CN116426193A - Water-based environment-friendly anticorrosive paint - Google Patents
Water-based environment-friendly anticorrosive paint Download PDFInfo
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- CN116426193A CN116426193A CN202310358313.3A CN202310358313A CN116426193A CN 116426193 A CN116426193 A CN 116426193A CN 202310358313 A CN202310358313 A CN 202310358313A CN 116426193 A CN116426193 A CN 116426193A
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- 239000003973 paint Substances 0.000 title claims abstract description 61
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- 239000002131 composite material Substances 0.000 claims abstract description 61
- 238000005260 corrosion Methods 0.000 claims abstract description 54
- 230000007797 corrosion Effects 0.000 claims abstract description 50
- 239000000839 emulsion Substances 0.000 claims abstract description 44
- 239000002105 nanoparticle Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 239000003112 inhibitor Substances 0.000 claims abstract description 32
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000661 sodium alginate Substances 0.000 claims abstract description 25
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 25
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 23
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- 238000009830 intercalation Methods 0.000 claims abstract description 16
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- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 12
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 8
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 8
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 8
- 150000004658 ketimines Chemical class 0.000 claims abstract description 8
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims abstract description 6
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004410 anthocyanin Substances 0.000 claims abstract description 6
- 229930002877 anthocyanin Natural products 0.000 claims abstract description 6
- 235000010208 anthocyanin Nutrition 0.000 claims abstract description 6
- 150000004636 anthocyanins Chemical class 0.000 claims abstract description 6
- 229940074360 caffeic acid Drugs 0.000 claims abstract description 6
- 235000004883 caffeic acid Nutrition 0.000 claims abstract description 6
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims abstract description 6
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000014304 histidine Nutrition 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 33
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 6
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 6
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 iron ions Chemical class 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 17
- 230000007774 longterm Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a water-based environment-friendly anticorrosive paint which comprises the following raw materials in parts by weight: 50-60 parts of aqueous composite emulsion and 4-10 parts of ketimine; 4-6 parts of polyaniline intercalation graphene, 16-18 parts of composite nano particles loaded with corrosion inhibitors and 5-10 parts of auxiliary agents; the aqueous composite emulsion consists of sodium alginate/acrylic acid/acrylamide copolymer emulsion and aqueous epoxy resin emulsion; the auxiliary agent comprises hydroxyethyl cellulose and expanded vermiculite powder; the composite nano particles are porous silica/titanium dioxide composite nano particles; the corrosion inhibitor consists of histidine, anthocyanin and caffeic acid; the invention takes aqueous composite emulsion as a matrix, and polyaniline intercalation graphene, composite nano particles loaded with corrosion inhibitors and auxiliary agents are added into the aqueous composite emulsion; the aqueous environment-friendly anticorrosive paint with long-term anticorrosive performance is prepared by taking ketimine as a curing agent.
Description
Technical Field
The invention belongs to the technical field of anti-corrosion paint, and particularly relates to a water-based environment-friendly anti-corrosion paint.
Background
The water-based anticorrosive paint is used as one of the development directions of the current heavy-duty anticorrosive paint, is a paint which uses water to replace an organic solvent in the traditional solvent-based paint, has the characteristics of low volatilization of the organic solvent and environmental protection, is limited by various factors, and is only about 10% in the current water-based anticorrosive paint in China, so that the research and development of the water-based anticorrosive paint with high anticorrosive performance becomes the research trend of the heavy-duty anticorrosive paint.
