CN105462444B - 一种水性防腐涂料及其制备方法 - Google Patents
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Abstract
一种水性防腐涂料及其制备方法，所述水性防腐涂料由木质素磺酸盐改性无机纳米填料、水性环氧树脂、水性固化剂、水制成。该制备方法根据木质素磺酸盐的化学特性，通过Mannich反应，在木质素磺酸盐上引入氨基，之后通过氢键作用将木质素磺酸盐接枝到纳米无机填料表面，得到的改性纳米无机填料与水性环氧树脂复合，制成水性防腐涂料。该制备方法引入木质素磺酸盐不仅有效降低了水的表面张力和界面张力，显著改善了纳米无机填料在水性环氧树脂涂料中易团聚、分散性差的问题，增强了涂料的阻隔性能和防腐性能；同时，改性木质素磺酸盐上的氨基基团有效促进环氧树脂的开环，增加了水性防腐涂料的交联点，从而进一步提高水性防腐涂料的防腐性能。
Description
技术领域
本发明涉及涂料技术领域，尤其涉及一种水性防腐涂料及其制备方法。
背景技术
随着科技的进步以及经济建设的发展，金属及合金被广泛应用于人们的生活生产中。然而，金属易受腐蚀性介质的侵蚀而遭到破坏，从而造成巨大的财产损失和安全隐患。因此，对金属采取防腐蚀措施是十分必要的。现如今，使用防腐涂料增强金属的防腐性能，成为一种既经济又有效的方法。
近年来，随着人们环保意识的增强，水性防腐涂料因具有VOC排放量小、快干等特点，越来越受到人们的重视。但是，传统的水性防腐涂料具有阻隔性能差的缺点，从而影响其防腐性能。因此，人们通常引入纳米无机粒子作为填料与水性防腐涂料复配来增强涂料的阻隔性能。然而，纳米无机粒子在涂料基体中易团聚、分散性差，在颗粒聚集处易产生应力开裂和防护缺陷，从而大大影响防腐涂料的防腐效率。
为了克服纳米无机填料在涂料基体中易团聚、分散性差的问题，本发明根据木质素磺酸盐的化学特性，通过Mannich反应在木质素上引入氨基，并通过氢键作用改性纳米无机填料，有效改善了纳米无机填料在水性涂料中易团聚、分散性差的问题，同时，氨基的引入有利于环氧树脂的开环，增加涂料的交联点，从而进一步增加了水性涂料的防腐性能。
发明内容
针对上述问题，本发明提供一种制备过程简单、防腐性能优良的水性防腐涂料及其制备方法。
为实现本发明的上述目的，本发明提供一种水性防腐涂料，由木质素磺酸盐改性无机纳米填料、水性环氧树脂、水性固化剂、水制成；所述木质素磺酸盐改性无机纳米填料由改性后木质素磺酸盐及纳米无机填料通过氢键结合制成。
本发明还提供一种水性防腐涂料的制备方法，包括以下步骤。
步骤1、取0.01～0.04mol的木质素磺酸盐、50～100ml蒸馏水放入洁净的带有冷凝管、搅拌器、温度计的三口瓶中，搅拌5～10min后加入0.01～0.04mol的脂肪族多胺，在室温下搅拌10～20min后，边搅拌边滴加33%～40%的甲醛溶液0.01～0.04mol，在40～60℃下搅拌反应1.5～2.5h，得改性木质素磺酸盐。
步骤2、取8～10g的纳米无机填料，超声分散在100～150ml蒸馏水中；称取4～8g改性木质素磺酸盐加入到上述体系中，在常温下搅拌20～24h，得木质素磺酸盐改性纳米无机填料。
步骤3、按质量份数取10～25份木质素磺酸盐改性纳米无机填料及25～50份水性固化剂，加入到50～100份水和100～200份水性环氧树脂的混合液中，在常温下搅拌0.5～1h，即得水性防腐涂料。
所述步骤1中木质素磺酸盐、脂肪族多胺、甲醛的摩尔比为1:1:1。
所述木质素磺酸盐为木质素磺酸钠或木质素磺酸钙。
所述脂肪族多胺为乙二胺、哌啶、二甲胺中的一种或几种。
所述纳米无机填料为纳米二氧化硅、纳米二氧化钛、介孔分子筛中的一种或几种。
所述介孔分子筛为MCM-41、SBA-15、MCM-48中的一种或几种。
所述水性固化剂为Aq419、H228B、W650。
与现有技术相比本发明的有益效果。
