CN108707107A - 一种联吡啶双子季铵盐缓蚀剂及其制备方法及应用 - Google Patents

一种联吡啶双子季铵盐缓蚀剂及其制备方法及应用 Download PDF

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CN108707107A
CN108707107A CN201810678952.7A CN201810678952A CN108707107A CN 108707107 A CN108707107 A CN 108707107A CN 201810678952 A CN201810678952 A CN 201810678952A CN 108707107 A CN108707107 A CN 108707107A
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corrosion inhibiter
bipyridyl
quaternary ammonium
ammonium salt
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张光华
董秋辰
张万斌
张策
杜伦
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Pyridine Compounds (AREA)

Abstract

一种联吡啶双子季铵盐缓蚀剂及此类化合物的制备方法，此类缓蚀剂的结构特点是在4,4‑联吡啶的两端通过季铵化反应连接了长度不同的碳链，该缓蚀剂的制备方法为：以4,4‑联吡啶和氯代十二烷为原料，溶于有机溶剂后，在40～80℃的条件下，经季铵化反应制备而得，该发明的有益效果在于，这类缓蚀剂的制备方法涉及的原料廉价易得，反应条件温和，合成步骤简单。同时其具有良好的缓蚀性能，在40ppm用量下，缓蚀率均可达到96％以上，缓蚀时间长且稳定性好，安全高效，适用于大规模应用。

Description

一种联吡啶双子季铵盐缓蚀剂及其制备方法及应用
技术领域
本发明涉及石油化工和表面活性剂技术领域，特别涉及一种联吡啶双子季铵盐缓蚀剂及其制备方法及应用。
背景技术
在油气开采和运输的过程中，由于高流速和各种腐蚀介质的联合作用，输送管道和金属设备会受到严重的腐蚀和磨蚀，使得设备的寿命减短，造成巨大的经济损失，同时也易出现安全隐患。据国外权威机构估计，如果防腐蚀技术能被充分有效的利用，腐蚀的损失可以挽回30％～40％。实践表明，缓蚀剂是防止金属材料及其合金在使用环境介质中发生腐蚀的有效防护措施，其广泛应用于石油化工、化学清洗、工业用水等领域。
目前，国内外大量采用亚硝酸盐、乌洛托品等作为水溶性缓蚀剂，这类缓蚀剂虽然性能良好，但是用量较大，故实际效果较差，而且当缓蚀剂用量不足时反而会导致严重的局部腐蚀，并且一般都有毒，由于生态环境日益受到重视，所以这类物质已被禁止或限制使用。
发明内容
为了克服上述现有技术的不足，本发明的目的在于提供一种联吡啶双子季铵盐缓蚀剂及其制备方法及应用，具有工艺简单，无污染，适于规模化生产的特点。
为了实现上述目的，本发明采用的技术方案是：
一种联吡啶双子季铵盐缓蚀剂，通过季铵化反应，将不同长度的碳链引入4,4-联吡啶的两端，其具有以下的结构：
其中：R为-C12H25,-C16H33,-C18H37。
一种联吡啶双子季铵盐缓蚀剂的制备方法，包括以下步骤：
步骤1：在装有搅拌棒和冷凝管的三口烧瓶中加入4,4-联吡啶、氯代烃以及有机溶剂，升温进行季铵化反应，反应结束后，得到混合液Ⅰ；
步骤2：将所述的混合液Ⅰ过滤除去多余的有机溶剂，得到粗产品Ⅱ；
步骤3：将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到此类联吡啶双子季铵盐缓蚀剂。
所述步骤1中所述的氯代烃是指氯代十二烷、氯代十六烷、氯代十八烷中的一种；
所述步骤1中的4,4-联吡啶和氯代烃的投料摩尔比为1:2～2.2，反应原料与有机溶剂的质量比为1:1～1.5。
所述步骤1中的反应温度为40～80℃，反应时间为4～8小时。
所述步骤1中的有机溶剂包括丙酮、N,N-二甲基甲酰胺、乙醇、四氢呋喃、氯仿中的任意一种或两种以上的组合；优选的，所述的有机溶剂选自丙酮或N,N-二甲基甲酰胺。
所述步骤2利用过滤除去多余的有机溶剂。
本发明的有益效果：
1、发明所提出的联吡啶双子季铵盐缓蚀剂，其合成工艺简单，原料廉价易得，反应条件温和，水溶性良好，绿色环保且对环境无污染，适用于规模化生产。
2、发明所提出的联吡啶双子季铵盐缓蚀剂，与现有技术相比，其使用方法简单，用水稀释即可，缓蚀时间长且稳定性好，安全环保，而且用量很少，使用效果好。例如当该含联苯基的缓蚀剂在40ppm用量下，缓蚀率均可达到96％以上，适用于大规模的应用。
具体实施方式
下面结合实施例对本发明作进一步详细说明。
一、制备实施例
实施例1
(1)在装有搅拌棒和冷凝管的三口烧瓶中加入15.62g4,4-联吡啶(100mmol)、40.96g氯代十二烷(200mmol)以及70ml有机溶剂丙酮，升温至40℃，进行季铵化反应5个小时。反应结束后，得到混合液Ⅰ；
(2)将所述的混合液Ⅰ利用过滤除去多余的丙酮，得到粗产品Ⅱ；
(3)将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到这种联吡啶双子季铵盐缓蚀剂。产率为80％。
实施例2
(1)在装有搅拌棒和冷凝管的三口烧瓶中加入15.62g4,4-联吡啶(100mmol)、52.99g氯代十六烷(220mmol)以及105ml有机溶剂丙酮，升温至50℃，进行季铵化反应6个小时。反应结束后，得到混合液Ⅰ；
(2)将所述的混合液Ⅰ利用过滤除去多余的丙酮，得到粗产品Ⅱ；
(3)将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到这种联吡啶双子季铵盐缓蚀剂。产率为86％。
实施例3
(1)在装有搅拌棒和冷凝管的三口烧瓶中加入15.62g4,4-联吡啶(100mmol)、59.17g氯代十八烷(220mmol)以及78ml有机溶剂N,N-二甲基甲酰胺，升温至70℃，进行季铵化反应8个小时。反应结束后，得到混合液Ⅰ；
(2)将所述的混合液Ⅰ利用过滤除去多余的N,N-二甲基甲酰胺，得到粗产品Ⅱ；
(3)将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到这种联吡啶双子季铵盐缓蚀剂。产率为82％。
实施例4
(1)在装有搅拌棒和冷凝管的三口烧瓶中加入15.62g4,4-联吡啶(100mmol)、40.96g氯代十二烷(200mmol)以及89ml有机溶剂N,N-二甲基甲酰胺，升温至80℃，进行季铵化反应7个小时。反应结束后，得到混合液Ⅰ；
(2)将所述的混合液Ⅰ利用过滤除去多余的N,N-二甲基甲酰胺，得到粗产品Ⅱ；
(3)将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到这种联吡啶双子季铵盐缓蚀剂。产率为90％。
实施例5
(1)在装有搅拌棒和冷凝管的三口烧瓶中加入15.62g4,4-联吡啶(100mmol)、52.99g氯代十六烷(220mmol)以及85ml有机溶剂丙酮，升温至55℃，进行季铵化反应6个小时。反应结束后，得到混合液Ⅰ；
(2)将所述的混合液Ⅰ利用过滤除去多余的丙酮，得到粗产品Ⅱ；
(3)将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到这种联吡啶双子季铵盐缓蚀剂。产率为93％。
实施例6
(1)在装有搅拌棒和冷凝管的三口烧瓶中加入15.62g4,4-联吡啶(100mmol)、57.79g氯代十八烷(200mmol)以及115ml有机溶剂N,N-二甲基甲酰胺，升温至75℃，进行季铵化反应6个小时。反应结束后，得到混合液Ⅰ；
(2)将所述的混合液Ⅰ利用过滤除去多余的N,N-二甲基甲酰胺，得到粗产品Ⅱ；
(3)将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到这种联吡啶双子季铵盐缓蚀剂。产率为88％。
二缓蚀性能实验
在30℃下，利用失重法测试了实施例Ⅰ、Ⅲ、Ⅴ中所制备的缓蚀剂在1M HCl腐蚀介质中对Q235普通碳钢的缓蚀率。经4h测试后发现：加入量为40ppm时缓蚀率分别为96％、97％、96％，均表现出优良的缓蚀性能。另外，经测试在高温环境中这种缓蚀剂的缓蚀效果依然良好。

