CN117143496B - Water-based epoxy anti-corrosion coating liquid and preparation method thereof - Google Patents
Water-based epoxy anti-corrosion coating liquid and preparation method thereof Download PDFInfo
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- CN117143496B CN117143496B CN202311426006.0A CN202311426006A CN117143496B CN 117143496 B CN117143496 B CN 117143496B CN 202311426006 A CN202311426006 A CN 202311426006A CN 117143496 B CN117143496 B CN 117143496B
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- pyrene
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- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000004593 Epoxy Substances 0.000 title claims abstract description 28
- 238000005260 corrosion Methods 0.000 title claims description 40
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 162
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 239000004952 Polyamide Substances 0.000 claims abstract description 42
- 229920002647 polyamide Polymers 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 239000004814 polyurethane Substances 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- QZAXONBUUURRQX-UHFFFAOYSA-N [B].CP(C)C1=CC=CC=C1 Chemical compound [B].CP(C)C1=CC=CC=C1 QZAXONBUUURRQX-UHFFFAOYSA-N 0.000 claims abstract description 15
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000001841 imino group Chemical group [H]N=* 0.000 claims abstract description 13
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims abstract description 8
- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 8
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 8
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 8
- JMLIZQVKDDUDQE-UHFFFAOYSA-N pyrene-1,2-diol Chemical compound C1=CC=C2C=CC3=C(O)C(O)=CC4=CC=C1C2=C43 JMLIZQVKDDUDQE-UHFFFAOYSA-N 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 46
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000003085 diluting agent Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- 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 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 150000002009 diols Chemical class 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000005536 corrosion prevention Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000012745 toughening agent Substances 0.000 abstract description 3
- 239000004970 Chain extender Substances 0.000 abstract description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 11
- 229940086542 triethylamine Drugs 0.000 description 7
- 229920006334 epoxy coating Polymers 0.000 description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000010485 coping Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 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
- 239000003973 paint Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 125000005581 pyrene group Chemical group 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
-
- 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
-
- 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
- C09D7/65—Additives macromolecular
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of corrosion prevention, in particular to a water-based epoxy corrosion prevention coating liquid and a preparation method thereof, wherein 1-thioglycerol and N- (1-pyrene) maleimide are used as raw materials, and dimethylphenylphosphine borane is used as a catalyst to obtain a pyrene-containing dihydric alcohol monomer; synthesizing pyrene branched epoxy resin by using a pyrene diol monomer, 4' -biphenol and trimethylolpropane triglycidyl ether; 1-thioglycerol and hexafluorobutyl methacrylate are used as raw materials, dimethylphenylphosphine borane is used as a catalyst to obtain a fluorine-containing monomer, isophorone diisocyanate and polycaprolactone are used for synthesizing a polyurethane prepolymer, then a pyrene-containing diol monomer and a fluorine-containing monomer are introduced, and 4,4' -dihydroxydiphenyl disulfide is used as a chain extender to obtain polyurethane containing pyrene branched chains as a toughening agent; the aqueous polyamide is modified by imino MXene to prepare the MXene modified aqueous polyamide as a curing agent.
Description
Technical Field
The invention relates to the technical field of corrosion prevention, in particular to an aqueous epoxy corrosion prevention coating liquid and a preparation method thereof.
Background
In the existing home decoration market, metal corrosion is always a hot topic, and the current common effective and economic anti-corrosion means is coating anti-corrosion, because the epoxy coating has good acid and alkali resistance, has higher adhesion to a substrate, and is an anti-corrosion coating with wider application in the field of home appliances.
The metal corrosion is generally the reaction that the metal loses electrons and is oxidized under the participation of water and oxygen, a large amount of hydroxyl groups in the epoxy resin make the formed coating have certain hydrophilicity, and the existing epoxy resin usually generates defects when being solidified, so that the corrosion resistance of the coating is reduced. The ultraviolet resistance of a single epoxy coating is poor, the higher glossiness cannot be kept for a long time under ultraviolet irradiation, the attractiveness of furniture is affected, and meanwhile, the coating formed by the epoxy coating used on the surface of the existing furniture cannot be self-healed after encountering mechanical damage, and the attractiveness of the furniture is damaged while the corrosion resistance of the coating is affected.
Disclosure of Invention
The invention aims to provide an aqueous epoxy anti-corrosion coating liquid and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the aqueous epoxy anti-corrosion coating liquid comprises A, B components, wherein the component A comprises 27-37 parts of pyrene branched epoxy resin, 23-33 parts of pyrene branched polyurethane and 1-20 parts of diluent in parts by weight; the component B comprises 1-12 parts of MXene modified aqueous polyamide and 1-3 parts of accelerator.
