WO2002010179A1 - Procede de preparation d'un complexe organique de chrome iii, son utilisation comme agent inhibiteur de la corrosion et revetement anticorrosion - Google Patents

Procede de preparation d'un complexe organique de chrome iii, son utilisation comme agent inhibiteur de la corrosion et revetement anticorrosion Download PDF

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Publication number
WO2002010179A1
WO2002010179A1 PCT/FR2001/002423 FR0102423W WO0210179A1 WO 2002010179 A1 WO2002010179 A1 WO 2002010179A1 FR 0102423 W FR0102423 W FR 0102423W WO 0210179 A1 WO0210179 A1 WO 0210179A1
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WO
WIPO (PCT)
Prior art keywords
organic
complex
water
reaction
chromium
Prior art date
Application number
PCT/FR2001/002423
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English (en)
French (fr)
Other versions
WO2002010179A8 (fr
Inventor
Serge Locquet
Michel Lagrenee
Julien Bonnans
Fouad Bentiss
Original Assignee
Societe Nouvelle Des Couleurs Zinciques
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.)
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Publication date
Application filed by Societe Nouvelle Des Couleurs Zinciques filed Critical Societe Nouvelle Des Couleurs Zinciques
Priority to AU2001278564A priority Critical patent/AU2001278564A1/en
Priority to JP2002515908A priority patent/JP2004520265A/ja
Priority to EP01956639A priority patent/EP1305325A1/fr
Publication of WO2002010179A1 publication Critical patent/WO2002010179A1/fr
Publication of WO2002010179A8 publication Critical patent/WO2002010179A8/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage

