CN113755036A - Modified graphene oxide, water-based anticorrosive paint and preparation method thereof - Google Patents
Modified graphene oxide, water-based anticorrosive paint and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of coatings, and particularly discloses a modified graphene oxide, a water-based anticorrosive coating and a preparation method thereof. The modified graphene oxide comprises the following components in parts by weight: and (3) graphene oxide: 0.1-0.4 parts, dopamine hydrochloride: 0.1-0.2 parts of Tris buffer, Tris buffer: 0.3-0.6 parts of silane coupling agent: 0.05 to 0.2 parts, zinc nitrate: 0.1 to 0.25 parts, pH regulator: 0.1 to 0.3 parts and deionized water: 50 to 150 portions. According to the invention, polydopamine is grafted on graphene oxide, so that the agglomeration phenomenon of the graphene oxide is improved, and the dispersibility of the graphene oxide is enhanced. When the modified graphene oxide is used for preparing the water-based anticorrosive coating, zinc ions are released from the modified graphene oxide when the coating cracks, and an oxide film is formed at the cracks, so that the self-repairing function is achieved, and the permeation of corrosive electrolyte is reduced.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a modified graphene oxide, a water-based anticorrosive coating and a preparation method thereof.
Background
With the rapid development of society and science and technology, the demand of coatings with protection and decoration functions is increasing, and with the gradual enhancement of environmental awareness, the green and environment-friendly water-based coatings with ultralow VOC content become the development direction of the coating industry. The water-based epoxy coating has the advantages of low toxicity, low volatile organic compounds, excellent adhesive force, chemical resistance and the like, and is more and more concerned, but the water-based epoxy coating also has the defects of poor durability, easy cracking, breakage and failure of a coating layer due to external force and aging, insufficient anticorrosion effect and the like.
Graphene as a typical 2D material has high conductivity, good thermal stability, impermeability and excellent barrier property, has good physical shielding property and chemical stability in a coating, and can be applied to preparation of a water-based epoxy composite coating. However, the graphene has a high aspect ratio, high van der waals force exists between each two sheets, and pi-pi bond function also exists between aromatic rings, so that the graphene is easy to agglomerate and can hardly be uniformly dispersed in water or an organic solvent, which affects the performance of graphene function in the coating. At present, graphene is modified mainly by an in-situ polymerization method, but the preparation process is complex and is not easy to realize industrialization; in addition, the dispersibility and the bonding force with a matrix interface of the modified graphene can be improved by adopting the modifier, but the corrosion resistance of the coating is obviously reduced, and the coating is accelerated to corrode when cracks appear, so that the coating does not have a self-repairing function.
Disclosure of Invention
In view of the above, the invention provides modified graphene oxide, a water-based anticorrosive coating and a preparation method thereof, wherein the graphene oxide is modified by polydopamine and a silane coupling agent, the agglomeration phenomenon of the graphene oxide is improved, the dispersibility and the compatibility of the graphene oxide in water-based epoxy resin are enhanced, and the anticorrosive performance of the water-based anticorrosive coating is improved.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
the first aspect of the application provides a modified graphene oxide, which comprises the following components in parts by mass: and (3) graphene oxide: 0.1-0.4 parts, dopamine hydrochloride: 0.1-0.2 parts of Tris buffer, Tris buffer: 0.3-0.6 parts of silane coupling agent: 0.05 to 0.2 parts, zinc nitrate: 0.1 to 0.25 parts, pH regulator: 0.1 to 0.3 parts and deionized water: 50-150 parts of silane coupling agent, wherein the silane coupling agent is 3-aminopropyl triethoxysilane (KH 550).
Compared with the prior art, the modified graphene oxide provided by the application has the following advantages:
according to the application, poly-dopamine is grafted on graphene oxide, so that the agglomeration phenomenon of the graphene oxide is improved, the dispersity of the graphene oxide is enhanced, the compatibility of the graphene oxide in water-based epoxy resin is further improved, and the corrosion resistance of the water-based anticorrosive paint is improved.
