CN116875145B - Rust-resistant primer and preparation method thereof - Google Patents
Rust-resistant primer and preparation method thereof Download PDFInfo
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- CN116875145B CN116875145B CN202310693659.9A CN202310693659A CN116875145B CN 116875145 B CN116875145 B CN 116875145B CN 202310693659 A CN202310693659 A CN 202310693659A CN 116875145 B CN116875145 B CN 116875145B
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- epoxy resin
- curing agent
- rust
- resistant primer
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 66
- 239000003822 epoxy resin Substances 0.000 claims description 60
- 229920000647 polyepoxide Polymers 0.000 claims description 60
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- 239000003085 diluting agent Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000000853 adhesive Substances 0.000 abstract description 14
- 230000001070 adhesive effect Effects 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 abstract description 6
- 238000005507 spraying Methods 0.000 abstract description 4
- 230000001680 brushing effect Effects 0.000 abstract description 3
- 238000007761 roller coating Methods 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 39
- 239000000758 substrate Substances 0.000 description 16
- 238000010276 construction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- -1 hydrogen ions Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005488 sandblasting Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007350 electrophilic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
-
- 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
- C09D5/002—Priming 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
- 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 invention provides a rust-resistant primer and a preparation method thereof. The product can be constructed under the conditions of rust and saturated humidity, and the performance of the primer is not affected. According to the current test, under the condition that the surface of the base material is lower than Sa-2 or WJ-4, the adhesive force pulling test (GB/T5210-2006) can still reach more than 9 MPa; the effect of the 100 mu m coating CASS test (GB/T10125-2021) can be more than 1000 hours, no rust and bubble exist, the accelerated line corrosion is less than 1mm, the final stripping radius of the cathode stripping test (NACE-TM 0115-2015) is less than 5mm, and the coating can be applied in various modes such as brushing, roller coating, spraying and the like.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a rust-resistant primer and a preparation method thereof.
Background
In order to ensure that the paint has higher adhesive force with the metal substrate, so that the paint has better protection effect on the substrate, the substrate is generally required to be sanded, the substrate is ensured to have no pollutants such as rust and the like, and the environmental humidity is required to be controlled during construction. Because the metal oxide tends to bond with the original substrate and become weak during the etching of the metal, the resulting etch layer is relatively loose, resulting in continued etching of the underlying metal and complete destruction of the metal. If the environmental humidity is high in the construction process, some hydrophilic raw materials in the coating can be diluted by water to influence the performance, and meanwhile, partial water remains on the surface of the substrate to cause the substrate to continuously corrode. At present, the existing paint product needs to treat a substrate before construction, dry sand blasting or water sand blasting is used, the treatment grade of the substrate reaches Sa-2 or WJ-4, other coatings are matched for achieving higher corrosion resistance, and the solvent-free product also has the problem of difficult spraying construction.
Disclosure of Invention
In view of the above, the invention aims to provide a wet rust resistant primer and a preparation method thereof, which are used for meeting the substrate treatment standard lower than Sa-2 or WJ-4, and simultaneously achieving the characteristics of higher adhesive force, high corrosion resistance, no VOC emission, excellent cathode stripping resistance and direct spray construction, thereby improving the construction efficiency and saving the cost.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
The rust-resistant primer is prepared from the following raw materials in parts by weight:
100 parts of modified epoxy resin, and the components are mixed,
10-30 Parts of a reducing curing agent,
1-4 Parts of an auxiliary agent,
20-40 Parts of powder;
the modified epoxy resin is prepared from raw materials including epoxy resin, epichlorohydrin, an active diluent and polyphosphoric acid; the reduced curing agent is prepared from a curing agent finished product, a curing agent monomer and a reducing agent serving as raw materials.
Further, the mass ratio of the epoxy resin, the epichlorohydrin, the reactive diluent and the polyphosphoric acid is 100:1-5:3-10:2.5-5.
Further, the epoxy resin viscosity is 7000-18000mPa.s and the epoxy resin viscosity is 400-4000mPa.s are mixed, the mass ratio of the epoxy resin viscosity is 8000-18000mPa.s and the epoxy resin viscosity is 400-400 mPa.s is (3-5): 1;
Preferably, the epoxy resin with the viscosity of 7000-18000mPa.s is one or two of NPEL L or Hunsted Mich GY289, and the epoxy resin with the viscosity of 400-5000mPa.s is one or more of Hunsted Mich GY282, south Asia NPEF-170 and Hunsted Mich DY 965.
