CN116410648B - Fast-curing phenolic epoxy paint - Google Patents
Fast-curing phenolic epoxy paint Download PDFInfo
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- CN116410648B CN116410648B CN202310500374.9A CN202310500374A CN116410648B CN 116410648 B CN116410648 B CN 116410648B CN 202310500374 A CN202310500374 A CN 202310500374A CN 116410648 B CN116410648 B CN 116410648B
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003973 paint Substances 0.000 title abstract description 11
- 239000004593 Epoxy Substances 0.000 title abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 67
- 229920006334 epoxy coating Polymers 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- PUINVXGYZJXMMX-UHFFFAOYSA-N 4-isocyanatobenzaldehyde Chemical compound O=CC1=CC=C(N=C=O)C=C1 PUINVXGYZJXMMX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 43
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 36
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 24
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- -1 modified alicyclic amine Chemical class 0.000 claims description 8
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000036541 health Effects 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000004808 2-ethylhexylester Substances 0.000 description 6
- 239000013530 defoamer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003487 anti-permeability effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OVOZYARDXPHRDL-UHFFFAOYSA-N 3,4-diaminophenol Chemical compound NC1=CC=C(O)C=C1N OVOZYARDXPHRDL-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000004888 barrier function Effects 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
- 239000005007 epoxy-phenolic resin Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic 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
- C09D163/04—Epoxynovolacs
-
- 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
- C09D7/20—Diluents or solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a fast-curing phenolic epoxy coating, and relates to the technical field of coatings. The invention takes the reactive diluent with low viscosity and being capable of participating in the curing reaction and the volatile absolute ethyl alcohol as the solvent, and the solvent is mixed with the phenolic epoxy resin, the auxiliary agent and the pigment filler to prepare the component A, so that the toughness of the coating film is improved, and the influence of the solvent on the coating film, the environment and the human health is reduced; the glass flake is sequentially reacted with 4-isocyanatobenzaldehyde and 4-hydroxyphthalenediamine to prepare modified glass flake, and then the modified glass flake is mixed with a curing agent and a curing accelerator to prepare a component B, and the diffusion path of a corrosive medium is prolonged, a single-molecule film is formed on the surface of a substrate, and the glass flake and resin form a tight interface, so that the toughness of a coating film is improved while the penetration of the corrosive medium is prevented; and packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating. The fast-curing phenolic epoxy paint prepared by the invention has anti-seepage and corrosion inhibition performances.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a fast-curing phenolic epoxy coating.
Background
The common epoxy resin paint is widely applied to the fields of automobile industry, shipbuilding industry, aviation industry, chemical industry, electric industry and the like because of the characteristics of excellent chemical resistance, better thermal stability, electric insulation, strong adhesive force with metal base materials and the like, but is difficult to meet the protection requirement of the corrosive environment containing stronger acidic substances because of the poor acid resistance, and has certain limitation in use. The epoxy phenolic resin is a linear structure polymer synthesized by novolac resin and common epichlorohydrin, the resin contains more epoxy groups (the epoxy functionality is more than 2) than the common epoxy resin, the crosslinking density of the coating after being cured by the crosslinking agent is high, and the heat resistance and the chemical resistance are higher than those of bisphenol A type epoxy resin.
The epoxy phenolic resin paint not only inherits the advantage of good adhesive force of the common epoxy paint, but also further improves the corrosion resistance, especially the acid resistance and the methanol resistance, and has wider application field. However, the disadvantage is that the impact resistance is weak, the coating film is easy to break after being impacted, the substrate is exposed and corroded, and the mechanical property of the substrate is weakened. In addition, the resin has poor permeation resistance, corrosive medium is easy to permeate into the coating film to finally corrode the substrate, foaming, cracking and substrate corrosion phenomena of the coating film occur, so that the corrosion resistance of the coating film is invalid, more volatile and toxic organic solvents are often used in the coating to reduce the viscosity, but the volatilization of the organic solvents can leave holes in the coating film, so that the impermeability of the coating film is further reduced, and the use effect of the coating film is seriously influenced.
Disclosure of Invention
The invention aims to provide a fast-curing phenolic epoxy coating to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a fast-curing phenolic epoxy paint is composed of a component A and a component B, wherein the component A comprises phenolic epoxy resin, reactive diluent, auxiliary agent, pigment filler and solvent, and the component B comprises modified glass flakes, curing agent and curing accelerator.