Epoxy groups, carboxyl groups and hydroxyl groups on the surface of graphene oxide provide grafting sites for modification of graphene oxide, dopamine is subjected to intramolecular cyclization in a Tris buffer to form polydopamine containing a biphenol structure, two hydroxyl groups in the polydopamine and a silicon-oxygen bond in a silane coupling agent are subjected to covalent reaction, a protective net in a covalent bond form is further formed on the surface of the graphene oxide, zinc ions in zinc nitrate provide positive charges, free hydrophilic groups providing negative charges are attached to the surface of the graphene oxide on a graphene oxide interface through hydrogen bonds and pi-pi interaction, and finally the neutral polydopamine modified graphene oxide zinc ion loaded nano composite filler is formed.
The nano composite filler of the polydopamine modified graphene oxide loaded zinc ions is added into the aqueous epoxy resin to form a coating, when the coating cracks, the zinc ions are released from the nano composite filler, a layer of oxide film is formed at the cracks, the permeation of corrosive electrolyte is reduced, the repair of the cracks is completed, the permeation of the corrosive electrolyte is reduced, and the defect that the aqueous epoxy resin is easy to age and crack is overcome.
Optionally, the pH regulator is sodium bicarbonate or sodium dihydrogen phosphate.
Optionally, the mass ratio of the dopamine hydrochloride to the graphene oxide is 1: 0.9-1.1.
Optionally, the mass ratio of the dopamine hydrochloride to the silane coupling agent is 1: 0.4-0.6.
The optimized proportion of the reactants can not only improve the utilization rate of raw materials and reduce the occurrence of side reactions, but also ensure that a specific protection net obtained by covalent reaction of polydopamine and a silane coupling agent is formed on the surface of the graphene oxide, avoid the waste of the raw materials and further reduce the production cost.
The second aspect of the present application further provides a preparation method of the modified graphene oxide, which at least includes the following steps:
s1, dispersing the graphene oxide and Tris (hydroxymethyl) aminomethane buffer in deionized water, adding dopamine hydrochloride, a silane coupling agent and a pH regulator, and reacting at 55-65 ℃ for 23-25 h to obtain a first reaction solution;
s2, adding zinc nitrate into the first reaction solution, and reacting for 1.5-2.5 h at 55-65 ℃ to obtain the modified graphene oxide.
According to the preparation method, the polydopamine is grafted to the graphene oxide by using the silane coupling agent, and zinc ions are formed into the modified graphene oxide loaded with the zinc ions by adding the zinc nitrate.
Optionally, in step S1 and step S2, the stirring speed of the reaction is 400rpm to 600 rpm.
Optionally, in step S1, the pH value of the reaction is 8.3 to 8.7.
Optionally, in step S2, the pH value of the reaction is 7.8 to 8.2.
The third aspect of the application also provides an aqueous anticorrosive paint, which comprises the modified graphene oxide.
After the graphene oxide is modified by polydopamine and zinc nitrate, the agglomeration phenomenon of the graphene oxide is obviously improved, the dispersity of the graphene oxide is enhanced, and the graphene oxide is used for preparing a water-based paint, so that the corrosion resistance of the water-based anticorrosive paint is greatly improved.
Optionally, the water-based anticorrosive paint comprises the following components in parts by weight: aqueous epoxy emulsion: 20-25 parts of modified graphene oxide: 0.1-0.3 parts of curing agent: 3-5 parts of dispersant: 0.3-0.6 parts of a quick-drying agent: 0.2-0.25 parts of defoaming agent: 0.3-0.8 parts of film forming additive: 0.1-0.3 parts of thickening agent: 0.3-0.6 parts and deionized water: 5 to 8 portions.
The application provides a modified graphene oxide endows waterborne epoxy composite coating self-repairing function, and zinc ion releases from modified graphene oxide when the coating cracks, forms a layer of oxide film at the crack, plays the self-repairing role, reduces the infiltration of corrosive electrolyte, improves the not enough of the easy ageing fracture of waterborne epoxy resin, accomplishes the restoration of crack.
The application provides a waterborne anticorrosive coating uses water as the solvent, realizes almost that zero VOCs discharges, and corrosion resisting property is good, simple process, convenient operation, safe and reliable, green.
Optionally, the aqueous epoxy emulsion is a non-ionic aqueous dispersion of bisphenol a epoxy resin.
The preferred bisphenol A epoxy resin contains more hydroxyl groups, has stronger polarity and chemical activity, is easy to act with a coated object and has stronger adhesive force.
Optionally, the epoxy equivalent of the aqueous epoxy emulsion is 450g/mol to 600g/mol or 900g/mol to 1100 g/mol.
