CN115181492B - 一种双重自修复水性聚氨酯防腐材料的制备方法 - Google Patents
一种双重自修复水性聚氨酯防腐材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种双重自修复水性聚氨酯防腐材料的制备方法，包括缓蚀剂的制备：铈改性埃洛石纳米管、植酸修饰的铈改性埃洛石纳米管，含二硒键的水性聚氨酯的制备，双重自修复水性聚氨酯防腐材料的制备。本发明的双重自修复水性聚氨酯防腐材料中缓蚀剂植酸和铈离子可以与腐蚀产物反应生成不溶物修复腐蚀区域，埃洛石纳米管起到物理阻隔作用，阻挡腐蚀介质的渗透，使涂料具有较好的耐水性和防腐性能；含二硒键的水性聚氨酯成膜物对物理损伤具有自我修复效果，且制备方法简单、环保，在防腐材料领域具有较大的应用前景。
Description
技术领域
本发明涉及防腐材料技术领域，具体而言，涉及一种双重自修复氨酯防腐材料的制备方法。
背景技术
据统计，每年金属材料因腐蚀直接或者间接造成的经济损失远远高于地震、洪灾和火灾等自然灾害造成经济损失总和，约占国民经济生产总值(GDP)的4％。表面涂层是最常用且有效的防腐技术，其中溶剂型涂层因含有大量有机溶剂，具有毒性和污染性，使其应用受到限制；水性涂料具有无毒无污染、节能等优点，但其耐水性、热稳定性和耐腐蚀性普遍较差。
目前，开展了许多关于提高水性聚氨酯涂料防腐性能的研究，并取得了一定的研究成果。专利申请号CN202110966530.1中提供自修复型水性聚氨酯防腐材料及其制备方法。专利申请号CN202111135854.7中提供一种氟改性室温自交联水性聚氨酯防腐材料及其制备方法。专利申请号202010696772.9中提供了一种水性氟碳改性丙烯酸聚氨酯涂料。虽然在一定程度上提高了涂层的耐腐蚀性，但在使用过程中难免会出现一些细小的肉眼难看的微裂纹，微裂纹的扩展会影响涂层的表面结构，降低保护性能。
在涂料领域，自修复技术应用广泛，如本体材料中具有可你共价键等化学结构，还可以加入包覆修复剂的载体等，不仅能实现材料的自愈合，又能根据需求给予更多功能性，从而增加涂料的应用范围。但是仅从本体材料进行设计改性，仅能在特殊环境改善裂纹等物理损伤，防腐性能没有明显的提高。
发明内容
针对上述现有技术的缺点与不足，本发明的首要目的是提供一种双重自修复水性聚氨酯防腐材料。
本发明的另一目的在于提供上述双重自修复水性聚氨酯防腐材料的制备方法。
本发明的再一目的在于提供上述双重自修复水性聚氨酯防腐材料在防腐领域中的应用。
本发明的目的通过下述方案实现：
一种双重自修复水性聚氨酯防腐材料的制备方法，包括如下步骤：
1)制备铈改性埃洛石纳米管：将埃洛石纳米管加入到去离子水中，室温搅拌得到悬浮液，加入六水硝酸铈(Ce(NO3)3·6H2O)，加热搅拌，反应物经过离心、干燥、研磨，得到铈改性埃洛石纳米管；
2)制备植酸修饰的铈改性埃洛石纳米管：将步骤1)中所得的铈改性埃洛石纳米管加入到去离子水中，室温搅拌得到悬浮液，加入植酸并调节悬浮液pH，室温继续搅拌反应，反应物经过离心、干燥、研磨，得到植酸修饰的铈改性埃洛石纳米管；
3)制备含二硒键的水性聚氨酯：称取多元醇、多元异氰酸酯、催化剂、二羟甲基丙酸(DMPA)，升温搅拌反应，加入1,4-丁二醇(BDO)和2-羟乙基二硒化物(HEDS)继续反应，降温加入三乙胺，将去离子水中缓慢加入并高速搅拌，乳化后得到含二硒键的水性聚氨酯；
4)制备双重自修复水性聚氨酯防腐材料：将步骤2)所得的植酸修饰的铈改性埃洛石纳米管分散在去离子水中，缓慢加入步骤3)所得的含二硒键的水性聚氨酯，均匀搅拌后得到双重自修复的水性聚氨酯防腐材料。
具体来说，步骤2)中所述悬浮液pH为8.0～8.5。
具体来说，步骤3)中所述多元醇为分子量为1000、2000的聚丙二醇(PPG)、聚四氢呋喃醚二醇、聚碳酸酯二醇、聚酯二元醇和分子量为3000的聚醚三元醇中的一种或多种混合物。
具体来说，步骤3)中所述二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI)中的一种或多种混合物。
具体来说，步骤3)中所述催化剂为二月桂酸二丁基锡(DBTDL)、有机铋、有机锌、N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、N,N,N',N'-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺中的一种或多种。
