EP0511163B1 - Dispersions aqueuses coulables d'acides polycarboxyliques, utilisés comme inhibiteurs de corrosion - Google Patents

Dispersions aqueuses coulables d'acides polycarboxyliques, utilisés comme inhibiteurs de corrosion Download PDF

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Publication number
EP0511163B1
EP0511163B1 EP92810280A EP92810280A EP0511163B1 EP 0511163 B1 EP0511163 B1 EP 0511163B1 EP 92810280 A EP92810280 A EP 92810280A EP 92810280 A EP92810280 A EP 92810280A EP 0511163 B1 EP0511163 B1 EP 0511163B1
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weight
hydrogen
acid
water
dispersant
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German (de)
English (en)
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EP0511163A1 (fr
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Martine Goliro
Martin Holer
Sandor Dr. Gati
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BASF Schweiz AG
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Ciba Geigy AG
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    • 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

Definitions

  • Dispersions which contain 40-53% by weight of a compound of the formula I or II, 45-58% by weight of water, 0.1 to 2% by weight of a dispersant and 0.01 to 0.5% by weight of a thickener are preferred.
  • the dispersion contains salts of polycarboxylic acids, it can be partial salts or full salts. Above all, sodium salts are suitable as alkali metal salts.
  • Amine salts can be salts of primary, secondary or tertiary amines, e.g.
  • the corrosion inhibitor can contain 10-50%, in particular 20-40%, of anthranilic acid.
  • the dispersions according to the invention may also contain other auxiliaries, for example hydrotropic agents, such as e.g. Urea or sodium xylene sulfonate; Antifreezing agents, e.g. Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol; Humectants, e.g. Polyethylene glycols or glycerin; Biocides such as Chloroacetamide, formalin or 1,2-benzisothiazolin-3-one; or complexing agents, e.g. Trisodium nitrilotriacetate.
  • hydrotropic agents such as e.g. Urea or sodium xylene sulfonate
  • Antifreezing agents e.g. Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol
  • Humectants e.g. Polyethylene glycols or glycerin
  • Biocides such as Chloro
  • biocides especially fungicides, which are intended to prevent fungal growth in the aqueous dispersion.
  • the biocid is preferably used in an amount of 0.05 to 0.5% by weight of the dispersion.
  • the filter cake already has the desired water content, it is of course not necessary to add water.
  • the polycarboxylic acid can be pressed so strongly that only 40% or less water remains in the filter cake.
  • the filter cake is stirred, enough water is then slowly added to produce a flowable dispersion. Once you have determined the optimal amount, you can choose the pressure when filtering so that the filter cake already has the desired water content.
  • the stirring is preferably carried out at room temperature, but it can be advantageous in certain cases to cool the material to be stirred gently.
  • the dispersions thus produced are stable for several months at room temperature and at temperatures up to 40 ° C. They keep their fluidity and do not separate. This is important for the storage and transportation of the dispersions Property.
  • the dispersions can be handled as a liquid and e.g. can be pumped during dosing. Another advantage is that the dispersions dissolve very quickly in alkaline aqueous systems. If the dispersions consist of the salts of the polycarboxylic acids, they also dissolve in neutral aqueous systems. The dissolution can be accelerated by stirring.
  • Example 1 99.2 parts of a 50% water-containing filter cake of 2,4,6-tris (5-carboxypentylamino) -1,3,5-triazine (Reocor® 190, Ciba-Geigy AG) are in a turbine agitator Fa-Polytron stirred at a stirring speed of 1000 rpm to flowability. This takes about 15 minutes.
