CN117986965A - UV aging-resistant waterborne epoxy anti-corrosion paint and method thereof - Google Patents
UV aging-resistant waterborne epoxy anti-corrosion paint and method thereof Download PDFInfo
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- CN117986965A CN117986965A CN202410082908.5A CN202410082908A CN117986965A CN 117986965 A CN117986965 A CN 117986965A CN 202410082908 A CN202410082908 A CN 202410082908A CN 117986965 A CN117986965 A CN 117986965A
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- citric acid
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- deionized water
- aqueous epoxy
- curing agent
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- 239000003973 paint Substances 0.000 title claims abstract description 46
- 239000004593 Epoxy Substances 0.000 title claims abstract description 44
- 230000032683 aging Effects 0.000 title claims abstract description 22
- 238000005260 corrosion Methods 0.000 title description 21
- 238000000034 method Methods 0.000 title description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 229920000768 polyamine Polymers 0.000 claims abstract description 26
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006184 cosolvent Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims abstract description 5
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 5
- 229960000892 attapulgite Drugs 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- -1 dodecanol ester Chemical class 0.000 claims description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 5
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 claims description 3
- 229920003319 Araldite® Polymers 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002023 wood Substances 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
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The UV aging resistant aqueous epoxy anticorrosive paint comprises a component A and a component B, wherein the component A comprises raw materials of aqueous epoxy emulsion, cosolvent, pigment filler and deionized water; the component B comprises a citric acid-amine carbon point modified polyamine curing agent, a cosolvent and deionized water. The preparation method of the citric acid-amine carbon point modified polyamine curing agent comprises the following steps: reacting epoxy resin with polyethylene glycol PEG2000 and a catalyst for 8-9 hours, and then cooling for standby; step two: heating tetraethylenepentamine diluent, slowly adding ring-opening condensed epoxy resin, reacting for 5-6 hours at constant temperature, adding grafting agent, cooling to 50 ℃, then adding carbon dot solution, and reacting for 5-6 hours at constant temperature; step three: cooling to room temperature, and adding propylene glycol methyl ether and deionized water to obtain the citric acid-amine carbon point modified polyamine curing agent.
Description
Technical Field
The invention relates to the technical field of paint, in particular to a low-VOCs (volatile organic compounds) environment-friendly type anti-corrosion paint based on citric acid-amine carbon point modified UV aging resistant waterborne epoxy primer-topcoat and a preparation method thereof.
Background
Carbon dots (Carbon Dos), which are a class of spherical particles with a size of less than 10nm, are composed of two parts, a carbonaceous core and a surface group. The carbon core may be formed of sp 2-hybridized graphite microcrystalline carbon or sp 3-hybridized amorphous carbon as a skeleton of carbon dots. Since the surface of the carbon dot can be regulated, the surface groups can be determined by selecting different carbon sources, and different surface functional groups can endow the carbon dot with different properties. When the carbon dots absorb high-energy ultraviolet light, the fluorescence peak can be red shifted along with the excitation wave, and according to the characteristic, the carbon dots can be applied to the aspect of ultraviolet light protection.
The epoxy resin is one of the most commonly used thermosetting resins used in the coating industry, has excellent physical and mechanical properties, the epoxy resin mainly used in the coating is glycidyl ether type epoxy resin, bisphenol A type epoxy resin is used as the main epoxy resin, the cured epoxy resin contains polar ether bonds and hydroxyl groups, and the main chain contains benzene rings, so that the epoxy resin has the advantages of compact structure and difficult rotation of molecules, and has stronger hardness and high bending strength, has strong adhesive force to polar substrates such as metal, cement, wood, glass and the like, and has excellent resistance to acid, alkali, organic solvents and the like. In addition, the epoxy resin contains benzene rings, ether bonds connected with the benzene rings and quaternary carbon atoms, and after the epoxy resin is irradiated by sunlight, the benzene rings absorb ultraviolet light, energy is transferred to the ether bonds and quaternary carbon atoms, and the weak bonds are easy to break to form free radicals, so that the paint prepared from the epoxy resin is not resistant to ultraviolet light, poor in weather resistance and easy to pulverize outdoors, and the physical properties of the paint are greatly reduced in the process, so that the epoxy resin is only limited to be used for preparing anti-corrosion primer or used in occasions with low weather resistance requirements.