The preferable epoxy resin has high crosslinking density after being cured, so that the adhesive force of the coating is improved, the preferable epoxy equivalent not only ensures complete curing reaction, but also avoids the condition that the viscosity of the coating system is too high to influence the curing reaction speed.
Optionally, the curing agent is at least one of an aliphatic amine curing agent or a modified polyamide curing agent; the amine value of the aliphatic amine curing agent is 230-250, and the amine value of the modified polyamide curing agent is 140-160.
The preferred amine number ensures complete curing of the epoxy resin and that the coating system does not contain free amine.
Optionally, the dispersant is an aqueous solution of a copolymer containing pigment affinity groups.
Optionally, the thickener is at least one of a modified urea aqueous solution or a polyether polyurethane thickener.
Optionally, the film-forming aid is an aliphatic alcohol ester compound with a boiling point of 170-180 ℃.
Optionally, the quick-drying agent is propylene glycol methyl ether.
Optionally, the defoaming agent is at least one of a polyethylene glycol-hydrophobic solid-foam breaking polysiloxane mixture or a polyether siloxane copolymer.
According to the invention, the modified graphene oxide is uniformly dispersed into the epoxy resin through compounding of the dispersing agent, the thickening agent, the quick drying agent, the defoaming agent and other auxiliaries, and the full curing reaction of the epoxy resin and the curing agent is promoted, so that the coating has excellent corrosion resistance.
The fourth aspect of the present application further provides a preparation method of the above aqueous anticorrosive paint, which at least comprises the following steps:
mixing a water-based epoxy emulsion, modified graphene oxide, a dispersing agent, a quick drying agent, a defoaming agent, a film forming aid, a thickening agent and deionized water to obtain a first mixture;
and mixing the first mixture and a curing agent to obtain the water-based anticorrosive paint.
The preparation method of the water-based anticorrosive paint is simple and is beneficial to industrial popularization.
Optionally, the preparation method of the water-based anticorrosive paint comprises the following steps:
dispersing the modified graphene oxide in 10-15 wt% of deionized water, performing ultrasonic treatment for 8-12 min, adding the aqueous epoxy emulsion, and uniformly stirring to obtain an aqueous epoxy emulsion mixture;
mixing a dispersing agent, a film-forming assistant and a defoaming agent, adding the mixture into the aqueous epoxy emulsion mixture, uniformly stirring, adding a quick-drying agent, a thickening agent and the rest deionized water, and uniformly stirring to obtain a first mixture;
and mixing the first mixture and a curing agent, and uniformly stirring to obtain the water-based anticorrosive paint.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an IR spectrum provided in test example 1 of the present invention;
FIG. 2 is a polarization curve provided in test example 2 of the present invention;
FIG. 3 is a salt water resistance plot of a scratch coating provided in test example 3 of the present invention;
FIG. 4 shows a NaCl solution Fe provided in test example 3 of the present invention3+Concentration profile.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment of the invention provides modified graphene oxide which comprises the following components in parts by weight: and (3) graphene oxide: 0.2 part, dopamine hydrochloride: 0.2 parts, Tris buffer: 0.3 part, silane coupling agent: 0.1 part, zinc nitrate: 0.2 part, pH regulator: 0.1 part and deionized water: 120 parts of (A); wherein the silane coupling agent is 3-aminopropyl triethoxysilane (KH 550).
The preparation method of the modified graphene oxide comprises the following steps:
s1, dispersing the graphene oxide and Tris (hydroxymethyl) aminomethane buffer in deionized water, adding dopamine hydrochloride for ultrasonic dispersion for 10min, then adding a silane coupling agent and a pH regulator, and reacting for 24h under the conditions of a pH value of 8.5, a rotation speed of 500rpm and a temperature of 60 ℃ to obtain a first reaction solution;
s2, adding zinc nitrate into the first reaction solution, and reacting for 2h under the conditions that the pH value is 8, the rotating speed is 500rpm, and the temperature is 60 ℃ to obtain the modified graphene oxide.
Example 2
The embodiment of the invention provides modified graphene oxide which comprises the following components in parts by weight: and (3) graphene oxide: 0.1 part, dopamine hydrochloride: 0.21 part, Tris buffer: 0.6 part, silane coupling agent: 0.2 part, zinc nitrate: 0.1 part, pH regulator: 0.3 part and deionized water: 150 parts; wherein the silane coupling agent is 3-aminopropyl triethoxysilane (KH 550).
