CN105802432B - 一种水性环氧防腐防锈漆及其制备方法 - Google Patents
一种水性环氧防腐防锈漆及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种水性环氧防腐防锈漆，以水性环氧乳液为基体，添加多种颜填料及助剂，包括水性环氧乳液、水性磷酸锌、改性三聚磷酸铝、金红石型钛白粉、成膜助剂、水性消泡剂、增稠剂SN‑636、润湿剂PE‑100、杀菌防腐剂、抗闪锈剂、分散剂5040、流平剂和去离子水。本发明的水性环氧防腐防锈漆不仅绿色环保、原材料价格低廉，而且制备过程简单；同时，耐盐水性能优良、附着力强和抗闪锈效果良好。
Description
技术领域
本发明属于防锈漆技术领域，特别是涉及一种水性环氧防腐防锈漆及其制备方法。
背景技术
传统溶剂型防锈涂料主要是以有机溶剂为分散介质。因此，在制备及使用过程中会挥发大量的有机化合物即Volatile Organic Composition(简称VOC)。VOC的挥发对生活环境以及人类的身体健康都是潜在的威胁。另一方面，原油的价格出现大幅度上涨，导致各地油性涂料的价格被迫不断提升，其原材料的成本也不断增加。因此，各国学者以及研究人员将研究重心逐渐由油性涂料转向水性涂料。
水性涂料是以水作为溶剂(或者作为分散介质)的涂料，具有无毒、无味、价格低廉、原材料资源丰富等特点，可以大大减少原材料成本，以及对大气造成的污染；并且可极大地提高涂料在储存、运输和施工过程中的安全性。
目前，国外一些公司在聚合物乳液合成上，采用无表面活性剂的自乳化技术，即用其它特定的聚合技术使多种不同单体组成的聚合物呈层状结构存在于同一胶粒中，从而达到调节玻璃化温度(Tg)，保证产品性能的目的，使产品既具有一定的硬度、耐污染性，又使施工易于进行。另外，通过定向聚合、辐射聚合、互穿网络聚合等制得聚合物乳液来改进涂料的性能和功能。
而国内水性防腐涂料的发展方向主要为以下三个方面：(1)水性富锌底漆：无机富锌底漆和环氧富锌底漆是长效的底漆之一，但其均为溶剂型涂料。以高模数的改性硅酸盐为基料的水性无机富锌底漆已是经实践考验的高性能防腐防污涂料，具有较大的发展潜力；(2)研发有机改性的无机防腐材料：近年来，国外应用有机乳液改性混凝土，以改进其强度、耐介质性，广泛应用于工业地坪的涂装，其中环氧水乳液发展最快。近10年来，已开始应用于我国的防腐工程领域中，但研发工作不系统，未形成系列产品。(3)研发钢结构用水性防腐底漆和面漆：水性防腐底漆必须解决基材的“闪蚀”和耐水性差的难题；而对于面漆，主要是在保证其具有优良的保护性能的前提下，提高其装饰性和耐久性；同时，水性涂料对施工环境的依赖性更强，如何保证在高湿、低温及封闭环境下获得性能良好的涂层是水性防腐涂料未来需着重解决的问题。
因此，开发一种耐盐水性能好、附着力强、抗腐蚀能力强的水性涂料迫在眉睫。目前，据报道已知，磷酸锌是一种性能优良的新型无毒防锈颜料，被广泛应用于涂料工业制备各类防锈涂料及水剂涂料。磷酸与金属基底反应，生成不溶的三代磷酸盐，三代磷酸盐沉积在腐蚀位置上，把腐蚀区封住形成了隔离层，从而阻止了腐蚀的进一步发生。三聚磷酸铝是聚磷酸盐防锈颜料的典型代表，其可用于制备多种无污染、节能的无机高分子防锈、防腐蚀、耐高温的颜料和涂料。三聚磷酸根离子P3010 5-具有很好的化学活性，能与多种金属离子形成络合物，对二价、三价铁离子具有很强的络合能力，形成三聚磷酸铁保护膜。此外，三聚磷酸根P3010 5-发生解聚反应生成从焦磷酸根离子到正磷酸根离子，这些离子进一步在金属表面形成坚韧的钝化膜。经复合改性的磷酸系颜料能提高传统磷酸盐防锈颜料的防锈性能，产品耐盐水性变好。但是将水性磷酸锌与三聚磷酸铝复合使用作为防腐填料确鲜见报道。
