、直接配位法、原位生成法。直接共混掺杂法则会导致荧光浓度聚集产生淬灭,且相容性不好,而原位生成法由于对稀土离子和聚合物的要求高,不利于工业应用。超疏水荧光涂层中高分子基体的制备有刻蚀法,电沉积法,共混法等,刻蚀法,电沉积法对设备要求高,对工业生产不适用,而用发光粒子和其他物质共混法会导致分相和发光不均匀及不稳定等现象。
发明内容
本发明的目的在于提供一种超疏水性自清洁荧光涂层的制备方法,解决了稀土配位不均匀、发光不均匀以及分相、不稳定的问题;且涂层制备简便,利于工业生产。
本发明的技术方案:
一种超疏水性自清洁荧光涂层的制备方法,步骤如下:
步骤1:用核壳乳液聚合法制备核壳乳液,将核壳乳液进行固液分离,得到固态的聚合物粒子,其中,聚合物粒子的核层为聚二乙烯基苯,聚合物粒子的壳层为二乙烯基苯、含羧基单体和含氟单体的共聚物,聚合物粒子的粒径为800nm~2um;
步骤2:将步骤1得到的聚合物粒子分散到有机溶剂中,然后加入小分子配体和稀土化合物,配位反应1-5h后得到悬浮液;有机溶剂中各物质的摩尔质量之比为:聚合物粒子中所含羧基:小分子配体:稀土化合物=1~2:2~4:1,所述悬浮液的固含量为0.005~0.05g:mL;
步骤3:将步骤2所得的悬浮液进行超声分散1~10min,然后涂布于基质上,待有机溶剂挥发后,得到超疏水涂层。
步骤1中所述的核壳乳液聚合法的步骤为:首先将二乙烯基苯滴加到含有乳化剂和助乳化剂的混合水溶液中,得到预乳化液;再将预乳化液置于冰水浴中,超声1~10min;然后在50~80℃下,向预乳化液中加入引发剂水溶液Ⅰ,反应4~10h得到种子乳液;最后在50~90℃下,向种子乳液中同时滴加单体水溶液和引发剂水溶液Ⅱ,制备壳层,反应2~6h后得到核壳乳液,其中,单体水溶液由二乙烯基苯、含羧基单体、含氟单体、助剂、乳化剂和去离子水组成。
所述种子乳液中各物质的质量比为:二乙烯基苯:乳化剂:助乳化剂:引发剂:去离子水质量比为1:0.01~0.05:0.03~0.1:0.002~0.0065:4~8;引发剂水溶液Ⅰ中引发剂与水的质量比为0.003~0.02:1,单体水溶液中各物质的质量比为二乙烯基苯:含羧基单体:含氟单体:乳化剂:助剂:去离子水为1:0.08~1:0.4~6:0.03~0.25:0.4~5:2.5~20;引发剂水溶液Ⅱ中引发剂与水的质量比为:0.0006~0.004:1;所述预乳化液中二乙烯基苯与单体水溶液中二乙烯基苯的质量比为2~13:1;所述引发剂水溶液Ⅰ与引发剂水溶液Ⅱ中引发剂的质量比为0.8~4.5:1。
所述乳化剂为十二烷基硫酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基苯磺酸钾、硬脂酸钠中的一种或两种以上混合;所述助乳化剂为碳数为4~20的烷基醇、脂肪烃、聚合物醇中的一种或两种以上混合;所述引发剂为过硫酸钾、过硫酸钠、过硫酸铵、过硫酸铵-亚硫酸氢钠、过氧化氢-氯化亚铁中的一种或两种以上混合;所述含羧基单体为含乙烯基的烷基酸或含乙烯基的芳香酸;所述含氟单体为1H,1H,2H-全氟-1-癸烯、2-全氟丙氧基全氟丙基三氟乙烯基醚、全氟正丙基乙烯基醚、全氟丁基乙烯、全氟辛酸2-羟基-3-甲基丙烯酰氧基丙酯中的一种或两种以上混合;所述助剂为环己酮、丙酮、甲基丁酮、甲基异丁酮中的一种或两种以上混合;