Further, the diluent is one or more of benzyl glycidyl ether, furfural and polypropylene glycol diglycidyl ether.
Further, the accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and triethanolamine.
Further, the preparation of the pyrene branched epoxy resin comprises the following steps:
mixing 4,4' -biphenol, a pyrene-containing dihydric alcohol monomer and N, N-dimethylformamide under nitrogen atmosphere, adding trimethylolpropane triglycidyl ether and tetrabutylammonium bromide, preserving heat for 5-6 hours at 95-100 ℃, adding diethyl ether, dissolving with tetrahydrofuran, repeating the operation for 3-5 times, and drying to obtain the pyrene-containing branched epoxy resin.
Further, the molar mass ratio of the 4,4' -biphenol to the pyrene-containing dihydric alcohol monomer to the trimethylolpropane triglycidyl ether is as follows: 10mmol:10mmol:18.2g.
Further, the preparation of the pyrene branched polyurethane comprises the following steps:
1) Mixing 1-thioglycerol, hexafluorobutyl methacrylate, acetone and dimethylphenylphosphine borane, and preserving heat at 45-50 ℃ for 5-6h to obtain a fluorine-containing monomer;
2) Mixing isophorone diisocyanate and acetone, preheating for 20-30min at 65-70 ℃, adding dibutyl tin dilaurate, adding a polycaprolactone and acetone mixed solution, preserving heat for 2-3h, adding a fluorine-containing monomer and a pyrene-containing dihydric alcohol monomer, continuously preserving heat for 1h, cooling to 60 ℃, adding 4,4' -dihydroxydiphenyl disulfide, and preserving heat for 1-2h to obtain pyrene-branched polyurethane.
Further, the preparation of the pyrene-containing diol monomer comprises the following steps: mixing 1-thioglycerol, N- (1-pyrene) maleimide, acetone and dimethylphenylphosphine borane, and preserving the temperature at 45-50 ℃ for 5-6h to obtain a pyrene-containing dihydric alcohol monomer.
Further, the preparation of the MXene modified aqueous polyamide comprises the following steps:
(1) Mixing sodium fluoride and concentrated hydrochloric acid, adding MAX, preserving heat at 55-60 ℃ for 44-48h, washing with water to be neutral, centrifuging at 3500r/min, dispersing into deionized water, carrying out ultrasonic treatment for 3h under the conditions of nitrogen and ice bath, and freeze-drying to obtain MXene nano-sheets;
(2) Mixing terephthalaldehyde, melamine and MXene nano-sheets, adding a mixed solution of 1, 4-ethylene oxide and mesitylene, stirring, adding an acetic acid solution, stirring for 4d at 25-30 ℃, washing with 1, 4-ethylene oxide, tetrahydrofuran and acetone in sequence, and drying to obtain imino MXene;
(3) Mixing alcohol-soluble polyamide, n-propanol and absolute ethyl alcohol, heating to 85 ℃ and stirring until the mixture is dissolved, adding butyl acrylate, methacrylic acid, styrene and benzoyl peroxide mixed solution, preserving heat for 1-2h, adding ethyl acetate and benzoyl peroxide mixed solution, preserving heat for 1-3h, cooling to 18-25 ℃, adding triethylamine and imino MXene, and adding deionized water to obtain the MXene modified waterborne polyamide.
Further, the mass ratio of the alcohol-soluble polyamide to the imino MXene is 20:1.
further, the preparation method of the aqueous epoxy anti-corrosion coating liquid comprises the following steps:
(1) Mixing the epoxy resin containing the pyrene branched chain, the polyurethane containing the pyrene branched chain and the diluent to obtain a component A;
(2) Mixing MXene modified aqueous polyamide and an accelerator to obtain a component B; and mixing the component A and the component B to obtain the aqueous epoxy anti-corrosion coating liquid.
The invention has the beneficial effects that:
the invention provides a waterborne epoxy anti-corrosion coating liquid and a preparation method thereof, wherein the components in an epoxy coating are limited, so that a coating formed by the prepared waterborne epoxy anti-corrosion coating liquid has excellent anti-corrosion property, hydrophobicity and self-repairing property.
