CN113463402B - 一种pH响应超疏水-亲水可逆转化材料表面的制备方法 - Google Patents

一种pH响应超疏水-亲水可逆转化材料表面的制备方法 Download PDF

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CN113463402B
CN113463402B CN202110719217.8A CN202110719217A CN113463402B CN 113463402 B CN113463402 B CN 113463402B CN 202110719217 A CN202110719217 A CN 202110719217A CN 113463402 B CN113463402 B CN 113463402B
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superhydrophobic
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侯成敏
杨佳琦
张�杰
张兴
刘甜
钱志云
严薇
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Shenzhen Wanzhida Technology Co ltd
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Abstract

本发明公开了一种pH响应超疏水‑亲水可逆转化材料表面的制备方法具体按照以下步骤实施：步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，经细乳液聚合法得到微胶囊；步骤2，在步骤1的体系中，滴加一滴三乙胺，加入七氟丁酸，将含氟聚合物接枝到步骤一所得微胶囊中，得到pH响应性微胶囊；步骤3，pH响应性微胶囊超声分散于去离子水中，用该微胶囊溶液处理材料表面，置于烘箱中干燥，得到pH应性超疏水‑亲水可逆转化材料表面。本发明提供的方法可实现从超疏水到亲水的可逆转化，转化次数可达到数十次，具有很强的耐久性和抵抗外界环境破坏的能力。

Description

一种pH响应超疏水-亲水可逆转化材料表面的制备方法
技术领域
本发明属于材料表面改性技术领域，涉及一种pH响应超疏水-亲水可逆转化材料表面的制备方法。
背景技术
超疏水材料是材料表面与水的接触角大于150°，滚动角小于10°的材料，其表面有很强的抗水能力，使其具备良好的自洁性、防潮性等。超疏水表面优异的非浸润性在工业生产和日常生活中具有非常大的应用前景。棉布、木材、木塑、纸张、陶瓷、水泥、混凝土、玻璃、大理石、塑料制品等常见传统材料，在生产生活中应用十分广泛，但是这些材料由于其具有明显的吸湿现象或者对材料表面的清洁度有要求，如果长时间放置在湿度较高的环境中，会发生霉变、腐蚀等现象，同时其尺寸稳定性也不能得到保障，这大大的减少了材料的使用寿命，限制了使用范围。
微胶囊是一种直径在纳米到微米尺度范围内的球形颗粒，利用人工或天然高分子材料作为壁材，将固态或液态、无机或有机、疏水或亲水性材料作为芯材封装在微胶囊内部，达到想要的目的。响应型微胶囊是指通过使用具有环境响应型的壁材制成微胶囊，使其具有环境响应性，当环境发生改变时，微胶囊会发生一系列的变化。目前有关微胶囊超疏水表面的制备研究比较少。
发明内容
本发明的目的是提供一种pH响应超疏水-亲水可逆转化材料表面的制备方法，该方法可实现疏水-超疏水-亲水三者之间的可逆转换。
本发明所采用的技术方案是，一种pH响应超疏水-亲水可逆转化材料表面的制备方法，具体包括如下步骤：
