CN101643322B - Vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, and preparation method thereof - Google Patents
Vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, and preparation method thereof Download PDFInfo
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- CN101643322B CN101643322B CN2008100126589A CN200810012658A CN101643322B CN 101643322 B CN101643322 B CN 101643322B CN 2008100126589 A CN2008100126589 A CN 2008100126589A CN 200810012658 A CN200810012658 A CN 200810012658A CN 101643322 B CN101643322 B CN 101643322B
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- polyaniline
- vinyl ester
- glass flakes
- modified glass
- coating
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- 239000011521 glass Substances 0.000 title claims abstract description 88
- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 36
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000467 phytic acid Substances 0.000 claims abstract description 36
- 229940068041 phytic acid Drugs 0.000 claims abstract description 36
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920000767 polyaniline Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 10
- 238000007665 sagging Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 7
- -1 phenol aldehyde Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical group CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000002345 surface coating layer Substances 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009827 uniform distribution Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 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 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 14
- 229910000831 Steel Inorganic materials 0.000 abstract description 8
- 239000010959 steel Substances 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003973 paint Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000037452 priming Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102100022587 Peroxisomal multifunctional enzyme type 2 Human genes 0.000 description 1
- 101710125609 Peroxisomal multifunctional enzyme type 2 Proteins 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- FUPMSLTYEIZSLZ-UHFFFAOYSA-N cobalt;naphthalene-1-carboxylic acid Chemical compound [Co].C1=CC=C2C(C(=O)O)=CC=CC2=C1 FUPMSLTYEIZSLZ-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention relates to coating technology, in particular to a vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, and a preparation method thereof, which solves the problem that the surfaces of steel or other metal substrates need to be coated with primer to increase anti-corrosion performance and prevent coatings and substrate interfaces from being corroded in the construction of most of the prior glass-flake anticorrosive coatings. The vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes comprises vinyl ester resin, the polyaniline-modified glass flakes, amine curing agent and the like. As polyaniline coating layers are formed on the surfaces of the glass flakes by an oxidative polymerization method, the treated glass flakes have the effect of passivating metal, and phytic-acid coating layers on the surfaces of the glass flakes play a role in inhibiting corrosion of metal. The vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes has strong corrosion resistance and permeation resistance, can be applied to heavy-duty engineering in the fields of petrochemical industry, wharf facilities, ships and the like, and is particularly applicable to the protection of spray splash areas and tidal range areas.
Description
Technical field
The present invention relates to coating technology, be specially a kind of vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes and preparation method thereof.
Background technology
Chinese invention patent (patent No. ZL 91111830.6) has proposed a kind of preparation method of glass flake anticorrosive coating, and it is made up of Resins, epoxy, glass flake, solvent, titanate coupling agent, modified amine curing agent.Chinese invention patent application (publication number CN 1789351A) has disclosed a kind of glass flake plasticine coating, comprises vinyl ester resin, glass flake and additive composition, is used for the high place of flue gas desulfurization requirement for anticorrosion.Chinese invention patent (patent No. ZL 93117158.X) has proposed to contain the preparation method of the boron modified phenolic resin protection against corrosion matrix material of glass flake.Chinese invention patent application (publication number CN 1861717A, 1861718A, 1861719A) proposes the vinyl ester resin glass flake painting coating of wet process of FGD equipment anticorrosion, has anti-medium osmosis and temperature resistance sex change.These glass flake anticorrosive coatings when construction major part will be at iron and steel or other metallic substrate surface coating prime lacquers to increase Corrosion Protection, prevent that coating and substrate interface place from corroding.These priming paint can be the rich no yellow zinc chromate primer paint of epoxy, epoxy phosphate yellow zinc chromate primer paint, epoxy zinc yellow anticorrosive paint, inorganic zinc rich paint etc.The construction of priming paint has increased construction cost, has prolonged the duration.Sometimes because construction problem also delamination can take place between priming paint and the glass flake anticorrosive coating, influence the protective value of coating in addition to base material.
Summary of the invention
The object of the present invention is to provide a kind of vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes and preparation method thereof, solve existing glass flake anticorrosive coating major part when construction and will prevent problems such as coating and substrate interface place generation corrosion at iron and steel or other metallic substrate surface coating prime lacquers to increase Corrosion Protection.