Definitions

  • the present invention relates to a process for the preparation of an organic chromium complex and its use as a corrosion-inhibiting agent, in particular in metal coatings.
  • a protective coating in the form of coatings, varnishes or paints.
  • Paints are mixtures of organic or mineral binders and solvents in which fillers and mineral or organic pigments are suspended. In addition to their covering and / or coloring power, some of these mineral pigments are used as anti-corrosion agents. These are for example lead orthoplombate called minium, zinc salts such as zinc phosphates, zinc borates, barium, chromates of zinc, strontium, barium ... Chromates are among the most effective against corrosion of metals, but have a high toxicity, because chromium is present there in the hexavalent form. An object of the present invention is therefore to find new chromium derivatives in another degree of oxidation (chromium of valence III being the most stable), effective against corrosion.
  • Organic chromium III complexes are already described in various patents. They are used either for tanning leathers and protecting fibers against micro-organisms (FR-B-1.115.088; US-A-2.273.040; US-A-2.356.161 and US-A-2.549. 220), either in paints mixed with high proportions of hexavalent chromium
  • Such chromium complexes have the major drawback of being soluble in water and therefore cannot be used as an anticorrosive pigment in paints, since they are rapidly leached from the coating.
  • their methods of manufacturing are of particular implementation, that is to say either in the presence in the reaction medium of concentrated sulfuric acid, or gaseous hydrochloric acid and boiling for several hours, or in an anhydrous medium in the absence of free water , or in solvents such as carbon tetrachloride. Therefore, one of the aims of the present invention is to provide chromium III compounds which are practically insoluble in water and in the usual solvents, particularly those used in anticorrosion coatings such as paints.
  • Another object of the present invention is to provide a process for the preparation of these organic chromium III complexes of simple implementation, and if possible using water as solvent.
  • the present invention provides a process for the preparation of an organic chromium III complex by reaction between at least one CrIII compound, formed in situ, and at least one organic compound carrying a carboxylic acid function or its salt , characterized in that the reaction takes place in an aqueous medium and at a temperature between about 15 and about 90 ° C, in that the organic compound has at least one aromatic ring, preferably benzene.
  • the chromium III complex obtained by the process according to the present invention is practically insoluble in water and the usual solvents used in anticorrosion coatings, and is practically free of chlorine. According to the present invention, the addition of additional mineral acid in high concentration is not essential for the complexing reaction.
  • said aromatic ring carries both at least one carboxylic acid group directly or via an alkyl radical and one or more groups among the hydroxy, thiol, methoxy, amine, amide or sulfonic groups, these groups being able to be attached directly to aromatic ring or via an alkyl chain.
  • the organic compound carrying a carboxylic acid function is chosen from hydroxybenzoic, aminobenzoic, thiobenzoic, dihydroxyphenylacetic, picolinic, salicylic, anthranilic, thiosalicylic, 2,6-benzoic, amino naphthalene dicarboxylic or trihydroxy-2,4 acids, 6-benzoic acid, 3,4-dimethoxysalicylic, 4-amino salicylic, 3-methyl salicylic, 5-sulfo salicylic, 1-hydroxy 2-naphthoic or 3-hydroxy 2-naphthoic.
  • the molar ratio between the organic compound carrying a carboxylic acid function and the chromium is between approximately 1: 3 and approximately 1: 1.
  • the CrIII compound is formed in situ by reduction of one or more hexavalent chromium compounds by at least one organic reducing agent.
  • the practically complete reduction of chromium NI to chromium III preferably takes place in the presence of the complexing agent.
  • the organic reducing agent can be chosen from: a) an alcoholic solution composed of an alcohol or a mixture of primary or secondary alcohol (s) comprising one or more alcohol functions, b) an aqueous solution of hydrazine , c) an aqueous solution of hexamethylenetetramine or d) a mixture of at least two of the reducing agents a), b) or c).
  • the alcoholic solution is chosen from: ethanol, methanol, propanol, isopropanol, 1,2-propanediol, a secondary butanol or a mixture of these alcohols.
  • the hexavalent chromium compound can be in the form of a bichromate or a chromate of potassium, sodium, ammonium or calcium, chromic acid, chromic anhydride, chromyl chloride or fluoride, of potassium chloro chromate, of pyridinium chloro chromate or of pyridinium dichromate in the presence or not of weakly concentrated mineral acid (for example 1 ⁇ ).
  • the reaction temperature can be higher than room temperature (15-25 ° C), but never exceeds 90 ° C, preferably 70 ° C.
  • the chromium III complex prepared by the process according to the invention has the characteristic of being practically insoluble in water, and the usual solvents in the field of paints. Preferably, it contains between 5 and 40% by weight of chromium, in the form of trivalent chromium.
  • Said organic chromium III complex exhibits excellent metal corrosion inhibiting properties. It can therefore be used as an inhibitor of corrosion, in anticorrosion coatings such as coatings, varnishes or paints. Preferably, it is present in a proportion of at least about 1% by weight. It can be used alone or mixed with corrosion inhibitors and / or with inhibiting organic or mineral pigments such as phosphates of zinc, calcium, barium or strontium, meta or tetra borates of zinc, calcium, strontium or magnesium or calcium silicates.
  • corrosion inhibitor is understood to mean compounds which are rather soluble in the application solvents and act quickly
  • anticorrosion pigment means compounds which are rather insoluble in the application solvent (suspension) and act over the longer term.
  • organic complex according to the invention whether or not mixed with other corrosion inhibitors or other anticorrosion mineral pigments, can be combined with organic binders which are either thermosetting or thermoplastic or else binders which harden by oxidation or by chemical reaction.
  • the complexing agent (s) are dissolved in the organic reducing agent (s) with the optional addition of water.
  • the amount of water is defined by the solubility of the complexing agent in the water-reducing mixture (s)).
