CN106700823A - 一种2‑巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法 - Google Patents

一种2‑巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法 Download PDF

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CN106700823A
CN106700823A CN201611036205.0A CN201611036205A CN106700823A CN 106700823 A CN106700823 A CN 106700823A CN 201611036205 A CN201611036205 A CN 201611036205A CN 106700823 A CN106700823 A CN 106700823A
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mercaptobenzothiazole
modified graphene
anticorrosive paint
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戴李宗
王世成
邵志恒
陈婷
袁丛辉
曾碧榕
许婷
许一婷
罗伟昂
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Xiamen University
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Abstract

本发明公开了一种2‑巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法，按其质量比，其原料包括：2‑巯基苯并噻唑改性氧化石墨烯5‑20；基体树脂30‑70；流平剂0.5‑1.0；消泡剂0.5‑1.0；分散剂0.5‑1.0；成膜助剂0.5‑1.0；稀释剂20‑35。本发明在分子设计的基础上，利用氧化石墨烯表面官能团，将2‑巯基苯并噻唑接枝到氧化石墨烯表面。合成的材料既具备氧化石墨烯的物理阻隔性，又具备2‑巯基苯并噻唑的缓蚀性。同时氧化石墨烯表面的含氧官能团够使其与环氧树脂等一些有机树脂之间具有优异的相容性和接合面结构。以此作为填料，能够提高在环氧树脂中的分散性，并且防腐蚀性能明显增强。同时氧化石墨烯的加入能有效提高防腐涂料的机械性能。