发明内容
本发明要解决的技术问题是提供一种制备过程简单、价格低廉、绿色环保、且效果优良的改性环氧防锈漆及其制备方法。
本发明通过如下技术方案解决上述技术问题：
一种水性环氧防腐防锈漆，以水性环氧乳液为基础，添加多种颜填料及助剂，其各组分及其质量百分比如下：
| 组分 | 质量百分比含量 |
| 水性环氧乳液 | 34.5％～54.0％ |
| 水性磷酸锌 | 6.0％～9.0％ |
| 改性三聚磷酸铝 | 3.0％～4.5％ |
| 金红石型钛白粉 | 10.0％～13.0％ |
| 成膜助剂 | 2.0％～3.0％ |
| 水性消泡剂 | 1.0％～2.0％ |
| 增稠剂SN-636 | 2.0％～3.5％ |
| 润湿剂PE-100 | 2.0％～3.0％ |
| 杀菌防腐剂 | 2.0％～4.0％ |
| 抗闪锈剂 | 2.0％～3.5％ |
| 分散剂5040 | 1.5％～2.0％ |
| 流平剂 | 2.5％～4.0％ |
| 去离子水 | 12.0％～14.0％ |
以上各组分的质量百分比总和为100％。
所述的水性环氧防腐防锈漆的制备方法，按所述质量百分比含量，先将改性三聚磷酸铝与水性磷酸锌混合，再加入金红石型钛白粉，研磨混匀得到混合颜填料；再将分散剂5040、润湿剂PE-100、杀菌防腐剂、50％的水性消泡剂依次加入到去离子水中，搅拌0.5小时，搅拌速度1500r/min，再加入上述改性三聚磷酸铝、水性磷酸锌与金红石型钛白粉混合颜填料，再搅拌1小时，搅拌速度2000r/min；再依次加入水性环氧乳液、剩余50％水性消泡剂、成膜助剂、流平剂、增稠剂SN-636和抗闪锈剂，搅拌3小时，混合均匀，即得所述水性环氧防腐防锈漆。
所述混合颜填料为改性三聚磷酸铝、水性磷酸锌与金红石型钛白粉混合颜填料，三者的质量比为1∶2∶3。
所述水性环氧乳液的制备方法为：将乳化剂op-10、十二烷基硫酸钠、碳酸氢铵以质量比4∶2∶1混合，所得混合物溶于去离子水制得浓度为21g/L的混合乳化液100mL；将环氧树脂、丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯和偶联剂以质量比6∶1.5∶1∶3∶1.5混合，得到浓度为1g/L环氧混合液100mL；配制质量浓度为20g/L的过硫酸铵溶液作为引发剂；取混合乳化液与环氧混合液各30mL混合得到混合液，将所得混合液加热至温度70℃～80℃，待反应出现蓝相，加入引发剂10mL，再分别通过恒压分液漏斗缓慢地滴加余下的混合乳化液和环氧混合液；滴加完成后，再加入引发剂10mL，保温1-2小时，再降温至30℃，反应2～3小时，滤液过200目筛，得水性环氧乳液。
所述偶联剂是KH-570。
本发明水性环氧防腐防锈漆的优点在于：
其绿色环保、原材料价格低廉，制备过程简单；同时，耐盐水性能优良、附着力强和抗闪锈效果良好。磷酸锌中的磷酸与金属基底反应，生成不溶的三代磷酸盐，三代磷酸盐沉积在腐蚀点上，把腐蚀区封住形成了隔离层，从而阻止了腐蚀的进一步发生。磷酸锌与基料中的羧基和羟基发生反应，生成络合物；而这种络合物能与腐蚀产物发生反应，在底材表面上形成紧密的保护膜，从而保护金属基底，不被腐蚀。三聚磷酸铝是聚磷酸盐防锈颜料的典型代表，其可用于制备多种无污染、节能的无机高分子防锈、防腐蚀、耐高温的颜料和涂料。三聚磷酸铝中的三聚磷酸根离子具有很好的化学活性，能与多种金属离子形成络合物，对二价、三价铁离子具有很强的络合能力，形成三聚磷酸铁保护膜。此外，三聚磷酸根P3010 5-发生解聚反应生成从焦磷酸根离子到正磷酸根离子，这些离子进一步在金属表面形成坚韧的钝化膜。改性三聚磷酸铝具有防锈力强、附着力高、白色、无毒等特点，原料易得，价格适宜，是铅、铬防锈颜料的替代品，因此受到各方面的注视。两者复合使用加上防腐填料金红石型钛白粉的共同作用可以使得防腐效果更佳显著。实际试验中也证实三者的复合使用比任一种单一使用的效果都要好。