  • a dispersant based on a 40% aqueous solution of dinaphthylmethane disulphosaem sodium (Dispersant CC, Ciba-Geigy AG) is added and after stirring for a further 15 minutes, 0.1 part of a polysaccharide of the xanthan type (Rhodopol® 23 , Rhone-Poulenc) as a thickener and 0.2 part of a 35% aqueous dispersion of 1,2-benzisothiazolin-3-one (Proxel® BD, JCJ Ltd.) as a biocide and stirred for another 15 minutes.
  • a dispersant based on a 40% aqueous solution of dinaphthylmethane disulphosaem sodium (Dispersant CC, Ciba-Geigy AG) is added and after stirring for a further 15 minutes, 0.1 part of a polysaccharide of the xanthan type (Rh
  • Example 2 The procedure is as in Example 1. 90.6 parts of a Reocor® 190 filter cake with 50% water content are mixed with 1 part of an anionic surfactant based on a formaldehyde condensation product of an aromatic sulfonic acid 10% aqueous solution (Dispersant H, Ciba-Geigy AG), 0.2 parts Rhodopol® 23 and 0.2 parts Proxel® BD.
  • Example 3 The procedure is as in Example 1, mixing the following components: 99.1 parts of Reocor® 190 filter cake with 50% water content 0.5 part of an ethylene oxide-propylene oxide block copolymer (Pluronic® F 108, BASF-Wyandotte Corp.) as a dispersant 0.2 parts Rhodopol® 23 as a thickener 0.2 parts of Proxel® BD as a biocid The resulting dispersion has a viscosity of 250 mPa / s.
  • Example 10 In a 1.5 l glass vessel with a stainless steel screw agitator, 3 g of a lignin sulfonate (Reax® 85-A) are dissolved in 44 g of water. At a stirring speed of approx. 50-70 U / pm, 900 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes. This results in a liquid dispersion, which for approx. 30 min at 50-70 Rpm is homogenized. The solution of 1 g Rhodopol® 23 in 50 g water is added. The dispersion is then stirred at 75 rpm for 1 h.
  • a lignin sulfonate Reax® 85-A
  • a flowable dispersion is formed with a content of 40% of the corrosion inhibitor, 59% water, 0.4% dispersant, 0.1% thickener, 0.2% biocide and 0.2% lubricant (polyethylene oxide).
  • Example 12 In a 600 ml glass vessel with a stainless steel screw agitator, 1.2 g of a lignin sulfonate (Reax® 85-A) is dissolved in 91 g of water. At a stirring speed of approx. 50-70 rpm, 256 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes. This results in a liquid dispersion to which 32 g of anthranilic acid are added within 15 minutes .
  • Reax® 85-A a lignin sulfonate
  • the mixture is then homogenized at 50-70 rpm for 30 minutes. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h. The dispersion prepared in this way has a viscosity of 200 mPa.s ⁇ 1 (at 25 ° C).
  • the dispersion contains 40% of the corrosion inhibitor (ratio 80 parts Reocor 190 and 20 parts anthranilic acid); 59.6% water, O, 3% dispersant, 0.1% thickener.
  • Example 13 In a glass vessel (600 ml) with a stainless steel screw agitator, 1.2 g of a lignin sulfonate (Reax® 85-A) is dissolved in 123 g of water. At a stirring speed of approx. 50-70 U / pm, 192 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes liquid dispersion to which 64 g of anthranilic acid (99% content) are added within 15 minutes. The mixture is then homogenized at 50-70 rpm for 30 minutes. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h.
  • a lignin sulfonate Reax® 85-A
  • the dispersion has a content of 45% of the corrosion inhibitor, 54.6% water, O, 3% dispersant, 0.1% thickener.
  • a solution of disodium hydrogen phosphate is added to Reocor 190 filter cake in aqueous suspension; the monosodium salt formed is isolated and can be liquefied using Reax as the dispersant.
  • the stoichiometric amount of diethanolamine is added to Reocor 190 filter cake in aqueous suspension; the mono-diethanolamine salt formed is isolated and can be liquefied using Reax as a dispersant.