Claims (7)

1.一种联吡啶双子季铵盐缓蚀剂，其特征在于，通过季铵化反应，将不同长度的碳链引入4,4-联吡啶的两端，其具有以下的结构：
其中：R为-C12H25,-C16H33,-C18H37。
2.基于权利要求1所述缓蚀剂的制备方法，其特征在于，包括以下步骤：
步骤1：在装有搅拌棒和冷凝管的三口烧瓶中加入4,4-联吡啶、氯代烃以及有机溶剂，升温进行季铵化反应，反应结束后，得到混合液Ⅰ；
步骤2：将所述的混合液Ⅰ利用过滤除去多余的有机溶剂，得到粗产品Ⅱ；
步骤3：将所述的粗产品Ⅱ使用乙酸乙酯进行多次重结晶后，经过滤、干燥即可得到此类联吡啶双子季铵盐缓蚀剂。
3.根据权利要求2所述的一种联吡啶双子季铵盐缓蚀剂的制备方法，其特征在于，所述的氯代烃是指氯代十二烷、氯代十六烷、氯代十八烷中的一种。
4.根据权利要求2所述的一种联吡啶双子季铵盐缓蚀剂的制备方法，其特征在于，所述步骤1中的4,4-联吡啶和氯代烃的投料摩尔比为1:2～2.2，两种反应原料与有机溶剂的比例均为1:1～1.5。
5.根据权利要求2所述的一种联吡啶双子季铵盐缓蚀剂的制备方法，其特征在于，所述步骤1中的反应温度为40～80℃，反应时间为4～8小时。
6.根据权利要求2所述的一种联吡啶双子季铵盐缓蚀剂的制备方法，其特征在于，所述步骤1中的有机溶剂包括丙酮、N,N-二甲基甲酰胺、乙醇、四氢呋喃、氯仿中的任意一种或两种以上的组合；优选的，所述的有机溶剂选自丙酮或N,N-二甲基甲酰胺。
7.根据权利要求1或2所述的一种联吡啶双子季铵盐缓蚀剂应用于金属酸洗、水处理等金属防腐蚀领域。
CN201810678952.7A 2018-06-27 2018-06-27 一种联吡啶双子季铵盐缓蚀剂及其制备方法及应用 Pending CN108707107A (zh)

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CN114591224A (zh) * 2020-12-03 2022-06-07 中国石油天然气股份有限公司 一种具备水合物抑制功能的缓蚀剂及其制备方法和应用

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CN114591224B (zh) * 2020-12-03 2024-04-30 中国石油天然气股份有限公司 一种具备水合物抑制功能的缓蚀剂及其制备方法和应用
CN112876487A (zh) * 2021-01-18 2021-06-01 邓万菁 一种共轭呸啶缓蚀剂及其制备方法
CN112876487B (zh) * 2021-01-18 2022-02-15 泰州先进化工有限公司 一种共轭呸啶缓蚀剂及其制备方法

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Application publication date: 20181026