CN110627097A - Preparation of intercalation material and application thereof in polar water-based anticorrosive paint - Google Patents
Preparation of intercalation material and application thereof in polar water-based anticorrosive paint Download PDFInfo
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- CN110627097A CN110627097A CN201910890790.8A CN201910890790A CN110627097A CN 110627097 A CN110627097 A CN 110627097A CN 201910890790 A CN201910890790 A CN 201910890790A CN 110627097 A CN110627097 A CN 110627097A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000009830 intercalation Methods 0.000 title claims abstract description 52
- 230000002687 intercalation Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000003973 paint Substances 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 62
- 239000011248 coating agent Substances 0.000 claims abstract description 59
- 238000005260 corrosion Methods 0.000 claims abstract description 38
- 230000007797 corrosion Effects 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000000049 pigment Substances 0.000 claims abstract description 15
- 230000005764 inhibitory process Effects 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 34
- 239000004593 Epoxy Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 24
- 238000001723 curing Methods 0.000 claims description 23
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 20
- 239000002518 antifoaming agent Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229960001545 hydrotalcite Drugs 0.000 claims description 15
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 12
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000010456 wollastonite Substances 0.000 claims description 10
- 229910052882 wollastonite Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 7
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- 239000004606 Fillers/Extenders Substances 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QBAITUUPZOBZFD-UHFFFAOYSA-N 11-imidazol-1-ylundecane-1-thiol Chemical compound SCCCCCCCCCCCN1C=CN=C1 QBAITUUPZOBZFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- MHLMPARDYWGGLE-UHFFFAOYSA-K aluminum;zinc;phosphate Chemical compound [Al+3].[Zn+2].[O-]P([O-])([O-])=O MHLMPARDYWGGLE-UHFFFAOYSA-K 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- AYGUCHAPOTYFRT-UHFFFAOYSA-H zinc molybdenum(4+) diphosphate Chemical compound [Zn+2].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AYGUCHAPOTYFRT-UHFFFAOYSA-H 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims 7
- 230000003628 erosive effect Effects 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000003822 epoxy resin Substances 0.000 abstract description 6
- 229920000647 polyepoxide Polymers 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract 1
- 238000005034 decoration Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000008199 coating composition Substances 0.000 description 22
- 239000002270 dispersing agent Substances 0.000 description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 13
- 239000007921 spray Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000012855 volatile organic compound Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 9
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 8
- 238000013035 low temperature curing Methods 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005536 corrosion prevention Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229940001007 aluminium phosphate Drugs 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical class C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical class O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical class O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/006—Compounds containing vanadium, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/006—Compounds containing chromium, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/84—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/28—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/72—2-Mercaptobenzothiazole
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/084—Inorganic compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a preparation method of an intercalation material with double effects of corrosion inhibition controllability and low-temperature catalysis, which is applied to a coating, and further develops a high-performance water-based anticorrosive coating used in polar regions and other low-temperature environments. The paint system comprises A, B two components, wherein the component A is a mixture of low-temperature resistant epoxy resin serving as a matrix and compounded with high-performance anticorrosive pigment and filler, and the component B is a modified amine curing agent. The coating has good long-term low temperature resistance and corrosion resistance, and is suitable for the protection and decoration of polar ships and equipment.
Description
Technical Field
The invention relates to the field of water-based anticorrosive coatings, in particular to preparation of an anticorrosive intercalation material and a preparation method and application of a low-temperature cured water-based anticorrosive coating. It is especially suitable for the anticorrosion and repair of facilities and equipment constructed and used under low temperature conditions, such as the inner surface of polar ships and warships, the surface of instruments and equipment in cold regions, etc.
Background
Epoxy resin has a wide variety of types and excellent physical and chemical properties after being cured, so that the epoxy resin is widely applied to the field of anticorrosive coatings. With the improvement of national requirements on environmental protection, the water-based epoxy resin coating has the characteristics of water serving as a dispersing agent, no toxicity, no combustion, easy construction, no VOC (volatile organic Compounds) emission and the like, and is a development trend in the field of anticorrosive coatings. At present, the proportion of the water-based anticorrosive paint in the fields of rail transit, ships and automobiles is continuously improved in addition to the trend of rising year by year in the field of industrial anticorrosion.
Although the performance of the waterborne anticorrosion is greatly improved, compared with a solvent-based anticorrosion coating, a waterborne epoxy system is difficult to volatilize due to large specific heat capacity of water in the system during curing, so that a coating film is difficult to dry, and the adhesion force of the coating film to a substrate is poor, thereby causing corrosion defects. These drawbacks are particularly evident when faced with low temperature construction environments, such as severe cold polar marine environments or cold inland environments throughout the year. With the increasing research on scientific research and resource collection in polar regions, the development of low-temperature curable high-anticorrosion coating for ships and related equipment becomes an important subject.
Curing temperatures for epoxy resins can be lowered by modifying the curing agents or by adding catalysts, such as tertiary amines, boron trifluoride etherate, triphenyl phosphine, imidazoles, are common methods. The tertiary nitrogen on the 3-position of the azole catalyst has good catalytic effect, and pi bonds, S, N and other atoms in the molecule are organically hybridized, so that the tertiary nitrogen is easy to form double bonding with the empty d-orbitals on the metal surface, is stably adsorbed on the metal surface, and plays a role in corrosion inhibition. However, most of the catalysts are solid and have poor water solubility, and are difficult to disperse in the curing agent. In addition, the catalyst has large catalytic activity, the activity of the catalyst needs to be modified, and the modified catalyst is used as a latent catalyst and can be directly added into an epoxy resin component.