The preparation method of the modified graphene oxide comprises the following steps:
s1, dispersing the graphene oxide and Tris (hydroxymethyl) aminomethane buffer in deionized water, adding dopamine hydrochloride for ultrasonic dispersion for 10min, then adding a silane coupling agent and a pH regulator, and reacting for 23h under the conditions of pH value of 8.3, rotation speed of 600rpm and temperature of 65 ℃ to obtain a first reaction solution;
s2, adding zinc nitrate into the first reaction solution, and reacting for 1.5h under the conditions that the pH value is 7.8, the rotating speed is 600rpm, and the temperature is 65 ℃ to obtain the modified graphene oxide.
Example 3
The embodiment of the invention provides modified graphene oxide which comprises the following components in parts by weight: and (3) graphene oxide: 0.4 part, dopamine hydrochloride: 0.15 parts, Tris buffer: 0.5 part, silane coupling agent: 0.15 part, zinc nitrate: 0.25 part, pH adjuster: 0.1 part and deionized water: 50 parts of a mixture; wherein the silane coupling agent is 3-aminopropyl triethoxysilane (KH 550).
The preparation method of the modified graphene oxide comprises the following steps:
s1, dispersing the graphene oxide and Tris (hydroxymethyl) aminomethane buffer in deionized water, adding dopamine hydrochloride for ultrasonic dispersion for 10min, then adding a silane coupling agent and a pH regulator, and reacting for 25h under the conditions that the pH value is 8.7, the rotating speed is 4600rpm, and the temperature is 55 ℃ to obtain a first reaction solution;
s2, adding zinc nitrate into the first reaction solution, and reacting for 2.5 hours under the conditions that the pH value is 7.8, the rotating speed is 400rpm, and the temperature is 55 ℃ to obtain the modified graphene oxide.
Example 4
The embodiment of the invention provides modified graphene oxide which comprises the following components in parts by weight: and (3) graphene oxide: 0.3 part, dopamine hydrochloride: 0.1 part, Tris buffer: 0.3 part, silane coupling agent: 0.05 part, zinc nitrate: 0.15 part, pH regulator: 0.2 part and deionized water: 100 parts of (A); wherein the silane coupling agent is 3-aminopropyl triethoxysilane (KH 550).
The preparation method of the modified graphene oxide comprises the following steps:
s1, dispersing the graphene oxide and Tris (hydroxymethyl) aminomethane buffer in deionized water, adding dopamine hydrochloride for ultrasonic dispersion for 10min, then adding a silane coupling agent and a pH regulator, and reacting for 24h under the conditions of a pH value of 8.5, a rotation speed of 550rpm and a temperature of 60 ℃ to obtain a first reaction solution;
s2, adding zinc nitrate into the first reaction solution, and reacting for 2h under the conditions that the pH value is 8, the rotation speed is 550rpm and the temperature is 60 ℃ to obtain the modified graphene oxide.
Example 5
The embodiment of the invention provides a water-based anticorrosive paint which comprises the following components in parts by weight: aqueous epoxy emulsion: 20 parts of modified graphene oxide: 0.3 part, curing agent: 3 parts, dispersant: 0.5 part, quick-drying agent: 0.2 part, defoaming agent: 0.4 part, film-forming assistant: 0.2 part, thickener: 0.4 part and deionized water: 8 parts.
The modified graphene oxide prepared in example 1 is the modified graphene oxide;
the epoxy equivalent of the epoxy emulsion is 550 g/mol-600 g/mol;
the defoaming agent is polyether siloxane copolymer
The thickening agent is a modified urea aqueous solution;
the curing agent is a fatty amine curing agent with an amine value of 240.
The preparation method of the water-based anticorrosive paint comprises the following steps:
dispersing the modified graphene oxide in 10 wt% of deionized water, performing ultrasonic treatment for 10min, then adding the aqueous epoxy emulsion, and uniformly stirring to obtain an aqueous epoxy emulsion mixture;
mixing a dispersing agent, a film-forming assistant and a defoaming agent, adding the mixture into the aqueous epoxy emulsion mixture, uniformly stirring, adding a quick-drying agent, a thickening agent and deionized water, and uniformly stirring to obtain a first mixture;
and mixing the first mixture and a curing agent, and uniformly stirring to obtain the water-based anticorrosive paint.