In order to solve the problems of insufficient toughness, easy falling, limited service life and the like of a coating formed by common epoxy paint in the market, the invention uses the pyrene branched chain-containing epoxy resin as a base material, uses the pyrene branched chain-containing polyurethane as a toughening agent, uses the MXene modified waterborne polyamide as a curing agent, greatly improves the mechanical properties of the coating formed by the epoxy paint, such as hardness, tensile strength and the like, and improves the adhesive force with a substrate, so that the formed coating has super-hydrophobic and self-repairing surfaces, and the formed coating has lasting mechanical damage resistance.
Based on mercapto-alkene clicking reaction, 1-thioglycerol and N- (1-pyrene) maleimide are used as raw materials, and dimethylphenylphosphine borane is used as a catalyst to obtain a pyrene-containing dihydric alcohol monomer; synthesizing pyrene branched epoxy resin by using pyrene diol monomer, 4' -biphenol and trimethylolpropane triglycidyl ether, so that the prepared epoxy resin is branched, the reaction sites on the epoxy resin are increased, and the modifiable property of the epoxy resin is improved;
1-thioglycerol and hexafluorobutyl methacrylate are used as raw materials, dimethylphenylphosphine borane is used as a catalyst to obtain a fluorine-containing monomer, isophorone diisocyanate and polycaprolactone are used for synthesizing a polyurethane prepolymer, then a pyrene-containing diol monomer and a fluorine-containing monomer are introduced, 4' -dihydroxydiphenyl disulfide is used as a chain extender to obtain pyrene-containing branched polyurethane which is used as a toughening agent, wherein the introduction of the pyrene-containing diol monomer effectively improves the compatibility between the pyrene-containing diol monomer and epoxy resin containing pyrene branched chains of a base material, so that the prepared coating has uniformity; the introduction of the fluorine-containing monomer can effectively improve the hydrophobicity of the surface of the coating formed by the coating liquid, and the introduction of disulfide bonds in the 4,4' -dihydroxydiphenyl disulfide can endow the coating with self-repairing property; wherein, the pyrene structure in the pyrene branched polyurethane and the pyrene branched epoxy resin and the MXene in the curing agent form pi-pi interaction, which strengthens the acting force of the curing agent and the resin, combines the dynamic reversibility of disulfide bonds and endows the coating formed by the coating liquid with excellent self-repairing performance;
in the invention, alcohol-soluble polyamide, butyl acrylate, methacrylic acid, styrene and triethylamine are used for preparing aqueous polyamide as a curing agent, in order to improve the thermal stability of the aqueous polyamide, a coating formed by the coating liquid has excellent corrosion resistance and ultraviolet resistance, and MXene is introduced for modifying the aqueous polyamide; because the MXene two-dimensional family and the graphene have similar structures, have natural physical barriers for coping with the invasion of corrosive media, can effectively improve the corrosion resistance of the organic coating, but the problems of compatibility and dispersion uniformity exist in direct addition.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications such as up, down, left, right, front, and rear … … are involved in the embodiment of the present invention, the directional indications are merely used to explain a relative positional relationship, a movement condition, and the like between a certain posture such as the respective components, and if the certain posture is changed, the directional indications are changed accordingly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1: the preparation method of the aqueous epoxy anti-corrosion coating liquid is characterized by comprising the following steps of:
(1) Mixing the epoxy resin containing the pyrene branched chain, the polyurethane containing the pyrene branched chain and the diluent to obtain a component A;
(2) Mixing MXene modified aqueous polyamide and an accelerator to obtain a component B; mixing the component A and the component B to obtain an aqueous epoxy anti-corrosion coating liquid;
the component A comprises 27 parts of epoxy resin containing pyrene branched chains, 23 parts of polyurethane containing pyrene branched chains and 1 part of diluent in parts by weight; the component B comprises 1 part of MXene modified aqueous polyamide and 1 part of accelerator;