The environment-friendly layered double hydroxide LDH (layered double hydroxides) is an inorganic functional material formed by stacking laminates with positive charges and interlayer anions, and can be used as an anti-corrosion coating to be applied to corrosion prevention of metal materials. This is mainly because it can form a layer of dense LDH membrane on the surface of the metal material, which can block the aggressive Cl in the solution-Contact with a base material; while due to the exchangeability of anions between the LDH layers, Cl-Can be accommodated between the layers and bonded to the positively charged laminate, limiting Cl-Movement between layers, extension of Cl-Time to substrate surface; in addition, the LDH can be used as a carrier of the corrosion inhibitor and Cl in the solution-After contact, the corrosion inhibitor between LDH layers can be immediately released to a metal/electrolyte interface to hinder the oxidation-reduction reaction from proceeding, and self-protection is carried out. Therefore, the LDH inserted with the corrosion inhibitor is applied to the metal surface for corrosion prevention, the intelligent protection of isolation, capture and active release of the corrosion inhibitor can be realized, and the corrosion resistance of the metal is improved.
In the field of anticorrosion of paint, the intercalation material is prepared by ion substitution mainly using metal salts of phosphoric acid, chromic acid, vanadic acid, tungstic acid, etc. as corrosion inhibitors, and then the intercalation material is added into the paint as a filler, for example, CN201611038558 discloses a method for preparing a hydrotalcite slow-release agent from aluminum, magnesium and molybdenum salts. CN200810137582 discloses a method for preparing hydrotalcite by chromic acid and vanadic acid. For example, CN201310343188 discloses a hydrotalcite intercalated with a slow release agent in a coating, and the hydrotalcite intercalated with the slow release agent is applied to an acid oil field delivery pipe, and has good corrosion prevention and self-repair performance.
The invention adopts LDH layered material as a nano container of azole and other anions with dual functions of catalysis and corrosion inhibition to prepare the controllable slow-release intercalation nano magnesium aluminum hydrotalcite (MgAl-LDH-S)xCyNz m) Materials, and incorporated directly into the coating formulation. On the premise of not destroying the anticorrosion effect of the coating, the controllable release effect of the corrosion inhibitor is achieved, and the anticorrosion capability of the coating is improved. And through screening and compounding of the resin, the coating has good low-temperature resistance and low-temperature construction performance, and can be widely applied to corrosion prevention of cabins and facilities and equipment under the low-temperature condition.
Disclosure of Invention
1. Controllable corrosion inhibition intercalation nano magnesium-aluminum hydrotalcite (MgAl-LDH-S)xCyNz m) The material and structure are shown in figure 7.
2. The controllable corrosion inhibition intercalation nano magnesium-aluminum hydrotalcite (MgAl-LDH-S)xCyNz m) The material is prepared by the following method:
(1) preparing a solution: solution A: weighing a certain amount of soluble magnesium salt and aluminum salt, placing the soluble magnesium salt and aluminum salt in a three-neck flask, and adding deionized water to dissolve. Solution B: weighing a certain amount of azole S with corrosion inhibition effectxCyNz m-And adding NaOH aqueous solution for dissolution, and adjusting the pH value to a proper value.
(2) Heating and reacting: heating the solution A to 50-80 ℃, and slowly dripping the solution B under the condition of vigorous stirring for about 0.5-1.5 h.
(3) Crystallization: after the dropwise addition is finished, adjusting the pH of the mixed solution to 9-12 by adopting 0.1mol/L NaOH, and heating to 70 DEGAbout 90 ℃. Performing crystallization reaction for 20-30 h to obtain MgAl-LDH-SxCyNz m-And (4) suspending the solution.
(4) Washing and drying: and (3) absorbing a small amount of turbid liquid, washing with water for three times, centrifuging, and drying at the low temperature of 55-65 ℃ to obtain the LDH intercalation material for later use.
Further, the soluble magnesium salt in the step (1) is one or two of magnesium nitrate and magnesium sulfate; the soluble aluminum salt is one or two of aluminum nitrate and aluminum sulfate. Mg (magnesium)2+：Al3+The molar ratio was 3: 1.
Further, in the step (1), SxCyNz m-Is one or more of 2-mercaptobenzimidazole (MBIMD), 2-Mercaptobenzothiazole (MBT), 2-mercapto-1-methylimidazole (MMIMD) and 1- (11-mercaptoundecyl) imidazole (MUI). SxCyNz m-：(Mg2++Al3+)＝1～2：1。
Further, in the step (1), the pH is controlled to be 9-12, and preferably 9.5-10.5.
Further, in the step (2), the heating temperature of the solution A is 50-80 ℃, and preferably 55-65 ℃.
Further, in the step (2), the dropwise adding time of the solution B is controlled to be 0.5-1.5 hours, and preferably 1 hour.
Further, in the step (3), the pH is controlled to be 9-12, and preferably 9.5-10.5.
Further, in the step (3), the heating temperature of the solution A is 70-90 ℃, and preferably 80-85 ℃.
Further, in the step (3), the time of the crystallization reaction is 20-30 hours, preferably 24-26 hours.