More preferably, the epoxy resin having a viscosity of 8000 Pa.s is NPEL L and the epoxy resin having a viscosity of 3000 Pa.s is Henscale 282.
Further, the mass concentration of the polyphosphoric acid is 75% -85%, and the reactive diluent is one or more of H7, H48, H61, H63 and H84.
Further, the mass ratio of the finished product of the curing agent, the monomer of the curing agent and the reducing agent is 100:1-10:5-10.
Further, the finished product of the curing agent is one or more of Henschel T-403, henschel 2965, neubai lai 5454, neubai lai 2003 and Jiadieda 466D; the curing agent monomer is one or more of hexamethylenediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine, hexamethylenetetramine, diethylaminopropylamine, maleic anhydride, phthalic anhydride and biphenyl dianhydride.
Further, the reducing agent is an acidic reducing agent, and the reducing agent is one or more of hydrochloric acid, phosphoric acid, anhydrous oxalic acid, citric acid and sulfamic acid.
Further, the auxiliary agent comprises a dispersing agent, a defoaming agent, a thickening agent and a coupling agent, wherein the mass ratio of the dispersing agent to the defoaming agent is as follows: 0.3-0.7:0.5-1.5:0.2-0.6:0.1-0.5; the powder is one or more of titanium dioxide, barium sulfate, glass powder, silicon micropowder, aluminum titanium powder, carbon black, zinc phosphate, aluminum tripolyphosphate and sodium hexametaphosphate, and can improve the covering power of the product, improve the hardness, chemical resistance, corrosion resistance and workability of the product and reduce the comprehensive cost of the product.
Preferably, the dispersing agent is one or two of byk-9077 and byk-9076, and can quickly lead the rust-resistant primer to reach the specified fineness in the production process of the product;
the defoaming agent is one or more of tego-900 and tego-N, byk-054, and can reduce foaming after the construction of the wet rust resistant primer, and increase the anti-corrosion effect of the product;
the thickener is one or more of SD-2, H-18, rheobyk-7211ES and MT6900-20X, and can improve the viscosity and anti-settling performance of the product and prolong the storage life of the product; the coupling agent is one or more of KH560, MP-200, GR-101 and GR-401, and can further improve the adhesive force after the wet rust resistant primer contacts the substrate.
The invention also provides a preparation method of the rust-resistant primer, which comprises the following steps:
1) Preparation of reduced curing agent
Mixing and stirring the finished product of the curing agent, the monomer of the curing agent and the reducing agent according to a proportion, uniformly stirring to prepare the reducing agent, and hermetically preserving for later use;
2) Preparation of modified epoxy resins
Mixing and stirring epoxy resin, epichlorohydrin and an active diluent according to a proportion, introducing nitrogen for protection, dripping polyphosphoric acid, reacting for 2-3h, and cooling to room temperature to obtain modified epoxy resin;
3) Sequentially adding the modified epoxy resin, the auxiliary agent, the powder and the reduction type curing agent, mixing, grinding the product on a three-roller machine until the fineness is not more than 20 micrometers, and standing to prepare the rust-resistant primer.
Further, in step 1), the mixing temperature is 20-40 ℃; in the step 2), the stirring rotating speed is 800-1000r/min, the dropping speed of the polyphosphoric acid is 12-15 drops/min, and the mixing temperature is 60-80 ℃; in the step 3), standing is carried out at 25 ℃ for 30-60min, and the addition speed of the auxiliary agent is 2-4ml/s.
Compared with the prior art, the rust-resistant primer disclosed by the invention has the following advantages:
(1) The invention provides a preparation method of a rust-resistant primer, which comprises the steps of preparing a reducing curing agent and modified epoxy resin through raw material screening and proportioning, and adding different auxiliary agents and powder materials to obtain the rust-resistant primer. The product can be constructed under the conditions of rust and saturated humidity, and the performance of the primer is not affected. According to the current test, under the condition that the surface of the base material is lower than Sa-2 or WJ-4, the adhesive force pulling test (GB/T5210-2006) can still reach more than 9 MPa; the effect of the 100 mu m coating CASS test (GB/T10125-2021) can be more than 1000 hours, no rust and bubble exist, the accelerated line corrosion is less than 1mm, the final stripping radius of the cathode stripping test (NACE-TM 0115-2015) is less than 5mm, and the coating can be applied in various modes such as brushing, roller coating, spraying and the like. Because the product has lower requirement on the sand blasting process, the labor cost and the time cost of sand blasting are greatly saved, and the construction efficiency is improved.
