CN108587437B - 一种石墨烯和有机氟硅水性聚氨酯复合乳液及其制备方法 - Google Patents
一种石墨烯和有机氟硅水性聚氨酯复合乳液及其制备方法 Download PDFInfo
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- CN108587437B CN108587437B CN201810449198.XA CN201810449198A CN108587437B CN 108587437 B CN108587437 B CN 108587437B CN 201810449198 A CN201810449198 A CN 201810449198A CN 108587437 B CN108587437 B CN 108587437B
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Abstract
本发明涉及防腐涂料领域，尤其是一种适用范围广、粘结力强、环保的高效防腐的石墨烯和有机氟硅水性聚氨酯复合乳液，复合乳液由水性有机氟硅聚氨酯乳液与氨基功能化石墨烯混合反应制得。水性有机氟硅聚氨酯由二异氰酸酯和聚醚二元醇为原料、具有含氟及环氧基团的羟基硅油为改性剂、二羟甲基丙酸为亲水单体、1,4‑丁二醇为扩链剂等合成。其中，石墨烯为氨基化还原石墨烯，片径为0.5~30um，单层率大于85%，用量为水性聚氨酯重量的0.1~5%。本发明提供的石墨烯和有机氟硅水性聚氨酯复合乳液，具有高效防腐、耐高温高湿、耐酸雨、耐盐雾且粘接力强的特点。
Description
技术领域
本发明涉及一种石墨烯和有机氟硅水性聚氨酯复合乳液及其制备方法，具体涉及到防腐涂料领域。
背景技术
当前我国经济快速发展，大量金属材料用于交通、建筑、机械、能源、化工、基础设施、铁路和海洋开发等领域。但是受自身特性和环境条件影响，金属腐蚀无法避免，由于腐蚀及劣化等问题带来的损失相当严重，因此对金属防腐处理的要求非常迫切。使用防腐涂料是当前一种成本低廉、防腐效果优异的方法之一，且能在较为恶劣的环境下对金属表面进行较好的保护。
防腐涂料对对材料表面通过屏蔽作用、缓蚀作用和阴极保护等多种协同作用，保护材料表面不受腐蚀。具有优异屏蔽作用的涂料不仅可以隔绝腐蚀介质与材料表面的接触，还可以隔断腐蚀电池的通，达到防腐蚀功能。当前，对涂料防腐蚀性能要求变高，普通防腐涂料很难满足长时间状态下的耐高温高湿、耐酸碱、耐盐雾等要求。
石墨烯是一种最理想的二维片状结构纳米材料，其厚度仅为一个碳原子，是世界上已知的最薄、强度最大的材料，且具有十分稳定的化学性质，对水、氧和腐蚀性药剂具有很好的耐性。石墨烯常用作防腐蚀涂料的功能填料，其防腐蚀作用主要有屏蔽作用、电化学防护作用。石墨烯具有疏水性表面，与水的接触角大，使得水分子很难被石墨烯吸收。在石墨烯与树脂基材料复合的过程中，石墨烯以其小尺寸效应可填充到涂层的孔洞中，有效阻碍小分子腐蚀介质的浸入，增强涂层的物理隔绝作用。石墨烯具有片层结构，通过层与层之间的叠加，可形成致密的物理隔绝层，进一步阻碍了基体与水、氧气、腐蚀性介质的接触，增强涂层的耐腐蚀性。石墨烯由于其特殊的能带结构表现出优异的电学性能，当腐蚀发生时，阳极反应Fe失去的电子就会通过石墨烯快速传递到涂层表面，使得电子在涂层表面富集，所以阴极得电子反应发生在涂层表面。因此，阳极产物Fe3+与阴极产物OH-隔绝开，随着Fe3+的不断累积，阻碍了反应向正方向进行。尽管石墨烯防腐涂料研究较多，由于石墨烯制备过程中会产生缺陷以及防腐涂层中石墨烯的分散层叠问题，并不能很好地带来优异的防腐性能。如何提高石墨烯防腐涂料的性能，依旧是一个重大的问题。