the diluent is benzyl glycidyl ether; the accelerator is 2-methylimidazole;
the preparation method of the pyrene branched chain-containing epoxy resin comprises the following steps:
under nitrogen atmosphere, mixing 20 mmole of 4,4' -biphenol, 20 mmole of pyrene-containing dihydric alcohol monomer, 20 mmon of N-dimethylformamide, adding 18.2g of trimethylolpropane triglycidyl ether and 1g of tetrabutylammonium bromide, preserving heat for 6 hours at 95 ℃, adding 250mL of diethyl ether, then dissolving with 200mL of tetrahydrofuran, repeating the operation for 3 times, and drying to obtain pyrene-containing branched epoxy resin;
the preparation of the pyrene branched polyurethane comprises the following steps:
1) Mixing 0.01mol of 1-thioglycerol, 0.01mol of hexafluorobutyl methacrylate, 4mL of acetone and 0.01mL of dimethylphenylphosphine borane, and preserving the temperature at 45 ℃ for 6 hours to obtain a fluorine-containing monomer;
2) Mixing 0.16mol of isophorone diisocyanate and 80mL of acetone, preheating for 30min at 65 ℃, adding 0.2mL of dibutyltin dilaurate, adding a mixed solution of 0.04mol of polycaprolactone and 20mL of acetone, preserving heat for 2h, adding 0.02mol of fluorine-containing monomer and 0.02mol of pyrene-containing diol monomer, preserving heat for 1h continuously, cooling to 60 ℃, adding 0.04mol of 4,4' -dihydroxydiphenyl disulfide, and preserving heat for 1h to obtain pyrene branched polyurethane;
the preparation of the pyrene-containing dihydric alcohol monomer comprises the following steps: mixing 0.01mol of 1-thioglycerol, 0.01mol of N- (1-pyrene) maleimide, 4mL of acetone and 0.01mL of dimethylphenylphosphine borane, and preserving the temperature at 45 ℃ for 6 hours to obtain a pyrene-containing dihydric alcohol monomer;
the preparation of the MXene modified aqueous polyamide comprises the following steps:
(1) Mixing 1g of sodium fluoride and 40mL of 12mol/L hydrochloric acid, adding 1gMAX, preserving heat for 48 hours at 55 ℃, washing with water to be neutral, centrifuging at 3500r/min, dispersing into 100mL of deionized water, performing ultrasonic treatment for 3 hours under the conditions of nitrogen and ice bath, and performing freeze drying to obtain MXene nano-sheets;
(2) Mixing 0.3g of terephthalaldehyde, 0.13g of melamine and 0.05g of MXene nano-sheets, adding 5mL of mixed solution of 1, 4-ethylene oxide and 5mL of mesitylene, stirring, adding 5mL of 3mol/L acetic acid solution, stirring for 4 days at 25 ℃, washing with 1, 4-ethylene oxide, tetrahydrofuran and acetone in sequence, and drying to obtain imino MXene;
(3) 3g of alcohol-soluble polyamide, 2.5g of n-propanol and 2.5mL of absolute ethyl alcohol are mixed, the temperature is raised, stirring is carried out until the mixture is dissolved, 0.8g of butyl acrylate, 0.45g of methacrylic acid, 0.45g of styrene and 0.01g of benzoyl peroxide are added, the mixture is kept for 1h, 0.45mL of ethyl acetate and 0.01g of benzoyl peroxide are added, the mixture is kept for 1h, water is cooled to 18 ℃, 0.5g of triethylamine and 0.15g of imino MXene are added, and 3mL of deionized water are added, so that the MXene modified waterborne polyamide is obtained.
Example 2: the preparation method of the aqueous epoxy anti-corrosion coating liquid is characterized by comprising the following steps of:
(1) Mixing the epoxy resin containing the pyrene branched chain, the polyurethane containing the pyrene branched chain and the diluent to obtain a component A;
(2) Mixing MXene modified aqueous polyamide and an accelerator to obtain a component B; mixing the component A and the component B to obtain an aqueous epoxy anti-corrosion coating liquid;
the component A comprises 33 parts of epoxy resin containing pyrene branched chains, 27 parts of polyurethane containing pyrene branched chains and 8 parts of diluent in parts by weight; the component B comprises 8 parts of MXene modified aqueous polyamide and 2 parts of accelerator;
the diluent is furfural; the accelerator is 2-ethyl-4-methylimidazole;
the preparation method of the pyrene branched chain-containing epoxy resin comprises the following steps:
under nitrogen atmosphere, 20 mmole of 4,4' -biphenol, 20 mmole of pyrene-containing dihydric alcohol monomer and 20 mmon, N-dimethylformamide are mixed, 18.2g of trimethylolpropane triglycidyl ether and 1g of tetrabutylammonium bromide are added, the temperature is kept at 98 ℃ for 5.5 hours, 250mL of diethyl ether is added, then 200mL of tetrahydrofuran is used for dissolution, the operation is repeated for 4 times, and the epoxy resin containing pyrene branched chains is obtained after drying;