Preferably, the reactive diluent is n-butyl glycidyl ether or octyl glycidyl ether; the pigment and filler is prepared by mixing sericite, barium sulfate and quartz powder; the solvent is absolute ethyl alcohol; the curing agent is a modified alicyclic amine curing agent R-2259; the curing accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol.
As optimization, the modified glass flake is prepared by reacting glass flake, 4-isocyanatobenzaldehyde and 4-hydroxy o-phenylenediamine.
As optimization, the auxiliary agent comprises a dispersing agent, a defoaming agent and a leveling agent; the dispersing agent is Anti-terra-U; the antifoaming agent is corning antifoaming agent 100F; the leveling agent is poly-2-ethylhexyl acrylate.
As optimization, the preparation method of the fast-curing phenolic epoxy paint mainly comprises the following preparation steps:
(1) Sequentially reacting the glass flake with 4-isocyanatobenzaldehyde and 4-hydroxyphthalenediamine to obtain modified glass flake;
(2) Preparing a component A from phenolic epoxy resin, a reactive diluent, an auxiliary agent, pigment and filler and a solvent; mixing the modified glass flakes, a curing agent and an accelerator to prepare a component B;
(3) And packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
As optimization, the preparation method of the fast-curing phenolic epoxy paint mainly comprises the following preparation steps:
(1) Mixing pre-modified glass flakes, chloroform and ammonium metavanadate according to a mass ratio of 5:10:0.01-7:10:0.03, stirring for 10min at 200-300 rpm, adding 4-hydroxyphthalenediamine with the mass of 0.2-0.4 times of that of the chloroform, carrying out reflux reaction for 3-5 h at 50-80 ℃ at 200-300 rpm, filtering, washing with chloroform and deionized water for 3-5 times in sequence, and drying at 60 ℃ for 6-8 h to obtain modified glass flakes;
(2) Mixing phenolic epoxy resin, an active diluent, an auxiliary agent, pigment and filler and a solvent according to a mass ratio of 40:6:2:10:5-50:9:3:20:5, and stirring at 1000-1500 rpm for 10-20 min to obtain a component A; mixing the modified glass flakes, the curing agent and the curing accelerator according to the mass ratio of 20:15:1-25:20:1, and stirring at 1000-1500 rpm for 30min to obtain a component B;
(3) And packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
As optimization, the preparation method of the pre-modified glass flake in the step (1) comprises the following steps: mixing glass flakes with the diameter of 45-75 mu m, dimethylbenzene and stannous octoate according to the mass ratio of 50:300:0.05-25:300:0.10, and carrying out ultrasonic treatment for 20min under the condition of 500-800W to obtain glass flake dispersion; mixing 4-isocyanatobenzaldehyde and dimethylbenzene according to a mass ratio of 1:10, performing ultrasonic treatment at 500-800W for 10min, then dripping the mixture into the glass flake dispersion liquid at 60 drops/min under the atmosphere of nitrogen at 300-500 rpm, then heating to 130-160 ℃, continuing to react for 4-6 h, filtering, washing with dimethylbenzene and tetrahydrofuran for 2-4 times in sequence, and performing vacuum drying at 0.08MPa and 110 ℃ for 12h to obtain the pre-modified glass flake.
As optimization, the auxiliary agent in the step (2) is prepared by mixing a dispersing agent, a defoaming agent and a leveling agent according to the mass ratio of 1:0.5:0.8-5:0.5:1.2; the pigment and filler is prepared by mixing sericite, barium sulfate and quartz powder according to the mass ratio of 11:3:1-15:5:1.
As optimization, when the fast-curing phenolic epoxy coating is used, the component A and the component B are mixed according to the mass ratio of 3:1, and are stirred for 10-20 min at 2000-2500 rpm and then are coated on the surface of a material, and the dry film thickness of the coating film is 300 mu m.
Compared with the prior art, the invention has the following beneficial effects:
the invention comprises a component A and a component B, wherein the component A comprises phenolic epoxy resin, reactive diluent, auxiliary agent, pigment filler and solvent, and the component B comprises modified glass flakes, curing agent and curing accelerator, thus having anti-seepage and corrosion-resistant properties.
Firstly, the invention takes low-viscosity n-butyl glycidyl ether or octyl glycidyl ether as a diluent, reduces the viscosity of the resin, reduces the use of solvents, can participate in the curing reaction, improves the toughness of the resin, and in addition, replaces the traditional organic solvent with absolute ethyl alcohol, thereby avoiding the pollution of the solvent volatilization to the environment and the harm to the human health.