The water-based anticorrosive paint commonly used in the market at present comprises a water-based acrylic paint, a water-based epoxy paint, a water-based inorganic zinc-rich paint, a water-based polyurethane paint and the like, but the water-based anticorrosive paint at present has the following problems: firstly, the water-based anticorrosive paint has the problem of low solid content, thereby increasing the production cost; secondly, the anticorrosive paint of a single system has a single function, and is difficult to meet the working condition requirements in a complex environment; thirdly, the corrosion resistance of the paint is still to be improved, and factors influencing the corrosion resistance such as mechanical strength, compactness, water resistance and the like of a coating film are still to be overcome;
compared with the traditional solvent-based paint, the water-based paint has the advantages of low VOC content, convenient construction, easy cleaning, environmental protection and the like, but the traditional water-based paint accelerates the penetration of corrosive substances such as water and the like due to the polar channel formed by hydrophilic groups, and reduces the corrosion resistance and durability of the formed anti-corrosion paint;
in the prior art, inorganic particles are added into the water-based paint to improve the wear resistance, ageing resistance and corrosion resistance of the paint; however, inorganic particles have poor dispersibility in a coating matrix and are easy to agglomerate to influence the interaction of inorganic phases and organic phases, so that the coating film performance of the coating is poor and the corrosion resistance is not effectively improved; and the agglomeration of inorganic particles is easy to have the problem of protection defect. Therefore, research and development of an environment-friendly water-based anticorrosive paint with long-term anticorrosive performance, low cost, good anticorrosive performance and environmental friendliness are needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the environment-friendly water-based environment-friendly anticorrosive paint with long-term anticorrosive performance, and solves the problems of poor anticorrosive performance and poor durability of the coating at present.
An aqueous environment-friendly anticorrosive paint comprises the following raw materials in parts by weight: 50-60 parts of aqueous composite emulsion and 4-10 parts of ketimine; 4-6 parts of polyaniline intercalation graphene, 16-18 parts of composite nano particles loaded with corrosion inhibitors and 5-10 parts of auxiliary agents; the aqueous composite emulsion consists of sodium alginate/acrylic acid/acrylamide copolymer emulsion and aqueous epoxy resin emulsion;
preferably, the mass ratio of the sodium alginate, the acrylic acid and the acrylamide copolymer emulsion to the aqueous epoxy resin emulsion is 1:10;
preferably, the composite nano-particles are porous silica/titanium dioxide composite nano-particles; the corrosion inhibitor consists of histidine, anthocyanin and caffeic acid;
further, the preparation method of the aqueous composite emulsion specifically comprises the following steps: preparing sodium alginate solution, adding acrylamide and acrylic acid into the sodium alginate solution to obtain a mixed solution, introducing nitrogen into the mixed solution, and sequentially adding ammonium persulfate and ethylenediamine into the mixed solution to react to obtain sodium alginate/acrylic acid/acrylamide copolymer emulsion; adding the sodium alginate/acrylic acid/acrylamide copolymer emulsion into the aqueous epoxy resin emulsion, adding microcrystalline cellulose into the aqueous epoxy resin emulsion, and uniformly stirring to obtain an aqueous composite emulsion;
preferably, the addition amount of the microcrystalline cellulose is 10% of the weight of the aqueous composite emulsion;
preferably, the aqueous epoxy resin is E44;
further, the preparation method of the polyaniline intercalation graphene oxide specifically comprises the following steps: dispersing graphene oxide in a hydrochloric acid solution of tyrosine, adding aniline and ammonium persulfate into the solution after uniform ultrasonic dispersion, and polymerizing under the ice salt bath condition to obtain polyaniline intercalation graphene oxide;
preferably, the weight ratio of the graphene oxide to the aniline is 6:1; the molar ratio of the aniline to the ammonium persulfate is 0.5:1, a step of;
preferably, the preparation method of the composite nano particle loaded with the corrosion inhibitor comprises the following steps: dispersing tetrabutyl titanate and tetraethyl silicate in a mixed solution of alcohol and glacial acetic acid, and obtaining a mixed dispersion liquid after uniform dispersion; fe is added to 3+ With Fe 2+ Dissolving in deionized water, adding Fe powder, and adding the mixed dispersion liquid into the solution under the water bath condition of 55 ℃; simultaneously adjusting the pH value of the system to be alkaline; heating to 80 ℃, adding sodium citrate solution, continuously stirring and reacting until the reaction is completed, and obtaining magnetic composite nano particles after magnetic separation; the magnetic composite nano particles are placed in hydrochloric acid solution for soaking treatment, filtered and washed until the solution does not contain iron ions, then the nano particles are dispersed in corrosion inhibitor solution, and the composite nano particles loaded with the corrosion inhibitor can be obtained after ultrasonic treatment;
preferably, tetrabutyl titanate, tetraethyl silicate and Fe in the reaction system 3+ 、Fe 2+ The molar ratio of (2) is 3:6:1:0.5; the corrosion inhibitor solution is obtained by dispersing histidine, anthocyanin and caffeic acid in water according to the weight ratio of 2:1:1;
further, the auxiliary agent comprises hydroxyethyl cellulose and expanded vermiculite powder;
the invention takes aqueous composite emulsion as a matrix, and polyaniline intercalation graphene, composite nano particles loaded with corrosion inhibitors and auxiliary agents are added into the aqueous composite emulsion; the aqueous environment-friendly anticorrosive paint with long-term anticorrosive performance is prepared by taking ketimine as a curing agent.
