CN115651485A - Water-based paint composition - Google Patents
Water-based paint composition Download PDFInfo
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- CN115651485A CN115651485A CN202211416436.XA CN202211416436A CN115651485A CN 115651485 A CN115651485 A CN 115651485A CN 202211416436 A CN202211416436 A CN 202211416436A CN 115651485 A CN115651485 A CN 115651485A
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Abstract
The invention provides a water-based coating composition which comprises a component A and a component B, wherein the component A comprises a water-based epoxy resin emulsion, a filler, a dispersing agent, an antifoaming agent, an anti-settling thixotropic agent, a leveling agent and a porphyrin modified graphene suspension, the suspension can increase the adsorption effect of an epoxy resin coating and a base material, the obtained coating is compact and high in adhesion, and the impact resistance, the friction resistance, the weather resistance and the corrosion resistance of the coating can be improved.
Description
Technical Field
The invention relates to the field of water-based paint, in particular to a water-based epoxy ester resin composition and a preparation method thereof.
Background
The epoxy resin is also called as artificial resin, and is a thermosetting plastic which has two or more than two epoxy groups in the molecular structure and can be cured in a chemical solvent to form a three-dimensional reticular high molecular polymer. Bisphenol A epoxy resin in glycidyl ether oxygen resin is the most widely applied epoxy resin in industrial production at present.
The aqueous epoxy resin is a uniform dispersion system having high stability obtained by dispersing an epoxy resin in water in the form of small particles or small droplets using water as a dispersion medium. Because the epoxy resin is in a linear structure, a water-based epoxy curing agent needs to be added when the water-based epoxy resin coating is prepared, and the water-based epoxy curing agent and the epoxy resin are crosslinked to prepare the water-based coating. The water-based epoxy resin coating has the excellent performances of environmental protection, strong adaptability, high safety, convenient construction and the like, and is more and more valued in the coating market, so that the environmental awareness of people is gradually enhanced, and the water-based epoxy resin coating has very excellent prospect.
The water-based epoxy resin coating is a main direction for the research and application of the water-based resin at present due to excellent physical and chemical properties, mechanical properties and process properties. However, the application of the existing water-based epoxy resin coating is less, mainly because the cross-linking density of a three-dimensional network structure formed after the epoxy resin is cured is too high, the coating is easy to have large brittleness and low fracture toughness, is easy to generate brittle fracture when being worn, has poor wear resistance, limits the application of the epoxy resin to a certain extent, and simultaneously puts higher requirements on the frictional wear performance of the coating.
Graphene (Graphene) is formed from carbon atoms in sp 2 The stable hexagonal honeycomb-shaped monoatomic layer structure formed by the hybrid forms is a novel two-dimensional carbon material. Since 2004, the unique electrical, optical and mechanical properties of the epoxy resin coating show great research value in various fields, if graphene is added into the water-based epoxy coating, the problems of high friction coefficient, high wear rate and the like of the water-based epoxy coating can be well solved, and the corrosion resistance of the water-based epoxy coating can be enhanced, so that the scratch resistance and wear resistance of the epoxy resin coating are improved by the graphene in the prior art.
For example, CN105838195A discloses a graphene oxide-containing waterborne epoxy anticorrosive paint and a preparation method thereof, which comprises the following substances by mass percent: 40-50% of water-based epoxy resin, 7-10% of anticorrosive pigment, 3-4% of hydrophobic agent, 1-2% of graphene oxide, 4-5% of filler, 33-35% of deionized water, 1-1.5% of anti-flash rust agent and 1-2% of water-based epoxy curing agent. The graphene oxide subjected to surface treatment is used for improving the wear resistance of the epoxy anticorrosive paint, reducing the friction coefficient and improving the corrosion resistance of the water-based epoxy anticorrosive paint.