Technical scheme of the present invention is:
A kind of vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, described vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes is counted by weight, comprises following component and content:
Vinyl ester resin 15～90;
Polyaniline-modified glass flakes 15～40;
Solvent 0.1～2;
Pigment 1～10;
Filler 1～10;
Anti-sagging agent 0.5～4;
Defoamer 0.05～2;
Promotor 0.5～4;
Initiator 0.5～3.
Described vinyl ester resin is phenol aldehyde type and bisphenol type vinyl ester resin.The bisphenol type vinyl ester resin can be selected Atlac 382, Atlac 4010, Atlac430ACT, Atlac 430LV, Atlac 580, Atlac 382, Atlac 4010, Atlac 430 or the Atlac580 etc. of Nanjing DSM resin company limited for use; The MFE-2 of East China University Of Science And Technology Huachang Polymer Co., Ltd, MFE-3, MFE-10, MFE-11, MFE-22 or MFE-30 etc.The phenol aldehyde type vinyl ester resin can be selected the Atlac 590 of Nanjing DSM resin company limited etc. for use; H630DAEX of Shanghai Zhaohe High Molecule Co., Ltd. or H630EX etc.; The W of East China University Of Science And Technology Huachang Polymer Co., Ltd
2-1 or W
2-3 etc.
In the vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, employed solvent is a vinylbenzene.
Described pigment is coating pigment commonly used, as titanium dioxide, white lead, zinc oxide, lithopone, phthalocyanine green, toluidine red, red iron oxide etc.; Filler is a coating filler commonly used, as ground barium sulfate, GL ground limestone, precipitated calcium carbonate, talcum powder, quartz sand etc.
Described anti-sagging agent is one of wilkinite, polynite, kaolin, aerosil or mixture.
Described defoamer is a coating auxiliary agent commonly used, as: as BYK-065, the BYK-066N of the Defom 5300,5400,5500 of the modest chemical company of moral or German Bi Ke chemical company.
Described promotor being contains the acid solution of cobalt, comprises naphthoic acid cobalt, cobalt naphthenate, cobalt octoate or cobalt iso-octoate.
Described initiator is methylethyl ketone peroxide or peroxidized t-butyl perbenzoate.
The particle diameter of described glass flake is 80～1000 orders, and its thickness is 1～20 μ m.
The structure of described polyaniline-modified glass flakes consists of for being sheet structure: surface coating layer is polyaniline and phytic acid, and inside is glass flake; In coating layer, polyaniline and phytic acid uniform distribution, polyaniline accounts for 50～99.98wt%, and phytic acid accounts for 0.02～50wt%.Preferable range is: polyaniline accounts for 70～99.8wt%, and phytic acid accounts for 0.2～30wt%.
The preparation method of described vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, carry out with step in the following order:
1) preparation method of polyaniline-modified glass flakes
(a) preparation phosphoric acid and phytic acid mixed aqueous solution: wherein phosphoric acid is 0.01～5 mol, is preferably 0.1～3 mol; Phytic acid is 0.01～1 mol, is preferably 0.05～0.5 mol.
(b) aniline is joined in phosphoric acid and the phytic acid mixed aqueous solution, mixed aniline concentration is: 0.01～1 mol.Be preferably 0.05～1 mol.Continue to stir (0.5～2 hour).Get phosphoric acid and phytic acid, aniline mixed aqueous solution 500ml, add 80～1000 order glass flakes of 5～1000g, and stir (5～30 minutes), be pre-chilled to 0～10 ℃.
(c) aqueous solution of preparation oxygenant: the concentration of oxygenant is 0.05～5 mol in the solution.Be preferably 0.1～2 mol.The aqueous solution of oxygenant is pre-chilled to 0～10 ℃.Oxygenant can be ammonium persulphate, hydrogen peroxide, Potassium Persulphate, benzoyl peroxide, iron trichloride, potassium bichromate, potassium permanganate or two or more mixtures.
(d) be slowly to add in 10～30 minutes in the 500ml acid that contains glass flake and phytic acid, the aniline mixed aqueous solution (b) (c) 500ml solution in the time, 0～10 ℃ of reaction 1～8 hour, centrifugal, use distilled water wash, 80～100 ℃ of dryings are after 1～5 hour, grind with mortar, and screening, the glass flake that bottle-green 80～1000 order electrically conductive polyanilines are handled obtained.