3. The water-based low-temperature-resistant anticorrosive coating composition consists of a component A and a component B, wherein the A, B component has the following formula:
the component A comprises:
| raw material | By weight parts/%) |
| Epoxy emulsion | 35～42 |
| Pigment and filler | 25～35 |
| Rust-proof pigment | 5～8 |
| Intercalation material | 3～5 |
| Auxiliary agent | 2～3 |
| Water (W) | 18～20 |
And B component:
| raw material | By weight parts/%) |
| Aqueous epoxy curing agent | 60～80 |
| Water (W) | 10～20 |
| Auxiliary agent | 1～2 |
5. The preparation method of the coating composition comprises the following steps:
(1) preparing slurry of the component A: dispersing and stirring uniformly 25-35% of pigment filler, 5-8% of antirust pigment, 3-5% of intercalation material, 18-20% of auxiliary agent (defoaming agent and dispersing auxiliary agent) and water in a mixing tank at a high speed, and grinding until the fineness is less than or equal to 30 mu m.
(2) Preparation of a component A: stirring and defoaming the slurry at a low speed, adding 35-42% of epoxy emulsion and auxiliaries (film-forming auxiliaries, flash corrosion inhibitors, wetting and leveling agents, rheological auxiliaries, thickening agents and anti-mildew auxiliaries), dispersing uniformly, filtering and discharging to obtain the component A.
(3) B, preparation of a component: and adding water and an auxiliary agent (a flash corrosion inhibitor and the like) into the weighed curing agent, uniformly dispersing, filtering and discharging to obtain a component B.
(4) Preparing a coating: the epoxy group content of the component A and the active hydrogen content of the component B are as follows: 0.65-0.8 of the above-mentioned components.
Further, in the step (1), the pigment and the filler comprise an extender and a pigment which are added according to specific conditions. The constitutional filler is one or more than two of talcum powder, precipitated barium sulfate, kaolin, hydrotalcite and wollastonite; the pigment is one or more than two of rutile titanium dioxide, iron oxide red, iron oxide yellow and carbon black.
Further, the rust-proof pigment in the step (1) is one or a mixture of more than two of zinc phosphate, aluminum zinc phosphate, basic molybdenum zinc phosphate and aluminum tripolyphosphate.
Further, the intercalation material in the step (1) is one or more than two of MgAl-LDH-MUI, MgAl-LDH-MMIMD, MgAl-LDH-MBIMD and MgAl-LDH-MBT.
Furthermore, the epoxy emulsion in the step (2) has good anticorrosion effect, excellent stability and low-temperature environment resistance. Such as commercial air chemical industry AR555, Vandasen chemical industry EPIKOTE6520, EPIKOTE5522, and brand new resins EP386, EP387, EP 2384.
Further, the auxiliary agent used in the step (1) and (2) is selected from environment-friendly auxiliary agents with extremely low VOC content, including defoaming agents, leveling agents, wetting and dispersing agents, thickening agents, preservatives, anti-mildew auxiliary agents and the like.
Furthermore, in the step (3), the epoxy curing agent mainly refers to a water-based epoxy curing agent which has good corrosion resistance and low glass transition temperature and can provide certain free volume, flexibility and cold resistance for a coating film. Such as commercially available products such as commercially available air chemical AR419, Varson chemical EK-6870, EK-8584, and brand number EH-2188, EH-616, EH-613.
6. The coating composition is applied by spraying, brushing and blade coating. Coating on a metal plate, and curing at room temperature to form a film. The performance indexes of the coating film are as follows:
VOC content: less than or equal to 100 g/L; (GB/T23986-2009)
Neutral salt spray resistance (paint film thickness 100 μm): the matched epoxy primer lasts more than 1000 hours, and the coating does not bubble, rust, crack or fall off (GB/T1771-)
Low-temperature curing performance: the lower surface drying time is less than or equal to 2h at the temperature of 5 ℃, and the actual drying time is less than or equal to 12h (GB/T1728-
Low temperature resistance: the coating does not bubble, rust, crack or fall off when stored for 240h at the low temperature of-55 ℃ (GJB150.4A-2009)
High and low temperature resistant cycle alternation test: 60 cycles of 55 ℃/2h to 75 ℃/2h, the coating does not bubble, rust, crack or fall off (GJB150.5A-2009)
7. Compared with the prior art, the invention has the following advantages:
(1) the invention synthesizes the intercalation material with the dual functions of controllable corrosion inhibition and curing catalysis, and the intercalation material is directly applied to the formula of the water-based coating. The coating has the advantages of improving the anticorrosion effect and the low-temperature curing capability of the coating, enabling the coating to have the effect matched with a solvent-based coating and reducing the emission of VOC.
(2) The invention adopts the coating which can resist low-temperature and severe cold climate and is solidified at low temperature, and is particularly suitable for the inner surfaces of cabins, equipment and the like which serve in polar regions and have higher requirements on corrosion resistance.
Drawings
FIG. 1 is a graph showing the effect of the neutral salt spray test (1000h) on a conventional coating prepared in example 6 of the present invention.
FIG. 2 shows MgAl-LDH-VO containing solution prepared in example 7 of the present invention4And (5) an effect graph of a neutral salt spray resistance test (1000h) of the intercalation material coating.
FIG. 3 shows MgAl-LDH-CrO contained in example 8 of the present invention4And (5) an effect graph of a neutral salt spray resistance test (1000h) of the intercalation material coating.
FIG. 4 is a graph showing the effect of the neutral salt spray resistance test (1000h) on the MgAl-LDH-MBIMD intercalation material-containing coating prepared in example 9 of the present invention.