Example 6
The embodiment of the invention provides a water-based anticorrosive paint which comprises the following components in parts by weight: aqueous epoxy emulsion: 25 parts of modified graphene oxide: 0.1 part, curing agent: 5 parts, dispersant: 0.3 part, quick-drying agent: 0.25 part, defoaming agent: 0.8 part, film-forming assistant: 0.1 part, thickening agent: 0.5 part and deionized water: 5 parts of the raw materials.
The modified graphene oxide prepared in example 1 is the modified graphene oxide;
the epoxy equivalent of the epoxy emulsion is 450g/mol to 550 g/mol;
the defoaming agent is a mixture of polyethylene glycol, hydrophobic solid and foam breaking polysiloxane
The thickener is polyether polyurethane thickener;
the curing agent is a modified polyamide curing agent with an amine value of 150.
The preparation method of the water-based anticorrosive paint is described in example 5, and is not repeated.
Example 7
The embodiment of the invention provides a water-based anticorrosive paint which comprises the following components in parts by weight: aqueous epoxy emulsion: 22 parts of modified graphene oxide: 0.2 part, curing agent: 4 parts, dispersant: 0.6 part, quick-drying agent: 0.23 part, defoaming agent: 0.3 part, film-forming assistant: 0.2 part, thickener: 0.6 part and deionized water: 7 parts.
The modified graphene oxide prepared in example 1 is the modified graphene oxide;
the epoxy equivalent of the epoxy emulsion is 900g/mol to 1100 g/mol;
the defoaming agent is a mixture of polyethylene glycol, hydrophobic solid and foam breaking polysiloxane
The thickening agent is a modified urea aqueous solution;
the curing agent is a modified polyamide curing agent with an amine value of 150.
The preparation method of the water-based anticorrosive paint is described in example 5, and is not repeated.
Example 8
The embodiment of the invention provides a water-based anticorrosive paint which comprises the following components in parts by weight: aqueous epoxy emulsion: 23 parts of modified graphene oxide: 0.15 part, curing agent: 4 parts, dispersant: 0.4 part, quick-drying agent: 0.24 part, defoaming agent: 0.6 part, film-forming assistant: 0.2 part, thickener: 0.3 part and deionized water: 6 parts.
The modified graphene oxide prepared in example 1 is the modified graphene oxide;
the epoxy equivalent of the epoxy emulsion is 900g/mol to 1100 g/mol;
the defoaming agent is a mixture of polyethylene glycol, hydrophobic solid and foam breaking polysiloxane
The thickener is polyether polyurethane thickener;
the curing agent is a fatty amine curing agent with an amine value of 250.
The preparation method of the water-based anticorrosive paint is described in example 5, and is not repeated.
In order to better illustrate the technical solution of the present invention, further comparison is made below by means of a comparative example and an example of the present invention.
Comparative example 1
The comparative example provides modified graphene oxide which comprises the following components in parts by mass: and (3) graphene oxide: 0.2 part, dopamine hydrochloride: 0.2 parts, Tris buffer: 0.3 part, silane coupling agent KH 550: 0.1 part, 0.1 part of pH regulator and 120 parts of deionized water.
The preparation method of the modified graphene oxide comprises the following steps:
and dispersing the graphene oxide and a Tris (hydroxymethyl) aminomethane buffer in deionized water, adding dopamine hydrochloride for ultrasonic dispersion for 10min, then adding a silane coupling agent and a pH regulator, and reacting for 24h under the conditions of a pH value of 8.5, a rotation speed of 500rpm and a temperature of 60 ℃ to obtain the modified graphene oxide.
The comparative example provides a water-based anticorrosive paint which comprises the following components in parts by weight: aqueous epoxy emulsion: 20 parts of modified graphene oxide prepared in comparative example 1: 0.3 part, curing agent: 3 parts, dispersant: 0.5 part, quick-drying agent: 0.2 part, defoaming agent: 0.4 part, film-forming assistant: 0.2 part, thickener: 0.4 part, 0.2 part of zinc nitrate and deionized water: 8 parts.
The selection of the waterborne epoxy resin, the curing agent, the defoaming agent and the thickening agent is the same as that of the embodiment 5, and the description is omitted.