步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为反应单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，充分混合均匀后作为油相，逐滴滴入水相中，乳化10～20min，然后将乳化后的溶液移入三口烧瓶中，在400～800rmin-1机械搅拌下反应8～10h，反应温度为60～100℃；
步骤2，在步骤1所得体系中，滴加一滴三乙胺，然后加入七氟丁酸，搅拌8～10h，经离心、清洗后，干燥，即得到pH响应性微胶囊；
步骤3，将步骤2制备的pH响应性微胶囊超声分散于去离子水中，得到微胶囊溶液，然后用微胶囊溶液处理材料表面，处理后的材料表面经铝片浸扎后，置于烘箱中干燥，即得。
本发明的特点还在于：
步骤1中甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的物质的摩尔比为0.5～2.0：0.5～2.0：1.0～3.0。
步骤1中偶氮二异丁腈和二乙烯基苯用量分别为反应单体质量的2％～5％和3％～8％，十六烷的用量为反应单体质量的30％～70％。
步骤1中的水相为以十二烷基苯磺酸钠为表面活性剂的去离子水。
步骤2中，七氟丁酸与步骤1中甲基丙烯酸缩水甘油酯的摩尔比为1.0～3.0：7.0～9.0；
步骤2中，干燥的温度为60～100℃；干燥时间为20～24h。
步骤3中处理的材料包括棉布、木材、木塑、纸张、陶瓷、水泥、混凝土。
步骤3中，微胶囊溶液处理材料表面的方法有四种：一种是浸扎法，微胶囊溶液浸泡材料，浸泡10～30min，用光滑的且大于材料面积的铝片进行挤压，干燥即得；
第二种是涂布法，将微胶囊溶液喷涂、旋涂、滚涂到材料表面，涂布1～5次；
第三种是印刷法，通过丝网印刷的方式将微胶囊溶液印刷到材料表面；第四种是浸渍法，即将材料直接浸泡到微胶囊溶液中。
本发明的有益效果如下：
1.本发明的方法适用材料可以是棉布、木材、木塑、纸张、陶瓷、水泥、混凝土、玻璃、大理石、塑料制品等。
2.本发明制备的pH响应性微胶囊，氟元素聚集在微胶囊表面，解决了合成微胶囊的过程中含氟物质聚合到微胶囊内部的问题，提高了微胶囊的疏水性。
3.本发明制备的pH响应性超疏水-亲水可逆转化材料具有pH响应特性，同时可疏水亲水可逆转化：用所得环境响应性微胶囊分散液浸泡或涂覆棉织物(棉布、木材、木塑、纸张、陶瓷、水泥、混凝土、玻璃、大理石、塑料制品等)亲水表面，经干燥后得到疏水表面。滴中性液滴于疏水表面，液滴与疏水表面的接触角总体保持在150°左右，具有超疏水性；滴pH＝13的液滴于疏水表面上，液滴与疏水表面的接触角总体保持在150°左右，具有超疏水性；滴pH＝1的液滴于疏水表面上，经120s液滴被完全吸收，具有亲水性，表面经润洗烘干后，继续滴加pH＝13的液滴于疏水表面上，液滴与疏水表面的接触角总体保持在148°左右。从而使得材料表面对不同pH值具有环境响应性，对于中性和碱性液体具有超疏水性，对于酸性溶液具有亲水性，且具有可逆转化的性质。
4.本发明制备的pH响应性微胶囊，可应用在诸多领域。本研究制备的pH响应微胶囊具有微小的尺寸结构、优异的分散稳定性和各组分的相容性等特性，具有智能响应性，可应用到生物传感、药物传递等方面。
5.本发明制备的pH响应性微胶囊可长期储存，使用时配制成分散液，省时省力，成本低。通过涂膜、印刷等设备可以实现大规模的pH响应性超疏水-亲水可逆转化材料表面的生产，避免了新设备的研究投入，具有重大的经济效益；
6.本发明扩大了超疏水材料的使用范围，本发明制备的pH响应性超疏水-亲水可逆转化材料表面，使得常用材料的亲水表面在中性和碱性条件下得到疏水表面，在酸性条件下得到亲水表面。这种特性在一些特殊的工业化应用中有着极其重要的使用价值。这种超疏水-亲水可逆转变可达数十次之多，扩大了超疏水材料的使用范围，未来有着非常广阔的应用前景。
附图说明