FIG. 5 is a graph showing the effect of the neutral salt spray resistance test (1000h) on the MgAl-LDH-MBT-containing intercalation material coating prepared in example 10 of the present invention.
FIG. 6 is a graph showing the effect of the neutral salt spray test (1000h) on the MgAl-LDH-MMIMD-containing intercalation material coating prepared in example 11 of the present invention.
FIG. 7 is a controllable corrosion inhibition intercalation nano magnesium aluminum hydrotalcite (MgAl-LDH-S)xCyNz m) The structure of the material.
Detailed Description
The present invention is illustrated in detail below by way of examples of preferred embodiments, which are not intended to limit the invention.
Example 1
Non-catalytic controllable corrosion inhibition intercalation nano magnesium aluminum hydrotalcite (MgAl-LDH-VO)4) Preparation of the material:
(1) preparing a solution: solution A: 44.4g of magnesium nitrate and 37.5g of aluminum nitrate are weighed into a three-neck flask, and 4000ml of deionized water is added to dissolve the magnesium nitrate and the aluminum nitrate. Solution B: 27.6g of sodium metavanadate NaVO are weighed out3And adding 1000ml of deionized water for dissolution, and adjusting the pH to 9.5-10.5 by adopting 0.1mol/L NaOH aqueous solution.
(2) Heating and reacting: the solution A is heated to 80 ℃, and the solution B is slowly dripped under the condition of vigorous stirring, and the dripping time is about 1 h.
(3) Crystallization: after the dropwise addition is finished, 0.1mol/L NaOH is adopted for adjustmentThe pH of the mixture was adjusted to 10 and the temperature was raised to 80 ℃. Crystallization reaction is carried out for about 24 hours, and MgAl-LDH-VO is obtained4And (4) suspending the solution.
(4) Washing and drying: absorbing a small amount of suspension, washing with water for three times, centrifuging, and drying at the low temperature of 60 ℃ to obtain MgAl-LDH-VO4The intercalation material is ready for use.
Example 2
Non-catalytic controllable corrosion inhibition intercalation nano magnesium aluminum hydrotalcite (MgAl-LDH-CrO)4) Preparation of the material:
(1) preparing a solution: solution A: 44.4g of magnesium nitrate and 37.5g of aluminum nitrate are weighed into a three-neck flask, and 4000ml of deionized water is added to dissolve the magnesium nitrate and the aluminum nitrate. Solution B: 35.1g of sodium metavanadate NaCrO are weighed4And adding 1000ml of deionized water for dissolution, and adjusting the pH to 9.5-10.5 by adopting 0.1mol/L NaOH aqueous solution.
(2) Heating and reacting: the solution A is heated to 75 ℃, and the solution B is slowly added dropwise under the condition of vigorous stirring, wherein the dropwise adding time is about 1 h.
(3) Crystallization: after the dropwise addition, the pH of the mixed solution is adjusted to 10 by using 0.1mol/L NaOH, and the temperature is increased to 75 ℃. Crystallization reaction is carried out for about 24 hours, and the obtained MgAl-LDH-CrO4And (4) suspending the solution.
(4) Washing and drying: absorbing a small amount of suspension, washing with water for three times, centrifuging, and drying at the low temperature of 60 ℃ to obtain MgAl-LDH-CrO4The intercalation material is ready for use.
Example 3
Preparing a catalytic controllable corrosion inhibition intercalation nano magnesium aluminum hydrotalcite (MgAl-LDH-MBIMD) material.
(1) Preparing a solution: solution A: 44.4g of magnesium nitrate and 37.5g of aluminum nitrate are weighed into a three-neck flask, and 4000ml of deionized water is added to dissolve the magnesium nitrate and the aluminum nitrate. Solution B: 44.3g of 2-mercaptobenzimidazole and 11.8g of NaOH are weighed out and dissolved in 1000ml, and the pH is adjusted to 9.5-10.5.
(2) Heating and reacting: the solution A is heated to 75 ℃, and the solution B is slowly added dropwise under the condition of vigorous stirring, wherein the dropwise adding time is about 1 h.
(3) Crystallization: after the dropwise addition, the pH of the mixed solution is adjusted to 10 by using 0.1mol/L NaOH, and the temperature is raised to 85 ℃. And (4) carrying out crystallization reaction for about 24 hours to obtain MgAl-LDH-MBIMD suspension.
(4) Washing and drying: and (3) absorbing a small amount of turbid liquid, washing with water for three times, centrifuging, and drying at the low temperature of 55-65 ℃ to obtain the MgAl-LDH-MBIMD intercalation material for later use.
Example 4
Preparing a catalytic controllable corrosion inhibition intercalation nano magnesium aluminum hydrotalcite (MgAl-LDH-MBT) material:
(1) preparing a solution: solution A: 44.4g of magnesium nitrate and 37.5g of aluminum nitrate are weighed into a three-neck flask, and 4000ml of deionized water is added to dissolve the magnesium nitrate and the aluminum nitrate. Solution B: 49.3g of 2-mercaptobenzothiazole and 11.8g of NaOH are weighed out and dissolved in 1000ml, and the pH value is adjusted to 9.5-10.5.
(2) Heating and reacting: the solution A is heated to 80 ℃, and the solution B is slowly dripped under the condition of vigorous stirring, and the dripping time is about 1 h.