具体实施方式
实施例1：
一种水性环氧防腐防锈漆，以水性环氧乳液为基础，添加多种颜填料及助剂，其各组分及其质量百分比如下：
| 组分 | 质量百分比含量 |
| 水性环氧乳液 | 54.0％ |
| 水性磷酸锌 | 6.0％ |
| 改性三聚磷酸铝 | 3.0％ |
| 金红石型钛白粉 | 10.0％ |
| 成膜助剂 | 2.0％ |
| 水性消泡剂 | 1.0％ |
| 增稠剂SN-636 | 2.0％ |
| 润湿剂PE-100 | 2.0％ |
| 杀菌防腐剂 | 2.0％ |
| 抗闪锈剂 | 2.0％ |
| 分散剂5040 | 1.5％ |
| 流平剂 | 2.5％ |
| 去离子水 | 12.0％ |
所述的水性环氧防腐防锈漆的制备方法，按所述质量百分比含量，先将改性三聚磷酸铝与水性磷酸锌混合，再加入金红石型钛白粉，研磨混匀得到混合颜填料；再将分散剂5040、润湿剂PE-100、杀菌防腐剂、50％的水性消泡剂依次加入到去离子水中，搅拌0.5小时，搅拌速度1500r/min，再加入上述改性三聚磷酸铝、水性磷酸锌与金红石型钛白粉混合颜填料，再搅拌1小时，搅拌速度2000r/min；再依次加入水性环氧乳液、剩余50％水性消泡剂、成膜助剂、流平剂、增稠剂SN-636和抗闪锈剂，搅拌3小时，混合均匀，即得所述水性环氧防腐防锈漆。
所述水性环氧乳液的制备方法为：将乳化剂op-10、十二烷基硫酸钠、碳酸氢铵以质量比4∶2∶1混合，所得混合物溶于去离子水制得浓度为21g/L的混合乳化液100mL；将环氧树脂、丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯和偶联剂KH-570以质量比6∶1.5∶1∶3∶1.5混合，得到浓度为1g/L环氧混合液100mL；配制质量浓度为20g/L的过硫酸铵溶液作为引发剂；取混合乳化液与环氧混合液各30mL混合得到混合液，将所得混合液加热至温度70℃～80℃，待反应出现蓝相，加入引发剂10mL，再分别通过恒压分液漏斗缓慢地滴加余下的混合乳化液和环氧混合液；滴加完成后，再加入引发剂10mL，保温1-2小时，再降温至30℃，反应2～3小时，滤液过200目筛，得水性环氧乳液。
实施例2：
一种水性环氧防腐防锈漆，以水性环氧乳液为基础，添加多种颜填料及助剂，其各组分及其质量百分比如下：
| 组分 | 质量百分比含量 |
| 水性环氧乳液 | 47.0％ |
| 水性磷酸锌 | 8.2％ |
| 改性三聚磷酸铝 | 4.1％ |
| 金红石型钛白粉 | 11.5％ |
| 成膜助剂 | 2.4％ |
| 水性消泡剂 | 1.0％ |
| 增稠剂SN-636 | 2.3％ |
| 润湿剂PE-100 | 2.2％ |
| 杀菌防腐剂 | 2.2％ |
| 抗闪锈剂 | 2.1％ |
| 分散剂5040 | 1.6％ |
| 流平剂 | 3.2％ |
| 去离子水 | 12.2％ |
所述的水性环氧防腐防锈漆的制备方法和水性环氧乳液的制备方法同实施例1。
实施例3：
一种水性环氧防腐防锈漆，以水性环氧乳液为基础，添加多种颜填料及助剂，其各组分及其质量百分比如下：
所述的水性环氧防腐防锈漆的制备方法和水性环氧乳液的制备方法同实施例1。
实施例4：
一种水性环氧防腐防锈漆，以水性环氧乳液为基础，添加多种颜填料及助剂，其各组分及其质量百分比如下：