步骤2中所述的有机溶剂为脂肪烃和芳香烃、氯代烃、烷基醇、烷基酮中的一种或两种以上混合;所述的小分子配体为水杨酸、邻苯二甲酸、苯甲酸、α-噻吩甲酰三氟丙酮、乙酰丙酮、苯甲酰丙酮、苯甲酰三氟丙酮、8-羟基喹啉、邻菲罗啉、2,2-联吡啶、三苯基氧化膦中的一种或两种以上混合;所述的稀土化合物为含铕、铽、镧、钐、钆、镝、钬、铒、铥、铈、镱或镥的硝酸盐、氯化盐。
步骤2所述固液分离方法为离心、过滤或冷冻干燥。
步骤3中所述的涂布的方式为浇注、刷涂或旋涂;所述的基质为玻璃片、木板、铁片、布或陶瓷。
所述的含羧基单体为丙烯酸、甲基丙烯酸、3-乙烯基苯甲酸、4-乙烯基苯甲酸中的一种或两种以上混合。
所述的助乳化剂为十六烷、十六醇、聚乙烯醇中的一种或两种以上混合。
本发明的有益效果:
1、本发明所制备的聚合物微球粒子与稀土离子及小分子配体发生了配位,避免了直接掺杂所导致的浓度淬灭,团聚等荧光不稳定的现象。
2、本发明所制备的聚合物微球粒子粒径均匀,与稀土离子及小分子配体配位均匀,呈现出以微球为单位的点状发光,发光均匀。且形成的涂层由微米级左右的上面具有配位的稀土离子的微米级左右微球组成,没有掺杂其他物质,避免了由于其他物质掺杂而导致的发光不均匀以及分相的问题。
3、本发明制备的聚合物微球粒子具有核壳结构,且核壳均为高分子,避免核壳见相容性不好的问题,在壳层添加具有配位基团的聚合单体,可减少具有配位基团的用量,保证配位的准确性,且核壳均具有交联结构,所制备的粒子及涂层能在高温下使用。
4、本发明制备微球粒径在微米级左右,相对于小粒径微球能提供足够的粗糙度,含氟单体保证微球表面具有低表面能,所制备的超疏水荧光涂层接触角能达到150°以上,能应用于不同基体,具有自清洁的功能,能带走涂层表面的污染物且所制备的超疏水荧光涂层能在潮湿环境以及水环境中使用,荧光发光稳定。本发明所用方法简单,经济,可应用于工业生产,且稀土离子与所制备的聚合物微球粒子可随配随用,改变稀土离子及配体可得不同发光颜色及发光强度的涂层,乳液聚合体系采用水作溶剂,干净,环保。
附图说明
图1是本发明所制备超疏水性荧光涂层的接触角图。
图2是本发明所制备超疏水性荧光涂层的荧光发射谱图。
图3是本发明所制备超疏水荧光涂层应用于不同基质上且具有自清洁的效果图。
具体实施方式
下面结合实施例对本发明进行更详细地说明。
实施例1
将13g二乙烯基苯滴加到含有0.3g十二烷基磺酸钠,0.8g十六醇,80mL去离子水的溶液中形成预乳化液后,在冰水浴中超声5min后,在70℃下,加入含0.05g过硫酸钾的5mL水溶液,反应8h后;滴加由1g二乙烯基苯,1g丙烯酸,6g全氟辛酸2-羟基-3-甲基丙烯酰氧基丙酯,0.25g十二烷基磺酸钠,5g环己酮,20mL水组成的单体溶液和由0.02g过硫酸钾组成的30mL的水溶液,滴加同时,70℃反应4h,得平均粒径为1.1um核壳乳液。将所制备的核壳乳液离心后分散于乙醇溶液中,向体系中加入邻菲罗琳和苯甲酰丙酮和硝酸铕进行配位得悬浮液,其中羧基粒子:邻菲罗啉:苯甲酰丙酮:氯化铕物质的量之比为1:2:1:1;将配位后固含量为0.05g/mL的悬浮液旋涂在玻璃片上,得到接触角为158°的疏水性荧光涂层。该荧光涂层滚动角在10°以下,具有自清洁功能,可利用水滴去除表面的灰,且在水溶液中24h能保持荧光强度基本不变;所制备荧光涂层接触图见图1,荧光发设谱图见图2,自清洁作用见图3。
实施例2