The preparation method of the water-based anticorrosive paint comprises the following steps:
dispersing the modified graphene oxide in 10 wt% of deionized water, performing ultrasonic treatment for 10min, then adding the aqueous epoxy emulsion, and uniformly stirring to obtain an aqueous epoxy emulsion mixture;
mixing a dispersing agent, a film-forming assistant, a defoaming agent and zinc nitrate, adding the mixture into the aqueous epoxy emulsion mixture, uniformly stirring, adding a quick drying agent, a thickening agent and deionized water, and uniformly stirring to obtain a first mixture;
and mixing the first mixture and a curing agent, and uniformly stirring to obtain the water-based anticorrosive paint.
Comparative example 2
The comparative example provides modified graphene oxide which comprises the following components in parts by mass: and (3) graphene oxide: 0.2 part, dopamine hydrochloride: 0.2 parts, Tris buffer: 0.3 part, silane coupling agent: 0.1 part, zinc nitrate: 0.2 part, 0.1 part of pH regulator and 120 parts of deionized water.
The silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560).
The preparation method of the modified graphene oxide is as described in example 1, and is not described again.
The comparative example also provides a water-based anticorrosive paint which comprises the following components in parts by weight: aqueous epoxy emulsion: 20 parts of modified graphene oxide prepared in comparative example 2: 0.3 part, curing agent: 3 parts, dispersant: 0.5 part, quick-drying agent: 0.2 part, defoaming agent: 0.4 part, film-forming assistant: 0.2 part, thickener: 0.4 part and deionized water: 8 parts.
The selection of the waterborne epoxy resin, the curing agent, the defoaming agent and the thickening agent is the same as that of the embodiment 5, and the description is omitted.
The preparation method of the water-based anticorrosive paint is described in example 5, and is not repeated.
Comparative example 3
The comparative example also provides a water-based anticorrosive paint which comprises the following components in parts by weight: aqueous epoxy emulsion: 20 parts, graphene oxide: 0.3 part, curing agent: 3 parts, dispersant: 0.5 part, quick-drying agent: 0.2 part, defoaming agent: 0.4 part, film-forming assistant: 0.2 part, thickener: 0.4 part, zinc nitrate: 0.2 part and deionized water: 8 parts.
The selection of the waterborne epoxy resin, the curing agent, the defoaming agent and the thickening agent is the same as that of the embodiment 5, and the description is omitted.
The preparation method of the water-based anticorrosive paint is as described in comparative example 1, and details are not repeated.
Test example 1
The modified graphene oxides prepared in example 1 and comparative example 1 of the present invention and graphene oxide were subjected to infrared spectroscopic analysis, and the results are shown in fig. 1.
As can be seen from FIG. 1, the graphene oxide is 3456cm-1The near part has a wide and strong-OH stretching vibration peak at 1723cm-1Has a stretching vibration peak of-C ═ O on the carboxyl group at 1624cm-1Has a C-OH bending vibration absorption peak at 1040cm-1And a C-O-C vibration absorption peak is formed, so that a reaction site is provided for the modification of the graphene oxide.
As can be seen from FIG. 1, new peaks appeared in the modified graphene oxide prepared in comparative example 1, which were 2984cm each-1The methylene group at (B) is symmetrical and 2908cm-1Asymmetric stretching vibration peak at position, Si-O-C and Si-O-Si is 1113cm-1And 1058cm-1Has a strong stretching vibration peak at 3684cm-1The smaller stretching vibration absorption peak formed by free-OH is less; the hydroxyl does not have a wide stretching vibration peak, which indicates that the hydroxyl on the surface of the graphene oxide participates in the reaction; at 1416cm-1And 1575cm-1The formation of aromatic amines is demonstrated by the presence of a-C ═ N and-C ═ C bond; at 924cm-1An out-of-plane bending vibration peak of-N-H is formed, which shows that amino groups in aminosilane (KH550) react with-OH on the surface of graphene oxide to graft polydopamine on the surface of the graphene oxide.
As can be seen from FIG. 1, the modified graphene oxide prepared in example 1 hardly showed a new peak in the IR spectrum compared to comparative example 1, thereby indicating that zinc ion was per-NH2The chemical adsorption of the groups is loaded on the graphene oxide.