Secondly, the glass flake reacts with 4-isocyanatobenzaldehyde and 4-hydroxyphthalenediamine in sequence to prepare modified glass flake; hydroxyl groups on the surface of the glass flakes react with isocyanate groups in the 4-isocyanatobenzaldehyde, so that the compatibility of the glass flakes and resin can be improved, the glass flakes are uniformly dispersed in a coating film to form a labyrinth diffusion path, and the migration path of a corrosive medium from the surface of the coating film to a substrate is prolonged, so that the coating has impermeability; the aldehyde group in the 4-isocyanatobenzaldehyde reacts with the diamino group in the 4-hydroxy o-phenylenediamine to form a benzimidazole structure, when a corrosive medium reaches a substrate, the benzimidazole structure can form a single-molecule film on the surface of the substrate, thereby inhibiting corrosion and bubble generation, so that the coating has impermeability, and simultaneously, amine groups in the benzimidazole structure can participate in the crosslinking curing reaction of the resin, so that glass flakes and the resin form a strong and compact bonding force interface, and the impact strength of a coating film is improved while the infiltration of the corrosive medium is prevented.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below 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.
For a clearer description of the method provided by the present invention, the following examples are provided for the purpose of illustrating in detail the methods for testing the various indices of the fast curing phenolic epoxy paint made in the following examples as follows:
mixing the component A and the component B of the fast-curing phenolic epoxy paint prepared in the example and the comparative example according to the mass ratio of 3:1, stirring at 23000rpm for 15min, coating the mixture on the surface of a tinplate with the size of 120mm multiplied by 50mm multiplied by 0.3mm, curing the mixture at normal temperature for 24h, and obtaining a test sample;
barrier properties: according to GB/T9274A method, after a test sample is immersed in a chemical medium solution for 90d, the change phenomenon of a coating film and a substrate is observed, wherein the chemical medium solution comprises 5% sulfuric acid aqueous solution, 5% sodium hydroxide aqueous solution and 5% sodium chloride aqueous solution;
impact resistance: test specimens were taken and tested for impact strength according to GB/T1732.
Example 1
A preparation method of a fast-curing phenolic epoxy coating mainly comprises the following preparation steps:
(1) Mixing glass flakes with the diameter of 45 mu m, dimethylbenzene and stannous octoate according to the mass ratio of 15:300:0.05, and carrying out ultrasonic treatment at 500W for 20min to obtain glass flake dispersion liquid; mixing 4-isocyanatobenzaldehyde and dimethylbenzene according to a mass ratio of 1:10, performing ultrasonic treatment at 500W for 10min, dripping the mixture into a glass flake dispersion liquid at 60 drops/min under a nitrogen atmosphere at 300rpm, heating to 130 ℃, continuously reacting for 4h, filtering, washing with dimethylbenzene and tetrahydrofuran for 2 times in sequence, and performing vacuum drying at 110 ℃ under 0.08MPa for 12h to obtain pre-modified glass flakes;
(2) Mixing the pre-modified glass flakes, chloroform and ammonium metavanadate according to the mass ratio of 5:10:0.01, stirring for 10min at 200rpm, adding 4-hydroxyphthalenediamine with the mass of 0.2 times of that of the chloroform, carrying out reflux reaction for 3h at 200rpm and 50 ℃, filtering, washing with chloroform and deionized water for 3 times in sequence, and drying at 60 ℃ for 6h to obtain the modified glass flakes;
(3) Mixing phenolic epoxy resin, n-butyl glycidyl ether, an auxiliary agent, pigment and filler and absolute ethyl alcohol according to a mass ratio of 40:6:2:10:5, wherein the mass ratio of Anti-terra-U, corning defoamer 100F and polyacrylic acid-2-ethylhexyl ester in the auxiliary agent is 1:0.5:0.8, and the mass ratio of sericite, barium sulfate and quartz powder in the pigment and filler is 11:3:1, and stirring for 10min at 1000rpm to obtain a component A; mixing modified glass flakes, modified alicyclic amine curing agent R-2259 and 2,4, 6-tris (dimethylaminomethyl) phenol according to a mass ratio of 20:15, and stirring at 1000rpm for 30min to obtain a component B; and packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
