CN110699677B - 一种碳钢表面的甲基吖啶盐的自组装膜及抗腐蚀性能 - Google Patents

一种碳钢表面的甲基吖啶盐的自组装膜及抗腐蚀性能 Download PDF

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CN110699677B
CN110699677B CN201910997588.5A CN201910997588A CN110699677B CN 110699677 B CN110699677 B CN 110699677B CN 201910997588 A CN201910997588 A CN 201910997588A CN 110699677 B CN110699677 B CN 110699677B
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李惠静
张维维
吴彦超
陈立伟
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Weihai Marine Biological Medicine Industry Technology Research Institute Co ltd
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Abstract

本发明涉及了一种碳钢表面的甲基吖啶盐的自组装膜及抗腐蚀性能，该自组装膜由吖啶化合物和碘甲烷制备而成，并用极化曲线和电化学阻抗法对其抗腐蚀性能进行了测试。所述自组装膜涉及的原料简单易得、价格低廉属于有机缓蚀剂,与传统的铬酸盐、重铬酸盐等无机缓蚀剂相比,低毒无害,符合环境友好缓蚀剂的发展趋势且持续作用能力强,能够长时间保持较高的缓蚀性能,具有用量低、缓蚀效果好的特点,具有广阔的市场应用前景。

Description

一种碳钢表面的甲基吖啶盐的自组装膜及抗腐蚀性能
技术领域
本发明涉及一种碳钢表面的甲基吖啶盐的自组装膜及抗腐蚀性能，属于海洋腐蚀与防护技术领域。
背景技术
金属材料受周围介质的作用而损坏，称为金属腐蚀。金属的锈蚀是最常见的腐蚀形态。腐蚀时，在金属的界面上发生了化学或电化学多相反应，使金属转入氧化状态。海洋环境因其具有极强而且复杂的腐蚀性的特点，金属材料在海水中常常发生特别严重的腐蚀（Sareni, M., et al.Corros. Sci. 2006, 48, 1404;Salehi, E., et al.Appl. Surf.Sci. 2017, 396, 1499）。金属材料一旦发生腐蚀，其机械性能将会降低，应有的强度、硬度、塑性也会丧失，导致材料完全失效，结构完全被破坏。每年因海水腐蚀造成的经济损失极为惊人。
海水是含有多种盐类的电解质溶液，以3.0%～5.0%氯化钠为主盐，PH值为8左右，并溶有一定量的氧气。大部分金属材料在海水中都易腐蚀。由于海水中氯离子含量高，大多数金属在海水中阳极极化阻滞很小，腐蚀速度高，而海浪、飞溅、流速等这些利于供氧的环境条件，都会促进氧的阴极去极化反应，促进金属的腐蚀。海水电导率大，所以不仅腐蚀微电池活性大，而且宏电池的活性也很大。海水中不同金属相接触时，容易发生电偶腐蚀。即使2种金属相距数十米，只要存在电位差，并实现电联结，就会发生电偶腐蚀。
在海水介质中在金属表面制备自组装膜对金属进行防护是较有效的措施之一。近几年自组装膜技术发展很快，已经形成了无机盐、有机醛类、有机胺等系列自组装膜防腐材料（Bahlakeh, G.,et al.J. Mol. Liq.2017, 248, 854; Ramezanzadeh, B., etal.Dyes Pigments2015, 122, 331）。但由于海水含盐量高，腐蚀、结垢离子的质量分数高，微生物、大生物种类多、含量高，所以这些化合物在金属表面形成的自组装膜对海水介质中金属的防腐效果不理想。
在海水防腐领域应用绿色化学概念的主要改进，是消除许多环境有毒化合物的应用，如硝酸盐、重铬酸盐，而代之以环境友好的化学品。吖啶盐类化合物，由于毒性低，合成简单，配位性能好，具有独特的抗菌活性，因此被人们广泛地研究（Li, G.P., etal.Pharm. Ind.1987, 18, 328;Hassan, S., et al.Cancer Sci.2011, 102, 2206）。它们含有的氮原子和共轭键结构，能与铁原子形成配位键，在钢表面形成致密的自组装单层膜。此外，吖啶盐类化合物具有成本效益高、环境友好等优点，在海水利用中对钢的缓蚀性能有很大的应用前景。
发明内容
针对现有技术存在的上述不足，本发明的目的在于提供一种抑制碳钢海水腐蚀的甲基吖啶盐自组装膜，该自组装膜的缓蚀效果优异、持续作用能力强，且涉及的原料简单易得、价格低廉、环境友好，适合推广应用。解决现有缓蚀剂制备的组装膜存在的寿命短大、成本高、工艺复杂、易对环境造成二次污染等问题。
实现上述目的，本发明采用如下技术方案：甲基吖啶盐自组装膜制备及抗腐蚀性能研究。
本发明是通过以下技术方案来实现的：
（1）由吖啶类化合物和碘甲烷，在乙腈中回流6~8h得到所述甲基吖啶盐化物。
（2）以去离子水与无水乙醇体积比为1∶4的混合液，配制50~300 mg/L到甲基吖啶盐组装液，室温下将碳钢浸泡于组装液中2小时，取出用无水乙醇清洗，氮气中吹干，100 ℃固化处理1小时。