Description

一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料及其制备方法
技术领域
本发明涉及一种防腐涂料，特别是涉及一种2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料及其制备方法。
背景技术
金属腐蚀现象十分普遍，给国民经济造成了严重损失。现阶段防止金属腐蚀的方法很多，表面涂层保护作为防腐烛的常用手段之一，以其施工简单，维护方便，适应性广，成本低廉，成为当前防腐烛最主要的选择。
石墨烯是一种新型二维材料，其诸多优异的理化性质引起广泛关注。氧化石墨烯与石墨烯相比，表面带有较多的含氧有机官能团，这些含氧有机官能团能够使其与环氧树脂等一些有机树脂之间具有优异的相容性和接合面结构，可充分发挥氧化石墨烯作为增强相在连续相树脂中的作用，同时这些含氧官能团表现出来的强亲水性可使氧化石墨烯在一些溶剂中稳定分散。2-巯基苯并噻唑是一种特殊的缓蚀剂，研究发现氮、氧、硫等电负性较大的原子可以很好的满足金属空轨道缺电子的需求，含这些原子的化合物大多数都是碳钢防腐蚀的高效缓蚀剂。这些特点可以使氧化石墨烯和2-巯基苯并噻唑应用在涂料中。
为了改善防腐涂料工艺，减少污染，需要一种新型掺杂型涂料。专利(CN1011108947A，CN1221768A)先后介绍了以无机填料作为填料的涂料，这些涂料需要添加大量无机导电填料，而无机填料与树脂相容性差，使得漆膜力学性能下降。专利(CN102604533A)介绍了聚苯胺与石墨烯复合材料的防腐蚀涂料，发明认为石墨烯有利于提高漆膜的物理防腐蚀性能，但其在分散过程中容易团聚，分散不稳定。专利(CN102978625A)介绍了一种2-巯基苯并噻唑防腐保护剂，但其是简单的物理混合，分散程度难以保证。
发明内容
本文旨在结合2-巯基苯并噻唑和氧化石墨烯的特点，提供一种同时具备缓蚀性和物理阻隔性的2-巯基苯并噻唑改性氧化石墨烯防腐涂料及制备方法。
所述改性氧化石墨烯的防腐蚀涂料，按质量比组成包括：
所述2-巯基苯并噻唑改性氧化石墨烯由氧化石墨烯、三聚氯氰与2-巯基苯并噻唑合成。
所述基体树脂可选自环氧树脂、氟碳树脂、氨基树脂、丙烯酸树脂、聚氨酯树脂、醇酸树脂、聚酯树脂等中的一种。
所述流平剂可选自有机硅、丙烯酸类、单丁醚类中的一种。
所述消泡剂可选自有机硅类消泡剂、无机硅类消泡剂、非有机硅消泡剂中的一种，如德国毕克公司生产的BYK302、BYK065、BYK20、BYK011、BYK053或埃夫卡公司生产的Efka2018中的一种。
所述分散剂可选自熔性分散剂或润湿分散剂，如德国毕克公司生产的BYK101，BYK161，BYK163，或埃夫卡公司生产的Efka5044。
所述成膜助剂可选自丁基卞醇乙酸酯、乙二醇丁醚醇酸脂、乙二醇苯醚、二元酸二甲酯类、丙二醇丙醚、二元酸二乙酯类等中的一种。
所述稀释剂可选自1,4-丁二醇二缩水甘油醚、乙二醇二缩水甘油醚、丙酮、二甲苯、正丁醇、甲基异丁基酮、无水乙醇、醋酸乙酯、醋酸丁酯等中的至少一种。
所述2-巯基苯并噻唑改性氧化石墨烯，其结构如(Ⅰ)
所述2-巯基苯并噻唑改性氧化石墨烯的制备方法，具体如下：
步骤1、取一定量的氧化石墨烯、三聚氯氰、碳酸氢钠于烧瓶中，取一定体积N，N-二甲基甲酰胺将其分散，室温下搅拌0.5～4h小时，升温至50℃搅拌10～24h，冷却并过滤得到沉淀物。其中氧化石墨烯、三聚氯氰、碳酸氢钠按照投料比为氧化石墨烯：三聚氯氰：碳酸氢钠＝1～30g：1～8mol：1～20mol，N，N-二甲基甲酰胺体积为100～2000ml。
步骤2、取步骤1中沉淀物、2-巯基苯并噻唑、氢氧化钾于烧瓶中，取一定量丙酮将其分散，反应6～10小时，冷却并过滤。其中沉淀物、2-巯基苯并噻唑、氢氧化钾的投料比为沉淀物：2-巯基苯并噻唑：氢氧化钾＝1～30g：1～8mol:1～8mol，丙酮体积为100～2000ml。
所述2-巯基苯并噻唑改性氧化石墨烯的合成路线，具体如下：
所述2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料的制备方法：
将各组分分散混合后1～4h，过滤后既得2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。
本发明首先制备了一种2-巯基苯并噻唑改性氧化石墨烯，按防腐涂料组份配比取5～20份改性氧化石墨烯、30～70份基体树脂、0.5～1.0份流平剂、0.5～1.0份消泡剂、0.5～1.0份分散剂、0.5～1.0份成膜助剂、20～35份稀释剂。在分散机上均匀分散，过滤后即可得到防腐涂料。
本发明在分子设计的基础上，利用氧化石墨烯表面官能团，将2-巯基苯并噻唑接枝到氧化石墨烯表面。合成的材料既具备氧化石墨烯的物理阻隔性，又具备2-巯基苯并噻唑的缓蚀性。同时氧化石墨烯表面的含氧官能团够使其与环氧树脂等一些有机树脂之间具有优异的相容性和接合面结构。以此作为填料，能够提高在环氧树脂中的分散性，并且防腐蚀性能明显增强。同时氧化石墨烯的加入能有效提高防腐涂料的机械性能。
具体实施方式
下面通过实施例具体说明本发明的内容
实施例1
(1)制备2-巯基苯并噻唑改性氧化石墨烯
a、取10g氧化石墨烯、2mol三聚氯氰、6mol碳酸氢钠分散于1000ml N，N-二甲基甲酰胺中，充入氮气保护，室温下搅拌2h，升温至50℃，搅拌22h。待反应结束用N，N-二甲基甲酰胺洗涤5次，水洗2次，真空干燥24h，得到沉淀。
b、取a中沉淀10g、2mol 2-巯基苯并噻唑、2mol氢氧化钾分散于1000ml丙酮中，充入氮气保护，45℃下反应8h，待反应结束用丙酮洗涤5次，水洗2次，真空干燥24h，得到沉淀。
(2)制备2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料
取5份改性氧化石墨烯、30份环氧树脂、0.5份有机硅、0.5份消泡剂BYK302、0.5份分散剂BYK101、0.5份乙二醇苯醚、20份1，4-丁二醇缩水甘油醚混合，在分散机上均匀分散4h，过滤后即可得到2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。其防腐性能如表1所示。
实施例2
(1)制备2-巯基苯并噻唑改性氧化石墨烯
a、取20g氧化石墨烯、4mol三聚氯氰、12mol碳酸氢钠分散于1500ml N，N-二甲基甲酰胺中，充入氮气保护，室温下搅拌3h，升温至50℃，搅拌24h。待反应结束用N，N-二甲基甲酰胺洗涤5次，水洗2次，真空干燥24h，得到沉淀。
b、取a中沉淀20g、4mol 2-巯基苯并噻唑、4mol氢氧化钾分散于1500ml丙酮中，充入氮气保护，45℃下反应10h，待反应结束用丙酮洗涤5次，水洗2次，真空干燥24h，得到沉淀。
(2)制备2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料
取10份改性氧化石墨烯、50份环氧树脂、0.8份有机硅、0.6份消泡剂BYK302、0.6份分散剂BYK101、0.8份乙二醇苯醚、30份1，4-丁二醇缩水甘油醚混合，在分散机上均匀分散4h，过滤后即可得到2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。其防腐性能如表1所示。
实施例3
(1)制备2-巯基苯并噻唑改性氧化石墨烯
a、取30g氧化石墨烯、6mol三聚氯氰、18mol碳酸氢钠分散于2000ml N，N-二甲基甲酰胺中，充入氮气保护，室温下搅拌4h，升温至50℃，搅拌24h。待反应结束用N，N-二甲基甲酰胺洗涤5次，水洗2次，真空干燥24h，得到沉淀。
b、取a中沉淀30g、6mol 2-巯基苯并噻唑、6mol氢氧化钾分散于2000ml丙酮中，充入氮气保护，50℃下反应10h，待反应结束用丙酮洗涤5次，水洗2次，真空干燥24h，得到沉淀。
(2)制备2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料
取20份改性氧化石墨烯、70份丙烯酸树脂、0.8份有机硅、1份消泡剂BYK302、1份分散剂BYK101、0.8份乙二醇苯醚、20份醋酸乙酯混合，在分散机上均匀分散4h，过滤后即可得到2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。其防腐性能如表1所示。
表1实施例1至3的防腐涂料腐蚀性能测试