the preparation of the pyrene branched polyurethane comprises the following steps:
1) Mixing 0.01mol of 1-thioglycerol, 0.01mol of hexafluorobutyl methacrylate, 4mL of acetone and 0.01mL of dimethylphenylphosphine borane, and preserving the temperature at 48 ℃ for 5.5 hours to obtain a fluorine-containing monomer;
2) Mixing 0.16mol of isophorone diisocyanate and 80mL of acetone, preheating at 68 ℃ for 25min, adding 0.2mL of dibutyltin dilaurate, adding a mixed solution of 0.04mol of polycaprolactone and 20mL of acetone, preserving heat for 2.5h, adding 0.02mol of fluorine-containing monomer and 0.02mol of pyrene-containing diol monomer, preserving heat for 1h, cooling to 60 ℃, adding 0.04mol of 4,4' -dihydroxydiphenyl disulfide, and preserving heat for 1.5h to obtain pyrene branched polyurethane;
the preparation of the pyrene-containing dihydric alcohol monomer comprises the following steps: mixing 0.01mol of 1-thioglycerol, 0.01mol of N- (1-pyrene) maleimide, 4mL of acetone and 0.01mL of dimethylphenylphosphine borane, and preserving the temperature at 48 ℃ for 5.5 hours to obtain a pyrene-containing dihydric alcohol monomer;
the preparation of the MXene modified aqueous polyamide comprises the following steps:
(1) Mixing 1g of sodium fluoride and 40mL of 12mol/L hydrochloric acid, adding 1gMAX, preserving heat for 46h at 58 ℃, washing with water to be neutral, centrifuging at 3500r/min, dispersing into 100mL of deionized water, performing ultrasonic treatment for 3h under the conditions of nitrogen and ice bath, and performing freeze drying to obtain MXene nano-sheets;
(2) Mixing 0.3g of terephthalaldehyde, 0.13g of melamine and 0.05g of MXene nano-sheets, adding 5mL of mixed solution of 1, 4-epoxyethane and 5mL of mesitylene, stirring, adding 5mL of 3mol/L acetic acid solution, stirring for 4 days at 28 ℃, washing with 1, 4-epoxyethane, tetrahydrofuran and acetone in sequence, and drying to obtain imino MXene;
(3) 3g of alcohol-soluble polyamide, 2.5g of n-propanol and 2.5mL of absolute ethyl alcohol are mixed, the temperature is raised, the mixture is stirred at 85 ℃ until the mixture is dissolved, 0.8g of butyl acrylate, 0.45g of methacrylic acid, 0.45g of styrene and 0.01g of benzoyl peroxide are added, the mixture is kept for 1.5h, 0.45mL of ethyl acetate and 0.01g of benzoyl peroxide are added, the mixture is kept for 2h, 0.5g of triethylamine and 0.15g of imino MXene are added after water cooling to 20 ℃, and 3mL of deionized water is added, so that the MXene modified aqueous polyamide is obtained.
Example 3: the preparation method of the aqueous epoxy anti-corrosion coating liquid is characterized by comprising the following steps of:
(1) Mixing the epoxy resin containing the pyrene branched chain, the polyurethane containing the pyrene branched chain and the diluent to obtain a component A;
(2) Mixing MXene modified aqueous polyamide and an accelerator to obtain a component B; mixing the component A and the component B to obtain an aqueous epoxy anti-corrosion coating liquid;
the component A comprises 37 parts of epoxy resin containing pyrene branched chains, 33 parts of polyurethane containing pyrene branched chains and 20 parts of diluent in parts by weight; the component B comprises 12 parts of MXene modified aqueous polyamide and 3 parts of accelerator;
the diluent is polypropylene glycol diglycidyl ether; the accelerator is triethanolamine;
the preparation method of the pyrene branched chain-containing epoxy resin comprises the following steps:
under nitrogen atmosphere, mixing 20 mmole of 4,4' -biphenol, 20 mmole of pyrene-containing dihydric alcohol monomer, 20 mmon of N-dimethylformamide, adding 18.2g of trimethylolpropane triglycidyl ether and 1g of tetrabutylammonium bromide, preserving heat at 100 ℃ for 5 hours, adding 250mL of diethyl ether, then dissolving with 200mL of tetrahydrofuran, repeating the operation for 5 times, and drying to obtain pyrene-containing branched epoxy resin;
the preparation of the pyrene branched polyurethane comprises the following steps:
1) Mixing 0.01mol of 1-thioglycerol, 0.01mol of hexafluorobutyl methacrylate, 4mL of acetone and 0.01mL of dimethylphenylphosphine borane, and preserving the temperature at 50 ℃ for 5 hours to obtain a fluorine-containing monomer;