Example 2
A preparation method of a fast-curing phenolic epoxy coating mainly comprises the following preparation steps:
(1) Mixing glass flakes with the diameter of 60 mu m, dimethylbenzene and stannous octoate according to the mass ratio of 20:300:0.08, and carrying out ultrasonic treatment at 650W for 20min to obtain glass flake dispersion liquid; mixing 4-isocyanatobenzaldehyde and dimethylbenzene according to a mass ratio of 1:10, performing ultrasonic treatment at 650W for 10min, dripping the mixture into a glass flake dispersion liquid at 60 drops/min under a nitrogen atmosphere at 400rpm, heating to 145 ℃, continuing to react for 5h, filtering, washing with dimethylbenzene and tetrahydrofuran for 3 times in sequence, and performing vacuum drying at 110 ℃ under 0.08MPa for 12h to obtain pre-modified glass flakes;
(2) Mixing the pre-modified glass flakes, chloroform and ammonium metavanadate according to the mass ratio of 6:10:0.02, stirring for 10min at 250rpm, adding 4-hydroxyphthalenediamine with the mass of 0.3 times of that of the chloroform, carrying out reflux reaction for 4h at the temperature of 65 ℃ at 250rpm, filtering, washing with chloroform and deionized water for 4 times in sequence, and drying for 7h at the temperature of 60 ℃ to obtain the modified glass flakes;
(3) Mixing phenolic epoxy resin, octyl glycidyl ether, an auxiliary agent, pigment and filler and absolute ethyl alcohol according to the mass ratio of 45:7.5:2.5:15:5, wherein the mass ratio of Anti-terra-U, corning defoamer 100F and polyacrylic acid-2-ethylhexyl ester in the auxiliary agent is 3:0.5:1, and the mass ratio of sericite, barium sulfate and quartz powder in the pigment and filler is 13:4:1, and stirring for 15min at 1300rpm to obtain a component A; mixing the modified glass flakes, the modified alicyclic amine curing agent R-2259 and the 2,4, 6-tris (dimethylaminomethyl) phenol according to a mass ratio of 23:20:1, and stirring at 1300rpm for 30min to obtain a component B; and packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
Example 3
A preparation method of a fast-curing phenolic epoxy coating mainly comprises the following preparation steps:
(1) Mixing glass flakes with the diameter of 75 mu m, dimethylbenzene and stannous octoate according to the mass ratio of 25:300:0.10, and carrying out ultrasonic treatment at 800W for 20min to obtain glass flake dispersion liquid; mixing 4-isocyanatobenzaldehyde and dimethylbenzene according to a mass ratio of 1:10, performing ultrasonic treatment at 800W for 10min, dripping the mixture into a glass flake dispersion liquid at 60 drops/min under a nitrogen atmosphere at 500rpm, heating to 160 ℃, continuously reacting for 6h, filtering, washing with dimethylbenzene and tetrahydrofuran for 4 times in sequence, and performing vacuum drying at 0.08MPa and 110 ℃ for 12h to obtain pre-modified glass flakes;
(2) Mixing the pre-modified glass flakes, chloroform and ammonium metavanadate according to the mass ratio of 7:10:0.03, stirring for 10min at 300rpm, adding 4-hydroxyphthalenediamine with the mass of 0.4 times of that of the chloroform, carrying out reflux reaction for 5h at 300rpm and 80 ℃, filtering, washing with chloroform and deionized water for 5 times in sequence, and drying at 60 ℃ for 8h to obtain the modified glass flakes;
(3) Mixing phenolic epoxy resin, n-butyl glycidyl ether, an auxiliary agent, pigment and filler and absolute ethyl alcohol according to a mass ratio of 50:9:3:20:5, wherein the mass ratio of Anti-terra-U, corning defoamer 100F and polyacrylic acid-2-ethylhexyl ester in the auxiliary agent is 5:0.5:1.2, and the mass ratio of sericite, barium sulfate and quartz powder in the pigment and filler is 15:5:1, and stirring for 20min at 1500rpm to obtain a component A; mixing the modified glass flakes, the modified alicyclic amine curing agent R-2259 and the 2,4, 6-tris (dimethylaminomethyl) phenol according to a mass ratio of 25:20:1, and stirring at 1500rpm for 30min to obtain a component B; and packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