图1为本发明一种pH响应超疏水-亲水可逆转化材料表面的制备方法实施例2制备的超疏水-亲水可逆转化材料表面经pH＝13的液滴处理后的超疏水表面与水的接触角照片；
图2为本发明一种pH响应超疏水-亲水可逆转化材料表面的制备方法实施例2制备的超疏水-亲水可逆转化表面经pH＝7的液滴处理后的超疏水表面与水的接触角照片；
图3为本发明一种pH响应超疏水-亲水可逆转化材料表面的制备方法实施例2制备的超疏水-亲水可逆转化表面经pH＝1的液滴处理后的亲水表面与水的接触角照片；
图4为未处理棉织物表面与水的接触角照片；
图5为本发明一种pH响应超疏水-亲水可逆转化材料表面的制备方法实施例4制备的pH响应性微胶囊分别经pH＝1、pH＝7溶液处理下粒径变化曲线图；
图6为本发明一种pH响应超疏水-亲水可逆转化材料表面的制备方法实施例4制备的超疏水-亲水可逆转化材料分别经pH＝1、pH＝7溶液处理后的水接触角变化曲线图；
图7为未处理棉织物的表面扫描电镜照片；
图8为本发明一种pH响应超疏水-亲水可逆转化材料表面的制备方法实施例4制备的超疏水-亲水可逆转化棉织物的表面扫描电镜照片。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明提供一种pH响应超疏水-亲水可逆转化材料表面的制备方法，具体按照以下步骤实施：
步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为反应单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，将以上物质充分混合均匀后作为油相，逐滴滴入水相中，乳化20～30min。再将其移入三口烧瓶中，在400～800rmin-1机械搅拌下反应8～10h，温度控制在60～100℃，经细乳液聚合法制备出微胶囊。其中，甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的摩尔比为0.5～2.0：0.5～2.0：1.0～3.0。步骤一中偶氮二异丁腈和二乙烯基苯用量分别为单体质量的2％～5％和3％～8％，十六烷的用量为单体质量的30％～70％。水相为以十二烷基苯磺酸钠(SDBS)为表面活性剂的去离子水，将油相滴入水相时，采用均质机进行搅拌，速度为10000r min-1～20000r min-1。
步骤2，在步骤一所得体系中，滴加一滴三乙胺，加入七氟丁酸，在常温下磁力搅拌8～10h，经离心、清洗后经60～100℃干燥，即得到pH响应性微胶囊；加入七氟丁酸，其与步骤一中甲基丙烯酸缩水甘油酯的摩尔比为1.0～3.0：7.0～9.0，目的为在微胶囊表面接枝含氟聚合物，即先聚合微胶囊，后接枝含氟聚合物。磁力搅拌的速率为400～800r min-1。
步骤3，将步骤2制备的pH响应性微胶囊超声分散于去离子水中，得到微胶囊溶液，然后用微胶囊溶液处理材料表面，处理后的材料表面经铝片浸扎后，置于烘箱中干燥得到pH响应性超疏水-亲水可逆转化材料表面。其中可处理的材料包括棉布、木材、木塑、纸张、陶瓷、水泥、混凝土、玻璃、大理石、塑料制品等。用微胶囊溶液处理材料表面的方法有四种：一种是浸扎法，微胶囊溶液浸泡材料，浸泡10～30min，用光滑的且大于材料面积的铝片进行挤压，烘箱干燥；第二种是涂布法，即将微胶囊溶液喷涂、旋涂、滚涂到材料表面，涂布1-5次；第三种是印刷法，即通过丝网印刷等方式将微胶囊溶液印刷到材料表面；第四种是浸渍法，即将材料直接浸泡到较稀的微胶囊溶液中。
本发明其响应性的实现过程主要靠离子化与去离子化来实现，随着微胶囊所处环境中的H+浓度增加，叔胺基被迅速质子化，从而使N原子带有一个正电荷；聚合物骨架上正电荷量增加，分子链因带有大量同号电荷而出现较强的库伦斥力，导致疏水微胶囊亲水性加强并伴随着尺寸的溶胀。反之，当环境pH提高后，微胶囊聚合物骨架随着H+浓度的下降，质子化程度降低，分子链之间的库伦斥力逐渐消失，导致微胶囊恢复到原始的紧实而疏水的状态。