The traditional solvent-based paint contains a large amount of volatile organic compounds, so that serious pollution is caused to the atmosphere, the environment-friendly paint is one of the research hot spots of the current paint system, the water-based paint is one of the effective ways for realizing the emission of low-volatile organic compounds, and the water-based paint is also greatly popularized and developed in China. In the field of metal corrosion protection, the structure of the conventional water-based epoxy coating in the current market is not greatly changed after the conventional water-based epoxy coating is watered, and the problems of ultraviolet ageing resistance and poor weather resistance still exist after the conventional water-based epoxy coating is solidified.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an environment-friendly aqueous epoxy primer-topcoat anticorrosion paint and a method which can not destroy the structure of aqueous epoxy resin, keep the excellent physical and chemical properties of the aqueous epoxy resin and can be singly applied to outdoor UV aging resistance, and the specific technical scheme is as follows:
the UV aging resistant aqueous epoxy anti-corrosion paint consists of a component A and a component B, wherein the component A comprises raw materials of aqueous epoxy emulsion, cosolvent, pigment filler and deionized water; the component B comprises a citric acid-amine carbon point modified polyamine curing agent, a cosolvent and deionized water.
As preferable: the mass ratio of the component A to the component B is 100:10-20;
the A component comprises the following raw materials in parts by mass:
The component B comprises the following raw materials in parts by weight:
9.5-12 percent of citric acid-amine carbon point modified polyamine curing agent
Cosolvent 1-2
2-4 Parts of deionized water.
As preferable: the component A and the component B also comprise raw material auxiliary agents, wherein the auxiliary agents comprise one or more of dispersing agents, wetting agents, defoamers, anti-settling agents, thickening agents, flash rust inhibitors and silane coupling agents.
As an optimization: the mass ratio of the auxiliary agent is 1:0.2:0.2:0.4: (0.2-0.5): 1:0.2 of Coadd TM D-6086, coadd TM W-6018 as wetting agent, coadd TM DF-6901 as defoamer, attapulgite as anti-settling agent, TAFIGEL PUR of thickener, coadd TM FR-6015 as flash rust inhibitor and CoatOSilMP as silane coupling agent.
As preferable: the aqueous epoxy emulsion is one or more of EPIKOTETM 6520-WH-53、EPIKOTETM 6530-WH-55、EPIKOTETM 6526-WH-56、Araldite PZ3961-1;
The cosolvent is one or more of propylene glycol methyl ether, dipropylene glycol butyl ether, propylene glycol phenyl ether and dodecanol ester;
The pigment and filler comprises one or more of titanium dioxide, iron oxide red, iron oxide black, 1250-mesh precipitated barium sulfate, 600-800-mesh sericite powder, 800-1250-mesh talcum powder, 800-1250-mesh wollastonite powder and modified zinc phosphate.
Preferably, the structure of the citric acid-amine carbon point modified polyamine curing agent is as follows:
Wherein n is an integer of 1 to 5.
As preferable: the structural formula of the citric acid-amine carbon point is as follows,
As preferable: the preparation method of the citric acid-amine carbon point comprises the following steps of,
Step one: premixing citric acid, N- (2-hydroxypropyl) -ethylenediamine and deionized water in a glass container uniformly;
step two: adding the mixture into a polytetrafluoroethylene reaction kettle, and reacting under a closed condition;
step three: cooling to room temperature, and dialyzing in deionized water by using a dialysis bag with molecular cutoff of 500-1000 DA;
Step four: and freeze-drying to obtain the citric acid-amine carbon dot powder.