For example, CN108929616A is a metal substrate graphene modified long-acting anticorrosive paint and a preparation method thereof. The composition comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 40 parts of epoxy resin, 10 parts of modified graphene, 15 parts of pigment, 15 parts of cosolvent, 0.3.8 part of defoaming agent, 0.3.8 part of flatting agent, 0.5 part of anti-settling agent and 0.5 part of dispersing agent; the component B comprises the following raw materials in parts by weight: 50 parts of etherified amino resin, 25 parts of phenolic aldehyde amine and 20 parts of cosolvent. The metal substrate graphene modified long-acting anticorrosive paint disclosed by the invention has the advantages of long-term excellent anticorrosive performance, strong substrate adhesion, high mechanical strength, excellent friction resistance, excellent salt spray resistance, better water resistance, chemical resistance, oil resistance and impact resistance, strong construction adaptability and the like.
For example, CN113248959A discloses a high-temperature wear-resistant anticorrosive coating, and a preparation method and an application thereof, wherein a combination of furan modified epoxy resin with a specific structure is selected as a film-forming substance, the high-temperature resistance, corrosion resistance and other properties of the epoxy resin and the furan resin are utilized, functionalized graphene is selected as a heat-conducting and corrosion-resistant component, and epoxy polyether-polysiloxane is selected as a dispersion functional component, so that good dispersion of graphene, a filler and other components is realized, and a coating with good and compact appearance is prepared.
Disclosure of Invention
Based on the above, the development and application of the waterborne epoxy resin coating in many fields are limited due to the defect of poor frictional wear performance of the waterborne epoxy resin coating, and in order to enhance the frictional wear performance of the waterborne epoxy resin coating, the modified graphene material is added into the coating composition, so that the bonding force of the friction surface of the coating is reduced, the mechanical property of the waterborne coating is obviously improved, the friction coefficient of the coating is reduced, and the coating has excellent mechanical property and wear resistance.
A water-based paint composition comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 10 (0.5-6), and the component A comprises the following raw materials in parts by mass:
20-60 parts of waterborne epoxy resin emulsion;
10-20 parts of a filler;
0.6-5 parts of a dispersing agent;
0.5-3 parts of a defoaming agent;
0.5-4 parts of anti-settling thixotropic agent;
0.5-3 parts of a leveling agent;
10-15 parts of 20-30wt.% porphyrin modified graphene suspension;
the component B comprises the following components in parts by weight:
30-100 parts of a curing agent;
20-50 parts of deionized water;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 1-5g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 4-5 hours at 90-95 ℃, then naturally cooling the three-neck flask to room temperature, washing and filtering the three-neck flask by using a large amount of deionized water until the filtrate is neutral, and obtaining 60-70wt.% acidified graphene suspension with pH =5-7, wherein the volume of the mixed acid solution is 500-700ml, the volume ratio of sulfuric acid to nitric acid is 1.5, the concentration of the sulfuric acid is 70wt.%, and the concentration of the nitric acid is 65wt.%;
(b) Taking 2-4g of 60-70wt.% acidified graphene suspension, sequentially adding 3-4g of DMAC (dimethylacetamide), 0.2-0.3mg of chiral cobalt Schiff base complex, 1.5-2g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1-2g of tetraethylammonium iodide, 10-20ml of triethylamine and 5-15ml of ethylene glycol, fully mixing the raw materials under the assistance of ultrasound, taking mesh vitreous carbon as an anode, a platinum sheet as a cathode and an electrolytic cell without an insulating membrane for electrochemical modification treatment, wherein the electrolysis parameters are as follows: stirring at 150-200rpm, performing constant current electrolysis under the protection of argon at 50-65 ℃, wherein the current density is 0.20-0.5A/cm 2 And the electrolysis time is 2-3h, and after the electrolysis is finished, partial solvent is removed by reduced pressure distillation, dried and dehydrated, and is resuspended in deionized water, so that 20-30wt.% porphyrin modified graphene suspension is obtained.
The filler is one or a mixture of more of talcum powder, sericite, heavy calcium, light calcium, kaolin and silicon micropowder.
The curing agent is aliphatic amine, alicyclic amine or polyamide epoxy curing agent.