(3) Crystallization: after the dropwise addition is finished, the pH of the mixed solution is adjusted to 10 by adopting 0.1mol/L NaOH, and the temperature is increased to 80 ℃. And (4) carrying out crystallization reaction for about 24 hours to obtain MgAl-LDH-MBT suspension.
(4) Washing and drying: and (3) absorbing a small amount of suspension, washing with water for three times, centrifuging, and drying at the low temperature of 60 ℃ to obtain the MgAl-LDH-MBT intercalation material for later use.
Example 5
Preparing a catalytic controllable corrosion inhibition intercalation nano magnesium aluminum hydrotalcite (MgAl-LDH-MMIMMD) material:
(1) preparing a solution: solution A: 44.4g of magnesium nitrate and 37.5g of aluminum nitrate are weighed into a three-neck flask, and 4000ml of deionized water is added to dissolve the magnesium nitrate and the aluminum nitrate. Solution B: 33.7g of 2-mercaptobenzimidazole and 11.8g of NaOH are weighed out and dissolved in 1000ml, and the pH is adjusted to 9.5-10.5.
(2) Heating and reacting: the solution A is heated to 75 ℃, and the solution B is slowly added dropwise under the condition of vigorous stirring, wherein the dropwise adding time is about 1 h.
(3) Crystallization: after the dropwise addition, the pH of the mixed solution is adjusted to 10 by using 0.1mol/L NaOH, and the temperature is increased to 75 ℃. And (4) carrying out crystallization reaction for about 24 hours to obtain MgAl-LDH-MMIMD suspension.
(4) Washing and drying: and (3) absorbing a small amount of suspension, washing with water for three times, centrifuging, and drying at the low temperature of 60 ℃ to obtain the MgAl-LDH-MMIMD intercalation material for later use.
EXAMPLE 6 preparation of coating composition without intercalated Material
Composition formula
The component A comprises:
and B component:
| raw material | By weight parts/%) |
| Aqueous epoxy curing agent | 60～80 |
| Water (W) | 10～20 |
| Auxiliary agent | 1～2 |
The preparation method of the non-intercalation material coating composition comprises the following steps:
(1) accurately weighing water, a dispersing agent and a defoaming agent in the component A, and uniformly dispersing the water, the dispersing agent and the defoaming agent in a slurry preparation container at 500-900 rpm by using a high-speed dispersing agent;
(2) sequentially adding wollastonite, precipitated barium sulfate, titanium dioxide and aluminum phosphate in the component A into a container, and dispersing at 1500-1700 rpm for half an hour;
(3) transferring the dispersed slurry to a grinder, and grinding at 2500rpm until the fineness is less than 30 microns to obtain slurry;
(4) transferring the obtained slurry into a paint mixing container, slowly stirring at low speed for 3 hours to remove air bubbles in the slurry, adding corresponding amounts of epoxy emulsion, film-forming assistant, flatting agent and thickening agent, and uniformly stirring;
(5) filtering with 400 mesh silk cloth, and packaging to obtain coating composition A component
(6) Mixing the component A, the obtained component B and water according to the weight ratio of 9:1:1, uniformly stirring, spraying, and curing at room temperature for 14 days to obtain a coating film with the following properties:
VOC content: 28 g/L; (GB/T23986-2009)
Neutral salt spray resistance (paint film thickness 80-90 um): epoxy primer, more than 1000 hours, bubbling, rusting, no cracking and no shedding of the coating (GB/T1771-: 5.87-6.49mm
Low-temperature curing performance: the following drying time is 8h at 5 ℃, and the actual drying time is 48h (GB/T1728-
Low temperature resistance: the coating does not bubble, rust, crack or fall off when stored for 240h at the low temperature of-55 ℃ (GJB150.4A-2009)
High and low temperature resistant cycle alternation test: 60 cycles of 55 ℃/2h to 75 ℃/2h, the coating does not bubble, rust, crack or fall off (GJB150.5A-2009)
Example 7 contains (MgAl-LDH-VO)4) Preparation of coating composition without catalytic intercalation material
Composition formula
The component A comprises:
and B component:
| raw material | By weight parts/%) |
| Aqueous epoxy curing agent | 60～80 |
| Water (W) | 10～20 |
| Auxiliary agent | 1～2 |
MgAl-LDH-VO4The preparation steps of the intercalation material coating composition are as follows:
(1) accurately weighing water, a dispersing agent and a defoaming agent in the component A, and uniformly dispersing the water, the dispersing agent and the defoaming agent in a slurry preparation container at 500-900 rpm by using a high-speed dispersing agent;
(2) wollastonite, precipitated barium sulfate, titanium dioxide, aluminum phosphate and MgAl-LDH-VO in the component A are mixed4Sequentially adding the intercalation materials into a container, and dispersing for half an hour at 1500-1700 rpm;
(3) transferring the dispersed slurry to a grinder, and grinding at 2500rpm until the fineness is less than 30 microns to obtain slurry;
(4) transferring the obtained slurry into a paint mixing container, slowly stirring at low speed for 3 hours to remove air bubbles in the slurry, adding corresponding amounts of epoxy emulsion, film-forming assistant, flatting agent and thickening agent, and uniformly stirring;
(5) filtering with 400 mesh silk cloth, and packaging to obtain coating composition A component
(6) Mixing the component A, the obtained component B and water according to the weight ratio of 9:1:1, uniformly stirring, spraying, and curing at room temperature for 14 days to obtain a coating film with the following properties:
VOC content: 29 g/L; (GB/T23986-2009)
Neutral salt spray resistance (paint film thickness 80-90 μm): epoxy primer, more than 1000 hours, no bubble, no rust, no crack and no fall-off at the non-marking position of the coating (GB/T1771-: 3.30-3.75mm