As preferable: the preparation method of the citric acid-amine carbon point modified polyamine curing agent comprises the following steps of,
Step one: ring-opening condensation of epoxy resin, reacting epoxy resin with polyethylene glycol PEG2000 and a catalyst at 90-100 ℃ for 8-9 hours, and then cooling to 70-75 ℃ for standby;
Step two: amine addition chain extension and grafting end capping, namely heating tetraethylenepentamine diluent to 70 ℃, slowly adding ring-opening condensed epoxy resin, reacting for 5-6 hours at constant temperature, adding grafting agent, cooling to 50 ℃, then adding carbon dot solution, and reacting for 5-6 hours at constant temperature;
Step three: diluting, cooling to room temperature, and adding propylene glycol methyl ether and deionized water to obtain the citric acid-amine carbon point modified polyamine curing agent.
As preferable: the preparation method of the component B comprises the step of uniformly stirring the citric acid-amine carbon dot modified polyamine curing agent, the cosolvent propylene glycol methyl ether, deionized water and flash rust inhibitor Coadd TM FR-6015 in parts by mass.
The beneficial effects of the invention are as follows: the invention provides a citric acid-amine carbon point modified UV aging resistant waterborne epoxy primer-topcoat anti-corrosion paint and a preparation method thereof. The technical route disclosed by the invention effectively overcomes the defect that the original structure of the water-based epoxy resin anticorrosive paint is reserved when the water-based epoxy resin anticorrosive paint is independently applied outdoors, and the UV ageing resistance can not be provided while the excellent physical and chemical properties of the water-based epoxy resin anticorrosive paint are reserved.
The invention effectively overcomes the defect that the conventional epoxy ultraviolet resistance modification needs to destroy the structure of epoxy emulsion and reduces the performance of the epoxy resin to improve the weather resistance of the epoxy resin by grafting and blocking the carbon point modified polyamine curing agent with the ultraviolet light conversion redshift capability;
In the preparation method of the citric acid-amine carbon point modified UV aging resistant water-based epoxy primer-topcoat anti-corrosion paint, the carbon point modified material is easy to obtain, the reaction synthesis process is simple, the production and manufacturing cost is greatly reduced, and the preparation method is more suitable for market popularization.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to enable those skilled in the art to more readily understand the advantages and features of the invention and to make a clear and concise definition of the scope of the invention. The raw materials, reagent materials and the like used in the examples described below are commercially available products unless otherwise specified.
Example 1
And (3) preparation of a component A: 13 parts by mass of deionized water, 1 part of dispersing agent Coadd TM D-6086, 0.2 part of defoaming agent Coadd TM DF-6901, 0.4 part of attapulgite, 10 parts of titanium dioxide, 5 parts of ferric oxide black, 5 parts of 600-800-mesh sericite powder, 10 parts of zinc phosphate and 10 parts of precipitated barium sulfate are uniformly stirred at a high speed, then ground by a sand mill until the fineness is less than or equal to 30 mu m, then 30 parts by mass of aqueous epoxy emulsion EPIKOTE TM -6520-WH-53 and 10 parts by mass of aqueous epoxy emulsion EPIKOTE TM -6530-WH-55 are added and uniformly stirred at a high speed, and then 2 parts by mass of cosolvent propylene glycol phenyl ether, 0.5 part of silane coupling agent Coatil MP200, 0.2 part of wetting agent Coadd TM W-6018 and 0.2 part of thickening agent TAFIGEL PUR.
And (2) preparing a component B:
Preparation of citric acid-amine carbon point modified polyamine curing agent
Step one: 16 parts by mass of citric acid, 10 parts by mass of N- (2-hydroxypropyl) -ethylenediamine and 200 parts by mass of deionized water are premixed uniformly in a glass container, then the mixture is added into a polytetrafluoroethylene reaction kettle, the mixture is reacted for 3 hours under the airtight condition of 180-200 ℃, the mixture is cooled to room temperature, and then the mixture is placed into deionized water for dialysis for 24 hours by using a dialysis bag with the molecular cutoff of 500-1000DA, and the mixture is freeze-dried for 24 hours to obtain the citric acid-amine carbon point powder for standby.