The invention discloses a water-based environment-friendly anticorrosive paint, which takes sodium alginate/acrylic acid/acrylamide copolymer and water-based epoxy resin as paint matrixes, wherein the existence of sodium alginate enhances the film forming property of the paint matrixes; sodium alginate is not polymerized in the sodium alginate/acrylic acid/acrylamide copolymer, and penetrates through the acrylic acid/acrylamide polymer in a chain structure, so that the elasticity of the polymer material is improved; the copolymer and the aqueous epoxy resin are compounded, so that the adhesiveness of the coating is effectively improved, and meanwhile, the coating has swelling performance, can be swelled when the coating is subjected to defects through long-term physical action, and the compactness and the self-repairing performance of the coating are improved; the composite nano particles loaded with the corrosion inhibitor and the polyaniline intercalation graphene are added into the matrix, so that the mechanical strength, corrosion resistance and durability of the coating can be effectively improved; the composite nano particles loaded by the corrosion inhibitor obviously reduce the secondary agglomeration of the nano particles in the coating matrix, and enhance the dispersibility of the composite nano particles in the coating; the corrosion inhibitor molecules are gradually released in the nano powder along with the change of environmental conditions, so that the corrosion durability is obviously improved; the composite nano particles have a skeleton effect in the coating, so that the mechanical strength of the coating is obviously improved; the polyaniline intercalated graphene oxide improves the dispersibility of graphene sheets in the aqueous epoxy resin matrix, and effectively avoids the stacking of graphene sheets; polyaniline is combined with epoxy resin in a chemical bonding way; meanwhile, pi-pi action exists between the aniline and the graphene, the dispersibility and the bonding stability of the graphene in the epoxy resin matrix are enhanced by the aniline, and the stable dispersed lamellar graphene effectively blocks the invasion of small molecules in a channel formed by the water-containing polar groups; the probability of small molecule corrosion is reduced. The three components cooperate with each other to form the water-based environment-friendly anticorrosive paint with good film coating property, strong mechanical strength, good compactness and excellent anticorrosive property.
According to the invention, the hydroxyethyl cellulose and the expanded vermiculite powder are used as additives, and the hydroxyethyl cellulose has a thickening effect, so that the coating performance of the coating is improved; the vermiculite has a lamellar structure, polymer molecules in the coating matrix can be inserted into the lamellar structure of the vermiculite, and the vermiculite is used as a connecting point among the polymer molecules, so that the mechanical strength of a coating film is improved; and simultaneously, the compactness of the coating is improved.
Advantageous effects
Compared with the existing water-based anticorrosive paint, the water-based environment-friendly anticorrosive paint has good storage stability, and the coating has good mechanical strength, has the effects of resisting chemical corrosion such as illumination, acid and alkali and self-healing after physical damage, and has long-term anticorrosive performance and good self-cleaning capability; effectively solves the problem of unsatisfactory corrosion resistance caused by poor mechanical strength, compactness and water resistance of the existing water-based paint.
Detailed Description
The technical scheme of the invention is explained in detail below with reference to specific embodiments.
