CN116622280B - High-temperature-resistant coating for metal substrate and preparation method thereof - Google Patents
High-temperature-resistant coating for metal substrate and preparation method thereof Download PDFInfo
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- CN116622280B CN116622280B CN202310657227.2A CN202310657227A CN116622280B CN 116622280 B CN116622280 B CN 116622280B CN 202310657227 A CN202310657227 A CN 202310657227A CN 116622280 B CN116622280 B CN 116622280B
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- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 239000000758 substrate Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 127
- 238000002156 mixing Methods 0.000 claims abstract description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 101
- 230000002457 bidirectional effect Effects 0.000 claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 claims abstract description 26
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 24
- 239000006184 cosolvent Substances 0.000 claims abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 230000002195 synergetic effect Effects 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000004115 Sodium Silicate Substances 0.000 claims description 76
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 76
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 76
- 239000000243 solution Substances 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 69
- 238000000498 ball milling Methods 0.000 claims description 55
- 239000007864 aqueous solution Substances 0.000 claims description 50
- 229920005610 lignin Polymers 0.000 claims description 49
- 238000011282 treatment Methods 0.000 claims description 44
- -1 alcohol amine Chemical class 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 32
- 238000012986 modification Methods 0.000 claims description 29
- 230000004048 modification Effects 0.000 claims description 29
- 238000005496 tempering Methods 0.000 claims description 29
- 239000011324 bead Substances 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000012747 synergistic agent Substances 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000007853 buffer solution Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 8
- 229920001661 Chitosan Polymers 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000661 sodium alginate Substances 0.000 claims description 8
- 235000010413 sodium alginate Nutrition 0.000 claims description 8
- 229940005550 sodium alginate Drugs 0.000 claims description 8
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000003607 modifier Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of metal substrate coatings, and in particular discloses a high-temperature resistant coating for a metal substrate, which comprises the following raw materials in parts by weight: 35-40 parts of polyurethane emulsion, 16-22 parts of blending modified nano graphene bidirectional agent, 7-11 parts of synergistic replenishing agent, 3-6 parts of silane coupling agent KH560, 2-5 parts of film forming cosolvent, 2-5 parts of defoaming agent and 1-3 parts of curing agent. The high-temperature resistant coating adopts the modified nano graphene bi-directional agent, the synergistic complementing agent and the silane coupling agent KH560 to coordinate and match with polyurethane emulsion, and then the film forming cosolvent, the defoaming agent and the curing agent are used for complementing and regulating together to improve the system function of the product, and the modified nano graphene bi-directional agent and the synergistic complementing agent are used for coordinating and synergistic, so that the adhesiveness and the impact resistance of the product are improved in a coordinated manner, and the performance of the product under the conditions of salt corrosion and high temperature resistance is more stable.
Description
Technical Field
The invention relates to the technical field of metal substrate coatings, in particular to a high-temperature resistant coating for a metal substrate and a preparation method thereof.
Background
The paint capable of delaying or preventing the corrosion of the metal material becomes a metal anti-corrosion paint, and the loss caused by metal corrosion is very large, so that the metal anti-corrosion problem is widely concerned, rust prevention and corrosion prevention are one of the most effective methods, and the metal anti-corrosion paint comprises a chlorine-containing anti-corrosion paint, an epoxy zinc-rich primer, a polyurethane anti-corrosion paint and the like.
The existing polyurethane metal substrate coating has corrosion resistance, but has low adhesiveness between the coating and the metal substrate, poor impact resistance, low performance coordination of the coating and the metal substrate, difficult improvement of the performance coordination, and poor high temperature resistance of the product, so that the applicability of the coating is obviously poor under the dual conditions of high temperature and salt corrosion of the product, and the service efficiency of the product is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-temperature resistant coating for a metal substrate and a preparation method thereof, so as to solve the problems in the prior art.
The invention solves the technical problems by adopting the following technical scheme:
the invention provides a high-temperature resistant coating for a metal substrate, which comprises the following raw materials in parts by weight:
35-40 parts of polyurethane emulsion, 16-22 parts of blending modified nano graphene bidirectional agent, 7-11 parts of synergistic replenishing agent, 3-6 parts of silane coupling agent KH560, 2-5 parts of film forming cosolvent, 2-5 parts of defoaming agent and 1-3 parts of curing agent.
Preferably, the high-temperature resistant coating for the metal substrate comprises the following raw materials in parts by weight:
37.5 parts of polyurethane emulsion, 20 parts of blending modified nano graphene bidirectional agent, 9 parts of synergistic complementing agent, 4.5 parts of silane coupling agent KH560, 3.5 parts of film forming cosolvent, 3.5 parts of defoaming agent and 2 parts of curing agent.
Preferably, the glass transition temperature of the polyurethane emulsion is 45-48 ℃, and the minimum film forming temperature is 26-28 ℃;
the film forming cosolvent is one of diethylene glycol butyl ether and propylene glycol;
the defoaming agent is at least one of glycerol trihydroxy polyether and tributyl phosphate; the curing agent is a polyisocyanate curing agent.