  • the mixture can be heated to promote the dissolution of the complexing agent (at a temperature not exceeding 90 ° C, preferably 70 ° C).
  • the compound (s) based on NI chromium as it (s) has (have) been defined previously (s) is (are) dissolved in water.
  • the NI chromium-based solution is added, with stirring and slowly, to the solution containing the complexing agent (s) and reducing agent (s).
  • the two solutions can also be poured simultaneously into a stirred reactor. At the end of the addition, the mixture is left under stirring for a few hours, preferably at reflux when an alcohol is used as a reducing agent.
  • part of the organic solvent can be distilled when an alcohol is used as a reducing agent; the distilled volume can be compensated with water to promote agitation.
  • the product can be collected in solid form by filtration or centrifugation before being dried in an oven.
  • the ⁇ ° 2 solution is heated to about 40 ° C to allow the salicylic acid to dissolve.
  • Solution No. 1 is introduced slowly with stirring into solution No. 2 so that the temperature does not exceed 70 ° C. After the end of the introduction, the mixture is left under stirring for 1 hour at approximately 70 ° C. The mixture is then heated to 90 ° C in order to distill part of the organic solvents. 1,200 g of solvent are collected and compensated with 1,200 g of water to facilitate agitation.
  • the complex obtained is filtered and then dried at 80-100 ° C.
  • the product which contains a concentration of chromium NI less than about 0.1% by weight of the complex, can after grinding be used as a corrosion-inhibiting agent (see examples 11 to 13 below).
  • Solution 1 is prepared at approximately 40 ° C. until the salicylic acid has dissolved.
  • Solution 2 is introduced slowly with stirring into solution 1 so that the temperature does not exceed 70 ° C. When all of solution 2 is introduced, stirring is continued for 1 hour at around 70 ° C. The mixture is then heated to 90 ° C in order to distill part of the organic solvents. During distillation it may be necessary to add water to the reactor to facilitate agitation. At this stage, the organic chromium complex takes on a dark green pasty appearance. This paste is collected and dehydrated at a temperature of 80 to 100 ° C. The dried and ground product will be used as a corrosion inhibitor.
  • the sodium dichromate can be replaced by potassium dichromate or any other dichromate and isopropyl alcohol by another alcohol, primary or preferably secondary, or a mixture of these alcohols.
  • Example 3
  • Solution 1 is prepared at 50 ° C to allow the dissolution of anthranilic acid.
  • Solution 2 is prepared cold. With stirring solution 2 is added to solution 1. At the end of the addition, the mixture is left stirring at approximately 70 ° C. for 1 hour. Then, the mixture is heated to 90 ° C to distill part of the solvents. During the distillation, water is added to compensate for the distillation of the alcohol. The complex is then collected by filtration and then dried at 90 ° C. This complex essentially contains chromium III (the chromium NI concentration is less than 0.1% by weight of the complex).
  • Example 5 According to a procedure identical to that of Example 1, the following solutions are prepared and then brought into contact:
  • the product after filtration and drying, is brown in color and contains less
  • Solution No. 2 salicylic acid 255 isopropyl alcohol 1,700 water 800
  • Examples 7 to 10 describe methods different from that of the present invention, in particular as regards stoichiometry. These complexes are prepared directly from chromium III.
  • Example 7 (comparative) in the presence of a base, and at a stoichiometry of 2: 1
  • Solution 1 is added over 2 hours to solution 2, the reaction mixture is kept for 2 hours at 60 ° C, then filtered, washed and the product obtained is dried at 100 ° C.
  • the pigment, green in color, is not very soluble in water and the usual solvents.
  • Example 9 (comparative) chromium alum 37.5 salicylic acid 30 NaOH 11.5 water 1000
  • Solution 2 is added to solution 1 over 2 hours, then the reaction mixture is left stirring for 1 hour.
  • the product obtained is filtered, washed and dried at 100 ° C.
  • This complex can be defined as a chromous mono-hydroxy salicylate. It is gray-blue in color and is sparingly soluble in water and common solvents.
  • Example 11 Polyurethane-based “coil-coating” primer
  • the primers are applied with a threaded bar to a Galfan type galvanized steel plate (ZincAlu) having received a Bonderit 4590 surface treatment.
  • the primers are baked 35 s at 350 ° C to reach a PMT (Peak Metal Temperature) of 224 ° C.
  • the dry thickness is 5 micrometers.
  • the primers are covered with a commercial polyester finish with a dry thickness of 20 micrometers.
  • the paints are applied to shot steel to a thickness of 40 micrometers dry film and dried for 8 days at 20 ° C and then exposed for 500 hours to salt spray according to standard ASTM B17. The results are evaluated according to the following rating:
  • Example 13 Painting on aluminum and light alloy The following composition formulas are prepared Table 3
  • the formulas are applied to 99.98% aluminum and TU2024 aluminum plates and covered with an aliphatic polyurethane finish.
  • the thickness of the primer is close to 30 ⁇ m, the finish 40 ⁇ m.
  • the panels are exposed to the humid chamber test after one hour of exposure to a 37% HCl vapor according to MIL-P-23377G and to salt spray according to ASTM B-117 to demonstrate filiform corrosion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
PCT/FR2001/002423 2000-08-01 2001-07-25 Procede de preparation d'un complexe organique de chrome iii, son utilisation comme agent inhibiteur de la corrosion et revetement anticorrosion WO2002010179A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2001278564A AU2001278564A1 (en) 2000-08-01 2001-07-25 Method for preparing a chromium iii organic complex, its use as corrosion inhibiting agent and as anticorrosive coating agent
JP2002515908A JP2004520265A (ja) 2000-08-01 2001-07-25 クロム（ｉｉｉ）有機錯体の調製法、腐食防止剤としてのその使用および防食．コーティング
EP01956639A EP1305325A1 (fr) 2000-08-01 2001-07-25 Procede de preparation d'un complexe organique de chrome iii, son utilisation comme agent inhibiteur de la corrosion et revetement anticorrosion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0010114A FR2812640B1 (fr) 2000-08-01 2000-08-01 Procede de preparation d'un complexe organique de chrome iii, son utilisation comme agent inhibiteur de la corrosion et revetement anticorrosion
FR00/10114 2000-08-01