Step two: in addition, 25.5 to 26 parts by mass of E-51 epoxy resin, 10 parts of polyethylene glycol PEG2000 and 1 part of dioctyltin mercaptide catalyst are reacted for 8 to 9 hours at the temperature of between 90 and 100 ℃, and then the temperature is reduced to between 70 and 75 ℃ for standby;
Step three: and mixing 15 parts by mass of tetraethylenepentamine and 2.5 parts by mass of deionized water, heating to 70 ℃, adding the second part by mass in a dropwise manner, dropwise adding the mixture for reacting for 5-6 hours at a constant temperature, adding 0.3-0.4 part by mass of a mixture of EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride), NHS (N-hydroxysuccinimide) and deionized water, wherein the mass ratio is 2.7:1:2.3, cooling to 50 ℃, adding 0.7-0.8 part by mass of the carbon dot solution prepared in the first part by mass, wherein the mass ratio of carbon dot powder to deionized water is 8:2, and reacting for 5-6 hours at a constant temperature.
Step four: and (3) cooling the material prepared in the step (III) to room temperature, and then adding 3 parts by mass of propylene glycol methyl ether and 30 parts by mass of deionized water to obtain the citric acid-amine carbon point modified polyamine curing agent.
Uniformly stirring 9.5 parts by mass of the citric acid-amine carbon point modified polyamine curing agent, 2 parts by mass of cosolvent propylene glycol methyl ether, 1 part of deionized water and 1 part of flash rust inhibitor Coadd TM FR-6015, and uniformly stirring the components A and B according to the mass part of 100:13, mixing to obtain the citric acid-amine carbon point-based modified UV aging resistant water-based epoxy primer-topcoat anti-corrosive paint.
Example 2
And (3) preparation of a component A: 14 parts by mass of deionized water, 1 part by mass of dispersing agent Coadd TM D-6086, 0.2 part by mass of defoaming agent Coadd TM DF-6901, 0.4 part by mass of attapulgite, 10 parts by mass of iron oxide red, 5 parts by mass of 800-1250-mesh talcum powder, 5 parts by mass of 600-800-mesh sericite powder, 10 parts by mass of zinc phosphate and 10 parts by mass of 800-1250-mesh wollastonite powder are uniformly stirred at a high speed, then ground by a sand mill until the fineness is less than or equal to 30 mu m, then 42 parts by mass of aqueous epoxy emulsion EPIKOTE TM 6526-WH-56 are added and uniformly stirred at a high speed, and then 2 parts by mass of cosolvent propylene glycol phenyl ether, 0.5 part by mass of silane coupling agent Coatil MP200, 0.2 part by mass of wetting agent Coadd TM W-6018 and 0.3 part by mass of thickener TAFIGEL PUR.
And (2) preparing a component B:
homemade citric acid-amine carbon dot modified polyamine curing agent was consistent with example 1
Uniformly stirring 10 parts by mass of self-made citric acid-amine carbon point modified polyamine curing agent, 2 parts of cosolvent propylene glycol methyl ether, 3 parts of deionized water and 1 part of flash rust inhibitor Coadd TM FR-6015
The component A and the component B are prepared from the following components in parts by mass: 15, mixing to obtain the citric acid-amine carbon point-based modified UV aging resistant water-based epoxy primer-topcoat anti-corrosive paint.
Example 3
And (3) preparation of a component A: 13 parts by mass of deionized water, 1 part of dispersing agent Coadd TM D-6086, 0.2 part of defoaming agent Coadd TM DF-6901, 0.4 part of attapulgite, 10 parts of iron oxide black, 3 parts of 600-800 mesh sericite powder, 10 parts of zinc phosphate and 15 parts of 800-1250 mesh wollastonite powder are uniformly stirred at a high speed, then the mixture is ground by a sand mill until the fineness is less than or equal to 30 mu m, then 50 parts by mass of aqueous epoxy emulsion Araldite PZ3961-1 are added and uniformly stirred at a high speed, and then 2 parts by mass of cosolvent propylene glycol phenyl ether, 0.5 part of silane coupling agent CoatOSil MP200, 0.2 part of wetting agent Coadd TM W-6018 and 0.4 part of thickening agent TAFIGEL PUR are added.