Preferably, the preparation method of the blending modified nano graphene bidirectional agent comprises the following steps:
s01: preheating nano graphene at 105-108 ℃ for 5-10 min, cooling to 55-60 ℃ at a speed of 1-3 ℃/min, and carrying out heat preservation treatment to obtain nano graphene Wen Runti;
s02: adding a ball milling blending agent accounting for 5-10% of the total amount of the nano graphene Wen Runti into the nano graphene Wen Runti, performing ball milling blending treatment, wherein the ball milling rotating speed of the ball milling blending treatment is 1200-1500 r/min, the ball milling time is 65-75 min, and washing and drying to obtain a nano graphene blending body; wherein the ball milling and mixing agent is chitosan water solution with the mass fraction of 5-8%;
s03: preparing sodium silicate and deionized water into sodium silicate aqueous solution at 55-60 ℃ according to the weight ratio of 1:5, then adding isopropyl tri (dioctyl acyloxy) titanate accounting for 4-8% of the total amount of the sodium silicate aqueous solution, organic alcohol amine accounting for 2-5% of the total amount of the sodium silicate aqueous solution and lignin regulator accounting for 1-3% of the total amount of the sodium silicate aqueous solution into the sodium silicate aqueous solution, and stirring fully to obtain sodium silicate solution blended organic alcohol amine compound agent;
s04: adding 10-15 parts of nano graphene blended body into 30-40 parts of deionized water, uniformly stirring, adding 2-6 parts of sodium silicate solution to blend organic alcohol amine compound agent and 1-4 parts of yttrium nitrate solution, and carrying out first modification blending treatment;
s05: and then adding 2-5 parts of sodium dodecyl sulfate and 1-3 parts of phosphoric acid buffer solution into the S03 product, and then carrying out second modification tempering treatment, and after tempering, washing and drying to obtain the tempering modified nano graphene bidirectional agent.
Preferably, the mass fraction of the yttrium nitrate solution is 2-5%; the pH value of the phosphoric acid buffer solution is 4.5-5.5.
Preferably, the preparation method of the lignin modifier comprises the following steps:
placing lignin in a sodium alginate aqueous solution with the weight ratio of 1:3 to be uniformly stirred and dispersed, then adding citric acid with the total weight of 15-20% of the lignin irradiator, stirring fully, washing with water and drying to obtain the lignin regulator.
Preferably, the blending rotation speed of the first modification blending treatment is 350-450 r/min, the blending time is 30-40 min, and the blending temperature is 42-45 ℃; the blending rotation speed of the second modification blending treatment is 750-850 r/min, the blending time is 10-20 min, and the blending temperature is 46-48 ℃.
Preferably, the preparation method of the synergistic agent comprises the following steps:
s101: adding 1-2 parts of hydrochloric acid and 2-5 parts of sulfuric acid into 5-10 parts of deionized water, stirring and mixing to form a mixed acid solution, then placing the nano glass beads into the mixed acid solution according to a weight ratio of 1:6, stirring and dispersing uniformly, and then washing and drying to obtain a pre-modified nano glass bead body;
s102: adding 3-6% of lanthanum nitrate solution, 1-5% of hydroxyapatite and 2-3% of silica sol into the pre-modified nano glass microsphere, ball milling for 1-2 h at 1000-1500 r/min, washing with water and drying to obtain the synergistic agent.
Preferably, the mass fraction of the lanthanum nitrate solution is 1-3%.
The invention also provides a preparation method of the high-temperature-resistant coating for the metal substrate, which comprises the following steps:
step one: adding the blending modified nano graphene bi-directional agent, the synergistic complementing agent and the silane coupling agent KH560 into a stirrer, and stirring at the speed of 500-700 r/min for 15-20 min to prepare a pre-additive;
step two: adding the pre-additive into polyurethane emulsion, and dispersing for 20-30 min at the speed of 300-400 r/min;
step three: then adding a film forming cosolvent and a defoaming agent, and continuously stirring for 10-15 min; and finally adding a curing agent, reducing the stirring rotation speed to 210-220 r/min, stirring for 45-55 min, and ending the stirring to obtain the high-temperature-resistant coating.
Compared with the prior art, the invention has the following beneficial effects:
1. the high-temperature resistant coating adopts the modified nano graphene bi-directional agent, the synergistic complementing agent and the silane coupling agent KH560 to coordinate and match with polyurethane emulsion, and then the film forming cosolvent, the defoaming agent and the curing agent are used for complementing and regulating together to improve the system function of the product, and the modified nano graphene bi-directional agent and the synergistic complementing agent are used for coordinating and synergistic, so that the adhesiveness and the impact resistance of the product are improved in a coordinated manner, and the performance of the product under the conditions of salt corrosion and high temperature resistance is more stable;
2. the nano graphene is preheated at a high temperature and cooled to 55-60 ℃ at a speed of 1-3 ℃/min, the graphene is cooled at a constant temperature, the activity and the performance mildness of the graphene are optimized, the improvement of the impact performance of the graphene and the convenience of the graphene distribution system are facilitated, the adhesiveness of the graphene is optimized, meanwhile, the chitosan aqueous solution is used as a ball milling regulator for ball milling modification of the nano graphene Wen Runti, the modified graphene surface is thoroughly wetted by the chitosan aqueous solution, the subsequent first modification tempering in a sodium silicate solution tempering organic alcohol amine tempering agent and a yttrium nitrate solution, the second modification tempering treatment in a dodecyl sodium sulfate and phosphoric acid buffer solution are facilitated, and the adhesiveness and the impact resistance of the system are optimized in a tempering nano graphene bi-directional agent re-system and the product performance is more stable under the conditions of salt corrosion and high temperature resistance through the double modification tempering;
3. the sodium silicate solution blending organic alcohol amine compound preparation adopts sodium silicate aqueous solution to match isopropyl tri (dioctyl phosphate acyloxy) titanate, organic alcohol amine and lignin regulator, through mutual coordination and mutual coordination among raw materials, the sodium silicate solution blending organic alcohol amine compound preparation can better coordinate and modify with a nano graphene blending body, a yttrium nitrate solution and the like in the preparation of the modified nano graphene bidirectional agent, thereby improving the functional effect of the modified nano graphene bidirectional agent and improving the coordination effect of a product;
4. the synergistic agent adopts nano glass beads to stir and pre-modify in a mixed acid solution, so that the activity and dispersity of the product are improved, the distribution efficiency of the nano glass beads modified by ball milling is stronger through the co-coordination of lanthanum nitrate solution, hydroxyapatite and silica sol, the synergistic effect of the optimized synergistic agent and the modified nano graphene bi-directional agent is more remarkable, and the product has more excellent adhesion and impact resistance, and the product has more stable salt corrosion and high temperature resistance.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. 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.