Low-temperature curing performance: the lower drying time is 8h at 5 ℃, and the actual drying time is 50h (GB/T1728-
Low temperature resistance: the coating does not bubble, rust, crack or fall off when stored for 240h at the low temperature of-55 ℃ (GJB150.4A-2009)
High and low temperature resistant cycle alternation test: 60 cycles of 55 ℃/2h to 75 ℃/2h, the coating does not bubble, rust, crack or fall off (GJB150.5A-2009)
Example 8 contains (MgAl-LDH-CrO)4) Preparation of coating composition without catalytic intercalation material
Composition formula
The component A comprises:
| raw material | By weight parts/%) |
| Epoxy emulsion | 40 |
| Precipitated barium sulfate | 8.2 |
| Titanium white powder | 12 |
| Wollastonite | 6.5 |
| Aluminium phosphate | 7 |
| MgAl-LDH-CrO4Intercalation material | 3.8 |
| Dispersing agent | 1.2 |
| Film forming aid | 0.8 |
| Defoaming agent | 0.2 |
| Leveling agent | 0.2 |
| Thickening agent | 0.1 |
| Water (W) | 20 |
And B component:
| raw material | By weight parts/%) |
| Aqueous epoxy curing agent | 60～80 |
| Water (W) | 10～20 |
| Auxiliary agent | 1～2 |
MgAl-LDH-CrO4The preparation steps of the intercalation material coating composition are as follows:
(1) accurately weighing water, a dispersing agent and a defoaming agent in the component A, and uniformly dispersing the water, the dispersing agent and the defoaming agent in a slurry preparation container at 500-900 rpm by using a high-speed dispersing agent;
(2) wollastonite, precipitated barium sulfate, titanium dioxide, aluminum phosphate and MgAl-LDH-CrO in the component A are mixed4Sequentially adding the intercalation materials into a container, and dispersing for half an hour at 1500-1700 rpm;
(3) transferring the dispersed slurry to a grinder, and grinding at 2500rpm until the fineness is less than 30 microns to obtain slurry;
(4) transferring the obtained slurry into a paint mixing container, slowly stirring at low speed for 3 hours to remove air bubbles in the slurry, adding corresponding amounts of epoxy emulsion, film-forming assistant, flatting agent and thickening agent, and uniformly stirring;
(5) filtering with 400 mesh silk cloth, and packaging to obtain coating composition A component
(6) Mixing the component A, the obtained component B and water according to the weight ratio of 9:1:1, uniformly stirring, spraying, and curing at room temperature for 14 days to obtain a coating film with the following properties:
VOC content: 29 g/L; (GB/T23986-2009)
Neutral salt spray resistance (paint film thickness 80-90 μm): epoxy primer, more than 1000 hours, no bubble, no rust, no crack and no fall-off at the non-marking position of the coating (GB/T1771-: 3.93-5.45mm
Low-temperature curing performance: the lower drying time is 8h at 5 ℃, and the actual drying time is 49h (GB/T1728-
Low temperature resistance: the coating does not bubble, rust, crack or fall off when stored for 240h at the low temperature of-55 ℃ (GJB150.4A-2009)
High and low temperature resistant cycle alternation test: 60 cycles of 55 ℃/2h to 75 ℃/2h, the coating does not bubble, rust, crack or fall off (GJB150.5A-2009)
EXAMPLE 9 preparation of a coating composition containing (MgAl-LDH-MBIMD) intercalation Material
Composition formula
The component A comprises:
| raw material | By weight parts/%) |
| Epoxy emulsion | 40 |
| Precipitated barium sulfate | 8.2 |
| Titanium white powder | 12 |
| Wollastonite | 6.5 |
| Aluminium phosphate | 7 |
| MgAl-LDH-MBIMD intercalation material | 3.8 |
| Dispersing agent | 1.2 |
| Film forming aid | 0.8 |
| Defoaming agent | 0.2 |
| Leveling agent | 0.2 |
| Thickening agent | 0.1 |
| Water (W) | 20 |
And B component:
| raw material | By weight parts/%) |
| Aqueous epoxy curing agent | 60～80 |
| Water (W) | 10～20 |
| Auxiliary agent | 1～2 |
The preparation method of the MgAl-LDH-MBIMD intercalation material coating composition comprises the following steps:
(1) accurately weighing water, a dispersing agent and a defoaming agent in the component A, and uniformly dispersing the water, the dispersing agent and the defoaming agent in a slurry preparation container at 500-900 rpm by using a high-speed dispersing agent;
(2) sequentially adding wollastonite, precipitated barium sulfate, titanium dioxide, aluminum phosphate and MgAl-LDH-MBIMD intercalation materials in the component A into a container, and dispersing at 1500-1700 rpm for half an hour;
(3) transferring the dispersed slurry to a grinder, and grinding at 2500rpm until the fineness is less than 30 microns to obtain slurry;
(4) transferring the obtained slurry into a paint mixing container, slowly stirring at low speed for 3 hours to remove air bubbles in the slurry, adding corresponding amounts of epoxy emulsion, film-forming assistant, flatting agent and thickening agent, and uniformly stirring;
(5) filtering with 400 mesh silk cloth, and packaging to obtain coating composition A component
(6) Mixing the component A, the obtained component B and water according to the weight ratio of 9:1:1, uniformly stirring, spraying, and curing at room temperature for 14 days to obtain a coating film with the following properties:
VOC content: 32 g/L; (GB/T23986-2009)
Neutral salt spray resistance (paint film thickness 80-90 μm): epoxy primer, more than 1000 hours, no bubble, no rust, no crack and no fall-off at the non-marking position of the coating (GB/T1771-: 4.09-4.70mm
Low-temperature curing performance: the lower drying time is 4h at 5 ℃, and the actual drying time is 24h (GB/T1728-
Low temperature resistance: the coating does not bubble, rust, crack or fall off when stored for 240h at the low temperature of-55 ℃ (GJB150.4A-2009)
High and low temperature resistant cycle alternation test: 60 cycles of 55 ℃/2h to 75 ℃/2h, the coating does not bubble, rust, crack or fall off (GJB150.5A-2009)
EXAMPLE 10 preparation of coating composition containing (MgAl-LDH-MBT) intercalation Material