The defoaming agent is an organic silicon defoaming agent, the dispersing agent is at least one of BYK191 and BYK180, the anti-settling thixotropic agent is polyamide wax or BYK410, and the leveling agent is at least one of polyacrylates and BYK 371.
The coating is prepared by the following method: a preparation method of a water-based paint comprises the following steps:
(1) Preparing a component A: adding the aqueous epoxy resin emulsion, the filler, the dispersing agent, the defoaming agent, the anti-settling thixotropic agent and the leveling agent into a high-speed dispersion machine according to the amount, uniformly dispersing, then grinding until the fineness is below 30 micrometers, adding the porphyrin modified graphene suspension, and uniformly stirring to obtain a component A;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 1-5g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 4-5 hours at 90-95 ℃, then naturally cooling to room temperature, washing and filtering the three-neck flask by using a large amount of deionized water until the filtrate is neutral, and obtaining a 60-70wt.% acidified graphene suspension with pH =5-7, wherein the volume of the mixed acid solution is 500-700ml, the volume ratio of sulfuric acid to nitric acid is 1.5, the concentration of the sulfuric acid is 70wt.%, and the concentration of the nitric acid is 65wt.%;
(b) Taking 2-4g of 60-70wt.% acidified graphene suspension, sequentially adding 3-4g of DMAC (dimethylacetamide), 0.2-0.3mg of chiral cobalt Schiff base complex, 1.5-2g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1-2g of tetraethylammonium iodide, 10-20ml of triethylamine and 5-15ml of ethylene glycol, fully mixing the raw materials under the assistance of ultrasound, taking mesh vitreous carbon as an anode, a platinum sheet as a cathode and an electrolytic cell without an insulating membrane for electrochemical modification treatment, wherein the electrolysis parameters are as follows: stirring at 150-200rpm, performing constant current electrolysis under the protection of argon at 50-65 ℃, wherein the current density is 0.20 to 0.5A/cm 2 The electrolysis time is 2-3h, after the electrolysis is finished, partial solvent is removed by reduced pressure distillation, and the solution is dried, dehydrated and resuspended in deionized water to obtain 20-30wt.% porphyrin modified graphene suspension;
(2) Preparing a component B: uniformly mixing a curing agent and deionized water according to the amount to obtain a component B;
(3) Mixing: mixing the component A and the component B according to the mass ratio of 10 (0.5-6), then coating the mixture on the surface of a base material, and curing at room temperature.
The invention uses 5,10,15, 20-tetra (4-aminophenyl) porphyrin to electrochemically modify graphene, firstly, strong acid modification is carried out on graphene, a large number of functional groups, mainly carboxylic acid and epoxy bonds, are introduced on the surface of the graphene through mixed acid treatment, and the introduction of the functional groups extremely improves the dispersion degree of the graphene.
Taking 60-70wt.% acidified graphene suspension subjected to mixed acid and washing treatment as an electrolyte, adding 5,10,15, 20-tetra (4-aminophenyl) porphyrin, a catalyst and dissolving to perform electrochemical modification treatment, wherein the surface of the 5,10,15, 20-tetra (4-aminophenyl) porphyrin contains a large number of-NH 2 groups, reducing and releasing hydrogen at a cathode to obtain active-NH groups, the groups are mainly bonded with carboxyl groups on the surface of graphene, introducing a large number of porphyrin heterocyclic compounds on the surface of graphene, and under the stirring condition, the graphene continuously touches an electrode to conduct electricity, so that the functional groups on the surface of the graphene and the active-NH groups on the surface of the porphyrin heterocyclic compounds are greatly promoted to react, and the porphyrin grafting to the surface is accelerated, while the distance between graphene layers is changed to a certain extent by introducing the porphyrin hybrid compounds, the dispersion uniformity of the graphene in epoxy resin is greatly improved, the porphyrin modified graphene suspension obtained by the electrochemical modification treatment has extremely high stability, the graphene suspension uniformly dispersed in 25wt.% is uniformly dispersed, and the graphene suspension can not be subjected to high suspension aggregation and high suspension sedimentation, and graphene is obtained as shown in a schematic drawing.