2) Mixing 0.16mol of isophorone diisocyanate and 80mL of acetone, preheating at 70 ℃ for 20min, adding 0.2mL of dibutyltin dilaurate, adding a mixed solution of 0.04mol of polycaprolactone and 20mL of acetone, preserving heat for 3h, adding 0.02mol of fluorine-containing monomer and 0.02mol of pyrene-containing diol monomer, preserving heat for 1h continuously, cooling to 60 ℃, adding 0.04mol of 4,4' -dihydroxydiphenyl disulfide, and preserving heat for 2h to obtain pyrene branched polyurethane;
the preparation of the pyrene-containing dihydric alcohol monomer comprises the following steps: mixing 0.01mol of 1-thioglycerol, 0.01mol of N- (1-pyrene) maleimide, 4mL of acetone and 0.01mL of dimethylphenylphosphine borane, and preserving the temperature at 50 ℃ for 5 hours to obtain a pyrene-containing dihydric alcohol monomer;
the preparation of the MXene modified aqueous polyamide comprises the following steps:
(1) Mixing 1g of sodium fluoride and 40mL of 12mol/L hydrochloric acid, adding 1gMAX, preserving heat for 44h at 60 ℃, washing with water to be neutral, centrifuging at 3500r/min, dispersing into 100mL of deionized water, performing ultrasonic treatment for 3h under the conditions of nitrogen and ice bath, and performing freeze drying to obtain MXene nano-sheets;
(2) Mixing 0.3g of terephthalaldehyde, 0.13g of melamine and 0.05g of MXene nano-sheets, adding 5mL of mixed solution of 1, 4-epoxyethane and 5mL of mesitylene, stirring, adding 5mL of 3mol/L acetic acid solution, stirring for 4 days at 30 ℃, washing with 1, 4-epoxyethane, tetrahydrofuran and acetone in sequence, and drying to obtain imino MXene;
(3) 3g of alcohol-soluble polyamide, 2.5g of n-propanol and 2.5mL of absolute ethyl alcohol are mixed, the temperature is raised, stirring is carried out until the mixture is dissolved, 0.8g of butyl acrylate, 0.45g of methacrylic acid, 0.45g of styrene and 0.01g of benzoyl peroxide are added, the mixture is kept for 2 hours, 0.45mL of ethyl acetate and 0.01g of benzoyl peroxide are added, the mixture is kept for 3 hours, water is cooled to 25 ℃, 0.5g of triethylamine and 0.15g of imino MXene are added, and 3mL of deionized water is added, so that the MXene modified waterborne polyamide is obtained.
Comparative example 1: in the case of using example 3 as a control group, when preparing the pyrene branched epoxy resin, the pyrene diol monomer was not added, and the other steps were normal.
Comparative example 2: in the case of using example 3 as a control group, when the pyrene branched polyurethane was prepared, the pyrene diol monomer was not added, and the other steps were normal.
Comparative example 3: in the case of using example 3 as a control group, when the pyrene branched polyurethane was prepared, the fluorine-containing monomer was not added, and the other steps were normal.
Comparative example 4: in the case of using example 3 as a control group, when preparing a pyrene branched polyurethane, 4' -dihydroxydiphenyl disulfide was not added, and the other steps were normal.
Comparative example 5: using example 3 as a control, the imine group MXene was replaced with an MXene nanoplatelet, and the other procedures were normal.
Comparative example 6: using example 3 as a control, the MXene-modified waterborne polyamide was replaced with the waterborne polyamide, and the other procedures were normal.
The raw material sources are as follows:
benzyl glycidyl ether P136148, furfural F100546, polypropylene glycol diglycidyl ether P135604, 2-methylimidazole M104839, 2-ethyl-4-methylimidazole E104846, triethanolamine T108151, N-dimethylformamide D111999, trimethylolpropane triglycidyl ether T303386, tetrabutylammonium bromide T501397, tetrahydrofuran T103263, 1-thioglycerol T141418, hexafluorobutyl methacrylate H100688, dimethylphenylphosphine borane D154516, isophorone diisocyanate I109582, dibutyltin dilaurate D100274, polycaprolactone P478241, 4' -dihydroxydiphenyl disulfide T101808, N- (1-pyrene) maleimide N493967, sodium fluoride S111591, terephthalaldehyde P105980, melamine M108433, 1, 4-ethylene oxide D116157, mesitylene M472043, butyl acrylate B100036, methacrylic acid M434201, styrene S110375, benzoyl peroxide B103285, triethyl amine T103285: ala Ding Shiji; alcohol-soluble polyamide (chemical grade): shenzhen Jitian chemical Co., ltd; MAX7303002: fosman technology (beijing) limited; 4,4' -biphenol S31338: shanghai Yuan Ye Biotech Co., ltd; diethyl ether, acetone, hydrochloric acid, acetic acid, n-propanol, absolute ethanol, ethyl acetate, analytically pure: national drug group reagent.