本发明提供的水性防腐涂料及其制备方法，根据木质素磺酸盐的化学特性，通过Mannich反应，在木质素磺酸盐上引入氨基，之后通过氢键作用将木质素磺酸盐接枝到纳米无机填料表面，得到的改性纳米无机填料与水性环氧树脂复合，制成水性防腐涂料。该制备方法引入木质素磺酸盐不仅有效降低了水的表面张力和界面张力，显著改善了纳米无机填料在水性环氧树脂涂料中易团聚、分散性差的问题，增强了涂料的阻隔性能和防腐性能；同时，改性木质素磺酸盐上的氨基基团有效促进环氧树脂的开环，增加了水性防腐涂料的交联点，从而进一步提高水性防腐涂料的防腐性能。
附图说明
图1为木质素磺酸盐改性纳米二氧化钛机理图。
具体实施方式
下面结合具体实施例进一步详细说明本发明。
本实施例提供一种水性防腐涂料，由木质素磺酸盐改性无机纳米填料、水性环氧树脂、水性固化剂、水制成；所述木质素磺酸盐改性无机纳米填料由改性后木质素磺酸盐及纳米二氧化钛通过氢键结合制成。
请参阅图1，本实施例还提供一种水性防腐涂料的制备方法，包括以下步骤。
步骤1、取0.01mol的木质素磺酸盐、100ml蒸馏水放入洁净的带有冷凝管、搅拌器、温度计的三口瓶中，搅拌5min后加入0.01mol的乙二胺，在室温下搅拌20min后，边搅拌边滴加33%的甲醛溶液0.01mol，在50℃下搅拌反应2h，得改性木质素磺酸盐。
所述木质素磺酸盐是一种由苯丙烷为骨架的疏水基团以及磺酸基和羧基等亲水基团组成的阴离子高分子化合物，具有良好的表面活性、粘合性等，具有很强的分散能力，适于将固体分散在水中。
步骤2、取10g的纳米二氧化钛，超声分散在100ml蒸馏水中；称取5g改性木质素磺酸盐加入到上述体系中，在常温下搅拌24h，得木质素磺酸盐改性纳米二氧化钛。
步骤3、按质量份数取25份木质素磺酸盐改性纳米二氧化钛及25份水性固化剂H228B，加入到100份水和100份水性环氧树脂的混合液中，在常温下搅拌0.5h，即得水性防腐涂料。
Claims (7)
1.一种水性防腐涂料，其特征在于，由木质素磺酸盐改性纳米无机填料、水性环氧树脂、水性固化剂、水制成；所述木质素磺酸盐改性纳米无机填料由改性后木质素磺酸盐及纳米无机填料通过氢键结合制成。
2.一种如权利要求1所述的水性防腐涂料的制备方法，其特征在于，包括以下步骤：
步骤1、取0.01～0.04mol的木质素磺酸盐、50～100mL蒸馏水放入洁净的带有冷凝管、搅拌器、温度计的三口瓶中，搅拌5～10min后加入0.01～0.04mol的脂肪族多胺，在室温下搅拌10～20min后，边搅拌边滴加33%～40%的甲醛溶液0.01～0.04mol，在40～60℃下搅拌反应1.5～2.5h，得改性木质素磺酸盐；
步骤2、取8～10g的纳米无机填料，超声分散在100～150mL蒸馏水中；称取4～8g改性木质素磺酸盐加入到上述体系中，在常温下搅拌20～24h，得木质素磺酸盐改性纳米无机填料；
步骤3、取10～25份木质素磺酸盐改性纳米无机填料及25～50份水性固化剂，加入到50～100份水和100～200份水性环氧树脂的混合液中，在常温下搅拌0.5～1h，即得水性防腐涂料；
所述步骤1中木质素磺酸盐、脂肪族多胺、甲醛的摩尔比为1:1:1。
3.如权利要求2所述的水性防腐涂料的制备方法，其特征在于，所述木质素磺酸盐为木质素磺酸钠或木质素磺酸钙。
4.如权利要求2所述的水性防腐涂料的制备方法，其特征在于，所述脂肪族多胺为乙二胺、哌啶、二甲胺中的一种或几种。
5.如权利要求2所述的水性防腐涂料的制备方法，其特征在于，所述纳米无机填料为纳米二氧化硅、纳米二氧化钛、介孔分子筛中的一种或几种。
6.如权利要求5所述的水性防腐涂料的制备方法，其特征在于，所述介孔分子筛为MCM-41、SBA-15、MCM-48中的一种或几种。
7.如权利要求2所述的水性防腐涂料的制备方法，其特征在于，所述水性固化剂为Aq419、H228B或W650。
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