The high-temperature resistant coating for the metal substrate comprises the following raw materials in parts by weight:
35-40 parts of polyurethane emulsion, 16-22 parts of blending modified nano graphene bidirectional agent, 7-11 parts of synergistic replenishing agent, 3-6 parts of silane coupling agent KH560, 2-5 parts of film forming cosolvent, 2-5 parts of defoaming agent and 1-3 parts of curing agent.
Preferably, the high-temperature resistant coating for the metal substrate comprises the following raw materials in parts by weight:
37.5 parts of polyurethane emulsion, 20 parts of blending modified nano graphene bidirectional agent, 9 parts of synergistic complementing agent, 4.5 parts of silane coupling agent KH560, 3.5 parts of film forming cosolvent, 3.5 parts of defoaming agent and 2 parts of curing agent.
The glass transition temperature of the polyurethane emulsion of the embodiment is 45-48 ℃, and the minimum film forming temperature is 26-28 ℃;
the film forming cosolvent is one of diethylene glycol butyl ether and propylene glycol;
the defoaming agent is at least one of glycerol trihydroxy polyether and tributyl phosphate; the curing agent is a polyisocyanate curing agent.
The preparation method of the blending modified nano graphene bidirectional agent in the embodiment comprises the following steps:
s01: preheating nano graphene at 105-108 ℃ for 5-10 min, cooling to 55-60 ℃ at a speed of 1-3 ℃/min, and carrying out heat preservation treatment to obtain nano graphene Wen Runti;
s02: adding a ball milling blending agent accounting for 5-10% of the total amount of the nano graphene Wen Runti into the nano graphene Wen Runti, performing ball milling blending treatment, wherein the ball milling rotating speed of the ball milling blending treatment is 1200-1500 r/min, the ball milling time is 65-75 min, and washing and drying to obtain a nano graphene blending body; wherein the ball milling and mixing agent is chitosan water solution with the mass fraction of 5-8%;
s03: preparing sodium silicate and deionized water into sodium silicate aqueous solution at 55-60 ℃ according to the weight ratio of 1:5, then adding isopropyl tri (dioctyl acyloxy) titanate accounting for 4-8% of the total amount of the sodium silicate aqueous solution, organic alcohol amine accounting for 2-5% of the total amount of the sodium silicate aqueous solution and lignin regulator accounting for 1-3% of the total amount of the sodium silicate aqueous solution into the sodium silicate aqueous solution, and stirring fully to obtain sodium silicate solution blended organic alcohol amine compound agent;
s04: adding 10-15 parts of nano graphene blended body into 30-40 parts of deionized water, uniformly stirring, adding 2-6 parts of sodium silicate solution to blend organic alcohol amine compound agent and 1-4 parts of yttrium nitrate solution, and carrying out first modification blending treatment;
s05: and then adding 2-5 parts of sodium dodecyl sulfate and 1-3 parts of phosphoric acid buffer solution into the S03 product, and then carrying out second modification tempering treatment, and after tempering, washing and drying to obtain the tempering modified nano graphene bidirectional agent.
The mass fraction of the yttrium nitrate solution in the embodiment is 2-5%; the pH value of the phosphoric acid buffer solution is 4.5-5.5.
The preparation method of the lignin modifier in the embodiment comprises the following steps:
placing lignin in a sodium alginate aqueous solution with the weight ratio of 1:3 to be uniformly stirred and dispersed, then adding citric acid with the total weight of 15-20% of the lignin irradiator, stirring fully, washing with water and drying to obtain the lignin regulator.
The blending rotation speed of the first modification blending treatment is 350-450 r/min, the blending time is 30-40 min, and the blending temperature is 42-45 ℃; the blending rotation speed of the second modification blending treatment is 750-850 r/min, the blending time is 10-20 min, and the blending temperature is 46-48 ℃.
The preparation method of the synergistic agent of the embodiment comprises the following steps:
s101: adding 1-2 parts of hydrochloric acid and 2-5 parts of sulfuric acid into 5-10 parts of deionized water, stirring and mixing to form a mixed acid solution, then placing the nano glass beads into the mixed acid solution according to a weight ratio of 1:6, stirring and dispersing uniformly, and then washing and drying to obtain a pre-modified nano glass bead body;
s102: adding 3-6% of lanthanum nitrate solution, 1-5% of hydroxyapatite and 2-3% of silica sol into the pre-modified nano glass microsphere, ball milling for 1-2 h at 1000-1500 r/min, washing with water and drying to obtain the synergistic agent.
The mass fraction of the lanthanum nitrate solution in the embodiment is 1-3%.
The preparation method of the high-temperature resistant coating for the metal substrate comprises the following steps:
step one: adding the blending modified nano graphene bi-directional agent, the synergistic complementing agent and the silane coupling agent KH560 into a stirrer, and stirring at the speed of 500-700 r/min for 15-20 min to prepare a pre-additive;
step two: adding the pre-additive into polyurethane emulsion, and dispersing for 20-30 min at the speed of 300-400 r/min;
step three: then adding a film forming cosolvent and a defoaming agent, and continuously stirring for 10-15 min; and finally adding a curing agent, reducing the stirring rotation speed to 210-220 r/min, stirring for 45-55 min, and ending the stirring to obtain the high-temperature-resistant coating.
