CN111635310A - 一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法 - Google Patents

一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法 Download PDF

Info

Publication number
CN111635310A
CN111635310A CN202010434508.8A CN202010434508A CN111635310A CN 111635310 A CN111635310 A CN 111635310A CN 202010434508 A CN202010434508 A CN 202010434508A CN 111635310 A CN111635310 A CN 111635310A
Authority
CN
China
Prior art keywords
corrosion inhibitor
salicylamide
copper
corrosion
type
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202010434508.8A
Other languages
English (en)
Inventor
姜文凤
张天保
王慧龙
张淑芬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202010434508.8A priority Critical patent/CN111635310A/zh
Publication of CN111635310A publication Critical patent/CN111635310A/zh
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
    • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/58—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/60—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/58—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/64—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C261/00—Derivatives of cyanic acid
    • C07C261/04—Cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
    • 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
    • C23F11/145—Amides; N-substituted amides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法，属于精细化工产品开发技术领域。该缓蚀剂的核心结构为

Description

一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂 及制备方法
技术领域
本发明属于精细化工产品开发技术领域，涉及一种用于5％碳酸氢钠溶液中的紫铜件保护的水杨酸酰胺型缓蚀剂及其制备方法。
背景技术
在制造业转型升级过程中，金属的腐蚀问题必须需要给予关注。金属腐蚀是一种悄无声息的破坏，每年由于金属材料的腐蚀失效问题所造成的各类经济损失巨大。金属铜是一种常见的有色金属材料，广泛应用于国民经济各个部门。其在大气中，以及中性、弱碱性环境中的腐蚀问题，值得关注。铜基中性、碱性条件下缓蚀剂主要为苯并三氮唑(BTA)，但是近年来，苯并三氮唑被发现有一定的致癌性，欧盟等一些国际组织已经逐步禁止BTA的广泛应用，因此开发新型应用于Cu的缓蚀剂开发成为研究的重点，目前文献中报道仍然以苯并三氮唑、巯基苯并咪唑等为主。它们合成困难，毒性较大，并不适合目前及以后的发展趋势。水杨酸是一种无毒的、常见的原料，被广泛用于医药等领域，以此为母体化合物开发新型缓蚀剂具有很大的意义。
发明内容
本发明的目的是提供一种在工业应用中少量、高效，适用于弱碱性条件下铜的缓蚀剂，它能够减小铜件的腐蚀速率，并且提供该缓蚀剂的制备方法。
为了达到上述目的，本发明采用的技术方案为：
一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂，所述水杨酸酰胺型缓蚀剂的结构式为：
Figure BDA0002501725600000011
式中，R代表脂肪基团、芳基、不饱和基团中的任意一种。
进一步的，所述脂肪基团包括正丁基、正丙基等，优选为正丁胺；芳基包括苯基、对甲苯基，优选为苯胺；不饱和基团为氰基，优选为氰胺。
一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂的制备方法，包括以下步骤：
Figure BDA0002501725600000012
(1)在0℃低温下，将水杨酸和酰化试剂按照摩尔比1：1～1：5混合加入溶剂中，低温搅拌3-12h。
所述的溶剂包括1,4-二氧六环、四氢呋喃、二氯甲烷中的一种。所述的酰化试剂包括二氯亚砜、草酰氯、三氯化磷中的一种。
(2)在步骤(1)的反应混合物中不经分离直接加入胺，在25～60℃温度条件下反应12-24h。所述胺与水杨酸摩尔比为1:1～3:1；所述胺为正丁胺、氰胺、苯胺中的任意一种。
(3)以盐酸调节体系的pH到6-7，再加入二氯甲烷萃取，置于0-5℃条件下，待沉淀析出后过滤得到产物。
与现有技术相比，本发明的有益效果为：
(1)与现有技术相比，分子中引入的酰胺基团能够增强分子与铜的配位能力。分子中引入的烷基、氰基、芳基能够增加分子的作用位点，有利于分子吸附在铜表面，形成稳定的吸附膜。
(2)本发明缓蚀剂水溶性好，很快溶解于弱碱性溶液中，与现有铜相比，合成路线简单，原料成本较低，具有较好的应用前景。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
(1)以二氯甲烷为溶剂，将水杨酸(13.8g)和二氯亚砜(11.8g)按1：1的摩尔比在0℃混合在一起，在低温度下搅拌3h。
(2)在反应混合物中加入正丁胺(7.3g)，其中，正丁胺与水杨酸摩尔比为1:1，在25℃反应12h。
(3)以盐酸酸调节体系pH为6-7，加入二氯甲烷萃取，置于低温，待沉淀析出、过滤，得产物。
实施例2
(1)以四氢呋喃为溶剂，将水杨酸(13.8g)和草酰氯(38.1g)按1：3的摩尔比在0℃混合在一起，在低温度下搅拌8h。
(2)在反应混合物中加入氰胺(8.4g)，其中，氰胺与水杨酸摩尔比为2:1，在40℃反应18h。
(3)以盐酸酸调节体系pH为6-7，加入二氯甲烷萃取，置于低温，待沉淀析出、过滤，得产物。
实施例3
(1)以1,4-二氧六环为溶剂，将水杨酸(13.8g)和三氯化磷(68.7g)按1：5的摩尔比在0℃混合在一起，在低温度下搅拌12h。
(2)在反应混合物中加入苯胺(27.9g)，其中，苯胺与水杨酸摩尔比为3:1，在60℃反应24h。
(3)以盐酸酸调节体系pH为6-7，加入二氯甲烷萃取，置于低温，待沉淀析出、过滤，得产物。
以氰胺为例，电化学实验证明铜在含有300ppm所合成缓蚀剂的5％碳酸氢钠中腐蚀速率最低。
Figure BDA0002501725600000031
由氰胺的缓蚀性能可知，该水杨酸酰胺型缓蚀剂具有抑制弱碱性溶液中的铜的腐蚀作用。说明分子中的杂原子与金属作用较强，在合金表面形成了稳定吸附膜，说明本发明水杨酸酰胺型缓蚀剂对弱碱溶液中铜的腐蚀具有优秀的抑制能力。
以上所述实施例仅表达本发明的实施方式，但并不能因此而理解为对本发明专利的范围的限制，应当指出，对于本领域的技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些均属于本发明的保护范围。