发明内容
本发明的目的在于克服已有技术存在的不足，提供一种石墨烯和有机氟硅水性聚氨酯复合乳液及其制备方法，利用水性聚氨酯的粘结力强、适用性强，有机氟硅与石墨烯的优异耐候性相结合等特点，将石墨烯/水性氟硅聚氨酯复合乳液用于钢铁及建筑物防腐涂层处理，极大增强了其在长时间状态下的耐高温高湿、耐酸碱、耐盐雾等能力。
本发明是通过以下技术方案得以实现的：
一种石墨烯和有机氟硅水性聚氨酯复合乳液及其制备方法，其特征复合乳液由水性有机氟硅聚氨酯乳液与氨基功能化石墨烯混合反应制得。水性有机氟硅聚氨酯由二异氰酸酯和聚醚二元醇为原料、具有含氟及环氧基团的羟基硅油为改性剂、二羟甲基丙酸为亲水单体、1,4-丁二醇为扩链剂等合成。其中，氨基化的还原石墨烯片径为0.5～30um，单层率大于85％，用量为水性有机氟硅聚氨酯重量的0.05～5％。
作为优选，上述石墨烯和有机氟硅水性聚氨酯复合乳液中所述石墨烯为氨基化还原石墨烯。作为优选，氨基化的还原石墨烯通过以片径为0.5～30um，单层率为85％以上的氧化石墨烯与二元胺、或多元胺制备，然后以水合肼或维生素C为还原剂制得。所述二元胺为：对苯二胺、乙二胺、己二胺等；多元胺为：二乙烯三胺、四乙烯五胺、支链聚乙烯亚胺等。作为优选，所述胺为对苯二胺、己二胺、二乙烯三胺等中的一种或多种组合。
作为优选，上述石墨烯和有机氟硅水性聚氨酯复合乳液中水性氟硅聚氨酯由二异氰酸酯、聚醚二元醇、具有含氟及环氧基团的羟基硅油、二羟甲基丙酸和1,4-丁二醇等合成。
作为优选，上述石墨烯和有机氟硅水性聚氨酯复合乳液中所述二异氰酸酯为：甲苯二异氰酸酯、异氟尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯中一种或两种组合。
作为优选，上述石墨烯和有机氟硅水性聚氨酯复合乳液中所述聚醚二元醇为二羟基聚醚(丙二醇聚醚),其特征在于该聚合物分子量为：6000～4000道尔顿。
作为优选，上述石墨烯和有机氟硅水性聚氨酯复合乳液中所述的具有含氟及环氧基团的羟基硅油结构为：
Rf＝(CF2)nCF3n＝0～12
其中，聚合物中环氧组分占1～10mol％；含氟组分占5～60mol％，羟基组分占2mol％。聚合物分子量为：600～4000道尔顿。该含氟及环氧基团的羟基硅油制备过程如下：在装有搅拌器、温度计和回流冷凝管的四口烧瓶中，依次加入含氢聚硅氧烷和烯丙基醇、丙烯酸缩水甘油酯、含氟丙烯酸酯，一定温度下搅拌均匀，加入一定量的催化剂氯铂酸，升温至反应温度，反应一定时间后，旋转蒸发除去低沸物，即得含氟及环氧基团的羟基聚硅氧烷。
作为优选，上述石墨烯和有机氟硅水性聚氨酯复合乳液中所述的亲水单体为二羟甲基丙酸、扩链剂为1,4-丁二醇。
上述的石墨烯和有机氟硅水性聚氨酯复合乳液，有机氟硅水性聚氨酯乳液制备过程如下：在装有搅拌器、温度计的圆底四口烧瓶中依次加入真空脱水处理的二异氰酸酯、聚醚二元醇、含氟及环氧的羟基聚硅氧烷，充分搅拌，加热至75℃左右，加一定量二羟甲基丙酸、二丁基二月桂酸锡以及丙酮，反应40min。升温至80℃，持续反应2h。降温至60℃，加入1,4-丁二醇，继续反应30min。降温至35℃，加入适量碳酸钠中和20min，加入去离子水乳化，最后得到含氟及环氧基团聚硅氧烷改性水性聚氨酯乳液。
上述的石墨烯和有机氟硅水性聚氨酯复合乳液的制备过程如下：将氨基功能化还原石墨烯经超声散在去离子水中，然后与一定量的有机氟硅水性聚氨酯高速搅拌混合反应，最后得到石墨烯和有机氟硅水性聚氨酯复合乳液。将复合乳液涂覆在经过处理的马口铁板上，经耐盐雾试验、耐酸碱性实验测试，结果表明涂覆该复合乳液的铁板具有优异的耐酸碱、盐雾的腐蚀性能。