实施例1
步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，以上材料为油相，选取十二烷基苯磺酸钠(SDBS)为表面活性剂溶解在去离子水中作为连续相(水相)。将油相充分混合均匀后，在均质机高速搅拌下，把油相逐滴滴入水相进行乳化20min。形成白色乳液静置30min待乳液稳定后，将其移入三口烧瓶中，在400r min-1机械搅拌下反应8h，温度控制在80℃，制备出微胶囊；
步骤1中甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的单体摩尔比例为1:1:2，偶氮二异丁腈的用量为0.172g，二乙烯基苯的用量为0.287g，十六烷的用量为2.865g。
步骤2，在步骤1所得体系中，滴加一滴三乙胺，加入七氟丁酸，在常温下磁力搅拌10h，经离心、清洗后经80℃干燥20h，即得到pH响应性微胶囊；
步骤2中的七氟丁酸的摩尔量为0.04mol。
步骤3，pH响应性微胶囊超声分散于去离子水中，得到微胶囊溶液，用该微胶囊溶液处理材料表面，处理后的材料表面经铝片浸扎后，置于烘箱中干燥，得到pH响应性超疏水-亲水可逆转化材料表面。
步骤3中聚合物水溶液中微胶囊的浓度为10mg/100mL。
实施例2
步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，以上材料为油相，选取十二烷基苯磺酸钠(SDBS)为表面活性剂溶解在去离子水中作为连续相(水相)。将油相充分混合均匀后，在均质机高速搅拌下，把油相逐滴滴入水相进行乳化10min。形成白色乳液静置30min待乳液稳定后，将其移入三口烧瓶中，在500r min-1机械搅拌下反应9h，温度控制在60℃，制备出微胶囊；
步骤1中甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的单体摩尔比例为0.5:0.5:1，偶氮二异丁腈的用量为0.088g，二乙烯基苯的用量为0.146g，十六烷的用量为1.461g。
步骤2，在步骤1所得体系中，滴加三乙胺，加入七氟丁酸，在常温下磁力搅拌9h，经离心、清洗后经60℃干燥22h，即得到pH响应性微胶囊；
步骤2中的七氟丁酸的摩尔量为0.06mol。
步骤3，pH响应性微胶囊超声分散于去离子水中，得到微胶囊溶液，用该微胶囊溶液处理材料表面，处理后的材料表面经铝片浸扎后，置于烘箱中干燥，得到pH响应性超疏水-亲水可逆转化材料表面。
步骤3中聚合物水溶液中微胶囊的浓度为50mg/100mL。
本发明实施例2得到的pH响应性超疏水-亲水可逆转化材料表面，经pH＝13的液滴处理后的超疏水表面，与水的接触角约为150°，如图1所示；经pH＝7的液滴处理后的超疏水表面，与水的接触角约为145°(见图2)；pH响应性超疏水-亲水可逆转化表面经pH＝1的液滴处理后变为亲水表面，与水的接触角在120s内下降到0°左右(见图3)；
实施例3
步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，以上材料为油相，选取十二烷基苯磺酸钠(SDBS)为表面活性剂溶解在去离子水中作为连续相(水相)。将油相充分混合均匀后，在均质机高速搅拌下，把油相逐滴滴入水相进行乳化15min。形成白色乳液静置30min待乳液稳定后，将其移入三口烧瓶中，在800r min-1机械搅拌下反应10h，温度控制在100℃，制备出微胶囊；