进一步来说，步骤3)中-NCO和-OH基团的摩尔比为1.2:1。
进一步来说，步骤3)中HEDS占HEDS和BDO总摩尔量的比重为30％-100％。
进一步来说，步骤4)中植酸修饰的铈改性埃洛石纳米管占水性聚氨酯树脂质量的1-5％。
本发明实施例的技术方案至少具有如下优点和有益效果：
(1)本发明制备了植酸(TA)修饰的铈改性埃洛石纳米管。首先，铈离子作为缓蚀剂可以与阴极产生的OH-反应生成不溶物沉积在腐蚀部位，有效的阻断腐蚀进程。其次，埃洛石纳米管的物理阻隔作用使涂料的耐渗透性得到提高。因此，植酸的加入使填料在树脂中的分散性得到提高，同时它也是有效的阳极抑制剂，与铁离子反应形成难溶的TA-Fe3+络合物，修复腐蚀区域；
(2)本发明制备含二硒键的水性聚氨酯。二硒键的引入会增加本体材料的自修复性能，更好的应对微裂纹及物理损伤。
(3)本发明制备了双重自修复水性聚氨酯防腐材料。加入具有协同作用的缓蚀剂后，涂层的腐蚀防护性能得到明显提升。
说明书附图
图1为本发明划痕自修复试验显微镜观察图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。通常在此处附图中描述和示出的本发明实施例的组件可以以各种不同的配置来布置和设计。
实施例1：
本实施例涉及一种双重自修复水性聚氨酯防腐材料的制备方法，准备步骤如下：
1)制备铈改性埃洛石纳米管：称取1g埃洛石纳米管浸入100mL去离子水中，室温下搅拌2h，向悬浮液中加入5.5g六水硝酸铈(Ce(NO3)3·6H2O)，80℃下搅拌24小时，将悬浮液冷却至室温，离心5次(5000r，5min)，置于烘箱中，80℃干燥12～14h，研磨后得到铈改性埃洛石纳米管；
2)制备植酸修饰的铈改性埃洛石纳米管：称取步骤1)中所得的铈改性埃洛石纳米管0.5g，加入50mL去离子水，搅拌4h得到稳定的悬浮液，加入1g的植酸,用三羟甲基氨基甲烷将悬浮液pH调到8～8.5，室温下搅拌6h，将所得产物离心5次(5000r，5min)，置于烘箱中，80℃干燥12～14h，研磨后得到植酸修饰的铈改性埃洛石纳米管；
3)含二硒键的水性聚氨酯涂料和涂层的制备：预先将PPG 2000和DMPA放置于120℃真空干燥箱中除水。将15g PPG 2000、12.37g IPDI、1.5g DMPA和0.025g DBTDL倒入三口烧瓶中，在80℃下搅拌反应3h，将温度降到60℃后加入1.25g BDO和2.14g HEDS，搅拌反应4h，将温度降到35℃后加入1.13g三乙胺，反应0.5h。安装好搅拌机，称取20g所制备的聚氨酯倒入500mL烧杯中，缓慢向其中加入46g去离子水并高速搅拌(转速为1000r/min，时间为45min)，乳化后得到含二硒键的水性聚氨酯。4)双重自修复水性聚氨酯防腐材料的制备：称取0.2g步骤2)制得的植酸修饰的铈改性埃洛石纳米管，加入步骤3)制备的含二硒键的水性聚氨酯中，进行充分搅拌得到稳定的悬浮液。将涂料均匀涂布在Q235钢片表面，依次放置于室温2d、50℃24h。
实施例2：
本实施例涉及一种植酸修饰的铈改性埃洛石纳米管水性聚氨酯防腐材料的制备方法，准备步骤如下：
1)制备铈改性埃洛石纳米管：称取1g Na-MMT浸入100mL去离子水中，室温下搅拌2h，向悬浮液中加入5.5g硝酸铈Ce(NO3)3·6H2O，80℃下搅拌24小时，将悬浮液冷却至室温，离心5次(5000r，5min)，置于烘箱中，80℃干燥12～14h，研磨后得到铈改性埃洛石纳米管；
2)制备植酸修饰的铈改性埃洛石纳米管：称取步骤1)中所得的铈改性埃洛石纳米管0.5g，加入50mL去离子水，搅拌4h得到稳定的悬浮液，加入1g的植酸,用三羟甲基氨基甲烷将悬浮液pH调到8～8.5，室温下搅拌6h，将所得产物离心5次(5000r，5min)，置于烘箱中，80℃干燥12～14h，研磨后得到植酸修饰的铈改性埃洛石纳米管；
3)含二硒键的水性聚氨酯涂料和涂层的制备：预先将PPG 2000和DMPA放置于120℃真空干燥箱中除水。将15g PPG 2000、12.37g IPDI、1.5g DMPA和0.025g DBTDL倒入三口烧瓶中，在80℃下搅拌反应3h，将温度降到60℃后加入4.28g HEDS，搅拌反应4h，将温度降到35℃后加入1.13g三乙胺，反应0.5h。安装好搅拌机，称取20g所制备的聚氨酯倒入500mL烧杯中，缓慢向其中加入46g去离子水并高速搅拌(转速为1000r/min，时间为45min)，乳化后得到含二硒键的水性聚氨酯；