Test example 2
The aqueous anticorrosive coatings prepared in examples 5 to 8 and comparative examples 1 to 3 were sprayed on the pretreated Q235 iron plate with a spray gun, the coating thickness was controlled to be 100 to 120 μm, and then Q235 with the coating was dried in an oven at 80 ℃ for 1 hour while being cured at ambient temperature (25 ℃) for 3 days.
The aqueous anticorrosive coatings prepared in examples 5 to 8 and comparative examples 1 to 3 were placed in 3.5 wt% NaCl solution, polarization curves of the coatings were respectively tested, corrosion resistance evaluation of the coatings was performed, and polarization resistance and corrosion rate were obtained according to the calculation method of Tafal fitting cathode and anode slopes, the polarization curves are shown in fig. 2, and the polarization resistance and corrosion rate are shown in table 1.
TABLE 1 polarization resistance and Corrosion Rate
As can be seen from FIG. 2 and Table 1, the water-based anticorrosive coatings prepared in the embodiments 5-8 of the invention have excellent anticorrosive performance, and the corrosion rate reaches 0.007 mm/year. In comparative example 1, modified graphene oxide without zinc ions and zinc nitrate alone are added, but the corrosion rate is 0.252mm/year, so that the corrosion prevention effect of the zinc ions in the coating is necessarily related to the structural state of the zinc ions in the coating, and the zinc ions are loaded on the graphene oxide through hydrogen bonds and large pi bonds, so that the corrosion resistance of the coating is improved. The corrosion rate of comparative example 2 was 3.062mm/year, thereby illustrating that the selection of silane coupling agent is also one of the keys for preparing modified graphene oxide, and KH550 tail end of silane coupling agent contains hydrophilic group-NH2Not only poly-dopamine is grafted on the surface of graphene oxide, but also zinc ions can pass through-NH2The chemical adsorption of the groups is carried, so that the dispersibility of the graphene oxide and the corrosion resistance of the water-based epoxy composite coating are greatly improved. The corrosion rate of comparative example 3 was 3.281mm/year, thereby demonstrating that even thoughThe zinc nitrate is added into the water-based anticorrosive paint, so that the coating has weak bonding force with an iron plate and unsatisfactory anticorrosive effect due to the problem that unmodified graphene oxide is easy to agglomerate in the coating.
Test example 3
In order to test the self-repairing anticorrosion effect of the water-based anticorrosion paint, scratches are made on the Q235 test piece with the coating sprayed in the examples 5-8 and the comparative examples 1-3, and the test piece is soaked in 150mL of 3.5 wt% NaCl solution for 15 days, and the volume of the solution is kept at 150mL all the time. The results of the scratch coating resistance to saline in 3.5 wt% NaCl solution are shown in FIG. 3, and NaCl solution Fe was separately tested3+The results of concentration are shown in FIG. 4.
As can be seen from fig. 3, the aqueous anticorrosive coating prepared by the method has excellent salt water corrosion resistance and excellent anticorrosive effect, so that a layer of protective film appears on the coating crack of the aqueous anticorrosive coating, and the corrosion speed is reduced.
As can be seen from FIG. 4, the aqueous anticorrosive coatings prepared in examples 5 to 8 and comparative examples 1 to 3 were soaked in sodium chloride for 15 days, and then Fe in the sodium chloride solution3+The concentration is 1.45mg/L respectively-1、2.08mg/L-1、2.21mg/L-1、1.73mg/L-1、6.12mg/L-1、6.94mg/L-1And 7.71mg/L-1Therefore, the zinc ions loaded by the modified graphene oxide are released when the waterborne epoxy composite coating is cracked, and form a layer of oxide film with oxygen in air or-OH in corrosive electrolyte in cracks, so that the further corrosion of the coating can be reduced, the coating has a self-repairing function, and the coating can have long-term corrosion resistance.
Test example 4
Adhesion tests were performed on the coatings of the water-based anticorrosive coatings prepared in examples 5 to 8 and comparative examples 1 to 3, and the test results are shown in table 2 below. The preparation process of the coating is as described in test example 2 and is not described again.