Claims (5)

1.一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂，其特征在于，所述水杨酸酰胺型缓蚀剂的结构式为：
Figure FDA0002501725590000011
式中，R代表脂肪基团、芳基、不饱和基团中的任意一种。
2.根据权利要求1所述的一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂，其特征在于，所述脂肪基团包括正丁基、正丙基；芳基包括苯基、对甲苯基；不饱和基团为氰基。
3.根据权利要求1或2所述的一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂，其特征在于，所述脂肪基团优选为正丁胺；芳基优选为苯胺；不饱和基团优选为氰胺。
4.一种权利要求1-3任一所述的用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂的制备方法，其特征在于，包括以下步骤：
(1)在0℃低温下，将水杨酸和酰化试剂按照摩尔比1：1～1：5混合加入溶剂中，低温搅拌3-12h；所述的酰化试剂包括二氯亚砜、草酰氯、三氯化磷中的一种；
(2)在步骤(1)的反应混合物中不经分离直接加入胺，在25～60℃温度条件下反应12-24h；所述胺与水杨酸摩尔比为1:1～3:1；所述胺为正丁胺、氰胺、苯胺中的任意一种；
(3)以盐酸调节体系的pH到6-7，再加入二氯甲烷萃取，置于0-5℃条件下，待沉淀析出后过滤得到产物。
5.根据权利要求4所述的用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂的制备方法，其特征在于，所述的溶剂包括1,4-二氧六环、四氢呋喃、二氯甲烷中的一种。
CN202010434508.8A 2020-05-21 2020-05-21 一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法 Withdrawn CN111635310A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010434508.8A CN111635310A (zh) 2020-05-21 2020-05-21 一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010434508.8A CN111635310A (zh) 2020-05-21 2020-05-21 一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法