本发明合成的石墨烯和有机氟硅水性聚氨酯复合乳液具以下优点，适用范围广，具有低表面能的有机氟硅与石墨烯片层双重的阻隔作用，能有效阻止水分以及其他腐蚀性分子的渗透，具有高效防腐、耐高温高湿、耐酸雨、耐盐雾且粘接力强的特点。
具体实施方式
下面结合实施例对本发明作进一步阐述。
实施例1
含氟及环氧的羟基聚硅氧烷的制备
在氮气保护的四口瓶中依次加入100ml甲苯、50g甲基含氢硅油和60g甲基丙烯酸全氟辛基乙酯(碳碳双键摩尔含量为硅氢键含量的30％)，温度控制在100～120℃，搅拌下滴加氯铂酸/异丙醇溶液，其中氯铂酸的质量分数为反应物质量之和的0.01～0.02％，滴加完毕后，反应3～4h，然后75～80℃下，加入100g的丙烯酸缩水甘油酯(环氧基摩尔含量为初始硅氢键含量的68％)以及2g丙烯醇(羟基摩尔含量为初始硅氢键含量的2％)，90℃下反应3～4h，减压除去溶剂和未反应物。
有机氟硅水性聚氨酯的制备
将15g聚醚210以及2g含氟及环氧的羟基聚硅氧烷加入到四口瓶中，通入氮气，缓慢滴入8.5g异佛尔酮二异氰酸酯IPDI，在80℃下反应2h。加入1.17g二羟甲基丙酸和1～2滴催化剂二丁基二月桂酸锡，升温至85℃，反应2h。加入0.5g 1,4-丁二醇，并用丙酮降黏，60℃反应1h。降温至室温，加入碳酸氢钠中和15min。再加入60g去离子水，用高速搅拌器乳化30min，即制得有机氟硅水性聚氨酯乳液。
石墨烯和有机氟硅水性聚氨酯复合乳液的制备
取相对有机氟硅水性聚氨酯乳液固含量质量为0.1％的氨基功能化石墨烯加入到复合乳液中，超声共混反应30分钟，得石墨烯/有机氟硅聚氨酯复合乳液。
将石墨烯/有机氟硅水性聚氨酯乳液均匀涂在马口铁上，保证涂膜厚度在100um左右，室温下干燥14天后进行性能测试。附着力1级；柔韧性1mm；耐盐雾200天无变化；耐酸性(8％H2SO4,25℃,50天)无起泡、无脱落、无锈蚀；耐碱性(8％NaOH,25℃,50天)无起泡、无脱落、无锈蚀；耐水性>3000h。
实施例2
含氟及环氧的羟基聚硅氧烷的制备
在氮气保护的四口瓶中依次加入100ml甲苯、50g甲基含氢硅油和45g甲基丙烯酸全氟辛基乙酯(碳碳双键摩尔含量为硅氢键含量的20％)，温度控制在100～120度，搅拌下滴加氯铂酸/异丙醇溶液，其中氯铂酸的质量分数为反应物质量之和的0.01～0.02％，滴加完毕后，反应3～4h，然后75～80℃下，加入120g的丙烯酸缩水甘油酯(环氧基摩尔含量为初始硅氢键含量的78％)以及2g丙烯醇(羟基摩尔含量为初始硅氢键含量的2％)，90℃下反应3～4h，减压除去溶剂和未反应物。
有机氟硅水性聚氨酯的制备
将12g聚醚210以及4g含氟及环氧的羟基聚硅氧烷加入到四口瓶中，通入氮气，缓慢滴入8.5g甲苯二异氰酸酯，在80℃下反应2h。加入1.5g二羟甲基丙酸和1～2滴催化剂二丁基二月桂酸锡，升温至85℃，反应2h。加入0.8g 1,4-丁二醇，并用丙酮降黏，60℃反应1h。降温至室温，加入碳酸氢钠中和15min。再加入60g去离子水，用高速搅拌器乳化30min，即制得有机氟硅水性聚氨酯乳液。
石墨烯和有机氟硅水性聚氨酯复合乳液的制备
取相对有机氟硅水性聚氨酯乳液固含量质量为0.5％的氨基功能化石墨烯加入到复合乳液中，超声共混反应30分钟，得石墨烯/有机氟硅聚氨酯复合乳液。
将石墨烯/有机氟硅水性聚氨酯乳液均匀涂在马口铁上，保证涂膜厚度在100um左右，室温下干燥14天后进行性能测试。附着力1级；柔韧性1mm；耐盐雾200天无变化；耐酸性(8％H2SO4,25℃,50天)无起泡、无脱落、无锈蚀；耐碱性(8％NaOH,25℃,50天)无起泡、无脱落、无锈蚀；耐水性>3000h。
