WO2002010179A1 - Method for preparing a chromium iii organic complex, its use as corrosion inhibiting agent and as anticorrosive coating agent - Google Patents
Method for preparing a chromium iii organic complex, its use as corrosion inhibiting agent and as anticorrosive coating agent Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic
- complex
- water
- reaction
- chromium
- Prior art date
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- 239000011651 chromium Substances 0.000 title claims abstract description 48
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 46
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005260 corrosion Methods 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 10
- 239000011707 mineral Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 13
- 150000002894 organic compounds Chemical class 0.000 claims description 12
- 150000003333 secondary alcohols Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical class [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- VQUIWLHMFOYFHJ-UHFFFAOYSA-N 3-aminonaphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C(N)=CC2=C1 VQUIWLHMFOYFHJ-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- GMPKIPWJBDOURN-UHFFFAOYSA-N Methoxyamine Chemical compound CON GMPKIPWJBDOURN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- RCBVKBFIWMOMHF-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1.O[Cr](=O)(=O)O[Cr](O)(=O)=O RCBVKBFIWMOMHF-UHFFFAOYSA-L 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- PEBPTQFCMJWPGZ-UHFFFAOYSA-M potassium;trioxochromium;chloride Chemical compound [Cl-].[K+].O=[Cr](=O)=O PEBPTQFCMJWPGZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical group 0.000 claims 3
- 229960004063 propylene glycol Drugs 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 12
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 4
- 150000001491 aromatic compounds Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 13
- 229960004889 salicylic acid Drugs 0.000 description 13
- 239000000049 pigment Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229940037003 alum Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 2
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 2
- 239000011696 chromium(III) sulphate Substances 0.000 description 2
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- ZAXXZBQODQDCOW-UHFFFAOYSA-N 1-methoxypropyl acetate Chemical compound CCC(OC)OC(C)=O ZAXXZBQODQDCOW-UHFFFAOYSA-N 0.000 description 1
- WQIAKSRYDHIZDB-UHFFFAOYSA-N 2-hydroxybenzenecarboperoxoic acid Chemical compound OOC(=O)C1=CC=CC=C1O WQIAKSRYDHIZDB-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 208000028626 extracranial carotid artery aneurysm Diseases 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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)
Abstract
Description
Claims
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 (en) | 2000-08-01 | 2001-07-25 | Preparation of chromium (III) organic complexes, their use as corrosion inhibitors and anticorrosion. coating |
EP01956639A EP1305325A1 (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 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0010114A FR2812640B1 (en) | 2000-08-01 | 2000-08-01 | PROCESS FOR THE PREPARATION OF AN ORGANIC COMPLEX OF CHROMIUM III, ITS USE AS A CORROSION INHIBITOR AND ANTICORROSION COATING |
FR00/10114 | 2000-08-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002010179A1 true WO2002010179A1 (en) | 2002-02-07 |
WO2002010179A8 WO2002010179A8 (en) | 2002-06-20 |
Family
ID=8853175
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2001/002423 WO2002010179A1 (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 |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1305325A1 (en) |
JP (1) | JP2004520265A (en) |
CN (1) | CN1444591A (en) |
AU (1) | AU2001278564A1 (en) |
FR (1) | FR2812640B1 (en) |
WO (1) | WO2002010179A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MD4321C1 (en) * | 2014-01-21 | 2015-09-30 | Институт Химии Академии Наук Молдовы | Inhibitor of steel corrosion in water |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4993959B2 (en) * | 2006-07-10 | 2012-08-08 | 日本化学工業株式会社 | Chromium (III) organic acid aqueous solution and method for producing the same |
CN101608311B (en) * | 2008-06-17 | 2011-06-15 | 攀钢集团钢铁钒钛股份有限公司 | Galvanized self-lubricating metal material |
SI23055A (en) * | 2009-05-22 | 2010-11-30 | Kemijski@inštitut | Aminosilane-modified pigments for spectrally selective paints, methodfor their preparation and application in paints |
CN102011118B (en) * | 2010-12-24 | 2012-09-26 | 杭州东方表面技术有限公司 | Trivalent chromium passivating agent for zinc and zinc alloy coatings |
CN102757741B (en) * | 2012-07-09 | 2014-03-26 | 苏州斯迪克新材料科技股份有限公司 | Frosted release material |
CN103694978B (en) * | 2013-12-16 | 2016-08-17 | 安东石油技术(集团)有限公司 | Organic chrome cross linker and the preparation method of organic chromium gel profile-controlling system |
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 (en) * | 2022-06-30 | 2024-03-12 | 湖南理工学院 | Preparation of novel metal organic polymer and high-efficiency high-selectivity adsorption of novel metal organic polymer on low-concentration gold |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1115088A (en) * | 1954-11-25 | 1956-04-19 | Cfmc | New chromiferous complexes, process for their manufacture and 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 |
-
2000
- 2000-08-01 FR FR0010114A patent/FR2812640B1/en not_active Expired - Lifetime
-
2001
- 2001-07-25 JP JP2002515908A patent/JP2004520265A/en active Pending
- 2001-07-25 WO PCT/FR2001/002423 patent/WO2002010179A1/en not_active Application Discontinuation
- 2001-07-25 CN CN 01813556 patent/CN1444591A/en active Pending
- 2001-07-25 AU AU2001278564A patent/AU2001278564A1/en not_active Abandoned
- 2001-07-25 EP EP01956639A patent/EP1305325A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1115088A (en) * | 1954-11-25 | 1956-04-19 | Cfmc | New chromiferous complexes, process for their manufacture and 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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MD4321C1 (en) * | 2014-01-21 | 2015-09-30 | Институт Химии Академии Наук Молдовы | Inhibitor of steel corrosion in water |
Also Published As
Publication number | Publication date |
---|---|
AU2001278564A1 (en) | 2002-02-13 |
EP1305325A1 (en) | 2003-05-02 |
WO2002010179A8 (en) | 2002-06-20 |
FR2812640A1 (en) | 2002-02-08 |
FR2812640B1 (en) | 2003-03-14 |
JP2004520265A (en) | 2004-07-08 |
CN1444591A (en) | 2003-09-24 |
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