| 组分 | 质量百分比含量 |
| 水性环氧乳液 | 40.0％ |
| 水性磷酸锌 | 7.7％ |
| 改性三聚磷酸铝 | 3.2％ |
| 金红石型钛白粉 | 12.8％ |
| 成膜助剂 | 2.9％ |
| 水性消泡剂 | 2.0％ |
| 增稠剂SN-636 | 3.3％ |
| 润湿剂PE-100 | 3.0％ |
| 杀菌防腐剂 | 3.7％ |
| 抗闪锈剂 | 3.3％ |
| 分散剂5040 | 2.0％ |
| 流平剂 | 4.0％ |
| 去离子水 | 12.1％ |
所述的水性环氧防腐防锈漆的制备方法和水性环氧乳液的制备方法同实施例1。
实施例5：
一种水性环氧防腐防锈漆，以水性环氧乳液为基础，添加多种颜填料及助剂，其各组分及其质量百分比如下：
| 组分 | 质量百分比含量 |
| 水性环氧乳液 | 34.5％ |
| 水性磷酸锌 | 9.0％ |
| 改性三聚磷酸铝 | 4.5％ |
| 金红石型钛白粉 | 13.0％ |
| 成膜助剂 | 3.0％ |
| 水性消泡剂 | 2.0％ |
| 增稠剂SN-636 | 3.5％ |
| 润湿剂PE-100 | 3.0％ |
| 杀菌防腐剂 | 4.0％ |
| 抗闪锈剂 | 3.5％ |
| 分散剂5040 | 2.0％ |
| 流平剂 | 4.0％ |
| 去离子水 | 14.0％ |
所述的水性环氧防腐防锈漆的制备方法和水性环氧乳液的制备方法同实施例1。
5个实施例产品主要性能指标：
| 耐盐水性/h≥ | 450 |
| 耐水性/d≥ | 22 |
| 硬度/H | 2-3 |
| 耐闪蚀 | 无 |
| 附着力/级 | 1 |
| 耐冲击性/cm | 50 |
Claims (1)
1.一种水性环氧防腐防锈漆，其特征在于，以水性环氧乳液为基体，添加多种颜填料及助剂，其各组分及其质量百分比如下：
以上各组分的质量百分比总和为100%；
按所述质量百分比含量，先将改性三聚磷酸铝与水性磷酸锌混合，再加入金红石型钛白粉，研磨混匀得到混合颜填料；再将分散剂5040、润湿剂PE-100、杀菌防腐剂和水性消泡剂质量百分比含量的50%依次加入到去离子水中，搅拌0.5小时，搅拌速度1500r/min，再加入上述所得的混合颜填料，再搅拌1小时，搅拌速度2000 r/min；再依次加入水性环氧乳液、剩余水性消泡剂、成膜助剂、流平剂、增稠剂SN-636和抗闪锈剂，搅拌3小时，混合均匀，即得所述水性环氧防腐防锈漆；
所述混合颜填料为改性三聚磷酸铝、水性磷酸锌与金红石型钛白粉混合颜填料，三者的质量比为1∶2∶3；
所述水性环氧乳液的制备方法为：将乳化剂op-10、十二烷基硫酸钠、碳酸氢铵以质量比4∶2∶1混合，所得混合物溶于去离子水制得浓度为21g/L的混合乳化液100mL；将环氧树脂、丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯和偶联剂以质量比6∶1.5∶1∶3∶1.5混合，得到浓度为1g/L环氧混合液100mL；配制质量浓度为20g/L的过硫酸铵溶液作为引发剂；取混合乳化液与环氧混合液各30mL混合得到混合液，将所得混合液加热至温度70℃～80℃，待反应出现蓝相，加入引发剂10 mL，再分别通过恒压分液漏斗缓慢地滴加余下的混合乳化液和环氧混合液；滴加完成后，再加入引发剂10 mL，保温1-2小时，再降温至30℃，反应2～3小时，滤液过200目筛，得水性环氧乳液；
所述偶联剂是KH-570。
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