（3）在室温下,以包封了环氧树脂且一端裸露面积为0.5cm2碳钢棒为工作电极，饱和甘汞电极作为参比电极，尺寸为1.0 cm×1.0 cm的铂片电极为对电极，采用CHI760e电化学工作站以传统三电极体系的方式测量组装前后碳钢工作电极在海水溶液中的Tafel极化曲线数据和交流阻抗数据，评价缓蚀性能。
进一步，所述吖啶类化合物为9-苯基吖啶、9-甲基吖啶，由邻氨基芳酮类化合物与环己酮制得。
进一步，所述甲基吖啶盐，由吖啶类化合物和碘甲烷按摩尔比为1：15~25制得。
进一步，所述吖啶盐自组装膜，以无水乙醇及其与水的混合液（体积比4∶1）作溶剂，分别配制50~300 mg/L到甲基吖啶盐溶液，并采用浸泡法在碳钢表面制备吖啶盐自组装膜。
与现有技术相比，本发明具有以下积极有益效果
（1）本发明制备的甲基吖啶盐自组装膜用量小，缓蚀效率高，对环境低毒无害，寿命长，热稳定性好，无刺激性气味，符合绿色缓蚀剂发展要求，能有效抑制在海水环境下碳钢的腐蚀，具有广泛的应用价值。
（2）本发明提供的自组装膜在添加量为200 mg/L时就可以有效的抑制碳钢材料的腐蚀，且持续作用能力强，能够长时间保持较高的缓蚀性能，具有用量低、缓蚀效果好的特点。
本发明甲基吖啶盐自组装膜制备方法，工艺流程简单，绿色环保，成本低，原料来源广泛，易于实现工业化生产，而且制备的缓蚀剂具有较好的环境友好性，增大了其应用范围，为制备绿色环保可持续发展的缓蚀剂提供了新的思路。
附图说明
图1是实施例1中碳钢表面9-苯基-10-甲基吖啶盐自组装前后的Tafel极化曲线图谱。
图2是实施例1中碳钢表面9-苯基-10-甲基吖啶盐自组装前后的Nyquist阻抗图谱。
图3是实施例2中碳钢表面9,10-二甲基吖啶盐自组装前后的Tafel极化曲线图谱。
图4是实施例2中中碳钢表面9,10-二甲基吖啶盐自组装前后的Nyquist阻抗图谱。
具体实施方式
本发明通过以下实施例进一步详述，但本实施例所述的技术内容是说明性的，而不是限定性的，不应依此来局限本发明的保护范围。
实施例1
（1）以9-苯基吖啶化合物和碘甲烷（摩尔比为1：20），在乙腈中回流6~8小时得到9-苯基-10-甲基吖啶盐海水防腐缓蚀剂。
（2）分别取5mg、10mg、20 mg、30 mg，9-苯基-10-甲基吖啶盐溶解在无水乙醇及其与水的混合液（体积比4∶1）中，室温下将碳钢浸泡于组装液中2小时，取出用无水乙醇清洗，氮气中吹干，100 ℃ 固化处理1小时。
（3）在室温下,以包封了环氧树脂且一端裸露面积为0.5cm2碳钢棒为工作电极，饱和甘汞电极作为参比电极，尺寸为1.0 cm×1.0 cm的铂片电极为对电极，采用CHI760e电化学工作站以传统三电极体系的方式测量组装前后碳钢工作电极在海水溶液中的Tafel极化曲线数据和交流阻抗数据，评价其缓蚀性能。
图1是实施例1得到的碳钢在添加不同浓度9-苯基-10-甲基吖啶盐组装前后的Tafel极化曲线图谱。图2是实施例1得到的碳钢在添加不同浓度9-苯基-10-甲基吖啶盐组装前后的Nyquist阻抗图谱。
实施例2
（1）以9-甲基吖啶化合物和碘甲烷（摩尔比为1：20），在乙腈中回流6~8小时得到9,10-二甲基吖啶盐海水防腐缓蚀剂。
（2）分别取5mg、10mg、20mg、30 mg，9,10-二甲基吖啶盐溶解在无水乙醇及其与水的混合液（体积比4∶1）中，室温下将碳钢浸泡于组装液中2小时，取出用无水乙醇清洗，氮气中吹干，100 ℃ 固化处理1小时。
（3）在室温下,以包封了环氧树脂且一端裸露面积为0.5cm2碳钢棒为工作电极，饱和甘汞电极作为参比电极，尺寸为1.0 cm×1.0 cm的铂片电极为对电极，采用CHI760e电化学工作站以传统三电极体系的方式测量组装前后碳钢工作电极在海水溶液中的Tafel极化曲线数据和交流阻抗数据，评价缓蚀性能。
图3是实施例2得到的碳钢在添加不同浓度9,10-二甲基吖啶盐组装前后的Tafel极化曲线图谱。图4是实施例2得到的碳钢在添加不同浓度9,10-二甲基吖啶盐组装前后的Nyquist阻抗图谱。
图1~图4可以突出本发明的特点。

Claims (1)

1.一种在碳钢表面的甲基吖啶盐的自组装膜的在抑制碳钢在海水中的腐蚀的用途，其特征在于采用式1甲基吖啶盐作为海水缓蚀剂：
Figure 609036DEST_PATH_IMAGE001
式1
式中，R为芳基、烷基；
包括以下步骤：（1）由吖啶类化合物和碘甲烷，在乙腈中回流6~8h得到所述甲基吖啶盐化物，所述吖啶类化合物为9-苯基吖啶、9-甲基吖啶，由邻氨基芳酮类化合物与环己酮制得；（2）以去离子水与无水乙醇体积比为1∶4的混合液，配制50~300 mg/L到甲基吖啶盐组装液，室温下将碳钢浸泡于组装液中2小时，取出用无水乙醇清洗，氮气中吹干，100 ℃固化处理1小时。
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CN107973719A (zh) * 2016-10-24 2018-05-01 中国石油化工股份有限公司 一种缓蚀组分的制备方法及其产品和应用
CN107090190A (zh) * 2017-04-24 2017-08-25 北京科技大学 一类吖啶盐染料及其制备方法和应用

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