2) solvent, defoamer, anti-sagging agent, pigment, filler are joined in the vinyl ester resin, grind in general coating apparatus such as sand mill or three-roller then stir (10 minutes～60 minutes), and fineness is less than discharging after 60 microns;
3) under high-speed stirring, polyaniline-modified glass flakes is added 2) in the vinyl ester resin mixture in, carry out high speed dispersion evenly (20～60 minutes), obtain the base-material of vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes;
Add promotor and initiator when 4) using in proportion, stir, the method of using roller coat, spraying, brushing trowel to be coated with is coated with substrate surface, forms polyaniline-modified glass flakes vinyl ester anticorrosion coat after solidifying 7～15 days under 5 ℃～40 ℃ the normal temperature condition; Perhaps, as required, also can be again 50～100 ℃ of after fixing 1～5 hour.
Advantage of the present invention is as follows:
1, adopt the present invention, the vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes of acquisition can be realized the passivation and the inhibition of metal base.
2, adopt the present invention, improved the solidity to corrosion and the permeability resistance of conventional glass-flake coating.
3, adopt the present invention, can replace the applied priming paint of glass-flake coating, directly be coated on substrate surface.
4, adopt the present invention, the vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes that is obtained has excellent storage stability, is difficult for sinking to the bottom.
Vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes of the present invention is made up of vinyl ester resin, polyaniline-modified glass flakes, amine curing agent etc.Utilize oxidative polymerization method to form the polyaniline coating layer on the glass flake surface, the glass flake after the processing has passivation to metal, and the phytic acid coating layer on glass flake surface also plays the effect of inhibition to metal.Vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes has very strong solidity to corrosion and permeability resistance, can be applicable to the heavy antiseptic project of petrochemical equipment, pipeline, offshore oil platform, terminal facilities, boats and ships etc.The protection in be specially adapted to that waves splash about district and tidal range district.
The performance evaluation of glass flake vinyl ester coating: from the coating sample for preparing, select three, and intersect cut until exposing ground at coatingsurface with special-purpose cut pen.A slice is used for reference in addition.The neutral salt spray test of the coating sample of cut adopts Japan must congratulate the ST-ISO-3 salt-fog test machine of trier Co., Ltd..The NaCl strength of solution is 3.5wt%, and test temperature is 40 ± 2 ℃, sprays continuously 500 hours, and neutral salt spray test operative norm GB1771-79 measures corrosion expansion maximum width in cut place after 500 hours salt-fog tests.
Embodiment
Unless outside specializing among the present invention, related ratio all is weight percentage or weight ratio.
Comparative example 1-3
0.5 part of vinylbenzene, 1.2 parts of defoamers (BYK-065), 0.6 part of anti-sagging agent (wilkinite), 2.5 parts of pigment (titanium dioxide), 3 parts of fillers (ground barium sulfate), join in 75 parts of Atlac 4010 vinyl ester resins, stirred 20 minutes, grind in sand mill then, fineness is less than discharging after 60 microns; Then 20 parts, 30 parts, 40 parts (comparative example 1, comparative example 2, comparative examples 3) are not had to stir 30 minutes in the material after treated 240 order glass flakes join above-mentioned grinding respectively.Make the base-material of vinyl ester glass-flake coating.
In above-mentioned base-material, add 1.5 parts of promotor (cobalt naphthenate) and 2 parts of initiators (methylethyl ketone peroxide) respectively, and mix, handle four 150mm * 75mm * No. 45 these coating of surface of steel plate Airless spraying of 2mm at commercial blast to the Sa2.5 level, Air drying 15 days, use weight ratio rosin then: 60 ℃ of liquid of paraffin=1: 1 carry out edge sealing, carry out the coating performance test.The build of paint film is 400 ± 10 μ m.
Comparative example 4-6
1 part of vinylbenzene, 0.5 part of defoamer (Defom 5400), 2.5 parts of anti-sagging agents (kaolin), 6 parts of pigment (zinc oxide), 3 parts of fillers (talcum powder), join 60 parts of W
2In-1 vinyl ester resin, stirred 40 minutes, grind in three-roller then, fineness is less than discharging after 30 microns; The 325 order glass flakes that 16 parts, 26 parts, 36 parts (comparative example 4, comparative example 5, comparative example 6) handled through silane coupling agent KH570 join respectively in the material after the above-mentioned grinding then, stir 30 minutes.Make the base-material of vinyl ester glass-flake coating.