Claims (8)

1.一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，其特征在于，按质量比原料包括：
其中，所述的2-巯基苯并噻唑改性氧化石墨烯，结构如下：
2.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，其特征在于所述基体树脂选自环氧树脂、氟碳树脂、氨基树脂、丙烯酸树脂、聚氨酯树脂、醇酸树脂、聚酯树脂中的至少一种。
3.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述流平剂选自有机硅、丙烯酸类、单丁醚类中的一种。
4.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述消泡剂选自有机硅类消泡剂、无机硅类消泡剂、非有机硅消泡剂中的一种，包括德国毕克公司生产的BYK302、BYK065、BYK20、BYK011、BYK053或埃夫卡公司生产的Efka2018中的一种。
5.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述分散剂选自熔性分散剂或润湿分散剂，包括德国毕克公司生产的BYK101，BYK161，BYK163，或埃夫卡公司生产的Efka5044。
6.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述成膜助剂选自丁基卞醇乙酸酯、乙二醇丁醚醇酸脂、乙二醇苯醚、二元酸二甲酯类、丙二醇丙醚、二元酸二乙酯类中的一种。
7.如权利要求1所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料，所述稀释剂选自1,4-丁二醇二缩水甘油醚、乙二醇二缩水甘油醚、丙酮、二甲苯、正丁醇、甲基异丁基酮、无水乙醇、醋酸乙酯、醋酸丁酯中的至少一种。
8.如权利要求1～7中所述的一种2-巯基苯并噻唑改性氧化石墨烯防腐涂料的制备方法，包括如下步骤：
(1)制备2-巯基苯并噻唑改性氧化石墨烯：
步骤1、取一定量的氧化石墨烯、三聚氯氰、碳酸氢钠于烧瓶中，取一定体积N，N-二甲基甲酰胺将其分散，室温下搅拌0.5～4h小时，升温至50℃搅拌10～24h，冷却并过滤得到沉淀物；其中氧化石墨烯、三聚氯氰、碳酸氢钠按照投料比为氧化石墨烯：三聚氯氰：碳酸氢钠＝1～30g：1～8mol：1～20mol，N，N-二甲基甲酰胺体积为100～2000ml；
步骤2、取步骤1中沉淀物、2-巯基苯并噻唑、氢氧化钾于烧瓶，取一定体积丙酮将其分散，反应6～10小时，冷却并过滤；其中沉淀物、2-巯基苯并噻唑、氢氧化钾的投料比为沉淀物：2-巯基苯并噻唑：氢氧化钾＝1～30g：1～8mol:1～8mol，丙酮体积为100～2000ml；
(2)将各组分分散混合后1～4h，过滤后即得2-巯基苯并噻唑改性氧化石墨烯复合防腐涂料。
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