可见，本发明提供的石墨烯/有机氟硅属性聚氨酯复合乳液具有优异的防腐蚀性能，其耐盐雾、耐酸碱、耐水性指标突出，且粘结力强。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。
Claims (7)
1.一种石墨烯和有机氟硅水性聚氨酯复合乳液，其特征在于，包括水性有机氟硅聚氨酯乳液和氨基功能化石墨烯，水性有机氟硅聚氨酯包括二异氰酸酯、聚醚二元醇、含氟及环氧基团的羟基硅油、二羟甲基丙酸和1,4-丁二醇，所述氨基功能化石墨烯片径为0.5~30um、单层率大于85%，氨基功能化石墨烯重量为水性有机聚氨酯重量的0.05~5%；
所述的含氟及环氧基团的羟基硅油结构为：
2.根据权利要求1所述的一种石墨烯和有机氟硅水性聚氨酯复合乳液，其特征在于所述二异氰酸酯为：甲苯二异氰酸酯、异氟尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯中的一种或两种组合。
3.根据权利要求1所述的一种石墨烯和有机氟硅水性聚氨酯复合乳液，其特征在于所述聚醚二元醇为二羟基聚醚，聚合物分子量为：600~4000道尔顿。
4.根据权利要求1所述的一种石墨烯和有机氟硅水性聚氨酯复合乳液，其特征在于，氨基功能化石墨烯，以片径为0.5~30um、单层率为85%以上的氧化石墨烯与二元胺或多元胺制备，然后以水合肼或维生素C为还原剂制得，所述二元胺为：对苯二胺、乙二胺或己二胺；多元胺为二乙烯三胺、四乙烯五胺或支链聚乙烯亚胺。
5.根据权利要求1所述的一种石墨烯和有机氟硅水性聚氨酯复合乳液，其特征在于，所述含氟及环氧基团的羟基硅油制备过程如下：
在装有搅拌器、温度计和回流冷凝管的四口烧瓶中，依次加入含氢聚硅氧烷和烯丙基醇、丙烯酸缩水甘油酯、含氟丙烯酸酯，一定温度下搅拌均匀，加入一定量的催化剂氯铂酸，升温至反应温度，反应一定时间后，旋转蒸发除去低沸物，即得含氟及环氧基团的羟基硅油。
6.一种权利要求1-5任一项所述的石墨烯和有机氟硅水性聚氨酯复合乳液的制备方法，其特征在于，包括如下步骤，在装有搅拌器、温度计的圆底四口烧瓶中依次加入真空脱水处理的二异氰酸酯、聚醚二元醇、含氟及环氧基团的羟基硅油，充分搅拌，加热至75℃；
加一定量二羟甲基丙酸、二丁基二月桂酸锡以及丙酮，反应 40min；升温至80℃，持续反应 2h；
降温至 60℃，加入 1,4-丁二醇，继续反应 30min；
降温至 35℃，加入适量碳酸钠中和 20min，
加入去离子水乳化，得到有机氟硅水性聚氨酯乳液。
7.根据权利要求6所述的一种石墨烯和有机氟硅水性聚氨酯复合乳液的制备方法，其特征在于，还包括如下步骤：
将氨基功能化还原石墨烯经超声散在去离子水中，
与一定量的有机氟硅水性聚氨酯乳液高速搅拌混合反应，
得到石墨烯和有机氟硅水性聚氨酯复合乳液，
将复合乳液涂覆在经过处理的马口铁板上。
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| CN109852173A (zh) * | 2018-12-12 | 2019-06-07 | 合众（佛山）化工有限公司 | 石墨烯改性硅丙乳液防腐防静电涂料 |
| CN109867279A (zh) * | 2019-04-19 | 2019-06-11 | 王敏 | 一种氨基化石墨烯及其制备方法 |
| CN110183844A (zh) * | 2019-05-30 | 2019-08-30 | 陕西科技大学 | 一种氨基化石墨烯增强水性聚氨酯及其制备方法 |
| CN111334177A (zh) * | 2020-04-24 | 2020-06-26 | 杨建伟 | 一种石墨烯改性聚氨酯超疏水防腐材料及其制法 |