Example 1.
The high-temperature resistant coating for the metal substrate comprises the following raw materials in parts by weight:
35 parts of polyurethane emulsion, 16 parts of blending modified nano graphene bidirectional agent, 7 parts of synergistic complementing agent, 3 parts of silane coupling agent KH560, 2 parts of film forming cosolvent, 2 parts of defoaming agent and 1 part of curing agent.
The glass transition temperature of the polyurethane emulsion of the embodiment is 45 ℃, and the minimum film forming temperature is 26 ℃;
the film forming cosolvent is diethylene glycol butyl ether;
the defoaming agent is glycerol trihydroxy polyether; the curing agent is a polyisocyanate curing agent.
The preparation method of the blending modified nano graphene bidirectional agent in the embodiment comprises the following steps:
s01: preheating the nano graphene at 105 ℃ for 5min, then cooling to 55 ℃ at a speed of 1 ℃/min, and carrying out heat preservation treatment to obtain nano graphene Wen Runti;
s02: adding a ball milling preparation agent accounting for 5% of the total amount of the nano graphene Wen Runti into the nano graphene Wen Runti, performing ball milling preparation treatment, wherein the ball milling rotation speed of the ball milling preparation treatment is 1200r/min, the ball milling time is 65min, and washing and drying to obtain a nano graphene preparation body; wherein the ball milling and mixing agent is chitosan water solution with the mass fraction of 5%;
s03: preparing sodium silicate and deionized water into sodium silicate aqueous solution according to the weight ratio of 1:5 at 55 ℃, then adding isopropyl tri (dioctyl acyloxy) titanate accounting for 4% of the total sodium silicate aqueous solution, organic alcohol amine accounting for 2% of the total sodium silicate aqueous solution and lignin regulator accounting for 1% of the total sodium silicate aqueous solution into the sodium silicate aqueous solution, and stirring fully to obtain sodium silicate solution blended organic alcohol amine compound preparation;
s04: adding 10 parts of nano graphene blended body into 30 parts of deionized water, uniformly stirring, adding 2 parts of sodium silicate solution to blend an organic alcohol amine compound agent and 1 part of yttrium nitrate solution, and carrying out first modification blending treatment;
s05: and then adding 2 parts of sodium dodecyl sulfate and 1 part of phosphoric acid buffer solution into the S03 product, and performing second modification tempering treatment, water washing and drying after tempering is finished to obtain the tempering modified nano graphene bidirectional agent.
The mass fraction of the yttrium nitrate solution in the embodiment is 2%; the pH of the phosphate buffer solution was 4.5.
The preparation method of the lignin modifier in the embodiment comprises the following steps:
placing lignin in a sodium alginate aqueous solution with 10% of the lignin irradiator according to the weight ratio of 1:3, stirring and dispersing uniformly, then adding citric acid with 15% of the total lignin irradiator, stirring sufficiently, washing with water and drying to obtain the lignin regulator.
The blending rotation speed of the first modification blending treatment is 350r/min, the blending time is 30min, and the blending temperature is 42 ℃; the blending rotation speed of the second modification blending treatment is 750r/min, the blending time is 10min, and the blending temperature is 46 ℃.
The preparation method of the synergistic agent of the embodiment comprises the following steps:
s101: adding 1 part of hydrochloric acid and 2 parts of sulfuric acid into 5 parts of deionized water, stirring and mixing to form a mixed acid solution, then placing the nano glass beads into the mixed acid solution according to a weight ratio of 1:6, stirring and dispersing uniformly, and then washing and drying to obtain a pre-modified nano glass bead body;
s102: adding lanthanum nitrate solution accounting for 3% of the total amount of the pre-modified nano glass beads, hydroxyapatite accounting for 1% of the total amount of the pre-modified nano glass beads and silica sol accounting for 2% of the total amount of the pre-modified nano glass beads into the pre-modified nano glass beads, then transferring the mixture into a ball mill for ball milling for 1h, wherein the ball milling rotating speed is 1000r/min, and after ball milling, washing and drying the mixture to obtain the synergistic agent.
The lanthanum nitrate solution of this example has a mass fraction of 1%.
The preparation method of the high-temperature resistant coating for the metal substrate comprises the following steps:
step one: adding the blending modified nano graphene bidirectional agent, the synergistic complementing agent and the silane coupling agent KH560 into a stirrer, and stirring at the speed of 500r/min for 15min to prepare a pre-additive;
step two: adding the pre-additive into the polyurethane emulsion, and dispersing for 20min at the speed of 300 r/min;
step three: then adding a film forming cosolvent and a defoaming agent, and continuously stirring for 10min; and finally adding a curing agent, reducing the stirring rotation speed to 210r/min, stirring for 45min, and ending the stirring to obtain the high-temperature-resistant coating.
Example 2.
The high-temperature resistant coating for the metal substrate comprises the following raw materials in parts by weight:
40 parts of polyurethane emulsion, 22 parts of blending modified nano graphene bidirectional agent, 11 parts of synergistic complementing agent, 6 parts of silane coupling agent KH560, 5 parts of film forming cosolvent, 5 parts of defoaming agent and 3 parts of curing agent.
The glass transition temperature of the polyurethane emulsion of the embodiment is 48 ℃, and the minimum film forming temperature is 28 ℃;
the film forming cosolvent is diethylene glycol butyl ether;
the defoaming agent is glycerol trihydroxy polyether; the curing agent is a polyisocyanate curing agent.