Raman characterization is carried out on the acidified graphene and the electrochemically modified porphyrin graphene, and the Raman characterization can be seen to be 1357cm -1 And 1589cm -1 Two characteristic peaks appear and respectively correspond to the acidified graphiteD peak and G peak of the alkene, wherein the D peak is a disordered vibration peak, which indicates that certain defects exist in the acidified graphene, and the G peak is a main characteristic peak, which indicates that GO has a hexagonal close-packed structure, sp 2 Hybridization predominates. And the intensity ratio of the D peak to the G peak indicates the dense defect degree of the homemade GO, i.e., ID/IG =0.89, the ratio is small, and the crystallinity is high, in contrast, ID/IG =0.96 of the modified porphyrin graphene is greater than 0.89 of the graphene, which indicates that the crystallinity of the modified graphene is low, i.e., the side instructions indicate that the porphyrin is modified and bonded on the surface of the graphene.
The prepared modified graphene suspension is mixed with a curing agent to obtain a solution B, and then the solution B is mixed with the solution A and coated on the surface of an aluminum material, stainless steel or other metal base materials, so that the metal base materials can be effectively protected, and the obtained epoxy resin coating has extremely high wear resistance, scratch resistance and mechanical properties.
Advantageous technical effects
(1) According to the invention, the porphyrin modified graphene suspension is prepared by electrochemical means modification, the graphene surface is functionalized by mixed acid treatment, the tetra (4-aminophenyl) porphyrin is reduced by an electrode to obtain active amino, the tetra (4-aminophenyl) porphyrin and the active amino are promoted to generate chemical bonding action by electrochemical means, the modified graphene participates in the curing and forming processes of the coating, the uniformly dispersed graphene laminated structure can have a bearing effect in the scratching and wearing processes, scratching or damage behaviors can be reduced or avoided, and the wear-resistant epoxy resin coating material is further obtained.
(2) The porphyrin hybrid compound changes the distance between graphene layers, improves the dispersion uniformity of graphene in epoxy resin, enables the graphene to play a role of high specific surface area in a coating, can increase the adsorption effect of the epoxy resin coating and a base material in the AB liquid mixing and drying process, has a sheet structure, is compact in obtained coating, has high adhesive force, and can improve the impact resistance, friction resistance, weather resistance and corrosion resistance of the coating.
Drawings
FIG. 1 is a schematic diagram of the chemical formula structure of porphyrin graphene.
FIG. 2 SEM images of the coating surfaces of comparative example 1 and example 3 of the present invention.
FIG. 3 SEM images of cross-sections of coatings of comparative example 1 and example 3 of the present invention.
FIG. 4 SEM image of coating shot of example 2 of the invention.
FIG. 5 is a scratch pattern of comparative example and example 1 of the present invention.
FIG. 6 is a friction coefficient chart of comparative example and example 1 of the present invention.
Detailed Description
Example 1
The water-based epoxy coating comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 10.5, and the component A comprises the following raw materials in parts by mass:
20 parts of water-based epoxy resin emulsion;
10 parts of talcum powder filler;
0.6 part of BYK180 dispersant;
0.5 part of an organic silicon defoamer;
0.5 part of polyamide wax anti-settling thixotropic agent;
0.5 part of polyacrylate leveling agent;
10 parts of 20wt.% porphyrin-modified graphene suspension;
the component B comprises the following components in parts by weight:
30 parts of a fatty amine curing agent;
20 parts of deionized water;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 1g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 4 hours at 90 ℃, then naturally cooling the three-neck flask to room temperature, washing and filtering the three-neck flask with a large amount of deionized water until the filtrate is neutral, and obtaining a 60wt.% acidified graphene suspension with the pH =6, wherein the volume of the mixed acid solution is 500ml, the volume ratio of sulfuric acid to nitric acid is 1.5, the concentration of sulfuric acid is 70wt.%, and the concentration of nitric acid is 65wt.%;
(b) Taking 2g 60wt.% acidified graphene suspension, and adding the acidified graphene suspension into the suspension3g of DMAC dimethylacetamide, 0.2mg of chiral Schiff base cobalt complex, 1.5g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1g of tetraethylammonium iodide, 10ml of triethylamine and 5ml of ethylene glycol are sequentially added, raw materials are fully mixed under the assistance of ultrasound, the carbon of a reticular vitreous body is taken as an anode, a platinum sheet is taken as a cathode, an electrolytic cell is a diaphragm-free electrolytic cell, electrochemical modification treatment is carried out, and the electrolytic parameters are as follows: stirring at 150rpm, performing constant current electrolysis under the protection of argon at 50 deg.C to obtain current density of 0.20A/cm 2 And the electrolysis time is 2h, after the electrolysis is finished, partial solvent is removed by reduced pressure distillation, and the solution is dried, dehydrated and resuspended in deionized water to obtain 20wt.% porphyrin modified graphene suspension.