Performance test:
the coating solutions prepared in the examples and the comparative examples were coated on the surface of GB708-65 steel plate (50 mm. Times.120 mm. Times.0.45 mm) to a thickness of 0.4mm, and left standing for 24 hours to form a coating layer, thereby obtaining a sample;
hydrophobicity: measuring the water contact angle for characterization, and testing with 4 [ mu ] L water drops:
self-repairability: scratch test, wherein scratches on a coating are 200 mu m long and 200 mu m deep, then heat preservation is carried out for 12 hours at 50 ℃, self-repairing rate is observed and represented under an electron microscope, and self-repairing rate= (L 0 -L 1 ）/L 0 X 100%, where L 0 For the initial scratch length, L 1 The length of the scratch after heat preservation;
adhesion force: the surface of the coating is marked with uniform grids, the substrate is exposed from the scratch, the edge is not dropped to the level-0, the cross damaged area is less than 5-1, the cross damaged area is less than 15-2, and the cross damaged area is less than 35-3;
alkali resistance: immersing the sample in 8% sodium hydroxide aqueous solution for 72h, and observing whether the coating is light-lost or bubble;
acid resistance: immersing the sample in 5% hydrochloric acid aqueous solution for 72h, and observing whether the coating is light-lost or bubble;
corrosion resistance: salt spray resistance is measured by referring to GB/T1771-1991, the temperature of a spray chamber is 37 ℃, the concentration of sodium chloride is 60g/L, and whether bubbling, peeling and corrosion occur after 2000 hours is observed, but not the salt spray resistance is excellent; the results are shown in Table 1 below;
TABLE 1
The invention provides a waterborne epoxy anti-corrosion coating liquid and a preparation method thereof, wherein the components in an epoxy coating are limited, so that a coating formed by the prepared waterborne epoxy anti-corrosion coating liquid has excellent anti-corrosion property, hydrophobicity and self-repairing property, and the performance is not tested in table 1, namely, the alkali resistance, acid resistance and salt fog resistance in comparative examples 1-6 are not tested.
By comparing the example 3 with the comparative examples 1 and 2, the pyrene structure in the pyrene branched polyurethane and the pyrene branched epoxy resin and the MXene in the curing agent form pi-pi interaction, so that the acting force of the curing agent and the resin is enhanced, and meanwhile, the dynamic reversibility of disulfide bonds is combined, so that the coating formed by the coating liquid is endowed with excellent self-repairing performance;
as can be obtained by comparing example 3 with comparative example 3, the introduction of the fluorine-containing monomer can effectively improve the hydrophobicity of the surface of the coating formed by the coating liquid;
comparison of example 3 with comparative example 4 results in the introduction of disulfide bonds in 4,4' -dihydroxydiphenyl disulfide, imparting self-healing properties to the coating;
comparing example 3 with comparative example 5 and comparative example 6, the invention uses alcohol-soluble polyamide, butyl acrylate, methacrylic acid, styrene and triethylamine to prepare aqueous polyamide as curing agent, in order to improve the thermal stability of the aqueous polyamide, and simultaneously, the coating formed by the coating liquid has excellent corrosion resistance, and MXene is introduced to modify the aqueous polyamide; because the MXene two-dimensional family and the graphene have similar structures, have natural physical barriers for coping with the invasion of corrosive media, can effectively improve the corrosion resistance of the organic coating, but the problems of compatibility and dispersion uniformity exist in direct addition.