Comparative example 1
A preparation method of a fast-curing phenolic epoxy coating mainly comprises the following preparation steps:
(1) Mixing phenolic epoxy resin, octyl glycidyl ether, an auxiliary agent, pigment and filler and absolute ethyl alcohol according to the mass ratio of 45:7.5:2.5:15:5, wherein the mass ratio of Anti-terra-U, corning defoamer 100F and polyacrylic acid-2-ethylhexyl ester in the auxiliary agent is 3:0.5:1, and the mass ratio of sericite, barium sulfate and quartz powder in the pigment and filler is 13:4:1, and stirring for 15min at 1300rpm to obtain a component A; mixing glass flakes, a modified alicyclic amine curing agent R-2259 and 2,4, 6-tris (dimethylaminomethyl) phenol according to a mass ratio of 23:20:1, and stirring at 1300rpm for 30min to obtain a component B; and packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
Comparative example 2
A preparation method of a fast-curing phenolic epoxy coating mainly comprises the following preparation steps:
(1) Mixing glass flakes with the diameter of 60 mu m, dimethylbenzene and stannous octoate according to the mass ratio of 20:300:0.08, and carrying out ultrasonic treatment at 700W for 20min to obtain glass flake dispersion liquid; mixing 4-isocyanatobenzaldehyde and dimethylbenzene according to a mass ratio of 1:10, performing ultrasonic treatment at 650W for 10min, dripping the mixture into a glass flake dispersion liquid at 60 drops/min under a nitrogen atmosphere at 400rpm, heating to 145 ℃, continuing to react for 5h, filtering, washing with dimethylbenzene and tetrahydrofuran for 3 times in sequence, and performing vacuum drying at 110 ℃ under 0.08MPa for 12h to obtain modified glass flakes;
(2) Mixing phenolic epoxy resin, octyl glycidyl ether, an auxiliary agent, pigment and filler and absolute ethyl alcohol according to the mass ratio of 45:7.5:2.5:15:5, wherein the mass ratio of Anti-terra-U, corning defoamer 100F and polyacrylic acid-2-ethylhexyl ester in the auxiliary agent is 3:0.5:1, and the mass ratio of sericite, barium sulfate and quartz powder in the pigment and filler is 13:4:1, and stirring for 15min at 1300rpm to obtain a component A; mixing the modified glass flakes, the modified alicyclic amine curing agent R-2259 and the 2,4, 6-tris (dimethylaminomethyl) phenol according to a mass ratio of 23:20:1, and stirring at 1300rpm for 30min to obtain a component B; and packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
Comparative example 3
A preparation method of a fast-curing phenolic epoxy coating mainly comprises the following preparation steps:
(1) Mixing 4-isocyanatobenzaldehyde, chloroform and ammonium metavanadate according to a mass ratio of 6:10:0.02, stirring for 10min at 250rpm, adding 4-hydroxyphthalenediamine with the mass of 0.3 times of that of the chloroform, carrying out reflux reaction for 4h at the temperature of 65 ℃ at 250rpm, filtering, washing with chloroform and deionized water for 4 times in sequence, and drying at the temperature of 60 ℃ for 7h to obtain a benzimidazole structure;
(2) Mixing phenolic epoxy resin, octyl glycidyl ether, an auxiliary agent, pigment and filler and absolute ethyl alcohol according to the mass ratio of 45:7.5:2.5:15:5, wherein the mass ratio of Anti-terra-U, corning defoamer 100F and polyacrylic acid-2-ethylhexyl ester in the auxiliary agent is 3:0.5:1, and the mass ratio of sericite, barium sulfate and quartz powder in the pigment and filler is 13:4:1, and stirring for 15min at 1300rpm to obtain a component A; mixing benzimidazole structure, modified alicyclic amine curing agent R-2259 and 2,4, 6-tris (dimethylaminomethyl) phenol according to a mass ratio of 23:20:1, and stirring at 1300rpm for 30min to obtain a component B; and packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
Effect example
The following Table 1 shows the results of performance analysis of impact resistance and barrier properties of the fast curing phenolic epoxy coatings of examples 1 to 3 and comparative examples 1 to 3 of the present invention.