Example 2
The water-based epoxy coating is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 10, and the component A comprises the following raw materials in parts by mass:
40 parts of water-based epoxy resin emulsion;
15 parts of kaolin filler;
3 parts of BYK191 dispersant;
1.5 parts of an organic silicon defoaming agent;
2 parts of BYK410 anti-settling thixotropic agent;
1.6 parts of BYK371 leveling agent;
10 parts of 25wt.% porphyrin-modified graphene suspension;
the component B comprises the following components in parts by weight:
65 parts of polyamide epoxy curing agent;
35 parts of deionized water;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 3g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 4.5 hours at 95 ℃, naturally cooling the three-neck flask to room temperature, washing and filtering the three-neck flask by using a large amount of deionized water until the filtrate is neutral, and obtaining 65wt.% acidified graphene suspension with pH =6, wherein the volume of the mixed acid solution is 600ml, the volume ratio of the sulfuric acid to the nitric acid is 1.5, the concentration of the sulfuric acid is 70wt.%, and the concentration of the nitric acid is 65wt.%;
(b) 3g of 65wt.% acidified graphene suspension is taken, 3.5g DMAC dimethyl acetamide, 0.25mg of chiral Schiff base cobalt complex, 1.75g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1.5g tetraethylammonium iodide, 15ml triethylamine and 10ml ethylene glycol are sequentially added into the acidified graphene suspension, the raw materials are fully mixed under the assistance of ultrasound, the electrochemical modification treatment is carried out by taking reticular vitreous carbon as an anode, a platinum sheet as a cathode and an electrolytic cell as a diaphragm-free electrolytic cell, and the electrolysis parameters are as follows: stirring at 175rpm, performing constant current electrolysis under the protection of argon at 55 deg.C, wherein the current density is 0.4A/cm 2 And the electrolysis time is 2.5h, and after the electrolysis is finished, partial solvent is removed by reduced pressure distillation, dried, dehydrated and resuspended in deionized water to obtain 25wt.% porphyrin modified graphene suspension.
Example 3
The water-based epoxy coating is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 10, and the component A comprises the following raw materials in parts by mass:
40 parts of water-based epoxy resin emulsion;
15 parts of kaolin filler;
3 parts of BYK191 dispersant;
1.5 parts of an organic silicon defoamer;
2 parts of BYK410 anti-settling thixotropic agent;
1.6 parts of BYK371 leveling agent;
12.5 parts of 25wt.% porphyrin-modified graphene suspension;
the component B comprises the following components in parts by weight:
65 parts of polyamide epoxy curing agent;
35 parts of deionized water;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 3g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 4.5 hours at 95 ℃, naturally cooling the three-neck flask to room temperature, washing and filtering the three-neck flask by using a large amount of deionized water until the filtrate is neutral, and obtaining 65wt.% acidified graphene suspension with pH =6, wherein the volume of the mixed acid solution is 600ml, the volume ratio of the sulfuric acid to the nitric acid is 1.5, the concentration of the sulfuric acid is 70wt.%, and the concentration of the nitric acid is 65wt.%;
(b) 3g of 65wt.% acidified graphene suspension is taken, 3.5g DMAC dimethyl acetamide, 0.25mg of chiral Schiff base cobalt complex, 1.75g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1.5g tetraethylammonium iodide, 15ml triethylamine and 10ml ethylene glycol are sequentially added into the acidified graphene suspension, the raw materials are fully mixed under the assistance of ultrasound, the electrochemical modification treatment is carried out by taking reticular vitreous carbon as an anode, a platinum sheet as a cathode and an electrolytic cell as a diaphragm-free electrolytic cell, and the electrolysis parameters are as follows: stirring at 175rpm, performing constant current electrolysis under the protection of argon at 55 deg.C, wherein the current density is 0.4A/cm 2 And the electrolysis time is 2.5h, and after the electrolysis is finished, partial solvent is removed by reduced pressure distillation, dried, dehydrated and resuspended in deionized water to obtain 25wt.% porphyrin modified graphene suspension.