The preparation method of the blending modified nano graphene bidirectional agent in the embodiment comprises the following steps:
s01: preheating the nano graphene at 108 ℃ for 10min, cooling to 60 ℃ at a speed of 3 ℃/min, and carrying out heat preservation treatment to obtain nano graphene Wen Runti;
s02: adding a ball milling preparation agent accounting for 10% of the total amount of the nano graphene Wen Runti into the nano graphene Wen Runti, performing ball milling preparation treatment, wherein the ball milling rotation speed of the ball milling preparation treatment is 1500r/min, the ball milling time is 75min, and after the ball milling is finished, washing and drying to obtain a nano graphene preparation body; wherein the ball milling and mixing agent is chitosan water solution with the mass fraction of 5-8%;
s03: preparing sodium silicate and deionized water into sodium silicate aqueous solution according to the weight ratio of 1:5 at 60 ℃, then adding isopropyl tri (dioctyl acyloxy) titanate accounting for 8% of the total sodium silicate aqueous solution, organic alcohol amine accounting for 5% of the total sodium silicate aqueous solution and lignin regulator accounting for 3% of the total sodium silicate aqueous solution into the sodium silicate aqueous solution, and stirring fully to obtain sodium silicate solution blended organic alcohol amine compound preparation;
s04: adding 15 parts of nano graphene blended body into 40 parts of deionized water, uniformly stirring, adding 6 parts of sodium silicate solution to blend an organic alcohol amine compound agent and 4 parts of yttrium nitrate solution, and carrying out first modification blending treatment;
s05: and then adding 5 parts of sodium dodecyl sulfate and 3 parts of phosphoric acid buffer solution into the S03 product, and performing second modification tempering treatment, water washing and drying after tempering is finished to obtain the tempering modified nano graphene bidirectional agent.
The mass fraction of the yttrium nitrate solution in the embodiment is 5%; the pH of the phosphate buffer solution was 5.5.
The preparation method of the lignin modifier in the embodiment comprises the following steps:
placing lignin in proton irradiation for 10min, wherein the irradiation power is 450W, and obtaining lignin irradiator after irradiation, adding lignin irradiator into 15% sodium alginate aqueous solution according to the weight ratio of 1:3, stirring and dispersing uniformly, then adding citric acid accounting for 20% of the total lignin irradiator, stirring thoroughly, washing with water, and drying to obtain lignin regulator.
The blending rotation speed of the first modification blending treatment is 450r/min, the blending time is 40min, and the blending temperature is 45 ℃; the blending rotation speed of the second modification blending treatment is 850r/min, the blending time is 20min, and the blending temperature is 48 ℃.
The preparation method of the synergistic agent of the embodiment comprises the following steps:
s101: adding 2 parts of hydrochloric acid and 5 parts of sulfuric acid into 10 parts of deionized water, stirring and mixing to form a mixed acid solution, then placing the nano glass beads into the mixed acid solution according to the weight ratio of 1:6, stirring and dispersing uniformly, and then washing and drying to obtain a pre-modified nano glass bead body;
s102: adding lanthanum nitrate solution accounting for 6% of the total amount of the pre-modified nano glass beads, hydroxyapatite accounting for 5% of the total amount of the pre-modified nano glass beads and silica sol accounting for 3% of the total amount of the pre-modified nano glass beads into the pre-modified nano glass beads, then transferring the mixture into a ball mill for ball milling for 2 hours, wherein the ball milling rotating speed is 1500r/min, and after ball milling, washing and drying the mixture to obtain the synergistic agent.
The lanthanum nitrate solution of this example was 3% by mass.
The preparation method of the high-temperature resistant coating for the metal substrate comprises the following steps:
step one: adding the blending modified nano graphene bidirectional agent, the synergistic complementing agent and the silane coupling agent KH560 into a stirrer, and stirring at the speed of 700r/min for 20min to prepare a pre-additive;
step two: adding the pre-additive into the polyurethane emulsion, and dispersing for 30min at the speed of 400 r/min;
step three: then adding a film forming cosolvent and a defoaming agent, and continuously stirring for 15min; and finally adding a curing agent, reducing the stirring rotation speed to 220r/min, stirring for 55min, and ending the stirring to obtain the high-temperature-resistant coating.
Example 3.
The high-temperature resistant coating for the metal substrate comprises the following raw materials in parts by weight:
37.5 parts of polyurethane emulsion, 20 parts of blending modified nano graphene bidirectional agent, 9 parts of synergistic complementing agent, 4.5 parts of silane coupling agent KH560, 3.5 parts of film forming cosolvent, 3.5 parts of defoaming agent and 2 parts of curing agent.
The glass transition temperature of the polyurethane emulsion of the embodiment is 46.5 ℃ and the minimum film forming temperature is 27 ℃;
the film forming cosolvent is diethylene glycol butyl ether;
the defoaming agent is glycerol trihydroxy polyether; the curing agent is a polyisocyanate curing agent.