(2) The modified epoxy resin can reduce the reaction time with the reduction type curing agent and improve the construction efficiency; the wet effect of the wet rust resistant primer can be improved under the condition that the substrate has a certain greasy dirt, the viscosity of the product can be reduced after the wet rust resistant primer is mixed with other components, the product can be directly combined with the surface of the substrate through the rust layer, and the final adhesive force and the corrosion resistance are improved.
(3) The solvent-free epoxy resin used for modifying the epoxy resin has higher viscosity, the product viscosity can be effectively reduced by adding the epichlorohydrin and the reactive diluent, the reaction functional group and the molecular weight of the product can be increased by post polymerization, the reaction efficiency is improved, the reaction speed is accelerated, the crosslinking density is increased, the drying speed is improved, and the post product recoating time is reduced; the epoxy chloropropane reacts with hydrogen and oxygen in the system in a nucleophilic way to form a C-O-C bond, when the hydrogen in the C-O-C bond is replaced by free hydrogen ions, hydroxide ions can be formed, and the hydroxide ions are used as catalysts to simultaneously trigger electrophilic reaction on epoxy groups to form new oxides, so that the epoxy chloropropane is added into the epoxy resin to increase the reaction rate and improve the chemical resistance of the coating; the addition of phosphoric acid can improve the polymerization degree of conventional epoxy and epichlorohydrin, and can reduce the surface smoothness after the mixture of the later-stage main agent (modified epoxy resin, auxiliary agent and powder) and the curing agent, thereby reducing the construction difficulty of the later-stage matched product.
(4) The reducing agent is added into the curing agent, so that the reducing agent can be effectively combined with the curing agent through hydrogen bonds, the later adhesive force effect is improved, strong stirring equipment is not required for site construction, and the requirement on workability is reduced; when the post-stage main agent and the curing agent are mixed and then constructed on the rusted base material with the water, the reducing agent can react with rust to reduce the rusted metal surface and form a passivation layer, so that further corrosion is prevented, the combination of the mixed coating and the base material can be effectively improved, and the adhesive force of the product is improved.
(5) After the main agent and the curing agent are mixed, a large amount of hydrogen ions exist in the main agent and the curing agent, so that the powder can be wrapped and coated, and a forward potential is formed around the powder, thereby ensuring the dispersibility of the powder, reducing the consumption of a dispersing agent, preventing the powder from being polymerized again due to the mutual repulsive force among charges, and improving the storage stability of the product.
(6) The curing agent finished product is selected to be matched with the curing agent monomer, wherein the curing agent monomer can reduce the overall viscosity of the curing agent, so that the construction is convenient; the crosslinking density can be integrally improved, so that the final coating is compact and has better anti-corrosion effect; the toughness and the impact resistance of the product can be improved.
(7) The epoxy resin with larger viscosity is matched with the epoxy resin with smaller viscosity, so that on one hand, the epoxy resin with smaller viscosity can reduce the viscosity of a product, and on the other hand, the modified epoxy resin prepared by adding some epoxy resins with smaller viscosity can improve the crosslinking density of a final product.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The present invention will be described in detail with reference to examples.
Specific information on the raw materials used in the examples are as follows:
H7 is available from HELOXY
H63 is available from HELOXY
Byk-9077 available from Pick
Byk-054 was purchased from Pick
H-18 was purchased from Wake
KH560 is purchased from silicon-bonded chemical industry
MP-200 is purchased from Michaelk
Tego-900 is purchased from Digao
Tego-N is purchased from Digao
Example 1
A method for preparing a rust-resistant primer, comprising the following steps:
1) Preparation of reduced curing agent
The curing agent finished product is selected from Neo Bil 5454 and Jia Di Da 466D, and the mass ratio of the curing agent finished product to the Jia Di Da 466D is 3.5:1, the curing agent monomer is triethylene tetramine, diethylaminopropylamine and phthalic anhydride with the mass ratio of 2:2:1, the reducing agent is citric acid. Wherein the mass ratio of the curing agent finished product to the curing agent monomer to the reducing agent is 100:3.5: and 6, mixing and stirring, wherein the mixing temperature is controlled to be 20 ℃, and the mixture is uniformly stirred to prepare the reduction type curing agent and is hermetically stored for standby.