Composition formula
The component A comprises:
and B component:
| raw material | By weight parts/%) |
| Aqueous epoxy curing agent | 60～80 |
| Water (W) | 10～20 |
| Auxiliary agent | 1～2 |
The preparation method of the MgAl-LDH-MBT intercalation material coating composition comprises the following steps:
(1) accurately weighing water, a dispersing agent and a defoaming agent in the component A, and uniformly dispersing the water, the dispersing agent and the defoaming agent in a slurry preparation container at 500-900 rpm by using a high-speed dispersing agent;
(2) sequentially adding wollastonite, precipitated barium sulfate, titanium dioxide, aluminum phosphate and MgAl-LDH-MBT intercalation materials in the component A into a container, and dispersing at 1500-1700 rpm for half an hour;
(3) transferring the dispersed slurry to a grinder, and grinding at 2500rpm until the fineness is less than 30 microns to obtain slurry;
(4) transferring the obtained slurry into a paint mixing container, slowly stirring at low speed for 3 hours to remove air bubbles in the slurry, adding corresponding amounts of epoxy emulsion, film-forming assistant, flatting agent and thickening agent, and uniformly stirring;
(5) filtering with 400 mesh silk cloth, and packaging to obtain coating composition A component
(6) Mixing the component A, the obtained component B and water according to the weight ratio of 9:1:1, uniformly stirring, spraying, and curing at room temperature for 14 days to obtain a coating film with the following properties:
VOC content: 29 g/L; (GB/T23986-2009)
Neutral salt spray resistance (paint film thickness 80-90 μm): epoxy primer, more than 1000 hours, no bubble, no rust, no crack and no fall-off at the non-marking position of the coating (GB/T1771-: 2.52-3.77mm
Low-temperature curing performance: the lower drying time is 6h and the actual drying time is 36h at 5 ℃ (GB/T1728-
Low temperature resistance: the coating does not bubble, rust, crack or fall off when stored for 240h at the low temperature of-55 ℃ (GJB150.4A-2009)
High and low temperature resistant cycle alternation test: 60 cycles of 55 ℃/2h to 75 ℃/2h, the coating does not bubble, rust, crack or fall off (GJB150.5A-2009)
EXAMPLE 11 preparation of a coating composition containing (MgAl-LDH-MMIMD) intercalated Material
Composition formula
The component A comprises:
and B component:
| raw material | By weight parts/%) |
| Aqueous epoxy curing agent | 60～80 |
| Water (W) | 10～20 |
| Auxiliary agent | 1～2 |
The preparation method of the MgAl-LDH-MMIMD intercalation material coating composition comprises the following steps:
(1) accurately weighing water, a dispersing agent and a defoaming agent in the component A, and uniformly dispersing the water, the dispersing agent and the defoaming agent in a slurry preparation container at 500-900 rpm by using a high-speed dispersing agent;
(2) sequentially adding wollastonite, precipitated barium sulfate, titanium dioxide, aluminum phosphate and MgAl-LDH-MMIMMD intercalation materials in the component A into a container, and dispersing at 1500-1700 rpm for half an hour;
(3) transferring the dispersed slurry to a grinder, and grinding at 2500rpm until the fineness is less than 30 microns to obtain slurry;
(4) transferring the obtained slurry into a paint mixing container, slowly stirring at low speed for 3 hours to remove air bubbles in the slurry, adding corresponding amounts of epoxy emulsion, film-forming assistant, flatting agent and thickening agent, and uniformly stirring;
(5) filtering with 400 mesh silk cloth, and packaging to obtain coating composition A component
(6) Mixing the component A, the obtained component B and water according to the weight ratio of 9:1:1, uniformly stirring, spraying, and curing at room temperature for 14 days to obtain a coating film with the following properties:
VOC content: 28 g/L; (GB/T23986-2009)
Neutral salt spray resistance (paint film thickness 80-90 μm): epoxy primer, more than 1000 hours, no bubble, no rust, no crack and no fall-off at the non-marking position of the coating (GB/T1771-: 4.57-5.11mm
Low-temperature curing performance: the lower drying time is 3h at 5 ℃, and the actual drying time is 18h (GB/T1728-
Low temperature resistance: the coating does not bubble, rust, crack or fall off when stored for 240h at the low temperature of-55 ℃ (GJB150.4A-2009)
High and low temperature resistant cycle alternation test: 60 cycles of 55 ℃/2h to 75 ℃/2h, the coating does not bubble, rust, crack or fall off (GJB150.5A-2009)
Claims (10)
1. Controllable bufferEtching intercalation nano MgAl-LDH-SxCyNz mThe preparation method of the material is characterized by comprising the following steps:
(1) preparing a solution: solution A: weighing a certain amount of soluble magnesium salt and aluminum salt, placing the soluble magnesium salt and aluminum salt in a three-neck flask, adding deionized water for dissolution, and adding the weight ratio of solution B: weighing a certain amount of azole S with corrosion inhibition effectxCyNz m-Adding NaOH aqueous solution for dissolving, and adjusting the pH value to a proper value;
(2) heating and reacting: heating the solution A to 50-80 ℃, slowly dripping the solution B under the condition of vigorous stirring, wherein the dripping time is about 0.5-1.5 h;
(3) crystallization: after the dropwise addition is finished, adjusting the pH of the mixed solution to 9-12 by adopting 0.1mol/L NaOH, heating to 70-90 ℃, and carrying out crystallization reaction for 20-30 h to obtain MgAl-LDH-SxCyNz m-Suspending liquid;
(4) washing and drying: absorbing a small amount of turbid liquid, washing with water for three times, centrifuging, and drying at the low temperature of 55-65 ℃ to obtain MgAl-LDH-SxCyNz mThe intercalation material is ready for use.