Preparation of raw materials
(1) Preparation of aqueous composite emulsion
Preparing a sodium alginate solution with the mass percentage concentration of 1-2%, adding acrylamide and acrylic acid into the sodium alginate solution to obtain a mixed solution, introducing nitrogen, and sequentially adding ammonium persulfate and ethylenediamine to react to obtain sodium alginate/acrylic acid/acrylamide copolymer emulsion;
adding the sodium alginate/acrylic acid/acrylamide copolymer emulsion into the aqueous epoxy resin (E44) emulsion with the mass of 10 times to obtain a mixed solution, adding microcrystalline cellulose (microcrystalline cellulose accounts for 10% of the total mass of the mixed solution) into the mixed solution, and uniformly stirring to obtain an aqueous composite emulsion; wherein the weight ratio of the sodium alginate to the acrylamide to the acrylic acid is 1:1:3; the addition amount of the ammonium persulfate is 0.1 weight percent of the total amount of the acrylic acid and the acrylamide; the addition amount of the ethylenediamine is 0.15wt% of the total amount of the acrylic acid and the acrylamide.
(2) Preparation of polyaniline intercalation graphene
Dispersing graphene oxide in hydrochloric acid solution of tyrosine with the weight being 2 times that of the graphene oxide, adding aniline and ammonium persulfate into the solution after the solution is uniformly dispersed by ultrasonic, and polymerizing the solution under the ice salt bath condition to obtain polyaniline intercalation graphene oxide; wherein the weight ratio of the graphene oxide to the aniline is 6:1; the molar ratio of the aniline to the ammonium persulfate is 0.5:1.
(3) Preparation of composite nano particles loaded with corrosion inhibitor
Preparing a corrosion inhibitor solution: dispersing histidine, anthocyanin and caffeic acid in water at a weight ratio of 2:1:1. Preparation of composite nano particles loaded with corrosion inhibitor:
dispersing tetrabutyl titanate and tetraethyl silicate in a mixed solution of alcohol and glacial acetic acid, and obtaining a mixed dispersion liquid after uniform dispersion; fe is added to 3+ With Fe 2+ Dissolving in deionized water, adding Fe powder, and adding the mixed dispersion liquid into the solution under the water bath condition of 55 ℃; simultaneously adjusting the pH value of the system to 9-10; heating to 80 ℃, adding sodium citrate solution, continuously stirring and reacting until the reaction is completed, and obtaining magnetic composite nano particles after magnetic separation; the magnetic composite nano particles are placed in hydrochloric acid solution for soaking treatment, filtered and washed until the solution does not contain iron ions, then the nano particles are dispersed in corrosion inhibitor solution, and the composite nano particles loaded with the corrosion inhibitor can be obtained after ultrasonic treatment; wherein tetrabutyl titanate, tetraethyl silicate and Fe in the reaction system 3+ 、Fe 2+ The molar ratio of (2) is 3:6:1:0.5.
Example 1
An aqueous environment-friendly anticorrosive paint comprises the following raw materials in parts by weight: 50 parts of aqueous composite emulsion and 4 parts of ketimine; 4 parts of polyaniline intercalation graphene, 16 parts of composite nano particles loaded with corrosion inhibitors and 5 parts of auxiliary agents; wherein the auxiliary agent consists of hydroxyethyl cellulose and expanded vermiculite powder in a weight ratio of 5:1;
example 2
An aqueous environment-friendly anticorrosive paint comprises the following raw materials in parts by weight: 55 parts of aqueous composite emulsion and 7 parts of ketimine; 5 parts of polyaniline intercalation graphene, 17 parts of composite nano particles loaded with corrosion inhibitors and 7.5 parts of auxiliary agent; the auxiliary agent consists of hydroxyethyl cellulose and expanded vermiculite powder in a weight ratio of 5:1;
example 3
An aqueous environment-friendly anticorrosive paint comprises the following raw materials in parts by weight: 60 parts of aqueous composite emulsion and 10 parts of ketimine; 6 parts of polyaniline intercalation graphene, 18 parts of composite nano particles loaded with corrosion inhibitors and 10 parts of auxiliary agents; the auxiliary agent consists of hydroxyethyl cellulose and expanded vermiculite powder in a weight ratio of 5:1;
comparative example 1
Comparative example 1 has substantially the same composition as the aqueous anticorrosive paint raw material of example 2 except that the aqueous composite emulsion is replaced with an equivalent amount of aqueous epoxy resin emulsion (E44);
comparative example 2
Comparative example 2 has substantially the same composition as the aqueous anticorrosive coating material of example 2 except that the polyaniline intercalated graphene is replaced with an equal amount of graphene;
comparative example 3
Comparative example 3 has substantially the same composition as the aqueous anticorrosive coating material of example 2 except that the composite nanoparticles supporting the corrosion inhibitor are replaced with equivalent amounts of composite nanoparticles;
comparative example 4
Comparative example 4 has substantially the same composition as the aqueous anticorrosive paint of example 2 except that the auxiliary does not contain expanded vermiculite powder;
the performance of the coatings prepared in inventive examples 1-3 and comparative examples 1-4 were tested, with reference to the aqueous epoxy resin test standard (HG/T4759-2014); the test results are shown in Table 1.