Example 4
The water-based epoxy coating is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 10, and the component A comprises the following raw materials in parts by mass:
40 parts of water-based epoxy resin emulsion;
15 parts of kaolin filler;
3 parts of BYK191 dispersant;
1.5 parts of an organic silicon defoamer;
2 parts of BYK410 anti-settling thixotropic agent;
1.6 parts of BYK371 leveling agent;
15 parts of 25wt.% porphyrin-modified graphene suspension;
the component B comprises the following components in parts by weight:
65 parts of polyamide epoxy curing agent;
35 parts of deionized water;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 3g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 4.5 hours at 95 ℃, naturally cooling the three-neck flask to room temperature, washing and filtering the three-neck flask by using a large amount of deionized water until the filtrate is neutral, and obtaining 65wt.% acidified graphene suspension with pH =6, wherein the volume of the mixed acid solution is 600ml, the volume ratio of the sulfuric acid to the nitric acid is 1.5, the concentration of the sulfuric acid is 70wt.%, and the concentration of the nitric acid is 65wt.%;
(b) Taking 3g of 65wt.% acidified graphene suspension, sequentially adding 3.5g of DMAC (dimethylacetamide), 0.25mg of chiral Schiff base cobalt complex, 1.75g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1.5g of tetraethylammonium iodide, 15ml of triethylamine and 10ml of ethylene glycol, fully mixing the raw materials under the assistance of ultrasound, taking mesh vitreous carbon as an anode, a platinum sheet as a cathode and an electrolytic cell as a diaphragm-free electrolytic cell, and carrying out electrochemical modification treatment, wherein the electrolysis parameters are as follows: stirring at 175rpm, performing constant current electrolysis under the protection of argon at 55 deg.C, wherein the current density is 0.4A/cm 2 And the electrolysis time is 2.5h, and after the electrolysis is finished, partial solvent is removed through reduced pressure distillation, dried, dehydrated and resuspended in deionized water to obtain 25wt.% porphyrin modified graphene suspension.
Example 5
The water-based epoxy coating is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 10: 6, and the component A comprises the following raw materials in parts by mass:
60 parts of water-based epoxy resin emulsion;
20 parts of silicon micro powder filler;
5 parts of BYK180 dispersant;
3 parts of an organic silicon defoamer;
4 parts of BYK410 anti-settling thixotropic agent;
3 parts of polyacrylate leveling agent;
15 parts of 30wt.% porphyrin-modified graphene suspension;
the component B comprises the following components in parts by weight:
100 parts of alicyclic amine curing agent;
50 parts of deionized water;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 5g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 5 hours at 95 ℃, then naturally cooling the three-neck flask to room temperature, washing and filtering the three-neck flask by using a large amount of deionized water until the filtrate is neutral, and obtaining a 70wt.% acidified graphene suspension with the pH =6, wherein the volume of the mixed acid solution is 700ml, the volume ratio of the sulfuric acid to the nitric acid is 1.5, the concentration of the sulfuric acid is 70wt.%, and the concentration of the nitric acid is 65wt.%;
(b) Taking 4g of 70wt.% acidified graphene suspension, sequentially adding 4g of DMAC (dimethylacetamide), 0.3mg of chiral Schiff base cobalt complex, 2g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 2g of tetraethylammonium iodide, 20ml of triethylamine and 15ml of ethylene glycol, and carrying out electrochemical modification treatment by using reticular vitreous carbon as an anode, a platinum sheet as a cathode and an electrolytic cell without a diaphragm under the ultrasonic assistance of fully mixing raw materials, wherein the electrolysis parameters are as follows: stirring at 200rpm, performing constant current electrolysis under the protection of argon at 65 deg.C, and controlling current density at 0.5A/cm 2 And the electrolysis time is 3h, and after the electrolysis is finished, partial solvent is removed by reduced pressure distillation, dried, dehydrated and resuspended in deionized water to obtain 30wt.% porphyrin modified graphene suspension.