In above-mentioned base-material, add 1 part of promotor (cobalt octoate) and 1.5 parts of initiators (peroxidized t-butyl perbenzoate) respectively, and mix, handle four 150mm * 75mm * No. 45 these coating of surface of steel plate roller coat of 2mm at commercial blast to the Sa2.5 level, Air drying 15 days, after fixing 2 hours in 70 ℃ loft drier again, use weight ratio rosin then: 60 ℃ of liquid of paraffin=1: 1 carry out edge sealing, carry out the coating performance test.The build of paint film is 400 ± 10 μ m.
Embodiment 1-3
Prepare polyaniline-modified glass flakes by the following method:
(a) preparation phosphoric acid and phytic acid mixed aqueous solution: wherein phosphoric acid is 1.2 mol; Phytic acid is 0.6 mol.
(b) aniline is joined in phosphoric acid and the phytic acid mixed aqueous solution, mixed aniline concentration is: 0.5 mol.Continue to stir 1.5 hours.Get phosphoric acid and phytic acid, aniline mixed aqueous solution 500ml, add the 240 order glass flakes of 500g, and stirred 30 minutes, be pre-chilled to 8 ℃.
(c) aqueous solution of preparation oxygenant: select benzoyl peroxide as oxygenant, the concentration of preparation benzoyl peroxide is 1.2 mol.The aqueous solution of benzoyl peroxide is pre-chilled to 8 ℃.
(d) (c) 500ml solution was slowly added in 10～30 minutes in the 500ml acid that contains glass flake and phytic acid, the aniline mixed aqueous solution (b), 5 ℃ of reactions 3 hours, centrifugal, use distilled water wash, 80 ℃ of dryings are after 3 hours, grind with mortar, obtain the glass flake of bottle-green 240 order electrically conductive polyaniline modifications after the screening.In the present embodiment, the structure of resulting polyaniline-modified glass flakes is a sheet structure, consists of: surface coating layer is polyaniline and phytic acid, and inside is glass flake; In the coating layer of present embodiment, polyaniline and phytic acid uniform distribution, polyaniline accounts for 80wt%, and phytic acid accounts for 20wt%.
0.5 part of vinylbenzene, 1.2 parts of defoamers (BYK-065), 0.6 part of anti-sagging agent (wilkinite), 2.5 parts of pigment (titanium dioxide), 3 parts of fillers (ground barium sulfate), join in 75 parts of Atlac 4010 vinyl ester resins, stirred 20 minutes, grind in sand mill then, fineness is less than discharging after 60 microns; The 240 order glass flakes that 20 parts, 30 parts, 40 parts (corresponding embodiment 1, embodiment 2, embodiment 3) handled through polyaniline join respectively in the material after the above-mentioned grinding then, stir 30 minutes.Make the base-material of vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes.
In above-mentioned base-material, add 1.5 parts of promotor (cobalt naphthenate) and 2 parts of initiators (methylethyl ketone peroxide) respectively, and mix, handle four 150mm * 75mm * No. 45 these coating of surface of steel plate Airless spraying of 2mm at commercial blast to the Sa2.5 level, Air drying 15 days, use weight ratio rosin then: 60 ℃ of liquid of paraffin=1: 1 carry out edge sealing, carry out the coating performance test.The build of paint film is 400 ± 10 μ m.
Embodiment 4-6
Prepare polyaniline-modified glass flakes by the following method:
(a) preparation phosphoric acid and phytic acid mixed aqueous solution: wherein phosphoric acid is 0.4 mol; Phytic acid is 0.1 mol.
(b) aniline is joined in phosphoric acid and the phytic acid mixed aqueous solution, mixed aniline concentration is: 0.1 mol.Continue to stir 1 hour.Get phosphoric acid and phytic acid, aniline mixed aqueous solution 500ml, add the 325 order glass flakes of 200g, and stirred 20 minutes, be pre-chilled to 2 ℃.
(c) aqueous solution of preparation oxygenant: select ammonium persulphate as oxygenant, the concentration of preparation ammonium persulphate is 0.5 mol.The aqueous solution of ammonium persulphate is pre-chilled to 2 ℃.