2) Preparation of modified epoxy resins
The epoxy resin is selected from the following components of NPEL L in Nanya and Hunsted GY282 in a mass ratio of 5:1, the reactive diluent is H7 and H63 mass, and the weight ratio of the two is 1:1, a step of; the mass ratio of the epoxy resin to the epichlorohydrin to the reactive diluent to the polyphosphoric acid is 100:3:6.5:3. mixing and stirring epoxy resin, epichlorohydrin and reactive diluent, controlling the rotation speed at 1000r/min, controlling the mixing temperature at 60 ℃, introducing nitrogen for protection, dripping polyphosphoric acid with the mass concentration of 85% according to 12 drops/min, reacting for 2-3h, and cooling to room temperature to obtain the modified epoxy resin.
3) Preparation of primer
The auxiliary agent is selected from dispersant byk-9077, defoamer byk-054, thickener H-18 and coupling agent with mass ratio of 2: the mass ratio of KH560 to MP-200 of 1 is: 0.4:1:0.3:0.3.
The powder material is selected from aluminum titanium powder, carbon black, zinc phosphate and sodium hexametaphosphate, and the mass ratio is 15:3:12.5:7.5.
The modified epoxy resin, the reducing curing agent, the auxiliary agent and the powder are mixed according to the mass ratio of 100:18.43:2:38, grinding the product on a three-roller machine until the fineness is not more than 20 micrometers, and standing for 40min at 25 ℃ to prepare the rust-resistant primer.
The wet rust resistant primer is sprayed on a substrate with water rust, the adhesive force is 11.46MPa after 168 hours, the CASS test effect of the 100 mu m coating can exceed 1000 hours, no rust and bubble exist, the accelerated line is expanded by 0.8mm, and the final stripping radius is 4.6mm.
Example 2
A method for preparing a rust-resistant primer, comprising the following steps:
1) Preparation of reduced curing agent
The curing agent finished product is prepared from Neo Bilai 2003 and Jia Di Da 466D with the mass ratio of 3.5:1, the curing agent monomer is triethylene tetramine, diethylaminopropylamine and phthalic anhydride with the mass ratio of 2:2:1, the reducing agent is anhydrous oxalic acid. Wherein the mass ratio of the curing agent finished product to the curing agent monomer to the reducing agent is 100:3: and 6, mixing and stirring, wherein the mixing temperature is controlled to be 20 ℃, and the mixture is uniformly stirred to prepare the reduction type curing agent and is hermetically stored for standby.
2) Preparation of modified epoxy resins
The epoxy resin is selected from the following components of NPEL L in Nanya and Hunsted GY282 in a mass ratio of 5:1, H63 is selected as an active diluent; the mass ratio of the epoxy resin to the epichlorohydrin to the reactive diluent to the polyphosphoric acid is 100:3:7:3.
Mixing and stirring epoxy resin, epichlorohydrin and reactive diluent according to the mass ratio, controlling the rotation speed to 1000r/min, controlling the mixing temperature to 60 ℃, introducing nitrogen for protection, dripping 85% of the reactive diluent according to 13 drops/min, reacting for 2-3h, and cooling to room temperature to obtain the modified epoxy resin.
3) Preparation of primer
The auxiliary agent is dispersant byk-9077 and defoamer with mass ratio of 7:3, the tego-900 and tego-N, the thickener is SD-2, and the coupling agent is mass ratio 2: the mass ratio of KH560 to MP-200 of 1 is: 0.4:1:0.5:0.5.
The powder material is selected from titanium dioxide, carbon black, zinc phosphate and sodium hexametaphosphate with the mass ratio of 10:3:12.5:7.5.
The preparation method comprises the following steps of (1) mixing modified epoxy resin, a reduction type curing agent, an auxiliary agent and powder according to mass ratio: 100:20.85:2.4:33, grinding the product on a three-roller machine until the fineness is not more than 20 micrometers, and standing for 40min at 25 ℃ to prepare the rust-resistant primer.
The wet rust resistant primer is sprayed on a substrate with water rust, the adhesive force is 13.08MPa after 168 hours, the CASS test effect of the 100 mu m coating can exceed 1000 hours, no rust and bubble exist, the accelerated line corrosion is 0.83mm, and the final stripping radius is 4.2mm.