The aqueous epoxy anti-corrosion coating liquid prepared by the invention has high corrosion resistance and good self-repairing property, and overcomes the defect of limited service life of the existing commercial products.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, but rather, the equivalent structural changes made by the present invention in the light of the inventive concept, or the direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (6)
1. The aqueous epoxy anti-corrosion coating liquid is characterized by comprising A, B components, wherein the component A comprises, by weight, 27-37 parts of pyrene branched epoxy resin, 23-33 parts of pyrene branched polyurethane and 1-20 parts of diluent; the component B comprises 1-12 parts of MXene modified aqueous polyamide and 1-3 parts of accelerator;
the preparation method of the pyrene branched chain-containing epoxy resin comprises the following steps:
mixing 4,4' -biphenol, a pyrene-containing dihydric alcohol monomer and N, N-dimethylformamide under nitrogen atmosphere, adding trimethylolpropane triglycidyl ether and tetrabutylammonium bromide, preserving heat for 5-6 hours at 95-100 ℃, adding diethyl ether, dissolving with tetrahydrofuran, repeating the operation for 3-5 times, and drying to obtain pyrene-containing branched epoxy resin;
the preparation of the pyrene branched polyurethane comprises the following steps:
1) Mixing 1-thioglycerol, hexafluorobutyl methacrylate, acetone and dimethylphenylphosphine borane, and preserving heat at 45-50 ℃ for 5-6h to obtain a fluorine-containing monomer;
2) Mixing isophorone diisocyanate and acetone, preheating for 20-30min at 65-70 ℃, adding dibutyl tin dilaurate, adding a polycaprolactone and acetone mixed solution, preserving heat for 2-3h, adding a fluorine-containing monomer and a pyrene-containing dihydric alcohol monomer, continuously preserving heat for 1h, cooling to 60 ℃, adding 4,4' -dihydroxydiphenyl disulfide, and preserving heat for 1-2h to obtain pyrene-branched polyurethane;
the preparation of the pyrene-containing dihydric alcohol monomer comprises the following steps: mixing 1-thioglycerol, N- (1-pyrene) maleimide, acetone and dimethylphenylphosphine borane, and preserving heat at 45-50 ℃ for 5-6h to obtain a pyrene-containing dihydric alcohol monomer;
the preparation of the MXene modified aqueous polyamide comprises the following steps:
(1) Mixing sodium fluoride and concentrated hydrochloric acid, adding MAX, preserving heat at 55-60 ℃ for 44-48h, washing with water to be neutral, centrifuging at 3500r/min, dispersing into deionized water, carrying out ultrasonic treatment for 3h under the conditions of nitrogen and ice bath, and freeze-drying to obtain MXene nano-sheets;
(2) Mixing terephthalaldehyde, melamine and MXene nano-sheets, adding a mixed solution of 1, 4-ethylene oxide and mesitylene, stirring, adding an acetic acid solution, stirring for 4d at 25-30 ℃, washing with 1, 4-ethylene oxide, tetrahydrofuran and acetone in sequence, and drying to obtain imino MXene;
(3) Mixing alcohol-soluble polyamide, n-propanol and absolute ethyl alcohol, heating to 85 ℃ and stirring until the mixture is dissolved, adding butyl acrylate, methacrylic acid, styrene and benzoyl peroxide mixed solution, preserving heat for 1-2h, adding ethyl acetate and benzoyl peroxide mixed solution, preserving heat for 1-3h, cooling to 18-25 ℃, adding triethylamine and imino MXene, and adding deionized water to obtain the MXene modified waterborne polyamide.
2. The aqueous epoxy anti-corrosion coating liquid according to claim 1, wherein the diluent is one or more of benzyl glycidyl ether, furfural and polypropylene glycol diglycidyl ether.
3. The aqueous epoxy anti-corrosion coating liquid according to claim 1, wherein the accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and triethanolamine.
4. The aqueous epoxy anti-corrosion coating liquid according to claim 1, wherein in the preparation of the pyrene branched epoxy resin, the molar mass ratio of 4,4' -biphenol, pyrene diol monomer and trimethylolpropane triglycidyl ether is: 10mmol:10mmol:18.2g.
5. The aqueous epoxy anti-corrosion coating liquid according to claim 1, wherein in the preparation of the MXene modified aqueous polyamide, the mass ratio of the alcohol-soluble polyamide to the imino MXene is 20:1.
6. the method for preparing the aqueous epoxy anti-corrosion coating liquid according to claim 1, which is characterized by comprising the following steps:
(1) Mixing the epoxy resin containing the pyrene branched chain, the polyurethane containing the pyrene branched chain and the diluent to obtain a component A;
(2) Mixing MXene modified aqueous polyamide and an accelerator to obtain a component B; and mixing the component A and the component B to obtain the aqueous epoxy anti-corrosion coating liquid.
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