Comparative example 1
The water-based epoxy coating is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 10, and the component A comprises the following raw materials in parts by mass:
40 parts of water-based epoxy resin emulsion;
15 parts of kaolin filler;
3 parts of BYK191 dispersant;
1.5 parts of an organic silicon defoaming agent;
2 parts of BYK410 anti-settling thixotropic agent;
1.6 parts of BYK371 leveling agent;
the component B comprises the following components in parts by weight:
65 parts of a polyamide epoxy curing agent;
and 35 parts of deionized water.
As shown above, the modified graphene added in the coating can significantly improve the tensile stress of the coating, wherein the embodiment 3 is the most preferable, the tensile stress is 4.53Mpa, which is much higher than that of the blank comparative example, and the main reason is that the graphene is a sheet-shaped nano structure, after porphyrin modification is introduced, the sheet-shaped structure is further peeled off to form a network structure, the epoxy resin is fixed, the interface compatibility between the modified graphene and the resin coating is higher, the flexibility of the coating is increased, and the tensile property of the coating is finally improved.
The wear resistance of the coating is characterized by testing the friction coefficient, according to the attached drawings 5 and 6 and shown by the data, the embodiment 3 shows the lowest friction coefficient, the comparative example 1 is a blank example and is a pure epoxy resin coating, the wear surface of the coating is rough, the worn groove surface mainly has fracture cracks and falling blocks, the friction and wear performance of the coating is reduced mainly due to the fact that the brittleness of the coating is high, the fracture cracks are formed and extend, the wear forms mainly include fatigue wear and adhesive wear, the temperature is gradually increased in the friction process, the epoxy resin is subjected to plastic deformation due to heat released by friction, wear debris is generated on the wear surface, the adhesive wear is formed when the wear debris is adhered to a friction object, and in contrast, after the modified graphene is added, the wear surface is relatively smooth and flat, only a small amount of fracture cracks exist, and the addition of the graphene improves the flexibility of the composite coating, so that the friction and wear performance of the coating is enhanced, abrasive particles are not easy to generate, and the friction and wear performance of the composite coating is enhanced; in addition, due to the fact that the graphene has the characteristic of large specific surface area, the coating can bear most of acting force and load of contact when the coating is in frictional wear, and the wear acts on the graphene to protect the coating.
The wear resistance and mechanical properties are shown in the attached figures 2, 3 and 4, and the morphological structure, such as the dispersion degree or compatibility of graphene, is closely related to the wear resistance and mechanical properties.