Example 3
A method for preparing a rust-resistant primer, comprising the following steps:
1) Preparation of reduced curing agent
The curing agent finished product is prepared from Neo Bilai 2003 and Jia Di Da 466D with the mass ratio of 3.5:1, the curing agent monomer is triethylene tetramine, diethylaminopropylamine and phthalic anhydride with the mass ratio of 2:2:1, the reducing agent is anhydrous oxalic acid. Wherein the mass ratio of the curing agent finished product to the curing agent monomer to the reducing agent is 100:3: and 6, mixing and stirring, wherein the mixing temperature is controlled to be 20 ℃, and the mixture is uniformly stirred to prepare the reduction type curing agent and is hermetically stored for standby.
2) Preparation of modified epoxy resins
The epoxy resin is prepared from NPEL L of Nanya and 965 of Hensmei, and the mass ratio of the two is 3:1, H63 is selected as an active diluent; the mass ratio of the epoxy resin to the epichlorohydrin to the reactive diluent to the polyphosphoric acid is 100:3:7:3.
Mixing and stirring epoxy resin, epichlorohydrin and reactive diluent according to the mass ratio, controlling the rotation speed to 800r/min, controlling the mixing temperature to 60 ℃, introducing nitrogen for protection, dripping 85% of the reactive diluent according to 15 drops/min, reacting for 2-3h, and cooling to room temperature to obtain the modified epoxy resin.
3) Preparation of primer
The auxiliary agent is dispersant byk-9077 and defoamer with mass ratio of 7:3, the mass ratio of tego-900 to tego-N, SD-2 as a thickener, MP-200 as a coupling agent is as follows: 0.4:1:0.5:0.5.
The powder material is selected from titanium dioxide, carbon black, zinc phosphate and sodium hexametaphosphate with the mass ratio of 10:3:12.5:7.5.
The preparation method comprises the following steps of (1) mixing modified epoxy resin, a reduction type curing agent, an auxiliary agent and powder according to mass ratio: 100:20.85:2.4:33, grinding the product on a three-roller machine until the fineness is not more than 20 micrometers, and standing for 40min at 25 ℃ to prepare the rust-resistant primer.
The wet rust resistant primer is sprayed on a substrate with water rust, the adhesive force is 12.72MPa after 168 hours, the CASS test effect of the 100 mu m coating can exceed 1000 hours, no rust and bubble exist, the accelerated line corrosion is 0.84mm, and the final stripping radius is 4.3mm.
Comparative example 1
In addition to example 1, no curing agent monomer was added to the reducing curing agent.
Comparative example 2
In addition to example 1, no reducing agent was added to the reducing agent.
Comparative example 3
Based on the above example 1, only a common epoxy resin NPEL was used, which was a raw material commonly used in primers, and had a viscosity of 12000 to 15000 (mPas).
Comparative example 4
In addition to the above example 1, only the epoxy resin NPEL L having a relatively high viscosity was used as the epoxy resin.
Comparative example 5
In addition to example 1, epichlorohydrin was not added.
Table 1 comparison of example performance
Table 2 comparative example performance comparison
As can be seen by comparing Table 1 with Table 2, the adhesion pull test (GB/T5210-2006) of the primer prepared according to the application reaches more than 9 MPa; the effect of the 100 mu m coating CASS test (GB/T10125-2021) can be more than 1000 hours, no rust and bubble exist, the accelerated line corrosion is less than 1mm, the final stripping radius of the cathode stripping test (NACE-TM 0115-2015) is less than 5mm, and the coating can be applied in various modes such as brushing, roller coating, spraying and the like.
Comparative example 1, in which no curing agent monomer was added, had reduced anticorrosive effect and toughness.
The comparative example 2 has no addition of the reducing agent, the adhesive force is obviously reduced, and the primer is easily separated after the adhesive force is reduced, so that phenomena such as rust, bubbles and the like are caused, the necessity of adding the reducing agent is proved, and the later adhesive force effect is improved.
Comparative examples 3-5 demonstrate that the adhesion and corrosion resistance of the primer obtained using a single epoxy resin are both poor, because the single epoxy resin does not allow good adjustment of the viscosity of the product, and does not facilitate the increase of the crosslink density of the product, thereby affecting the adhesion of the primer.