TABLE 1
From the data in Table 1, it can be seen that the water-based environment-friendly anticorrosive paint provided by the invention has good stability and anticorrosive performance, and meets the requirements of the water-based epoxy resin paint.
As can be seen from comparison of the detection results of example 2 and comparative examples 1-4 in table 1, the sodium alginate/acrylic acid/acrylamide copolymer, polyaniline intercalated graphene oxide, composite nano particles loaded with corrosion inhibitors and expanded vermiculite in the auxiliary agent have significant influence on the corrosion resistance of the paint; the raw materials of the paint have mutual synergistic effect in the aspect of ensuring the performance of the paint.
Compared with example 2, the coating matrix of comparative example 1 does not contain sodium alginate/acrylic acid/acrylamide copolymer, the adhesion of the coating to the matrix is reduced, and the impact resistance, acid, alkali, water, salt mist and wet heat resistance are reduced; the analysis reasons may be that the sodium alginate/acrylic acid/acrylamide copolymer is used as a matrix to be added to help to improve the viscoelasticity of the coating so as to improve the adhesive force of the coating, and meanwhile, the aqueous epoxy resin is filled between epoxy resin molecule layers under the action of chemical bonding, has swelling property, and effectively relieves the problem that the blocking capability of polar channels formed by hydrophilic groups on inorganic acid, alkali, water molecules and other small molecules is poor; and the self-repairing capability is endowed to the coating, so that the corrosion resistance of the coating is improved.
The impact resistance and the corrosion resistance of the coating obtained by replacing the polyaniline intercalation graphene oxide in the coating of the comparative example 2 with the same amount of graphene are reduced; the polyaniline intercalated graphene promotes the dispersibility of the graphene in the coating matrix, can have a chemical bonding effect with the coating matrix, improves the compactness of the coating matrix, and avoids protection defects; the stably dispersed lamellar graphene effectively blocks invasion of small molecules in a channel formed by the water-containing polar groups to cause corrosion; the anti-corrosion performance of the paint is obviously improved.
The composite nano particles loaded with the corrosion inhibitor in the coating of the comparative example 3 are replaced by equivalent composite nano particles, the composite nano particles have poor stability in a coating matrix, secondary agglomeration is easy to occur, the coating is agglomerated, and the corrosion resistance of the formed coating is also obviously reduced; the dispersibility of the composite nano particles loaded with the corrosion inhibitor in a coating matrix is obviously improved, and the secondary agglomeration of the composite nano particles is effectively avoided; preventing caking in the coating and uneven coating; and along with the change of environmental conditions, the corrosion inhibitor molecules are released, so that the corrosion resistance of the coating is effectively improved.
The coating auxiliary agent of comparative example 4 is not added with expanded vermiculite powder, the corrosion resistance of the coating is reduced, the analysis reasons are probably that the vermiculite is not added, the compactness and the mechanical strength of the coating are reduced, polymer molecules in a coating matrix can be interpenetrated into a vermiculite lamellar structure, and the vermiculite is used as a connecting point among the polymer molecules, so that the mechanical strength of a coating film can be improved; meanwhile, the compactness of the coating can be improved, and the corrosion resistance can be improved.
In conclusion, the water-based anticorrosive paint with good chemical stability, good anticorrosive performance and long durability is formed by the interaction of the raw materials in the water-based anticorrosive paint.
The above embodiments are merely preferred embodiments of the present invention, the protection scope of the present invention is not limited thereto, and any simple changes or equivalent alternatives of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed herein fall within the protection scope of the present invention.
