CN105860723B - 环保型水性涂料及其制备方法 - Google Patents
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Abstract
本发明提供一种环保型水性涂料及其制备方法。该水性涂料的主要原料为水溶性丙烯酸酯聚合物15～30wt％、改性乳化剂1～5wt％、磷酸锌12～26wt％、成膜剂3～10wt％、填料6～10wt％、三乙醇胺0.1～3wt％、羟基乙叉二膦酸2～6wt％和水18～30wt％；所述的水溶性丙烯酸酯聚合物由丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和苯乙烯按质量比14:3:1:2聚合得到；所述的改性乳化剂由聚乙烯吡咯烷酮和聚乙烯醚进行复配，其质量比为1:5。本发明所得水性涂料无毒无污染，绿色环保；附着力0级，不易脱落，耐腐蚀性强，具有良好的遮盖力，综合性能好；本发明生产工艺简单，使用范围广范，成本低，有利于工业化生产。
Description
技术领域
本发明属于涂料领域，具体涉及一种环保型水性涂料及该涂料的制备方法。
背景技术
水性涂料是一种以水为稀释剂、不含有机溶剂的涂料，具有无毒、无刺激气味、对人体无害不污染环境等特点，近年来受到了人们的普遍关注，可用于金属、塑料、玻璃等多种材质上。
目前国内的水性涂料多数存在涂膜软、不耐磨、附着力差等缺陷，虽然现有技术中，通常通过加入无机填料对其进行改性，但是无机填料加入又造成粉化脱落等现象。
水性涂料存在以上缺陷的主要原因是由于其以水作为溶剂或分散介质，由于水的特性与有机溶剂有很大不同，如表面张力大，汽化温度高，难润湿、不易溶等，因此其存在附着力差，涂料喷涂时不易挥发，受湿度的影响大，很难控制，耐腐蚀性差等问题。所以，工业用水性涂料在使用过程中往往受到限制。工业应用的条件多数情况比较苛刻，一般要求该涂料具有一定的耐高温、耐腐蚀、附着力等优异性能，但是，目前国内的水性涂料还不能完全满足以上标准。
发明内容
本发明为解决现有技术中，水性涂料附着力差、易脱落、耐腐蚀性不好等问题，提供了一种环保型水性涂料。
为了达到上述目的，本发明是这样实现的：水溶性丙烯酸酯聚合物15～30wt％、改性乳化剂1～5wt％、磷酸锌12～26wt％、成膜剂3～10wt％、填料6～10wt％、三乙醇胺0.1～3wt％、羟基乙叉二膦酸2～6wt％和水18～30wt％。
所述的水溶性丙烯酸酯聚合物由丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和苯乙烯按质量比14:3:1:2反应得到。
所述的改性乳化剂由聚乙烯吡咯烷酮和聚乙烯醚进行复配，其质量比为1:5。
进一步的，所述水性涂料主要原料为水溶性丙烯酸酯聚合物20～28wt％、改性乳化剂2～4wt％、磷酸锌13.5～25wt％、成膜剂4～8.5wt％、填料6.5～9wt％、三乙醇胺0.5～2.5wt％、羟基乙叉二膦酸3～5wt％和水20～25wt％。
所述的水溶性丙烯酸酯聚合物的制备方法如下：按比例称取各原料，向乙二醇中依次加入丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和苯乙烯的混合单体再加入引发剂偶氮二异丁腈，在80～85℃下搅拌回流，反应3～4小时，保温2～3小时，取样分析转化率达99％以上后停止反应，得水溶性丙烯酸酯聚合物。
进一步的，所述的成膜剂为丙二醇甲醚醋酸酯。
进一步的，所述的填料为纳米二氧化钛、纳米二氧化硅或纳米碳酸钙中至少一种。