| CN111613367B (zh) * | 2020-06-17 | 2021-09-10 | 中国人民解放军国防科技大学 | 聚氨酯交联还原氧化石墨烯复合导电薄膜及其制备方法和应用 |
| CN112708297B (zh) * | 2020-12-24 | 2022-01-11 | 山东世纪盛科新材料科技有限公司 | 水性防腐涂料及其制备方法 |
| CN114181605B (zh) * | 2022-01-17 | 2023-03-21 | 雨中情防水技术集团股份有限公司 | 一种单组分水性聚氨酯防水涂料及其制备方法 |
| CN116289305A (zh) * | 2023-03-17 | 2023-06-23 | 浙江理工大学 | 一种可降解、可染色、防水防油的水性有机氟硅聚氨酯涂层材料及其制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432768A (zh) * | 2011-10-10 | 2012-05-02 | 嘉兴禾欣化学工业有限公司 | 含氟硅聚氨酯-丙烯酸酯乳液的制备方法 |
| CN103865026A (zh) * | 2014-03-18 | 2014-06-18 | 山东大学 | 一种含短氟碳链的有机氟硅改性聚氨酯乳液的制备方法 |
| CN105348449A (zh) * | 2015-12-16 | 2016-02-24 | 江南大学 | 一种氟硅改性聚氨酯丙烯酸酯复合乳液的制备方法 |
| CN105622855A (zh) * | 2014-10-31 | 2016-06-01 | 郁丁丁 | 一种水性氟硅聚氨酯的制备方法 |
| CN107880237A (zh) * | 2017-12-26 | 2018-04-06 | 海安常州大学高新技术研发中心 | 一种氧化石墨烯改性水性聚氨酯防腐乳液的制备方法 |
-
2018
- 2018-05-11 CN CN201810449198.XA patent/CN108587437B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432768A (zh) * | 2011-10-10 | 2012-05-02 | 嘉兴禾欣化学工业有限公司 | 含氟硅聚氨酯-丙烯酸酯乳液的制备方法 |
| CN103865026A (zh) * | 2014-03-18 | 2014-06-18 | 山东大学 | 一种含短氟碳链的有机氟硅改性聚氨酯乳液的制备方法 |
| CN105622855A (zh) * | 2014-10-31 | 2016-06-01 | 郁丁丁 | 一种水性氟硅聚氨酯的制备方法 |
| CN105348449A (zh) * | 2015-12-16 | 2016-02-24 | 江南大学 | 一种氟硅改性聚氨酯丙烯酸酯复合乳液的制备方法 |
| CN107880237A (zh) * | 2017-12-26 | 2018-04-06 | 海安常州大学高新技术研发中心 | 一种氧化石墨烯改性水性聚氨酯防腐乳液的制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 乙二胺化氧化石墨烯-羟基硅油/超支化聚氨酯三元复合材料的制备与性能;闰彦玲;《复合材料学报》;20180430;第35卷(第4期);第775页左栏倒数第1段，右栏倒数1-8段，776页左栏第1段 * |
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