And (2) preparing a component B:
homemade citric acid-amine carbon dot modified polyamine curing agent was consistent with example 1
Uniformly stirring 14 parts by mass of a self-made citric acid-amine carbon dot modified polyamine curing agent, 3 parts of cosolvent dipropylene glycol methyl ether, 4 parts of deionized water and 1 part of flash rust inhibitor Coadd TM FR-6015, and mixing the components A and B according to the mass ratio of 100:20 to obtain the citric acid-amine carbon point-based modified UV aging resistant water-based epoxy primer-topcoat anti-corrosive paint.
Comparative example 1:
the A component is the same as in example 1
And (2) preparing a component B: uniformly stirring 14 parts by mass of a commercial aqueous epoxy polyamine curing agent, 3 parts by mass of a cosolvent dipropylene glycol methyl ether, 4 parts by mass of deionized water and 1 part by mass of a flash rust inhibitor Coadd TM FR-6015;
Comparative example 2
Commercial water-based epoxy anticorrosive paint
Performance tests were performed on examples 1-3 and comparative examples 1-2, and the test items and criteria are shown in table 1:
the results of performance tests performed on examples 1-3 and comparative examples 1-2 are as follows:
From the above table, the physical properties of the citric acid-amine carbon point modified waterborne epoxy primer-topcoat anti-corrosion paint based on the UV aging resistance of the invention, namely, the physical properties of adhesion, flexibility, impact resistance and pencil hardness, are almost the same as those of the anti-corrosion paint based on the citric acid-amine carbon point modified waterborne epoxy primer-topcoat anti-corrosion paint of the invention, and the chemical properties of the anti-corrosion paint based on the high temperature engine oil, acid resistance and alkali resistance are almost the same as those of the anti-corrosion paint based on the citric acid-amine carbon point modified waterborne epoxy primer-topcoat anti-corrosion paint of the invention, so that the physical properties and chemical resistance of the cured epoxy system are not affected.
From the table, the anti-corrosion paint based on the citric acid-amine carbon point modified UV aging resistant waterborne epoxy primer-topcoat, which is disclosed by the invention, can pass through 504 hours of salt fog on salt fog resistance, so that the anti-corrosion property of the anti-corrosion paint based on the citric acid-amine carbon point modified polyamine curing agent disclosed by the invention is equivalent to that of a commercially available conventional waterborne epoxy curing agent, and the anti-corrosion property is not influenced by modification; compared with the commercial aqueous epoxy anticorrosive paint of comparative example 2, the salt tolerance is higher than 240h, so that the anticorrosive property is proved to be improved rather than not to be reduced.
As can be seen from the table, the citric acid-amine carbon point modified UV aging resistant waterborne epoxy primer-topcoat anti-corrosion paint prepared by adopting the self-made citric acid-amine carbon point modified polyamine curing agent is compared with comparative examples 1-2 in terms of UV aging resistance, after 504 hours of UV light accelerated aging, the citric acid-amine carbon point modified UV aging resistant waterborne epoxy primer-topcoat anti-corrosion paint disclosed by the invention has the advantages that the light loss is 10%, no obvious pulverization cracking and other anomalies exist, and the surface pulverization and light loss rate is as high as 80% in comparative examples 1-2, so that the UV light accelerated aging resistant performance of the citric acid-amine carbon point modified UV aging resistant waterborne epoxy primer-topcoat anti-corrosion paint disclosed by the invention can be greatly improved.
Claims (10)
1. A UV aging resistant waterborne epoxy anticorrosive paint is characterized in that: the paint comprises a component A and a component B, wherein the component A comprises raw materials of aqueous epoxy emulsion, cosolvent, pigment filler and deionized water; the component B comprises a citric acid-amine carbon point modified polyamine curing agent, a cosolvent and deionized water.
2. The UV-ageing-resistant aqueous epoxy anticorrosive paint according to claim 1, characterized in that: the mass ratio of the component A to the component B is 100:10-20;
the A component comprises the following raw materials in parts by mass:
The component B comprises the following raw materials in parts by weight:
9.5-12 percent of citric acid-amine carbon point modified polyamine curing agent
Cosolvent 1-2
2-4 Parts of deionized water.