(d) (c) 500ml solution was slowly added in 20 minutes in the 500ml acid that contains glass flake and phytic acid, the aniline mixed aqueous solution (b), 2 ℃ of reactions 1 hour, centrifugal, use distilled water wash, 100 ℃ of dryings are after 1 hour, grind with mortar, obtain the glass flake of bottle-green 325 order electrically conductive polyaniline modifications after the screening.In the present embodiment, the structure of resulting polyaniline-modified glass flakes is a sheet structure, consists of: surface coating layer is polyaniline and phytic acid, and inside is glass flake; In the coating layer of present embodiment, polyaniline and phytic acid uniform distribution, polyaniline accounts for 90wt%, and phytic acid accounts for 10wt%.
1 part of vinylbenzene, 0.5 part of defoamer (Defom 5400), 2.5 parts of anti-sagging agents (kaolin), 6 parts of pigment (zinc oxide), 3 parts of fillers (talcum powder), join 60 parts of W
2In-1 unsaturated ethylene thiazolinyl ester resin, stirred 40 minutes, grind in three-roller then, fineness is less than discharging after 30 microns; Then 16 parts, 26 parts, 36 parts (corresponding embodiment 4, embodiment 5, embodiment 6) passed through in the material after polyaniline-modified glass flake joins above-mentioned grinding respectively, stirred 30 minutes.Make the base-material of the heavy anticorrosion vinyl ester coating of polyaniline-modified glass flakes.
In above-mentioned base-material, add 1 part of promotor (cobalt octoate) and 1.5 parts of initiators (peroxidized t-butyl perbenzoate) respectively, and mix, handle four 150mm * 75mm * No. 45 some roads of this coating of surface of steel plate roller coat of 2mm at commercial blast to the Sa2.5 level, Air drying 15 days, after fixing 2 hours in 70 ℃ loft drier again, use weight ratio rosin then: 60 ℃ of liquid of paraffin=1: 1 carry out edge sealing, carry out the coating performance test.The build of paint film is 400 ± 10 μ m.
Table 1 glass flake vinyl ester coating property evaluation table
| Cut place corrosion expansion maximum width, mm | |
| Comparative example 1 | 2.8 |
| Comparative example 2 | 2.5 |
| Comparative example 3 | 2.2 |
| Comparative example 4 | 2.3 |
| Comparative example 5 | 2.1 |
| Comparative example 6 | 1.7 |
| Embodiment 1 | 0.7 |
| Embodiment 2 | 0.6 |
| Embodiment 3 | 0.4 |
| Embodiment 4 | 0.6 |
| Embodiment 5 | 0.5 |
| Embodiment 6 | 0.5 |
Illustrate: according to the test-results of table 1, embodiment compares with corresponding comparative example, and corrosion extension width in cut place obviously narrows down, and shows the solidity to corrosion that has significantly been increased coating by polyaniline-modified glass flake.
Because the solidity to corrosion of polyaniline-modified glass flakes coating obviously is better than conventional glass-flake coating, it can the really heavy rot-resistant effect of performance under rigorous environment.And overcome the shortcoming that the glass flake anticorrosive coating that exists in the prior art needs coating prime lacquer, and proposed the anticorrosive coating scheme of single coating.The vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes of being invented utilizes polyaniline can make metal base generation passivations such as iron and steel; phytic acid produces corrosion inhibition and has strengthened the provide protection of glass flake anticorrosive coating to base material, and making no longer needs the application rust-proofing primer before application glass flake anticorrosive coating.Be very beneficial particularly to ocean heavy construction painting operation.This coating excellent storage stability is difficult for sinking to the bottom.Polyaniline-modified glass flake and resin compatible are good, chemically stable.