The preparation method of the blending modified nano graphene bidirectional agent in the embodiment comprises the following steps:
s01: preheating nano graphene at 106 ℃ for 7.5min, cooling to 57.5 ℃ at the speed of 2 ℃/min, and carrying out heat preservation treatment to obtain nano graphene Wen Runti;
s02: adding a ball milling preparation agent accounting for 7.5% of the total amount of the nano graphene Wen Runti into the nano graphene Wen Runti, performing ball milling preparation treatment, wherein the ball milling rotation speed of the ball milling preparation treatment is 1350r/min, the ball milling time is 70min, and after ball milling, washing and drying to obtain a nano graphene preparation body; wherein the ball milling and mixing agent is chitosan aqueous solution with the mass fraction of 6.5%;
s03: preparing sodium silicate and deionized water into sodium silicate aqueous solution at 57.5 ℃ according to the weight ratio of 1:5, then adding isopropyl tri (dioctyl acyloxy) titanate with the total amount of 6% of the sodium silicate aqueous solution, organic alcohol amine with the total amount of 3.5% of the sodium silicate aqueous solution and lignin regulator with the total amount of 2% of the sodium silicate aqueous solution into the sodium silicate aqueous solution, and stirring fully to obtain sodium silicate solution and organic alcohol amine compound regulator;
s04: adding 12.5 parts of nano graphene blended body into 35 parts of deionized water, uniformly stirring, adding 4 parts of sodium silicate solution to blend an organic alcohol amine compound agent and 2 parts of yttrium nitrate solution, and carrying out first modification blending treatment;
s05: and then adding 3.5 parts of sodium dodecyl sulfate and 2 parts of phosphoric acid buffer solution into the S03 product, and then carrying out second modification tempering treatment, and after tempering, washing and drying to obtain the tempering modified nano graphene bidirectional agent.
The mass fraction of the yttrium nitrate solution in the embodiment is 3.5%; the pH value of the phosphate buffer solution is 5.0.
The preparation method of the lignin modifier in the embodiment comprises the following steps:
placing lignin in a sodium alginate aqueous solution with the weight ratio of 12.5% for stirring and dispersing uniformly, placing lignin in a proton irradiation state for 7.5min, wherein the irradiation power is 400W, and the irradiation is finished to obtain a lignin irradiator, adding the lignin irradiator into the sodium alginate aqueous solution with the weight ratio of 1:3, then adding citric acid with the total amount of 17.5% of the lignin irradiator, stirring fully, washing with water, and drying to obtain the lignin regulator.
The blending rotation speed of the first modification blending treatment is 400r/min, the blending time is 35min, and the blending temperature is 43.5 ℃; the blending rotation speed of the second modification blending treatment is 800r/min, the blending time is 15min, and the blending temperature is 47 ℃.
The preparation method of the synergistic agent of the embodiment comprises the following steps:
s101: adding 1.5 parts of hydrochloric acid and 3.5 parts of sulfuric acid into 7.5 parts of deionized water, stirring and mixing to form a mixed acid solution, then placing the nano glass beads in the mixed acid solution according to a weight ratio of 1:6, stirring and dispersing uniformly, and then washing and drying to obtain a pre-modified nano glass bead body;
s102: adding 4.5% of lanthanum nitrate solution, 3% of hydroxyapatite and 2.5% of silica sol into the pre-modified nano glass microsphere, ball milling for 1.5h at 1250r/min, washing with water and drying to obtain the synergistic agent.
The lanthanum nitrate solution of this example has a mass fraction of 2%.
The preparation method of the high-temperature resistant coating for the metal substrate comprises the following steps:
step one: adding the blending modified nano graphene bidirectional agent, the synergistic complementing agent and the silane coupling agent KH560 into a stirrer, and stirring at the speed of 600r/min for 17.5min to prepare a pre-additive;
step two: adding the pre-additive into the polyurethane emulsion, and dispersing for 25min at the speed of 350 r/min;
step three: then adding a film forming cosolvent and a defoaming agent, and continuously stirring for 12.5min; and finally adding a curing agent, reducing the stirring rotation speed to 215r/min, stirring for 50min, and ending the stirring to obtain the high-temperature-resistant coating.
Comparative example 1.
The difference from example 3 is that no tempering modified nanographene bi-directional agent was added.
Comparative example 2.
The difference from example 3 is that nano graphene Wen Runti is replaced by nano graphene in the preparation of the blending modified nano graphene bidirectional agent
Comparative example 3.
The difference from example 3 is that the preparation of the blending modified nano graphene bi-directional agent does not adopt the S02 step treatment, and the nano graphene blending body in S04 is replaced by nano graphene Wen Runti.
Comparative example 4.
The difference from example 3 is that in the preparation of the blending modified nano graphene bi-directional agent, 12.5 parts of nano graphene blending body is added into 35 parts of deionized water, uniformly stirred, then 4 parts of sodium silicate solution is added to blend organic alcohol amine compound agent, 2 parts of yttrium nitrate solution is added, 3.5 parts of sodium dodecyl sulfate and 2 parts of phosphoric acid buffer solution are added, the blending rotation speed is 800r/min, the blending time is 35min, the blending temperature is 47 ℃, and the blending is finished, and the blending modified nano graphene bi-directional agent is obtained by washing and drying.
Comparative example 5.
The difference from example 3 is that yttrium nitrate solution is not added in the preparation of the blending modified nano-graphene bi-directional agent.
Comparative example 6.
The difference from example 3 is that the sodium silicate solution is not added in the preparation of the blending modified nano graphene bidirectional agent to blend the organic alcohol amine compound agent.
Comparative example 7.
The difference from example 3 is that no synergistic agent was added.
Comparative example 8.
The difference from example 3 is that the pre-modified nano glass bead body in the preparation of the synergistic agent is replaced by nano glass bead body raw material.
Comparative example 9.