TABLE 1
As can be found from the comparison of the impact strength data of the examples and the comparative examples in the table 1, the fast-curing phenolic epoxy coating prepared by the invention has good impact resistance, the reaction of glass flakes and 4-isocyanatobenzaldehyde can improve the compatibility of the glass flakes and resin, the impact resistance effect of the coating is improved, the fast-curing phenolic epoxy coating further reacts with 4-hydroxyphthalenediamine to form a benzimidazole structure, the fast-curing phenolic epoxy coating can participate in the crosslinking curing reaction of the resin, the interface relation between the glass flakes and the resin is improved, the crosslinking density of the coating is improved, and the impact resistance effect is enhanced; as can be found from the comparison of the data of the chemical-resistant aqueous solution of the examples and the comparative examples in the table 1, the prepared fast-curing phenolic epoxy coating has good anti-permeability and anti-corrosion performance, and the compatibility of glass flakes and resin is improved, so that the glass flakes are dispersed in a coating film to form a labyrinth diffusion path, and the migration path of corrosive medium from the surface of the coating film to a base material is prolonged, thereby the coating has anti-permeability and anti-corrosion performance, a benzimidazole structure can react with the resin to improve the interfacial compactness between the base material and the resin, and the benzimidazole structure is released and forms a single-molecule film on the surface of the base material after the corrosive medium reaches the surface of the base material while preventing the penetration of the corrosive medium, thereby inhibiting the generation of corrosion and bubbles, and improving the anti-permeability and anti-corrosion effects.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (6)
1. The fast-curing phenolic epoxy coating is characterized by comprising a component A and a component B, wherein the component A comprises phenolic epoxy resin, reactive diluent, auxiliary agent, pigment filler and solvent, and the component B comprises modified glass flakes, curing agent and curing accelerator;
the fast curing phenolic epoxy coating comprises the following preparation steps:
(1) Mixing glass flakes with the diameter of 45-75 mu m, dimethylbenzene and stannous octoate according to the mass ratio of 50:300:0.05-25:300:0.10, and carrying out ultrasonic treatment for 20min at the temperature of 500-800W to obtain a glass flake dispersion liquid: mixing 4-isocyanatobenzaldehyde and dimethylbenzene according to a mass ratio of 1:10, performing ultrasonic treatment at 500-800W for 10min, then dripping the mixture into a glass flake dispersion liquid at 60 drops/min under the atmosphere of nitrogen at 300-500 rpm, heating to 130-160 ℃, continuing to react for 4-6 h, filtering, washing with dimethylbenzene and tetrahydrofuran for 2-4 times in sequence, and performing vacuum drying at 0.08MPa and 110 ℃ for 12h to obtain pre-modified glass flakes; mixing the pre-modified glass flakes, chloroform and ammonium metavanadate according to a mass ratio of 5:10:0.01-7:10:0.03, stirring for 10min at 200-300 rpm, adding 4-hydroxyphthalenediamine with the mass of 0.2-0.4 times of that of the chloroform, carrying out reflux reaction for 3-5 h at 50-80 ℃ at 200-300 rpm, filtering, washing with chloroform and deionized water for 3-5 times in sequence, and drying at 60 ℃ for 6-8 h to obtain the modified glass flakes;
(2) Mixing phenolic epoxy resin, an active diluent, an auxiliary agent, pigment and filler and a solvent according to a mass ratio of 40:6:2:10:5-50:9:3:20:5, and stirring at 1000-1500 rpm for 10-20 min to obtain a component A; mixing the modified glass flakes, the curing agent and the curing accelerator according to the mass ratio of 20:15:1-25:20:1, and stirring at 1000-1500 rpm for 30min to obtain a component B;
(3) And packaging the component A and the component B respectively to prepare the fast-curing phenolic epoxy coating.
2. A quick setting phenolic epoxy coating as claimed in claim 1 wherein said reactive diluent is n-butyl glycidyl ether or octyl glycidyl ether; the pigment and filler is prepared by mixing sericite, barium sulfate and quartz powder; the solvent is absolute ethyl alcohol; the curing agent is a modified alicyclic amine curing agent R-2259; the curing accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol.
3. The fast curing phenolic epoxy coating of claim 1 wherein the modified glass flakes are made by reacting glass flakes, 4-isocyanatobenzaldehyde, 4-hydroxyphthalenediamine.
4. A fast curing phenolic epoxy coating according to claim 1 wherein the auxiliary agents include dispersants, defoamers, leveling agents; the dispersing agent is Anti-terra-U; the antifoaming agent is corning antifoaming agent 100F; the leveling agent is poly-2-ethylhexyl acrylate.
5. The fast-curing phenolic epoxy coating according to claim 1, wherein the auxiliary agent in the step (2) is prepared by mixing a dispersing agent, a defoaming agent and a leveling agent according to a mass ratio of 1:0.5:0.8-5:0.5:1.2; the pigment and filler is prepared by mixing sericite, barium sulfate and quartz powder according to the mass ratio of 11:3:1-15:5:1.
6. The fast curing phenolic epoxy coating of claim 1, wherein the fast curing phenolic epoxy coating is applied to the surface of a material after mixing an A component and a B component according to a mass ratio of 3:1 and stirring for 10-20 min at 2000-2500 rpm, and the dry film thickness of the coating film is 300 μm.
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