Claims (12)

  1. Dispersion liquide fluide d'un inhibiteur de corrosion solide à base d'acide polycarboxylique, contenant de 25 à 50 % en poids de l'inhibiteur de corrosion ayant les formules I ou II :
    Figure imgb0004
     dans lesquelles Z est un radical alkylène en C₁ à C₁₁, cyclohexylène ou phénylène,
       R₁ et R₂, indépendamment l'un de l'autre, sont H ou un radical alkyle en C₁ à C₄ ou un groupe -Z-COOH,
       R₃ est un radical alkyle en C₁ à C₁₂, un groupe phényle ou un groupe -N(R₄)(R₅), -OR₆ ou -SR₆,
       R₄ et R₅, indépendamment l'un de l'autre, représentent chacun H ou un radical alkyle en C₁ à C₁₂, hydroxyalkyle en C₂ à C₄, cyclohexyle, phényle, ou encore un groupe -Z-COOH, ou bien R₄ et R₅ représentent ensemble un radical alkylène en C₄ à C₆ ou 3-oxapentylène,
       R₆ est un hydrogène ou un radical alkyle en C₁ à C₁₂ ou le groupe phényle,
       m vaut 0 ou 1, X est le soufre, l'oxygène ou NH,
       R₇ est un hydrogène ou un radical alkyle en C₁ à C₄, halogéno ou alcoxy en C₁ à C₄, ou le radical carboxy, amino ou nitro,
       R₈, R₉, R₁₀ et R₁₁, indépendamment les uns des autres, sont chacun un hydrogène ou un radical alkyle en C₁ à C₁₂, hydroxyalkyle en C₁ à C₄, carboxyalkyle en C₂ à C₆, alcoxyalkyle en C₂ à C₁₀, carboxyle, phényle ou benzyle, ou bien R₈ et R₉ forment ensemble une liaison directe, où au moins deux des groupes R₈, R₉, R₁₀ et R₁₁ sont des groupes carboxyle ou carboxyalkyle, ou d'un sel d'un métal alcalin, d'ammonium ou d'amine d'un tel acide polycarboxylique,
       40 à 72 % en poids d'eau, 0,1 à 2 % en poids d'un dispersant et 0,01 à 0,5 % en poids d'un épaississant.
  2. Dispersion selon la revendication 1, dans laquelle :
       Z est un radical alkylène en C₁ à C₈, R₁ et R₂ sont chacun un hydrogène ou un groupe alkyle en C₁ à C₄,
       R₃ est un groupe -N(R₄)(R₅), R₄ est un hydrogène ou un radical cyclohexyle ou alkyle en C₁ à C₁₂,
       R₅ est un radical alkyle en C₁ à C₁₂ ou phényle, ou un groupe -Z-COOH, ou bien R₄ et R₅ forment ensemble un radical 1,5-pentylène ou 3-oxa-1,5-pentylène,
       m vaut 0 ou 1, X est le soufre, R₇ est un hydrogène ou le radical ou chloro, R₈ et R₁₀ sont des hydrogènes,
       R₉ et R₁₁ sont chacun un radical carboxyle ou carboxyalkyle en C₂ à C₄.
  3. Dispersion selon la revendication 1, dans laquelle Z est le radical pentaméthylène, R₁ et R₂ sont des hydrogènes, R₃ est un groupe -NH-(CH₂)₅-COOH, X est le soufre, R₇ est l'hydrogène, m vaut 0 ou 1, R₈ et R₁₀ sont des hydrogènes, R₉ est le radical carboxyle, R₁₁ est le radical carboxyméthyle.
  4. Dispersion selon la revendication 1, caractérisée en ce que l'inhibiteur de corrosion à base d'acide polycarboxylique est la 2,4,6-tris(5-carboxypentylamino)-1,3,5-triazine ou l'acide benzothiazole-2-yl-thiosuccinique.
  5. Dispersion selon la revendication 1, qui contient 40 à 53 % en poids d'un composé de formules I ou II, 45 à 58 % en poids d'eau, 0,1 à 2 % en poids d'un dispersant et 0,01 à 0,5 % en poids d'un épaississant.
  6. Dispersion selon la revendication 1, caractérisée en ce que le dispersant est un tensioactif anionique ou non ionique.
  7. Dispersion selon la revendication 6, caractérisée en ce que l'épaississant est un polysaccharide modifié.
  8. Dispersion selon la revendication 1, qui contient en outre 0,05 à 0,5 % en poids d'un biocide, notamment d'un fongicide.
  9. Dispersion selon la revendication 1, caractérisée en ce qu'elle contient comme inhibiteur de corrosion additionnel 10 à 50 % en poids, par rapport au poids total d'inhibiteurs de corrosion, d'acide anthranilique.
  10. Dispersion selon la revendication 1, caractérisée en ce qu'elle contient, comme inhibiteur de corrosion additionnel, 20 à 40 % en poids, par rapport au poids total des inhibiteurs de corrosion, d'acide anthranilique.
  11. Procédé pour préparer une dispersion aqueuse fluide d'un inhibiteur de corrosion à base d'acide polycarboxylique de formules I ou II selon la revendication 1, contenant 25 à 57 % en poids de l'inhibiteur de corrosion, 40 à 72 % en poids d'eau, 0,1 à 2 % en poids d'un dispersant et 0,01 à 0,5 % en poids d'un épaississant, caractérisé en ce qu'on mélange l'inhibiteur de corrosion humide, obtenu par filtration, au dispersant et à l'épaississant, et éventuellement à la quantité nécessaire d'eau, et on agite le mélange jusqu'à ce qu'il soit fluide.
  12. Procédé selon la revendication 11, caractérisé en ce que l'agitation a lieu à la température ambiante.
EP92810280A 1991-04-24 1992-04-15 Dispersions aqueuses coulables d'acides polycarboxyliques, utilisés comme inhibiteurs de corrosion Expired - Lifetime EP0511163B1 (fr)