本发明另一个目的是请求保护上述环保型水性涂料的制备方法，包括以下步骤：按比例称取各原料，将磷酸锌12～26wt％、羟基乙叉二膦酸2～6wt％和填料6～10wt％加入水中，搅拌均匀后，加入三乙醇胺调节pH；加入水溶性丙烯酸酯聚合物15～30wt％和改性乳化剂1～5wt％，边加入边搅拌，最后加入成膜剂3～10wt％反应2～3小时即得环保型水性涂料。
进一步的，所述pH范围为7～8。
水溶性丙烯酸酯一般是作为粘结剂来使用，发明人发现将其利用到水性涂料中，该水溶性丙烯酸树脂与附着基能够形成良好的附着力，但是现有技术中水溶性丙烯酸酯成本较高，甚至高于普通的溶液型聚丙烯酸酯产品，本发明制备所得的水溶性丙烯酸酯聚合物原料成本低。本发明所使用的改性乳化剂侧端带有亲水性基团，使乳化剂具有良好的耐水性。磷酸锌作为分散剂，可以减少完成分散过程所需的时间，使颜料分散体系稳定，有效避免填料絮凝、结块，羟基乙叉二膦酸的加入与剩余的锌离子形成稳定的螯合物，减少沉渣的产生，提高涂料的性能。
与现有技术相比，本发明具有如下优点：本发明所得水性涂料无毒无污染，绿色环保；附着力0级，不易脱落，耐腐蚀性强，抗冲击强度高，具有良好的遮盖力，综合性能好；本发明生产工艺简单，使用范围广范，成本低，有利于工业化生产。
具体实施方式
下面通过具体实施例对本发明进行说明，但本发明并不局限于此。下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
制备水溶性丙烯酸酯聚合物：分别称取21g丙烯酸丁酯、4.5g丙烯酸羟乙酯、1.5g丙烯酸和3g苯乙烯，向乙二醇中依次加入丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和苯乙烯的混合单体再加入引发剂偶氮二异丁腈，在80～85℃下搅拌回流，反应3～4小时，保温2～3小时，取样分析转化率达99％以上后停止反应。
所述的改性乳化剂由聚乙烯吡咯烷酮和聚乙烯醚进行复配，其质量比为1:5。
实施例1
| 水溶性丙烯酸酯聚合物 | 40.3g |
| 改性乳化剂 | 6.4g |
| 磷酸锌 | 25g |
| 丙二醇甲醚醋酸酯 | 20g |
| 纳米二氧化钛 | 16g |
| 三乙醇胺 | 4g |
| 羟基乙叉二膦酸 | 10g |
| 水 | 60g |
制备方法：
将磷酸锌、羟基乙叉二膦酸和纳米二氧化钛加入水中，室温搅拌均匀后，测定溶液pH值，缓慢滴加三乙醇胺调节pH为7.5；向上述混合液中加入水溶性丙烯酸酯聚合物和改性乳化剂，边加入边搅拌，最后加入丙二醇甲醚醋酸酯反应2～3小时后即得环保型水性涂料。
实施例2
| 水溶性丙烯酸酯聚合物 | 31.7g |
| 改性乳化剂 | 4.6g |
| 磷酸锌 | 25.5g |
| 丙二醇甲醚醋酸酯 | 10g |
| 纳米二氧化硅 | 15g |
| 三乙醇胺 | 0.5g |
| 羟基乙叉二膦酸 | 6g |
| 水 | 40g |
制备方法：
将磷酸锌、羟基乙叉二膦酸和纳米二氧化钛加入水中，室温搅拌均匀后，测定溶液pH值，缓慢滴加三乙醇胺调节pH为8；向上述混合液中加入水溶性丙烯酸酯聚合物和改性乳化剂，边加入边搅拌，最后加入丙二醇甲醚醋酸酯反应2～3小时后即得环保型水性涂料。
实施例3
| 水溶性丙烯酸酯聚合物 | 42.5g |
| 改性乳化剂 | 6.6g |
| 磷酸锌 | 30g |
| 丙二醇甲醚醋酸酯 | 10g |
| 纳米碳酸钙 | 15g |
| 三乙醇胺 | 5.5g |
| 羟基乙叉二膦酸 | 10g |