Claims (10)
1. The water-based environment-friendly anticorrosive paint is characterized by comprising the following raw materials in parts by weight: 50-60 parts of aqueous composite emulsion and 4-10 parts of ketimine; 4-6 parts of polyaniline intercalation graphene, 16-18 parts of composite nano particles loaded with corrosion inhibitors and 5-10 parts of auxiliary agents; the aqueous composite emulsion consists of sodium alginate/acrylic acid/acrylamide copolymer emulsion and aqueous epoxy resin emulsion.
2. The water-based environment-friendly anticorrosive paint as claimed in claim 1, wherein the mass ratio of the sodium alginate, acrylic acid and acrylamide copolymer emulsion to the water-based epoxy resin emulsion is 1:10.
3. the aqueous environment-friendly anticorrosive paint according to claim 1, wherein the composite nano particles are porous silica/titanium dioxide composite nano particles; the corrosion inhibitor consists of histidine, anthocyanin and caffeic acid.
4. The aqueous environment-friendly anticorrosive paint according to claim 1, wherein the preparation method of the aqueous composite emulsion is specifically as follows: preparing sodium alginate solution, adding acrylamide and acrylic acid into the sodium alginate solution to obtain a mixed solution, introducing nitrogen into the mixed solution, and sequentially adding ammonium persulfate and ethylenediamine into the mixed solution to react to obtain sodium alginate/acrylic acid/acrylamide copolymer emulsion; adding the sodium alginate/acrylic acid/acrylamide copolymer emulsion into the aqueous epoxy resin emulsion, adding microcrystalline cellulose into the aqueous epoxy resin emulsion, and uniformly stirring to obtain the aqueous composite emulsion.
5. The aqueous environment-friendly anticorrosive coating according to claim 4, wherein the microcrystalline cellulose is added in an amount of 10% by weight of the aqueous composite emulsion.
6. The aqueous environment-friendly anticorrosive paint according to claim 1, wherein the preparation method of polyaniline intercalation graphene oxide is specifically as follows: dispersing graphene oxide in a hydrochloric acid solution of tyrosine, adding aniline and ammonium persulfate into the solution after uniform ultrasonic dispersion, and polymerizing under the ice salt bath condition to obtain polyaniline intercalation graphene oxide.
7. The aqueous environment-friendly anticorrosive paint according to claim 6, wherein the weight ratio of graphene oxide to aniline is 6:1; the molar ratio of the aniline to the ammonium persulfate is 0.5:1.
8. the water-based environment-friendly anticorrosive paint as claimed in claim 1, wherein the preparation method of the composite nano particles loaded with the corrosion inhibitor comprises the following steps: dispersing tetrabutyl titanate and tetraethyl silicate in a mixed solution of alcohol and glacial acetic acid, and obtaining a mixed dispersion liquid after uniform dispersion; fe is added to 3+ With Fe 2+ Dissolving in deionized water, adding Fe powder, and adding the mixed dispersion liquid into the solution under the water bath condition of 55 ℃; simultaneously adjusting the pH value of the system to be alkaline; heating to 80 ℃, adding sodium citrate solution, continuously stirring and reacting until the reaction is completed, and obtaining magnetic composite nano particles after magnetic separation; and (3) placing the magnetic composite nano particles in hydrochloric acid solution for soaking treatment, filtering and washing until the solution does not contain iron ions, dispersing the nano particles in corrosion inhibitor solution, and carrying out ultrasonic treatment to obtain the corrosion inhibitor-loaded composite nano particles.
9. As claimed in claim 8The water-based environment-friendly anticorrosive paint is characterized in that tetrabutyl titanate, tetraethyl silicate and Fe in a reaction system 3+ 、Fe 2+ The molar ratio of (2) is 3:6:1:0.5; the corrosion inhibitor solution is obtained by dispersing histidine, anthocyanin and caffeic acid in water according to the weight ratio of 2:1:1.
10. The aqueous environment-friendly anticorrosive paint according to claim 1, wherein the auxiliary agent comprises hydroxyethyl cellulose and expanded vermiculite powder.
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