Publications (1)

Publication Number Publication Date
CN111635310A true CN111635310A (zh) 2020-09-08

Family

ID=72326636

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010434508.8A Withdrawn CN111635310A (zh) 2020-05-21 2020-05-21 一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法

Country Status (1)

Country Link
CN (1) CN111635310A (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4563253A (en) * 1982-10-27 1986-01-07 Lehigh University Method of making corrosion inhibited metal
CN101050537A (zh) * 2006-04-04 2007-10-10 中国石油天然气股份有限公司 一种抑制金属腐蚀的缓蚀剂及其制备方法
CN103351309A (zh) * 2013-07-24 2013-10-16 中国船舶重工集团公司第七二五研究所 一种柳酰胺类防污剂及其制备方法
CN105523955A (zh) * 2015-12-14 2016-04-27 清华大学 化合物及其在制备药物中的用途

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4563253A (en) * 1982-10-27 1986-01-07 Lehigh University Method of making corrosion inhibited metal
CN101050537A (zh) * 2006-04-04 2007-10-10 中国石油天然气股份有限公司 一种抑制金属腐蚀的缓蚀剂及其制备方法
CN103351309A (zh) * 2013-07-24 2013-10-16 中国船舶重工集团公司第七二五研究所 一种柳酰胺类防污剂及其制备方法
CN105523955A (zh) * 2015-12-14 2016-04-27 清华大学 化合物及其在制备药物中的用途

Similar Documents

Publication Publication Date Title
CN107935822B (zh) 1，2-二(2-(4-甲氧基苯氧基)乙氧基)乙烷的制备方法
JPS62270603A (ja) アルコキシ化した／カチオンで改質したアミドを含むポリマ−およびその製造法
CN109438252B (zh) 一种三(2-氨基乙基)胺的合成工艺
CN109516919B (zh) 一种三(2-氨基乙基)胺的制备方法
CN111635310A (zh) 一种用于防护铜在弱碱性介质中腐蚀的水杨酸酰胺型缓蚀剂及制备方法
CN109913879B (zh) 一种用于硝酸酸洗黄铜件的复配型吡啶脒缓蚀剂及其制备方法
US4676911A (en) Scale inhibitors which contain sulfate-containing polymers
US4978786A (en) Chemical process for the preparation of oxamide derivatives and compounds prepared thereby
JPS6315284B2 (zh)
CN115028273B (zh) 一种用于化工管线的阻垢剂
US3787482A (en) Method of synthesizing hydrazine compounds carboxylic acids
JP2007308460A (ja) ２−メチル−２−アダマンタノールおよびそのマグネシウムクロリド塩の製造方法
CN101193873A (zh) 取代的唑类的制备方法
CN110627746B (zh) 一种蓖麻油基季铵盐抗泥剂及其制备方法
US2624756A (en) Metal ion chelating compounds consisting of mono phenyl poly alkylene polyamino polycarboxylic acids and salts
SK45395A3 (en) Method of production of dimethylaminborane
EP0140229B1 (en) Process for producing a halogen-containing ethylbenzene derivative
CN113801047B (zh) 一种金属缓蚀剂及其制备方法
CN112759612B (zh) 润滑油生物降解促进剂及其制备方法
CN110343047B (zh) 一种氨基芘类化合物的制备方法
US3230173A (en) Method and compositions for inhibiting corrosion
US2929841A (en) Process for the production of monoamides of dicarboxylic acids
JP2999920B2 (ja) イソニトロソアセトアニリド類の製造方法
CA2021656C (en) Water soluble 1,2-dithio-3-thiones
US3175011A (en) Preparation of 1-nitrosoalkyl dimers

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20200908