In the comparative example 6, the acid and alkali resistance effect is poor, the surface drying speed is slow, because the epoxy chloropropane reacts with hydrogen and oxygen in a system in a nucleophilic way to form a C-O-C bond, when the hydrogen in the C-O-C bond is replaced by free hydrogen ions, hydroxide ions can be formed, and the hydroxide ions serve as a catalyst to simultaneously trigger electrophilic reaction on epoxy groups to form new oxides, the epoxy chloropropane is added into the epoxy resin, so that the reaction rate can be increased, and the chemical resistance of the coating can be improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. A wet rust resistant primer, characterized in that: the wet rust resistant primer is prepared from the following raw materials in parts by weight:
100 parts of modified epoxy resin, and the components are mixed,
10-30 Parts of a reducing curing agent,
1-4 Parts of an auxiliary agent,
20-40 Parts of powder;
Wherein the modified epoxy resin is prepared from epoxy resin, epichlorohydrin, an active diluent and polyphosphoric acid serving as raw materials; the reduced curing agent is prepared from a curing agent finished product, a curing agent monomer and a reducing agent serving as raw materials;
the mass ratio of the epoxy resin, the epichlorohydrin, the reactive diluent and the polyphosphoric acid in the modified epoxy resin is 100:1-5:3-10:2.5-5;
The epoxy resin in the modified epoxy resin is obtained by mixing the epoxy resin with the viscosity of 7000-18000mPa.s and the viscosity of 400-4000 mPa.s;
The mass ratio of the finished product of the curing agent, the monomer of the curing agent and the reducing agent in the reducing curing agent is 100:1-10:5-10;
The curing agent finished product is one or more of Henschel T-403, henschel 2965 and Jiadieda 466D; the curing agent monomer is one or more of hexamethylenediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine, hexamethylenetetramine, diethylaminopropylamine, maleic anhydride, phthalic anhydride and biphenyl dianhydride;
The reducing agent is an acidic reducing agent, and the reducing agent is one or more of phosphoric acid, anhydrous oxalic acid, citric acid and sulfamic acid.
2. The wet rust resistant primer according to claim 1, wherein: the epoxy resin with the viscosity of 7000-18000mPa.s is one or two of NPEL L or Hummine GY289, and the epoxy resin with the viscosity of 400-4000mPa.s is one or more of Hummine GY282, nanya NPEF-170 and Hummine DY 965.
3. The wet rust resistant primer according to claim 1, wherein: the mass concentration of the polyphosphoric acid is 75-85%, and the reactive diluent is one or more of H7, H48, H61, H63 and H84.
4. The wet rust resistant primer according to claim 1, wherein: the auxiliary agent comprises a dispersing agent, a defoaming agent, a thickening agent and a coupling agent, wherein the mass ratio of the dispersing agent to the defoaming agent is as follows: 0.3-0.7:0.5-1.5:0.2-0.6:0.1-0.5; the powder is one or more of titanium dioxide, barium sulfate, glass powder, silicon micropowder, aluminum titanium powder, carbon black, zinc phosphate, aluminum tripolyphosphate and sodium hexametaphosphate.
5. A method of preparing the rust resistant primer according to any one of claims 1 to 4, wherein: the method comprises the following steps:
1) Preparation of reduced curing agent
Mixing and stirring the finished product of the curing agent, the monomer of the curing agent and the reducing agent according to a proportion, uniformly stirring to prepare the reducing agent, and hermetically preserving for later use;
2) Preparation of modified epoxy resins
Mixing and stirring epoxy resin, epichlorohydrin and an active diluent according to a proportion, introducing nitrogen for protection, dripping polyphosphoric acid, reacting for 2-3h, and cooling to room temperature to obtain modified epoxy resin;
3) Sequentially adding the modified epoxy resin, the auxiliary agent, the powder and the reduction type curing agent, mixing, grinding the product on a three-roller machine until the fineness is not more than 20 micrometers, and standing to prepare the rust-resistant primer.
6. The method for preparing the rust resistant primer according to claim 5, wherein: in the step 1), the mixing temperature is 20-40 ℃; in the step 2), the stirring rotating speed is 800-1000r/min, the dropping speed of the polyphosphoric acid is 12-15 drops/min, and the mixing temperature is 60-80 ℃; in the step 3), standing is carried out at 25 ℃ for 30-60min, and the addition speed of the auxiliary agent is 2-4ml/s.
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| CN113307984A (en) * | 2021-04-29 | 2021-08-27 | 广西桂林荣鑫新材料科技有限公司 | Preparation method of aqueous epoxy resin dispersion |
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| CN113307984A (en) * | 2021-04-29 | 2021-08-27 | 广西桂林荣鑫新材料科技有限公司 | Preparation method of aqueous epoxy resin dispersion |
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