将12g二乙烯基苯滴加到含有0.6g十二烷基硫酸钠,0.36g十六醇,96mL去离子水的溶液中形成预乳化液后,在冰水浴中超声6min后,在70℃下,加入含0.04g过硫酸铵的5mL水溶液,反应7h后;滴加由2g二乙烯基苯,2g的4-乙烯基苯甲酸,6g全氟正丙基乙烯基醚,0.5g十二烷基硫酸钠,6g丙酮,25mL水组成的单体溶液和由0.05g过硫酸钾组成的35mL的水溶液,滴加同时,75℃反应3h,得平均粒径为900m核壳乳液。将所制备的核壳乳液离心后分散于丙酮溶液中,向体系中加入8-羟基喹啉和已酰丙酮和硝酸铽,其中羧基粒子:8-羟基喹啉:已酰丙酮:硝酸铽物质的量之比为1:2:2:1;将配位后固含量为0.008g/mL的悬浮液刷涂在玻璃片上,得到接触角为155°的疏水性荧光涂层。该荧光涂层滚动角在10°以下,具有自清洁功能,可利用水滴去除表面的灰,且在水溶液中24h能保持荧光强度基本不变。
实施例3
将14g二乙烯基苯滴加到含有0.14g十二烷基磺酸钾,1.4g十六醇,75mL去离子水的溶液中形成预乳化液后,在冰水浴中超声2min后,在75℃下,加入含0.09g过硫酸钾的10mL水溶液,反应7h后;滴加由5g二乙烯基苯,1g甲基丙烯酸,2g的2-全氟丙氧基全氟丙基三氟乙烯基醚,0.2g十二烷基磺酸钾,2g的甲基丁酮,25mL水组成的单体溶液和由0.02g过硫酸钠组成的30mL的水溶液,滴加同时,70℃反应5h,得平均粒径为1.3um的核壳乳液。将所制备的核壳乳液过滤后分散于四氢呋喃溶液中,向体系中加入乙酰丙酮和氯化铕进行配位得悬浮液,其中羧基粒子:乙酰丙酮:氯化铕物质的量之比为1:3:1,将配位后固含量为0.007g/mL的悬浮液超声5min后浇注涂在玻璃片上,得到接触角为150°的疏水性荧光涂层。该荧光涂层滚动角在10°以下,具有自清洁功能,可利用水滴去除表面的灰,且在水溶液中24h能保持荧光强度基本不变。
实施例4
将13g二乙烯基苯滴加到含有0.4g十二烷基苯磺酸钠,0.85g十六醇,95mL去离子水的溶液中形成预乳化液后,在冰水浴中超声8min后,在75℃下加入含0.06g过硫酸铵-亚硫酸氢钠的5mL水溶液,反应7h后;滴加由6g二乙烯基苯,0.48g丙烯酸,3g的1H,1H,2H-全氟-1-癸烯,0.2g十二烷基苯磺酸钠,3g甲基异丁酮,15mL水组成的单体溶液和由0.06g过氧化氢-氯化亚铁组成的15mL的水溶液,滴加同时,80℃,反应3h,得平均粒径为1.5um核壳乳液。将所制备的核壳乳液冷冻干燥后分散于二乙醚溶液中,向体系中加入苯甲酰丙酮和三苯基氧化膦中和硝酸镧进行配位得悬浮液,羧基粒子:苯甲酰丙酮:三苯基氧化膦:硝酸镧物质的量之比为2:1:1:1,将配位后固含量为0.005g/mL的悬浮液浇注涂在玻璃片上,得到接触角为152°的疏水性荧光涂层。该荧光涂层滚动角在10°以下,具有自清洁功能,可利用水滴去除表面的灰,且在水溶液中24h能保持荧光强度基本不变。
实施例5
将16g二乙烯基苯滴加到含有0.3g十二烷基硫酸钠,0.9g十六醇,65mL去离子水的溶液中形成预乳化液后,在冰水浴中超声7min后,在50℃下,加入含0.1g过硫酸铵-亚硫酸氢钠的5mL水溶液,反应9h后;滴加由2g二乙烯基苯,2g的4-乙烯基苯甲酸,6g全氟丁基乙烯,0.3g十二烷基硫酸钠,7g环己酮和丙酮,40mL水组成的单体溶液和由0.07g过硫酸钾和过硫酸钠组成的30mL的水溶液,滴加同时,70℃,反应5h,得平均粒径为1.9um核壳乳液。将所制备的核壳乳液离心后分散于二氯甲烷溶液中,向体系中加入苯甲酰三氟丙酮和苯甲酸和硝酸铒进行配位得悬浮液,羧基粒子:苯甲酰三氟丙酮:苯甲酸:硝酸铒物质的量之比为1:2:1:1,将配位后固含量为0.009g/mL的悬浮液刷涂在玻璃片上,得到接触角为157°的疏水性荧光涂层。该荧光涂层滚动角在10°以下,具有自清洁功能,可利用水滴去除表面的灰,且在水溶液中24h能保持荧光强度基本不变。