| 水 | 60g |
制备方法：
将磷酸锌、羟基乙叉二膦酸和纳米二氧化钛加入水中，室温搅拌均匀后，测定溶液pH值，缓慢滴加三乙醇胺调节pH为7.5；向上述混合液中加入水溶性丙烯酸酯聚合物和改性乳化剂，边加入边搅拌，最后加入丙二醇甲醚醋酸酯反应2～3小时后即得环保型水性涂料。
实施例4
| 水溶性丙烯酸酯聚合物 | 45g |
| 改性乳化剂 | 10g |
| 磷酸锌 | 30g |
| 丙二醇甲醚醋酸酯 | 20g |
| 纳米二氧化钛 | 9g |
| 纳米碳酸钙 | 6g |
| 三乙醇胺 | 6g |
| 羟基乙叉二膦酸 | 11g |
| 水 | 60g |
制备方法：
将磷酸锌、羟基乙叉二膦酸和纳米二氧化钛加入水中，室温搅拌均匀后，测定溶液pH值，缓慢滴加三乙醇胺调节pH为7；向上述混合液中加入水溶性丙烯酸酯聚合物和改性乳化剂，边加入边搅拌，最后加入丙二醇甲醚醋酸酯反应2～3小时后即得环保型水性涂料。
将实施例1～4所得水性涂料预涂金属试验块表面上，在室温下晾晒2-4小时即可成干膜，对膜进行主要性能测试，其中附着力按照GB/T9286-1998的规定标准进行检测，耐冲击性按照GB/T1732-1993的规定标准进行检测。将上述干膜进行耐酸、碱性试验，分别置于0.1mol/L的硫酸和氢氧化钠中，在15～25℃下，保持规定的时间，取出试样洗净、吹干，目视检查磷化表面是否出现锈蚀。具体实验数据请详见表1。
表1实施例1～4水性涂料性能测试结果
由以上实验结果表明，本发明制备的水性涂料具有良好的附着力和抗冲击性能，能够满足工业领域对于涂料耐酸性和耐碱性的要求，对环境无污染，绿色环保。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (3)
1.一种环保型水性涂料，其特征在于，其主要原料为水溶性丙烯酸酯聚合物20～28wt％、改性乳化剂2～4wt％、磷酸锌13.5～25wt％、丙二醇甲醚醋酸酯4～8.5wt％、填料6.5～9wt％、三乙醇胺0.5～2.5wt％、羟基乙叉二膦酸3～5wt％和水20～25wt％；
所述的水溶性丙烯酸酯聚合物由丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和苯乙烯按质量比14:3:1:2聚合得到；
所述的水溶性丙烯酸酯聚合物的制备方法如下：向乙二醇中依次加入丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和苯乙烯的混合单体再加入引发剂偶氮二异丁腈，在80～85℃下搅拌回流，反应3～4小时，保温2～3小时，取样分析转化率达99％以上后停止反应，得水溶性丙烯酸酯聚合物；
所述的改性乳化剂由聚乙烯吡咯烷酮和聚乙烯醚进行复配，其质量比为1:5；
所述的填料为纳米二氧化钛、纳米二氧化硅或纳米碳酸钙中至少一种。
2.一种如权利要求1所述的环保型水性涂料的制备方法，其特征在于，包括以下步骤：按比例称取各原料，将磷酸锌13.5～25wt％、羟基乙叉二膦酸3～5wt％和填料6.5～9wt％加入水中，搅拌均匀后，加入三乙醇胺0.5～2.5wt％调节pH；加入水溶性丙烯酸酯聚合物20～28wt％和改性乳化剂2～4wt％，边加入边搅拌，最后加入丙二醇甲醚醋酸酯4～8.5wt％反应2～3小时即得环保型水性涂料。
3.根据权利要求2所述的环保型水性涂料的制备方法，其特征在于，所述pH范围为7～8。
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