Claims (5)
1. a vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes is characterized in that, described vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes is counted by weight, comprises following component and content:
Vinyl ester resin 15～90;
Polyaniline-modified glass flakes 15～40;
Solvent 0.1～2;
Pigment 1～10;
Filler 1～10;
Anti-sagging agent 0.5～4;
Defoamer 0.05～2;
Promotor 0.5～4;
Initiator 0.5～3;
The structure of described polyaniline-modified glass flakes is a sheet structure, consists of: surface coating layer is polyaniline and phytic acid, and inside is glass flake; In coating layer, polyaniline and phytic acid uniform distribution, polyaniline accounts for 50～99.98wt%, and phytic acid accounts for 0.02～50wt%;
Described vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes is prepared with step in the following order:
1) preparation method of polyaniline-modified glass flakes
(a) preparation phosphoric acid and phytic acid mixed aqueous solution: wherein phosphoric acid is 0.01～5 mol, and phytic acid is 0.01～1 mol;
(b) aniline is joined in phosphoric acid and the phytic acid mixed aqueous solution, mixed aniline concentration is: 0.01～1 mol, continue to stir, get phosphoric acid and phytic acid, aniline mixed aqueous solution 500ml, add the 80-1000 order glass flake of 5～1000g, and stir, be pre-chilled to 0～10 ℃;
(c) aqueous solution of preparation oxygenant: the concentration of oxygenant is 0.05～5 mol in the solution, and the aqueous solution of oxygenant is pre-chilled to 0～10 ℃; Oxygenant is ammonium persulphate, hydrogen peroxide, Potassium Persulphate, benzoyl peroxide, iron trichloride, potassium bichromate, potassium permanganate or two or more mixtures;
(d) solution that 500ml step (c) is made is to add in 10～30 minutes in the 500ml phosphoric acid that contains glass flake that step (b) makes and phytic acid, the aniline mixed aqueous solution in the time, 0～10 ℃ of reaction 1～8 hour, centrifugal, use distilled water wash, 80～100 ℃ of dryings are after 1～5 hour, grind with mortar, and screening, the glass flake that bottle-green 80～1000 order electrically conductive polyanilines are handled obtained;
2) solvent, defoamer, anti-sagging agent, pigment, filler are joined in the vinyl ester resin, stir, grind in general coating apparatus then, fineness is less than discharging after 60 microns;
3) under agitation polyaniline-modified glass flakes is added 2) in the vinyl ester resin mixture in, be uniformly dispersed, obtain the base-material of vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes;
Add promotor and initiator when 4) using, stir, the method for using roller coat, spraying, brushing trowel to be coated with is coated with substrate surface, forms polyaniline-modified glass flakes vinyl ester anticorrosion coat after solidifying 7～15 days under 5 ℃～40 ℃ the normal temperature condition; Perhaps, as required, solidified 1～5 hour at 50～100 ℃ again.
2. vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes according to claim 1 is characterized in that: described vinyl ester resin is phenol aldehyde type and bisphenol type vinyl ester resin.
3. vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes according to claim 1 is characterized in that: described initiator is methylethyl ketone peroxide or peroxidized t-butyl perbenzoate.
4. vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes according to claim 1 is characterized in that: the particle diameter of described glass flake is 80～1000 orders, and its thickness is 1～20 μ m.
5. vinyl ester heavy-duty anticorrosive coating with polyaniline-modified glass flakes according to claim 1 is characterized in that: described solvent is a vinylbenzene.
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| CN102732124A (en) * | 2012-06-04 | 2012-10-17 | 上海大学 | Fluorine-containing heavy-duty anticorrosive coating and its application |
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| CN1035622C (en) * | 1991-12-27 | 1997-08-13 | 中国石油天然气总公司工程技术研究所 | Glass flake anticorrosion paint and its making method |
| CN1789351A (en) * | 2005-12-23 | 2006-06-21 | 吴凡 | Glass flake plasticine coating |
| EP1717279A1 (en) * | 2005-04-27 | 2006-11-02 | United Technologies Corporation | Chromate-free corrosion resistant epoxy primer |
| CN100393829C (en) * | 2006-06-01 | 2008-06-11 | 江苏兰陵化工集团有限公司 | Anticorrosive ethenyl ester resin glass flake paint for wet flue desulfating equipment |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035622C (en) * | 1991-12-27 | 1997-08-13 | 中国石油天然气总公司工程技术研究所 | Glass flake anticorrosion paint and its making method |
| EP1717279A1 (en) * | 2005-04-27 | 2006-11-02 | United Technologies Corporation | Chromate-free corrosion resistant epoxy primer |
| CN1789351A (en) * | 2005-12-23 | 2006-06-21 | 吴凡 | Glass flake plasticine coating |
| CN100393829C (en) * | 2006-06-01 | 2008-06-11 | 江苏兰陵化工集团有限公司 | Anticorrosive ethenyl ester resin glass flake paint for wet flue desulfating equipment |
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