2. The controlled corrosion inhibiting intercalated nano MgAl-LDH-S of claim 1xCyNz mThe preparation method of the material is characterized in that in the step (1), the pH is controlled to be 9.5-10.5.
3. The controlled corrosion inhibiting intercalated nano MgAl-LDH-S of claim 1xCyNz mThe preparation method of the material is characterized in that in the step (2), the heating temperature of the solution A is 55-65 ℃.
4. The controlled corrosion inhibiting intercalated nano MgAl-LDH-S of claim 1xCyNz mThe preparation method of the material is characterized in that in the step (2), the dropping time of the solution B is controlled to be 1 h.
5. According toThe controlled corrosion inhibiting intercalated nano MgAl-LDH-S as recited in claim 1xCyNz mThe preparation method of the material is characterized in that in the step (3), the pH is controlled to be 9.5-10.5.
6. The controlled corrosion inhibiting intercalated nano MgAl-LDH-S of claim 1xCyNz mThe preparation method of the material is characterized in that in the step (3), the heating temperature of the solution A is 80-85 ℃, and the crystallization reaction time is 24-26 h.
7. The controlled corrosion inhibiting intercalated nano MgAl-LDH-S of claim 1xCyNz mThe preparation method of the material is characterized in that the soluble magnesium salt in the step (1) is one or two of magnesium nitrate and magnesium sulfate; the soluble aluminum salt is one or two of aluminum nitrate and aluminum sulfate, and Mg2+：Al3+The molar ratio is 3: 1; sxCyNz m-Is one or more corrosion inhibiting ions of 2-mercaptobenzimidazole (MBIMD), 2-Mercaptobenzothiazole (MBT), 2-mercapto-1-methylimidazole (MMIMD) and 1- (11-mercaptoundecyl) imidazole (MUI), SxCyNz m-：(Mg2++Al3+)＝1～2：1。
8. The water-based low-temperature-resistant anticorrosive paint is characterized by consisting of a component A and a component B, wherein the A, B component has the following formula:
the component A comprises:
and B component:
the auxiliary agent 1 is a defoaming agent, a dispersing auxiliary agent, a film-forming auxiliary agent, a flash corrosion inhibitor, a wetting and leveling agent, a rheological auxiliary agent, a thickening agent and an anti-mildew auxiliary agent, and the auxiliary agent 2 is a flash corrosion inhibitor.
9. The preparation method of the water-based low-temperature-resistant anticorrosive paint according to claim 8, characterized by comprising the following steps:
(1) preparing slurry of the component A: dispersing and stirring 25-35% of pigment filler, 5-9% of antirust pigment, 3-5% of intercalation material, 18-20% of defoaming agent, dispersing aid and water in a mixing tank at a high speed, and grinding until the fineness is less than or equal to 30 mu m;
(2) preparation of a component A: stirring and defoaming the slurry at a low speed, adding 35-42% of epoxy emulsion, a film-forming aid, a flash corrosion inhibitor, a wetting and leveling agent, a rheological aid, a thickening agent and an anti-mildew aid, dispersing uniformly, filtering and discharging to obtain a component A;
(3) b, preparation of a component: adding water and a flash erosion inhibitor into the weighed curing agent, uniformly dispersing, filtering and discharging to obtain a component B;
(4) preparing a coating: the epoxy group content of the component A and the active hydrogen content of the component B are as follows: 0.65-0.8 of the above-mentioned components.
10. The preparation method of the water-based low-temperature-resistant anticorrosive paint according to claim 9, characterized in that, in the step (1), the pigment and filler comprise an extender and a pigment, and the extender is one or more of talcum powder, precipitated barium sulfate, kaolin, hydrotalcite and wollastonite; the pigment is one or more than two of rutile titanium dioxide, iron oxide red, iron oxide yellow and carbon black, the antirust pigment is one or more than two of zinc phosphate, aluminum zinc phosphate, basic molybdenum zinc phosphate and aluminum tripolyphosphate, and the intercalation material is one or more than two of MgAl-LDH-MUI, MgAl-LDH-MMIMD, MgAl-LDH-MBIMD and MgAl-LDH-MBT.
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