The coatings prepared in examples 2-4 and comparative example 1 are coated on the surface of an aluminum alloy, and the corrosion resistance of the protective substrate is characterized by a polarization curve, as shown in the table above, the corrosion resistance current density of example 3 is almost 90 times higher than that of comparative example 1, and extremely high corrosion resistance is shown, mainly due to the uniform dispersion of graphene in the coating and the high interfacial compatibility of graphene and the coating, the obtained coating is compact, and further the corrosion resistance is excellent.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications and improvements made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The water-based paint composition is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 10 (0.5-6), and the component A comprises the following raw materials in parts by mass:
20-60 parts of waterborne epoxy resin emulsion;
10-20 parts of a filler;
0.6-5 parts of a dispersant;
0.5-3 parts of a defoaming agent;
0.5-4 parts of anti-settling thixotropic agent;
0.5-3 parts of a leveling agent;
10-15 parts of 20-30wt.% porphyrin-modified graphene suspension;
the component B comprises the following components in parts by weight:
30-100 parts of a curing agent;
20-50 parts of deionized water;
the preparation method of the porphyrin modified graphene suspension comprises the following steps:
(a) Placing 1-5g of graphene in a three-neck flask, adding a mixed acid solution of sulfuric acid and nitric acid into the three-neck flask, sealing one neck of the three-neck flask, stirring one neck of the three-neck flask, refluxing one neck of the three-neck flask for 4-5 hours at 90-95 ℃, then naturally cooling the three-neck flask to room temperature, washing and filtering the three-neck flask by using a large amount of deionized water until the filtrate is neutral, and obtaining 60-70wt.% acidified graphene suspension with pH =5-7, wherein the volume of the mixed acid solution is 500-700ml, the volume ratio of sulfuric acid to nitric acid is 1.5, the concentration of the sulfuric acid is 70wt.%, and the concentration of the nitric acid is 65wt.%;
(b) Taking 2-4g of 60-70wt.% acidified graphene suspension, sequentially adding 3-4g of DMAC (dimethylacetamide), 0.2-0.3mg of chiral Schiff base cobalt complex, 1.5-2g of 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1-2g of tetraethylammonium iodide, 10-20ml of triethylamine and 5-15ml of ethylene glycol, fully mixing the raw materials with ultrasonic assistance, taking mesh vitreous carbon as an anode, a platinum sheet as a cathode and an electrolytic cell as a diaphragm-free electrolytic cell, and carrying out electrochemical modification treatment, wherein the electrolysis parameters are as follows: stirring at 150-200rpm, performing constant current electrolysis under the protection of argon at 50-65 ℃, wherein the current density is 0.20 to 0.5A/cm 2 And (3) electrolyzing for 2-3h, removing part of the solvent by reduced pressure distillation after the electrolysis is finished, drying and dehydrating, and resuspending in deionized water to obtain 20-30wt.% porphyrin modified graphene suspension.
2. The water-based paint composition as claimed in claim 1, wherein the filler is one or more of talc, sericite, heavy calcium, light calcium, kaolin, and fine silica powder;
the curing agent is aliphatic amine, alicyclic amine or polyamide epoxy curing agent.
3. The aqueous coating composition of claim 1, wherein the defoaming agent is a silicone defoaming agent, the dispersing agent is at least one selected from BYK191 and BYK180, the anti-settling thixotropic agent is one selected from polyamide wax and BYK410, and the leveling agent is at least one selected from polyacrylates and BYK 371.
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| CN117363055A (en) * | 2023-10-16 | 2024-01-09 | 甘肃省交通规划勘察设计院股份有限公司 | Porphyrin modified graphene and preparation method and application thereof |
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| CN106928239A (en) * | 2017-03-27 | 2017-07-07 | 盐城工学院 | Graphene porphyrin type organic nano material and preparation method thereof |
| CN112194952A (en) * | 2019-07-08 | 2021-01-08 | 常州市大使涂料有限公司 | Water-based graphene epoxy aging-resistant coating |
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| CN106928239A (en) * | 2017-03-27 | 2017-07-07 | 盐城工学院 | Graphene porphyrin type organic nano material and preparation method thereof |
| CN112194952A (en) * | 2019-07-08 | 2021-01-08 | 常州市大使涂料有限公司 | Water-based graphene epoxy aging-resistant coating |
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| 黄毅等: ""石墨烯的功能化及其相关应用"", 《中国科学 B辑：化学》, vol. 39, no. 9, pages 887 - 896 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117363055A (en) * | 2023-10-16 | 2024-01-09 | 甘肃省交通规划勘察设计院股份有限公司 | Porphyrin modified graphene and preparation method and application thereof |
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