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CH1228/91 1991-04-24
CH122891 1991-04-24

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EP0511163B1 true EP0511163B1 (fr) 1995-07-26

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US (1) US5549847A (fr)
EP (1) EP0511163B1 (fr)
JP (1) JP3259185B2 (fr)
BR (1) BR9201495A (fr)
CA (1) CA2066806C (fr)
DE (1) DE59203008D1 (fr)
ES (1) ES2075671T3 (fr)
MX (1) MX9201868A (fr)

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GB9201165D0 (en) * 1992-01-18 1992-03-11 Ciba Geigy Corrosion inhibiting compositions
US5665688A (en) * 1996-01-23 1997-09-09 Olin Microelectronics Chemicals, Inc. Photoresist stripping composition
US6241898B1 (en) 1996-04-19 2001-06-05 Betzdearborn Inc. Method for inhibiting microbial adhesion on surfaces
US6110381A (en) * 1996-04-19 2000-08-29 Betzdearborn Inc. Method and composition for inhibiting microbial adhesion on surfaces
US5780406A (en) * 1996-09-06 1998-07-14 Honda; Kenji Non-corrosive cleaning composition for removing plasma etching residues
DE19648843C2 (de) * 1996-11-26 1998-09-17 Zts Chemie Gmbh Melamin-polycarbonsäureamide und ihre Verwendung als Korrosionsschutzmittel
ATE230400T1 (de) * 1998-03-27 2003-01-15 Stefan Graichen Melamin-azomethin-derivate und ein diese enthaltendes korrosionsschutzmittel
ES2253267T3 (es) 1999-10-20 2006-06-01 Ciba Specialty Chemicals Holding Inc. Formulaciones de fotoiniciadores.
US6413923B2 (en) 1999-11-15 2002-07-02 Arch Specialty Chemicals, Inc. Non-corrosive cleaning composition for removing plasma etching residues
JP2005325300A (ja) * 2004-05-17 2005-11-24 Toyota Motor Corp 冷却液組成物
JP2007016167A (ja) * 2005-07-08 2007-01-25 Taiyu Kk 水溶性金属工作油剤
WO2014005861A1 (fr) * 2012-07-03 2014-01-09 Basf Se Dérivés de 1,3,5-triazine en tant qu'inhibiteurs de corrosions destinés à des surfaces métalliques
EP3060697B1 (fr) * 2013-10-23 2021-05-19 Autonomic Materials, Inc. Formulations d'agent d'auto-réparation contenant des inhibiteurs de corrosion liquides
CN104649987A (zh) * 2013-11-25 2015-05-27 刘现梅 一种三嗪三巯基丁酸羟烷基叔胺盐及其制备方法
CN104649990B (zh) * 2013-11-26 2018-01-16 烟台恒鑫化工科技有限公司 一种三嗪三氨基戊二酸醇胺盐及其制备方法
CN110550750A (zh) * 2019-09-10 2019-12-10 神美科技有限公司 一种制氧厂专用可示踪无磷缓蚀阻垢剂

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Also Published As

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DE59203008D1 (de) 1995-08-31
JPH05179243A (ja) 1993-07-20
US5549847A (en) 1996-08-27
CA2066806C (fr) 2002-03-12
CA2066806A1 (fr) 1992-10-25
JP3259185B2 (ja) 2002-02-25
MX9201868A (es) 1992-10-01
ES2075671T3 (es) 1995-10-01
EP0511163A1 (fr) 1992-10-28
BR9201495A (pt) 1992-11-24

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