4)双重自修复水性聚氨酯防腐材料的制备：称取1g步骤2)制得的植酸修饰的铈改性埃洛石纳米管，加入步骤3)制备的含二硒键的水性聚氨酯中，进行充分搅拌得到稳定的悬浮液。将涂料均匀涂布在Q235钢片表面，依次放置于室温2d、50℃24h。
对比例1：
不添加HEDS的水性聚氨酯防腐材料的制备。
预先将PPG 2000和DMPA放置于120℃真空干燥箱中除水。将15g PPG 2000、12.37gIPDI、1.5g DMPA和4滴DBTDL倒入三口烧瓶中，在80℃下搅拌反应3h，将温度降到60℃后加入2.5g BDO，搅拌反应4h，将温度降到35℃后加入1.13g三乙胺，反应0.5h。安装好搅拌机，称取20g所制备的聚氨酯倒入500mL烧杯中，缓慢向其中加入46g去离子水并高速搅拌(转速为1000r/min，时间为45min)，乳化后得到不含二硒键的水性聚氨酯。称取0.1g植酸修饰的铈改性埃洛石纳米管加入，进行充分搅拌得到稳定的悬浮液。将涂料均匀涂布在Q235钢片表面，依次放置于室温2d、50℃24h。
将本发明实施例1所得的双重自修复水性聚氨酯防腐材料与对比例1进行相同的划痕自修复试验，如图1所示，图1.(a1)、(a2)、(a3)分别为对比例修复0h、1h和8h的显微镜图；(b1)、(b2)、(b3)分别为实施例1例修复0h、1h和8h的显微镜图。从图1中可以看到实施例1所得防腐涂层应对裂纹的物理损伤能力明显强于对比例1。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (5)
1.一种双重自修复水性聚氨酯防腐材料的制备方法，其特征在于，包括如下步骤：
1)制备铈改性埃洛石纳米管：将埃洛石纳米管加入到去离子水中，室温搅拌得到悬浮液，加入六水硝酸铈(Ce(NO3)3·6H2O)，加热搅拌，反应物经过离心、干燥、研磨，得到铈改性埃洛石纳米管；
2)制备植酸修饰的铈改性埃洛石纳米管：将步骤1)中所得的铈改性埃洛石纳米管加入到去离子水中，室温搅拌得到悬浮液，加入植酸并调节悬浮液pH，pH调到8～8.5，室温继续搅拌反应，反应物经过离心、干燥、研磨，得到植酸修饰的铈改性埃洛石纳米管；
3)制备含二硒键的水性聚氨酯：称取多元醇、多元异氰酸酯、催化剂、二羟甲基丙酸(DMPA)，升温搅拌反应，加入1,4-丁二醇(BDO)和2-羟乙基二硒化物(HEDS)继续反应，降温加入三乙胺，将去离子水中缓慢加入并高速搅拌，乳化后得到含二硒键的水性聚氨酯；所述多元醇为分子量为1000、2000的聚丙二醇、聚四氢呋喃醚二醇、聚碳酸酯二醇、聚酯二元醇和分子量为3000的聚醚三元醇中的一种或多种混合物；所述多元异氰酸酯为二异氰酸酯，所述二异氰酸酯具体为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)和六亚甲基二异氰酸酯(HDI)中的一种或多种混合物；
4)制备双重自修复水性聚氨酯防腐材料：将步骤2)所得的植酸修饰的铈改性埃洛石纳米管分散在去离子水中，缓慢加入步骤3)所得的含二硒键的水性聚氨酯，均匀搅拌后得到双重自修复的水性聚氨酯防腐材料。
2.根据权利要求1所述的一种双重自修复水性聚氨酯防腐材料的制备方法，其特征在于，步骤3)中所述催化剂为二月桂酸二丁基锡(DBTDL)、有机铋、有机锌、N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、N,N,N',N'-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺中的一种或多种。
3.根据权利要求1所述的一种双重自修复水性聚氨酯防腐材料的制备方法，其特征在于，步骤3)中-NCO和-OH基团的摩尔比为1.2:1。
4.根据权利要求1所述的一种双重自修复水性聚氨酯防腐材料的制备方法，其特征在于，步骤3)中HEDS占HEDS和BDO总摩尔量的比重为30％-100％。
5.根据权利要求1所述的一种双重自修复水性聚氨酯防腐材料的制备方法，其特征在于，步骤4)中植酸修饰的铈改性埃洛石纳米管占水性聚氨酯树脂质量的1-5％。
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