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WO2002010179A1 true WO2002010179A1 (fr) 2002-02-07
WO2002010179A8 WO2002010179A8 (fr) 2002-06-20

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Country Status (6)

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EP (1) EP1305325A1 (zh)
JP (1) JP2004520265A (zh)
CN (1) CN1444591A (zh)
AU (1) AU2001278564A1 (zh)
FR (1) FR2812640B1 (zh)
WO (1) WO2002010179A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD4321C1 (ro) * 2014-01-21 2015-09-30 Институт Химии Академии Наук Молдовы Inhibitor de coroziune a oţelului în apă

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4993959B2 (ja) * 2006-07-10 2012-08-08 日本化学工業株式会社 有機酸クロム（ｉｉｉ）水溶液及びその製造方法
CN101608311B (zh) * 2008-06-17 2011-06-15 攀钢集团钢铁钒钛股份有限公司 一种镀锌自润滑金属材料
SI23055A (sl) * 2009-05-22 2010-11-30 Kemijski@inštitut Pigmenti modificirani z aminosilani za spektralne selektivne premaze metoda za njihovo pripravo in uporabo v premazih
CN102011118B (zh) * 2010-12-24 2012-09-26 杭州东方表面技术有限公司 锌及锌合金镀层用三价铬钝化剂
CN102757741B (zh) * 2012-07-09 2014-03-26 苏州斯迪克新材料科技股份有限公司 一种雾面离型材料
CN103694978B (zh) * 2013-12-16 2016-08-17 安东石油技术（集团）有限公司 有机铬交联剂和有机铬凝胶调剖体系的制备方法
EP3156518A1 (en) * 2015-10-14 2017-04-19 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Corrosion inhibitor composition for magnesium or magnesium alloys
CN115160580B (zh) * 2022-06-30 2024-03-12 湖南理工学院 一种新型金属有机聚合物的制备及其对低浓度金的高效高选择性吸附

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1115088A (fr) * 1954-11-25 1956-04-19 Cfmc Nouveaux complexes chromifères, procédé pour leur fabrication et leurs applications
US4101567A (en) * 1976-02-13 1978-07-18 Graesser Salicylates Limited Method of preparing chromium alkanoates
US4161409A (en) * 1978-03-06 1979-07-17 Louis Schiffman Corrosion inhibitive pigment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1115088A (fr) * 1954-11-25 1956-04-19 Cfmc Nouveaux complexes chromifères, procédé pour leur fabrication et leurs applications
US4101567A (en) * 1976-02-13 1978-07-18 Graesser Salicylates Limited Method of preparing chromium alkanoates
US4161409A (en) * 1978-03-06 1979-07-17 Louis Schiffman Corrosion inhibitive pigment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD4321C1 (ro) * 2014-01-21 2015-09-30 Институт Химии Академии Наук Молдовы Inhibitor de coroziune a oţelului în apă

Also Published As

Publication number Publication date
AU2001278564A1 (en) 2002-02-13
EP1305325A1 (fr) 2003-05-02
WO2002010179A8 (fr) 2002-06-20
FR2812640A1 (fr) 2002-02-08
FR2812640B1 (fr) 2003-03-14
JP2004520265A (ja) 2004-07-08
CN1444591A (zh) 2003-09-24

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