步骤1中甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸九氟己酯、甲基丙烯酸缩水甘油酯的单体摩尔比例为2:2:3，偶氮二异丁腈的用量为0.075g，二乙烯基苯的用量为0.188g，十六烷的用量为1.878g。
步骤2，在步骤1所得体系中，滴加一滴三乙胺，加入七氟丁酸，在常温下磁力搅拌8h，经离心、清洗后经100℃干燥24h，即得到pH响应性微胶囊；
步骤2中的七氟丁酸的摩尔量为0.08mol。
步骤3，pH响应性微胶囊超声分散于去离子水中，得到微胶囊溶液，用该微胶囊溶液处理材料表面，处理后的材料表面经铝片浸扎后，置于烘箱中干燥，得到pH响应性超疏水-亲水可逆转化材料表面。
步骤3中聚合物水溶液中微胶囊的浓度为70mg/100mL。
实施例4
步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，以上材料为油相，选取十二烷基苯磺酸钠(SDBS)为表面活性剂溶解在去离子水中作为连续相(水相)。将油相充分混合均匀后，在均质机高速搅拌下，把油相逐滴滴入水相进行乳化20min。形成白色乳液静置30min待乳液稳定后，将其移入三口烧瓶中，在400r min-1机械搅拌下反应8h，温度控制在80℃，制备出微胶囊；
步骤1中甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的单体摩尔比例为0.5:0.5:1，偶氮二异丁腈的用量为0.096g，二乙烯基苯的用量为0.16g，十六烷的用量为1.6g。
步骤2，在步骤1所得体系中，滴加一滴三乙胺，加入七氟丁酸，在常温下磁力搅拌10h，经离心、清洗后经80℃干燥，即得到pH响应性微胶囊；
步骤2中的七氟丁酸的摩尔量为0.06mol。
步骤3pH响应性微胶囊超声分散于去离子水中，用该微胶囊溶液处理材料表面，处理后的材料表面经铝片浸扎后，置于烘箱中干燥，得到pH响应性超疏水-亲水可逆转化材料表面。
步骤3中聚合物水溶液中微胶囊的浓度为20mg/100mL。
图4为未处理棉织物表面与水的接触角照片，从图4中可以看出，水能快速的渗透且浸湿纸张，接触角为0度，说明没有处理的棉织物表面与水具有良好的亲和性能，不具有疏水的能力。
图5为实施例4制备的pH响应性微胶囊分别经pH＝1，pH＝7溶液处理下粒径变化曲线图，微胶囊在不同pH条件下出现了显著的尺寸差异，从pH7逐渐滴加酸液至pH1，微胶囊平均粒径从40nm提高到70nm左右；之后滴加碱液将pH调节到pH7，粒径恢复到40nm左右；再滴加酸液至pH1，粒径又增加到70nm左右，依此在pH7和pH1之间进行了10次循环处理，微胶囊平均粒径始终在40nm和70nm左右循环，说明pH响应溶胀-收缩的转变是可逆的，且具有较好的耐疲劳性。
如图6为将实施例4制备的超疏水-亲水可逆转化材料分别经pH＝1、pH＝7溶液处理10次。每次将溶液pH调制中性时，基材表面与水的接触角约为150度，具有超疏水性能；每次滴加酸液至pH＝1，基材表面与水的接触角在120s内都会降至0度，具有亲水性能。这些行为表明基材表面经pH响应型材料处理后，润湿性能发生了巨大变化，在不同酸碱性溶液的刺激下，材料表面可以在超疏水、亲水性能之间进行可调性转换。
图7为未处理棉织物的表面扫描电镜照片，可以看出棉织物表面的纤维很光滑，没有任何物质和粗糙结构。
图8为实施例5制备的超疏水-亲水可逆转化棉织物的表面扫描电镜照片，从图8可以看出，经pH响应性微胶囊分散液处理的棉织物，其纤维表面拥有一层较薄的、微纳米的粗糙突起结构，且纤维的外轮廓清晰，没有与其他纤维发生粘连，说明该pH响应性微胶囊处理的棉织物的纤维表观性能没有受到影响。
采用下述实验验证发明效果：
不同单体比例对接触角的影响
仅步骤1采用的甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的单体比例不同，其他反应参数与实施例1相同，材料为纸张，与水的接触角如表1所示：