The difference from example 3 is that the preparation method of the synergistic agent is different:
s101: adding 1.5 parts of hydrochloric acid and 3.5 parts of sulfuric acid into 7.5 parts of deionized water, stirring and mixing to form a mixed acid solution, then placing the nano glass beads in the mixed acid solution according to a weight ratio of 1:6, stirring and dispersing uniformly, and then washing and drying to obtain a pre-modified nano glass bead body;
s102: adding silica sol accounting for 2.5% of the total amount of the pre-modified nano glass beads into the pre-modified nano glass beads, then transferring the mixture into a ball mill for ball milling for 1.5 hours, wherein the ball milling rotating speed is 1250r/min, and after ball milling, washing and drying the mixture to obtain the synergistic agent.
The products of examples 1 to 3 and comparative examples 1 to 9 were tested for adhesion and impact resistance, and the products were placed in a 2% sodium chloride salt fog for 2 hours, and then placed at 65℃for 5 hours, and then tested for corrosion resistance and heat resistance stability, with the following test results
As can be seen from comparative examples 1-9 and examples 1-3;
the product of the embodiment 3 has excellent pull-out adhesive force and excellent impact resistance, and can be improved in a coordinated manner, and in addition, the product has excellent stability under corrosion resistance and temperature resistance;
as shown in comparative examples 1-6 and example 3, the performance of the product is obviously degraded without adding the blending modified nano graphene bi-directional agent, meanwhile, the nano graphene Wen Runti is replaced by nano graphene in the preparation of the blending modified nano graphene bi-directional agent, the step S02 is not adopted for processing, the nano graphene blending body in the step S04 is replaced by nano graphene Wen Runti, the condition of double modification blending processing is changed into one-stage single condition blending, and the performance of the product is obviously degraded only by adopting the blending modified nano graphene bi-directional agent prepared by the method of the invention without adding yttrium nitrate solution and sodium silicate solution or organic alcohol amine compound agent in the preparation of the blending modified nano graphene bi-directional agent;
the inventor of the invention also finds that the sodium silicate solution is not added into the product to blend the organic alcohol amine compound agent, the performance of the product is obviously poor, and the sodium silicate solution to blend the organic alcohol amine compound agent has obvious improvement effect on the performance improvement of the product;
as shown in comparative examples 7 to 9 and example 3, the product was not added with the co-effect toner, the performance of the product was remarkably deteriorated, and the performance of the product was liable to be deteriorated due to the different preparation methods of the co-effect toner;
as shown in comparative example 1, comparative example 7 and example 3, the product has a significant deterioration tendency due to the fact that the blending modified nano graphene bi-directional agent is not added and the synergistic agent is not added, and the product has the most significant performance effect due to the fact that the blending modified nano graphene bi-directional agent and the synergistic agent are only adopted for cooperation.
The invention further explores the product performance through the preparation of the sodium silicate solution blended organic alcohol amine compound agent;
the preparation method of the sodium silicate solution blended organic alcohol amine compound preparation comprises the following steps:
firstly placing lignin in a sodium alginate aqueous solution with the weight ratio of 12.5% to uniformly stir and disperse, then adding citric acid with the total weight of 17.5% of the lignin irradiator, stirring fully, washing with water and drying to obtain a lignin regulator;
preparing sodium silicate and deionized water into a sodium silicate aqueous solution at 57.5 ℃ according to the weight ratio of 1:5, then adding isopropyl tri (dioctyl acyloxy) titanate accounting for 6% of the total amount of the sodium silicate aqueous solution, organic alcohol amine accounting for 3.5% of the total amount of the sodium silicate aqueous solution and lignin regulator accounting for 2% of the total amount of the sodium silicate aqueous solution into the sodium silicate aqueous solution, and stirring thoroughly to obtain a sodium silicate solution blended organic alcohol amine compound agent.
Experimental example 1.
The same as in example 3, except that no lignin modifier was added in the preparation of the sodium silicate solution-blended organic alcohol amine complex formulation.
Experimental example 2.
The same as in example 3, except that lignin modifier was replaced with lignin in the preparation of the sodium silicate solution-blended organic alcohol amine complex formulation.
Experimental example 3.
The same as in example 3, except that no organic alcohol amine was added in the preparation of the sodium silicate solution-blended organic alcohol amine complex formulation.
Experimental example 4.
The same as in example 3, except that isopropyl tris (dioctyl acyloxy) titanate was not added in the preparation of the sodium silicate solution-blended organic alcohol amine complex formulation.
Experimental example 5.
The same as in example 3, except that the sodium silicate solution was replaced with deionized water in the preparation of the sodium silicate solution-blended organic alcohol amine complex formulation.
The performance test results for examples 1-5 are as follows:
from experimental examples 1-5, the lignin regulator is not added in the preparation of the sodium silicate solution blended organic alcohol amine compound preparation, the performance of the product is obviously deteriorated, the lignin regulator is replaced by lignin, compared with the preparation without the lignin regulator, the performance improvement effect is not obvious, the sodium silicate aqueous solution is replaced by deionized water, the organic alcohol amine is not added, and the isopropyl tri (dioctyl phosphate acyloxy) titanate is not added in the preparation of the sodium silicate solution blended organic alcohol amine compound preparation, the performance of the product is in a deterioration trend, and only the lignin regulator prepared by the method is matched with the raw materials such as the sodium silicate aqueous solution, the organic alcohol amine and the like, the performance effect of the product is most obvious, and the effect is not obvious compared with the effect of the invention by adopting other methods for replacement.