3. UV-ageing-resistant aqueous epoxy anticorrosive paint according to claim 1 or 2, characterized in that: the component A and the component B also comprise raw material auxiliary agents, wherein the auxiliary agents comprise one or more of dispersing agents, wetting agents, defoamers, anti-settling agents, thickening agents, flash rust inhibitors and silane coupling agents.
4. A UV-ageing-resistant aqueous epoxy anticorrosive paint according to claim 3, characterized in that: the auxiliary agent comprises the following components in percentage by mass: 0.2:0.2:0.4: (0.2-0.5): 1:0.2 of Coadd TM D-6086, coadd TM W-6018 as wetting agent, coadd TM DF-6901 as defoamer, attapulgite as anti-settling agent, TAFIGEL PUR of thickener, coadd TM FR-6015 as flash rust inhibitor and CoatOSilMP as silane coupling agent.
5. UV-ageing-resistant aqueous epoxy anticorrosive paint according to claim 1 or 2, characterized in that: the aqueous epoxy emulsion is one or more of EPIKOTETM 6520-WH-53、EPIKOTETM 6530-WH-55、EPIKOTETM6526-WH-56、Araldite PZ3961-1;
The cosolvent is one or more of propylene glycol methyl ether, dipropylene glycol butyl ether, propylene glycol phenyl ether and dodecanol ester;
The pigment and filler comprises one or more of titanium dioxide, iron oxide red, iron oxide black, 1250-mesh precipitated barium sulfate, 600-800-mesh sericite powder, 800-1250-mesh talcum powder, 800-1250-mesh wollastonite powder and modified zinc phosphate.
6. The UV-aging resistant aqueous epoxy anticorrosive paint of claim 1 or 2, wherein the structure of the citric acid-amine carbon dot modified polyamine curing agent is:
Wherein n is an integer of 1 to 5.
7. UV-ageing-resistant aqueous epoxy anticorrosive paint according to claim 1 or 2, characterized in that: the structural formula of the citric acid-amine carbon point is as follows,
8. The UV-aging-resistant aqueous epoxy anticorrosive paint according to claim 7, wherein: the preparation method of the citric acid-amine carbon point comprises the following steps of,
Step one: premixing citric acid, N- (2-hydroxypropyl) -ethylenediamine and deionized water in a glass container uniformly;
step two: adding the mixture into a polytetrafluoroethylene reaction kettle, and reacting under a closed condition;
step three: cooling to room temperature, and dialyzing in deionized water by using a dialysis bag with molecular cutoff of 500-1000 DA;
Step four: and freeze-drying to obtain the citric acid-amine carbon dot powder.
9. The UV-aging-resistant aqueous epoxy anticorrosive paint according to claim 8, wherein: the preparation method of the citric acid-amine carbon point modified polyamine curing agent comprises the following steps of,
Step one: ring-opening condensation of epoxy resin, reacting epoxy resin with polyethylene glycol PEG2000 and a catalyst at 90-100 ℃ for 8-9 hours, and then cooling to 70-75 ℃ for standby;
Step two: amine addition chain extension and grafting end capping, namely heating tetraethylenepentamine diluent to 70 ℃, slowly adding ring-opening condensed epoxy resin, reacting for 5-6 hours at constant temperature, adding grafting agent, cooling to 50 ℃, then adding carbon dot solution, and reacting for 5-6 hours at constant temperature;
Step three: diluting, cooling to room temperature, and adding propylene glycol methyl ether and deionized water to obtain the citric acid-amine carbon point modified polyamine curing agent.
10. The UV-ageing-resistant aqueous epoxy anticorrosive paint of claim 9, wherein: the preparation method of the component B comprises the step of uniformly stirring the citric acid-amine carbon dot modified polyamine curing agent, the cosolvent propylene glycol methyl ether, deionized water and flash rust inhibitor Coadd TM FR-6015 in parts by mass.
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