表1：不同单体比例对接触角的影响
nDEAEMA:nst:nGMA 0.5:0.5:3 0.75:1:1 0.5:2:3 1.5:1:1 2:1:1
与水的接触角(pH＝1) 10±1° 10±1° 20±5° 130±5° 130±2°
与水的接触角(pH＝7) 120±1° 150±5° 150±5° 150±5° 150±5°
与水的接触角(pH＝13) 130±1° 150±5° 145±5° 145±5° 150±5°
由表1可知，使用甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的单体比例为0.75:1:1时，由pH响应性微胶囊制备的pH响应性超疏水-亲水可逆转变纸张具有较好的疏水性能以及环境响应性能。
2、七氟丁酸使用量对接触角的影响
仅步骤二中加入的七氟丁酸的摩尔量不同，其他反应参数与实施例2相同，材料为纸张，与水的接触角如表2所示
表2：不同七氟丁酸量对接触角的影响
nPDFMA(mol) 0.02 0.04 0.06 0.08
与水的接触角(pH＝1) 10±1° 10±1° 10±1° 110±5°
与水的接触角(pH＝7) 10±1° 120±1° 150±5° 150±5°
与水的接触角(pH＝13) 10±1° 110±1° 150±5° 150±5°
由表2可知，使用七氟丁酸的量为0.06mol时，由pH响应性微胶囊制备的pH响应性超疏水-亲水可逆转变纸张具有较好的疏水性能以及pH响应性能。
3、不同微胶囊分散液浓度对接触角的影响
仅仅在于微胶囊溶液浓度不同，其它反应条件和参数与实施例3相同，材料是棉布，结果见表3：
表3：不同微胶囊浓度对接触角的影响
由表3可知，30mg环境响应性微胶囊溶解在100mL去离子水中，所得溶液浸泡棉布，棉布表面与水的接触角达到162±2°，微胶囊含量继续增加还会使得接触角变小。

Claims (3)

1.一种pH响应超疏水-亲水可逆转化材料表面的制备方法，其特征在于：具体包括如下步骤：
步骤1，以甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯为反应单体，偶氮二异丁腈为热引发剂，二乙烯基苯为交联剂，十六烷为稳定剂，充分混合均匀后作为油相，逐滴滴入水相中，乳化10～20min，然后将乳化后的溶液移入三口烧瓶中，在400～800rmin-1机械搅拌下反应8～10h，反应温度为60～100℃；
所述步骤1中甲基丙烯酸二乙氨基乙酯、苯乙烯、甲基丙烯酸缩水甘油酯的物质的摩尔比为0.75:1：1；
步骤1中偶氮二异丁腈和二乙烯基苯用量分别为反应单体质量的2％～5％和3％～8％，十六烷的用量为反应单体质量的30％～70％；
所述步骤1中的水相为以十二烷基苯磺酸钠为表面活性剂的去离子水；
步骤2，在步骤1所得体系中，滴加一滴三乙胺，然后加入七氟丁酸，搅拌8～10h，经离心、清洗后，干燥，即得到pH响应性微胶囊；
步骤3，将步骤2制备的pH响应性微胶囊超声分散于去离子水中，得到微胶囊溶液，然后用微胶囊溶液处理材料表面，处理后的材料表面经铝片浸轧后，置于烘箱中干燥，即得。
2.根据权利要求1所述的一种pH响应超疏水-亲水可逆转化材料表面的制备方法，其特征在于：所述步骤2中，七氟丁酸与步骤1中甲基丙烯酸缩水甘油酯的摩尔比为1.0～3.0：7.0～9.0；
步骤2中，干燥的温度为60～100℃；干燥时间为20～24h。
3.根据权利要求1所述的一种pH响应超疏水-亲水可逆转化材料表面的制备方法，其特征在于：所述步骤3中处理的材料包括棉布、木材、纸张、陶瓷、水泥、混凝土。
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