实施例6
将13g二乙烯基苯滴加到含有0.3g十二烷基磺酸钠,0.7g十六醇,80mL去离子水的溶液中形成预乳化液后,在冰水浴中超声4min后,在75℃下,加入含0.03g过硫酸钾的10mL水溶液,反应5h后;滴加由3g二乙烯基苯,1g甲基丙烯酸,4g全氟丁基乙烯和全氟正丙基乙烯基醚,0.25g十二烷基磺酸钠,3g丙酮,25mL水组成的单体溶液和由0.02g过硫酸铵组成的30mL的水溶液,滴加同时,85℃,反应3h,得平均粒径为1.0um核壳乳液。将所制备的核壳乳液离心后分散于正戊烷和二氯甲烷溶液中,向体系中加入邻菲罗琳和苯甲酰丙酮和硝酸镝进行配位得悬浮液,羧基粒子:α-噻吩甲酰三氟丙酮:2,2-联吡啶:硝酸铒物质的量之比为2:2:1:1,将配位后固含量为0.02g/mL的悬浮液旋涂在玻璃片上,得到接触角为151°的疏水性荧光涂层。该荧光涂层滚动角在10°以下,具有自清洁功能,可利用水滴去除表面的灰,且在水溶液中24h能保持荧光强度基本不变。
上述实施例为本发明的实施方案,但本发明的实施方式并不受所述实施例的限制,其他任何未背离本发明的原理和精神实质下所做的改变,都包含在本发明的保护范围内。
Claims (10)
1.一种超疏水性自清洁荧光涂层的制备方法,其特征在于,步骤如下:
步骤1:用核壳乳液聚合法制备核壳乳液,将核壳乳液进行固液分离,得到固态的聚合物粒子,其中,聚合物粒子的核层为聚二乙烯基苯,聚合物粒子的壳层为二乙烯基苯、含羧基单体和含氟单体的共聚物,聚合物粒子的粒径为800nm~2um;
步骤2:将步骤1得到的聚合物粒子分散到有机溶剂中,然后加入小分子配体和稀土化合物,配位反应1-5h后得到悬浮液;有机溶剂中各物质的摩尔质量之比为:聚合物粒子中所含羧基:小分子配体:稀土化合物=1~2:2~4:1,所述悬浮液的固含量为0.005~0.05g:mL;
步骤3:将步骤2所得的悬浮液进行超声分散1~10min,然后涂布于基质上,待有机溶剂挥发后,得到超疏水涂层。
2.根据权利要求1所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,步骤1中所述的核壳乳液聚合法的步骤为:首先将二乙烯基苯滴加到含有乳化剂和助乳化剂的混合水溶液中,得到预乳化液;再将预乳化液置于冰水浴中,超声1~10min;然后在50~80℃下,向预乳化液中加入引发剂水溶液Ⅰ,反应4~10h得到种子乳液;最后在50~90℃下,向种子乳液中同时滴加单体水溶液和引发剂水溶液Ⅱ,制备壳层,反应2~6h后得到核壳乳液,其中,单体水溶液由二乙烯基苯、含羧基单体、含氟单体、助剂、乳化剂和去离子水组成。
3.根据权利要求2所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,所述种子乳液中各物质的质量比为:二乙烯基苯:乳化剂:助乳化剂:引发剂:去离子水质量比为1:0.01~0.05:0.03~0.1:0.002~0.0065:4~8;引发剂水溶液Ⅰ中引发剂与水的质量比为0.003~0.02:1,单体水溶液中各物质的质量比为二乙烯基苯:含羧基单体:含氟单体:乳化剂:助剂:去离子水为1:0.08~1:0.4~6:0.03~0.25:0.4~5:2.5~20;引发剂水溶液Ⅱ中引发剂与水的质量比为:0.0006~0.004:1;所述预乳化液中二乙烯基苯与单体水溶液中二乙烯基苯的质量比为2~13:1;所述引发剂水溶液Ⅰ与引发剂水溶液Ⅱ中引发剂的质量比为0.8~4.5:1。