Table 2 adhesion test results
| Adhesion (MPa) | |
| Example 5 | 2.41 |
| Example 6 | 2.17 |
| Example 7 | 2.28 |
| Example 8 | 2.35 |
| Comparative example 1 | 2.38 |
| Comparative example 2 | 2.06 |
| Comparative example 3 | 1.78 |
As can be seen from table 2, the aqueous anticorrosive coatings prepared from the poly-dopamine-modified graphene oxide all have excellent adhesion, which is caused by the simultaneous presence of catechol and amine in the poly-dopamine structure, can be adsorbed on a substrate to form a film, and the adhesion is not affected by the use of epoxy resins with different epoxy equivalent weights and curing agents with different amine values.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A modified graphene oxide characterized by: the composition comprises the following components in parts by mass: and (3) graphene oxide: 0.1-0.4 parts, dopamine hydrochloride: 0.1-0.2 parts of Tris buffer, Tris buffer: 0.3-0.6 parts of silane coupling agent: 0.05 to 0.2 parts, zinc nitrate: 0.1 to 0.25 parts, pH regulator: 0.1 to 0.3 parts and deionized water: 50-150 parts; the silane coupling agent is 3-aminopropyl triethoxysilane.
2. The modified graphene oxide of claim 1, wherein: the pH regulator is sodium bicarbonate or sodium dihydrogen phosphate; and/or
The mass ratio of the dopamine hydrochloride to the graphene oxide is 1: 0.9-1.1; and/or
The mass ratio of the dopamine hydrochloride to the silane coupling agent is 1: 0.4-0.6.
3. The method for producing a modified graphene oxide according to any one of claims 1 to 2, wherein: at least comprises the following steps:
s1, dispersing the graphene oxide and Tris (hydroxymethyl) aminomethane buffer in deionized water, adding dopamine hydrochloride, a silane coupling agent and a pH regulator, and reacting at 55-65 ℃ for 23-25 h to obtain a first reaction solution;
s2, adding zinc nitrate into the first reaction solution, and reacting for 1.5-2.5 h at 55-65 ℃ to obtain the modified graphene oxide.
4. The method for preparing modified graphene oxide according to claim 3, wherein: in step S1 and step S2, the stirring speed of the reaction is 400rpm to 600 rpm; and/or
In the step S1, the pH value of the reaction is 8.3-8.7; and/or
In step S2, the pH value of the reaction is 7.8-8.2.
5. The water-based anticorrosive paint is characterized in that: comprising the modified graphene oxide according to any one of claims 1 to 2.
6. The aqueous anticorrosive paint according to claim 5, characterized in that: the composition comprises the following components in parts by weight: aqueous epoxy emulsion: 20-25 parts of modified graphene oxide: 0.1-0.3 parts of curing agent: 3-5 parts of dispersant: 0.3-0.6 parts of a quick-drying agent: 0.2-0.25 parts of defoaming agent: 0.3-0.8 parts of film forming additive: 0.1-0.3 parts of thickening agent: 0.3-0.6 parts and deionized water: 5 to 8 portions.
7. The aqueous anticorrosive paint according to claim 6, characterized in that: the water-based epoxy emulsion is a non-ionic water dispersion of bisphenol A type epoxy resin; and/or
The epoxy equivalent of the water-based epoxy emulsion is 450 g/mol-600 g/mol or 900 g/mol-1100 g/mol.
8. The aqueous anticorrosive paint according to claim 6, characterized in that: the curing agent is at least one of fatty amine curing agent or modified polyamide curing agent; the amine value of the aliphatic amine curing agent is 230-250, and the amine value of the modified polyamide curing agent is 140-160.
9. The aqueous anticorrosive paint according to claim 6, characterized in that: the dispersing agent is a copolymer aqueous solution containing pigment affinity groups; and/or
The thickening agent is at least one of a modified urea aqueous solution or a polyether polyurethane thickening agent; and/or
The film-forming additive is an aliphatic alcohol ester compound with the boiling point of 170-180 ℃; and/or
The quick drying agent is propylene glycol methyl ether; and/or
The defoaming agent is at least one of polyethylene glycol-hydrophobic solid-foam breaking polysiloxane mixture or polyether siloxane copolymer.
10. The method for preparing the water-based anticorrosive paint according to claims 5 to 9, characterized in that: at least comprises the following steps:
mixing a water-based epoxy emulsion, modified graphene oxide, a dispersing agent, a quick drying agent, a defoaming agent, a film forming aid, a thickening agent and deionized water to obtain a first mixture;
and mixing the first mixture and a curing agent to obtain the water-based anticorrosive paint.
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