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.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. The high-temperature-resistant coating for the metal base material is characterized by comprising the following raw materials in parts by weight:
35-40 parts of polyurethane emulsion, 16-22 parts of blending modified nano graphene bi-directional agent, 7-11 parts of synergistic agent, 3-6 parts of silane coupling agent KH560, 2-5 parts of film forming cosolvent, 2-5 parts of defoaming agent and 1-3 parts of curing agent;
the preparation method of the blending modified nano graphene bidirectional agent comprises the following steps:
s01: preheating the nano graphene at 105-108 ℃ for 5-10 min, cooling to 55-60 ℃ at a speed of 1-3 ℃/min, and carrying out heat preservation treatment to obtain nano graphene Wen Runti;
s02: adding a ball milling preparation agent accounting for 5-10% of the total amount of the nano graphene Wen Runti into the nano graphene Wen Runti, performing ball milling preparation treatment, wherein the ball milling rotation speed of the ball milling preparation treatment is 1200-1500 r/min, the ball milling time is 65-75 min, and after ball milling, washing and drying to obtain a nano graphene preparation body; wherein the ball milling and mixing agent is chitosan aqueous solution with the mass fraction of 5-8%;
s03: preparing sodium silicate and deionized water into sodium silicate aqueous solution at 55-60 ℃ according to the weight ratio of 1:5, then adding isopropyl tri (dioctyl acyloxy) titanate accounting for 4-8% of the total amount of the sodium silicate aqueous solution, organic alcohol amine accounting for 2-5% of the total amount of the sodium silicate aqueous solution and lignin regulator accounting for 1-3% of the total amount of the sodium silicate aqueous solution into the sodium silicate aqueous solution, and stirring fully to obtain sodium silicate solution blended organic alcohol amine compound agent;
s04: adding 10-15 parts of nano graphene blended body into 30-40 parts of deionized water, uniformly stirring, adding 2-6 parts of sodium silicate solution to blend organic alcohol amine compound agent and 1-4 parts of yttrium nitrate solution, and carrying out first modification blending treatment;
s05: then adding 2-5 parts of sodium dodecyl sulfate and 1-3 parts of phosphoric acid buffer solution into the S04 product, carrying out second modification tempering treatment, and washing and drying after tempering is finished to obtain a tempering modified nano graphene bidirectional agent; the preparation method of the lignin regulator comprises the following steps:
firstly placing lignin in a sodium alginate aqueous solution with the weight ratio of 1:3 to be uniformly stirred and dispersed, then adding citric acid with the total weight of 15-20% of the lignin irradiator, stirring fully, washing with water and drying to obtain a lignin regulator;
the preparation method of the synergistic replenishing agent comprises the following steps:
s101: adding 1-2 parts of hydrochloric acid and 2-5 parts of sulfuric acid into 5-10 parts of deionized water, stirring and mixing to form a mixed acid solution, then placing the nano glass beads into the mixed acid solution according to a weight ratio of 1:6, stirring and dispersing uniformly, and then washing and drying to obtain a pre-modified nano glass bead body;
s102: adding 3-6% of lanthanum nitrate solution, 1-5% of hydroxyapatite and 2-3% of silica sol into the pre-modified nano glass microsphere, ball milling for 1-2 h at a speed of 1000-1500 r/min, washing and drying to obtain the synergistic agent.
2. The high-temperature resistant coating for a metal substrate according to claim 1, wherein the high-temperature resistant coating for the metal substrate comprises the following raw materials in parts by weight:
37.5 parts of polyurethane emulsion, 20 parts of blending modified nano graphene bidirectional agent, 9 parts of synergistic complementing agent, 4.5 parts of silane coupling agent KH560, 3.5 parts of film forming cosolvent, 3.5 parts of defoaming agent and 2 parts of curing agent.
3. The high temperature resistant coating for a metal substrate according to claim 1, wherein the glass transition temperature of the polyurethane emulsion is 45-48 ℃ and the minimum film forming temperature is 26-28 ℃;
the film forming cosolvent is one of diethylene glycol butyl ether and propylene glycol;
the defoaming agent is at least one of glycerol trihydroxy polyether and tributyl phosphate; the curing agent is a polyisocyanate curing agent.
4. The high-temperature-resistant coating for a metal substrate according to claim 1, wherein the mass fraction of the yttrium nitrate solution is 2-5%; the pH value of the phosphoric acid buffer solution is 4.5-5.5.
5. The high temperature resistant coating for metal substrates according to claim 1, wherein the tempering speed of the first modification tempering treatment is 350-450 r/min, the tempering time is 30-40 min, and the tempering temperature is 42-45 ℃; the blending rotation speed of the second modification blending treatment is 750-850 r/min, the blending time is 10-20 min, and the blending temperature is 46-48 ℃.
6. The high-temperature-resistant coating for a metal substrate according to claim 1, wherein the mass fraction of the lanthanum nitrate solution is 1-3%.
7. A method for preparing the high temperature resistant coating for a metal substrate according to any one of claims 1 to 6, comprising the steps of:
step one: adding the blending modified nano graphene bi-directional agent, the synergistic agent and the silane coupling agent KH560 into a stirrer, and stirring at the speed of 500-700 r/min for 15-20 min to prepare a pre-additive;
step two: adding the pre-additive into the polyurethane emulsion, and dispersing for 20-30 min at the speed of 300-400 r/min;
step three: then adding a film forming cosolvent and a defoaming agent, and continuously stirring for 10-15 min; and finally adding a curing agent, reducing the stirring rotation speed to 210-220 r/min, stirring for 45-55 min, and obtaining the high-temperature-resistant coating after stirring.
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| CN117511056B (en) * | 2023-11-07 | 2024-05-14 | 贵州省纳米材料工程中心 | Polypropylene antibacterial material and preparation method thereof |
| CN117285851B (en) * | 2023-11-24 | 2024-03-08 | 广东睿智环保科技股份有限公司 | Transfer powder coating and preparation method thereof |
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