4.根据权利要求2或3所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,所述乳化剂为十二烷基硫酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基苯磺酸钾、硬脂酸钠中的一种或两种以上混合;所述助乳化剂为碳数为4~20的烷基醇、脂肪烃、聚合物醇中的一种或两种以上混合;所述引发剂为过硫酸钾、过硫酸钠、过硫酸铵、过硫酸铵-亚硫酸氢钠、过氧化氢-氯化亚铁中的一种或两种以上混合;所述含羧基单体为含乙烯基的烷基酸或含乙烯基的芳香酸;所述含氟单体为1H,1H,2H-全氟-1-癸烯、2-全氟丙氧基全氟丙基三氟乙烯基醚、全氟正丙基乙烯基醚、全氟丁基乙烯、全氟辛酸2-羟基-3-甲基丙烯酰氧基丙酯中的一种或两种以上混合;所述助剂为环己酮、丙酮、甲基丁酮、甲基异丁酮中的一种或两种以上混合。
5.根据权利要求1、2或3所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,步骤2中所述的有机溶剂为脂肪烃和芳香烃、氯代烃、烷基醇、烷基酮中的一种或两种以上混合;所述的小分子配体为水杨酸、邻苯二甲酸、苯甲酸、α-噻吩甲酰三氟丙酮、乙酰丙酮、苯甲酰丙酮、苯甲酰三氟丙酮、8-羟基喹啉、邻菲罗啉、2,2-联吡啶、三苯基氧化膦中的一种或两种以上混合;所述的稀土化合物为含铕、铽、镧、钐、钆、镝、钬、铒、铥、铈、镱或镥的硝酸盐、氯化盐。
6.根据权利要求4所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,步骤2中所述的有机溶剂为脂肪烃和芳香烃、氯代烃、烷基醇、烷基酮中的一种或两种以上混合;所述的小分子配体为水杨酸、邻苯二甲酸、苯甲酸、α-噻吩甲酰三氟丙酮、乙酰丙酮、苯甲酰丙酮、苯甲酰三氟丙酮、8-羟基喹啉、邻菲罗啉、2,2-联吡啶、三苯基氧化膦中的一种或两种以上混合;所述的稀土化合物为含铕、铽、镧、钐、钆、镝、钬、铒、铥、铈、镱或镥的硝酸盐、氯化盐。
7.根据权利要求1、2、3或6所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,步骤3中所述的涂布的方式为浇注、刷涂或旋涂;所述的基质为玻璃片、木板、铁片、布或陶瓷。
8.根据权利要求4所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,步骤3中所述的涂布的方式为浇注、刷涂或旋涂;所述的基质为玻璃片、木板、铁片、布或陶瓷。
9.根据权利要求5所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,步骤3中所述的涂布的方式为浇注、刷涂或旋涂;所述的基质为玻璃片、木板、铁片、布或陶瓷。
10.根据权利要求4所述的一种超疏水性自清洁荧光涂层的制备方法,其特征在于,所述的含羧基单体为丙烯酸、甲基丙烯酸、3-乙烯基苯甲酸、4-乙烯基苯甲酸中的一种或两种以上混合;所述的助乳化剂为十六烷、十六醇、聚乙烯醇中的一种或两种以上混合。
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