CN114643027A - Composite graphene microcapsule and preparation method and application thereof - Google Patents
Composite graphene microcapsule and preparation method and application thereof Download PDFInfo
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000000839 emulsion Substances 0.000 claims abstract description 39
- 239000011162 core material Substances 0.000 claims abstract description 34
- 230000007797 corrosion Effects 0.000 claims abstract description 26
- 238000005260 corrosion Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000010959 steel Substances 0.000 claims abstract description 23
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- 239000003822 epoxy resin Substances 0.000 claims abstract description 18
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- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 13
- 239000012498 ultrapure water Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 37
- 239000000463 material Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
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- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
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- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
Abstract
The invention discloses a composite graphene microcapsule as well as a preparation method and application thereof, wherein the method comprises the following steps: dissolving urea into formaldehyde, adjusting the pH value to be alkaline, and heating and stirring to obtain a prepolymer; adding graphene into epoxy resin, and uniformly mixing to obtain a core material; dissolving the corrosion inhibitor in ultrapure water, adding the core material, and uniformly mixing to prepare a composite emulsion; respectively adding a prepolymer, a curing agent and a reaction promoter into the composite emulsion, uniformly mixing to obtain a microcapsule pre-synthesized emulsion system, heating the system and adjusting the pH, and obtaining a microcapsule product after the reaction is finished; and filtering, washing and drying the microcapsule product to obtain the composite graphene microcapsule. The invention can be applied to steel coatings by loading graphene and a corrosion inhibitor by utilizing a microcapsule technology, and is used for improving the corrosion resistance of the damaged steel of the coatings, prolonging the service life of the base material and reducing the using amount of the coating.
Description
Technical Field
The invention relates to a composite graphene microcapsule and a preparation method and application thereof, belonging to the technical field of microcapsules.
Background
At present, the corrosion protection method for steel mainly comprises an organic coating method and an electroplating method. In recent years, microcapsule technology which is started up can be used for doping microcapsules encapsulated with corrosion inhibitors as fillers into a coating, so that the service life of the coating is further prolonged.
The excellent physical and chemical properties of graphene enable the graphene to have excellent potential in the aspect of anticorrosive coating additives, meanwhile, the traditional corrosion inhibitor has good effect on the premise of proper application, and the graphene and the traditional corrosion inhibitor are effectively combined to theoretically have the effect of greatly optimizing various properties of the coating. At present, the problems of the dispersibility of graphene and the preparation process of microcapsules thereof are solved, but the application of the graphene and a corrosion inhibitor together is still less explored.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a composite graphene microcapsule and a preparation method and application thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a method for preparing a composite graphene microcapsule, comprising the steps of:
dissolving urea into formaldehyde, adjusting the pH value to be alkaline, and heating and stirring to obtain a prepolymer;
adding graphene into epoxy resin, and uniformly mixing to obtain a core material;
dissolving the corrosion inhibitor in ultrapure water, adding the core material, and uniformly mixing to prepare a composite emulsion;
respectively adding a prepolymer, a curing agent and a reaction promoter into the composite emulsion, uniformly mixing to obtain a microcapsule pre-synthesized emulsion system, heating the system and adjusting the pH, and obtaining a microcapsule product after the reaction is finished;
and filtering, washing and drying the microcapsule product to obtain the composite graphene microcapsule.
In some embodiments, the step of obtaining a prepolymer comprises: regulating the pH value to 7-8 by triethanolamine, heating to 50-100 ℃ by water bath, reacting for 0.5-3 h, and preparing a prepolymer, wherein the mass ratio of formaldehyde to urea is 1-8: 1.
In some embodiments, the step of making the core material comprises: adding graphene into epoxy resin, and performing ball milling by using a ball mill at the ball milling speed of 200-800 rpm for 0.5-3 h to obtain the core material.
In some embodiments, the step of making the composite emulsion comprises: dissolving the corrosion inhibitor in ultrapure water, adding the core material, uniformly mixing at a stirring speed of 300-1000 rpm for 0.5-3 h to prepare the composite emulsion.
In some embodiments, the step of obtaining the microcapsule product comprises: and (3) heating the system to 30-80 ℃, wherein the heating time is 0.5-2 h, adjusting the pH to 2-5 by adopting hydrochloric acid, and reacting for 1-8 h to obtain a microcapsule product.
In some embodiments, the corrosion inhibitor comprises one or more of sodium tungstate, sodium molybdate, potassium chromate, sodium nitrite, benzimidazole, sodium polyphosphate, benzothiazole, or sodium dodecyl benzene sulfonate.
In some embodiments, the curing agent comprises resorcinol and the reaction promoter comprises ammonium chloride.
In a second aspect, the invention also provides a composite graphene microcapsule prepared by the preparation method.
In a third aspect, the invention also provides an application of the composite graphene microcapsule in a steel coating.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation method of the composite graphene microcapsule, provided by the invention, urea is dissolved in formaldehyde, the pH is adjusted to be alkaline, and a prepolymer is obtained after heating and stirring; adding graphene into epoxy resin, and uniformly mixing to obtain a core material; dissolving the corrosion inhibitor in ultrapure water, adding the core material, and uniformly mixing to prepare a composite emulsion; respectively adding a prepolymer, a curing agent and a reaction promoter into the composite emulsion, uniformly mixing to obtain a microcapsule pre-synthesized emulsion system, heating the system and adjusting the pH, and obtaining a microcapsule product after the reaction is finished; and filtering, washing and drying the microcapsule product to obtain the composite graphene microcapsule. The preparation method is simple and low in cost.
2. According to the composite graphene microcapsule provided by the invention, the composite graphene microcapsule is applied to a steel coating by loading graphene and a corrosion inhibitor by using a microcapsule technology, so that the corrosion resistance of the damaged steel of the coating is improved, the service life of the steel in a high-acid, high-alkali and high-salt environment is prolonged, the service life of a base material is prolonged, and the use amount of the coating is reduced.
Drawings
Fig. 1 is a scanning electron microscope image of a composite graphene microcapsule 1# provided by an embodiment of the present invention;
fig. 2 is a scanning electron microscope image of composite graphene microcapsule 2# provided by an embodiment of the present invention;
fig. 3 is a raman spectrum of composite graphene microcapsule 2# provided in the embodiment of the present invention;
fig. 4 is a graph of immersion resistance of a substrate containing a composite type graphene microcapsule 1# coating provided by an embodiment of the present invention;
fig. 5 is a graph of immersion resistance of a substrate containing a composite graphene microcapsule # 2 coating according to an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The invention provides a preparation method of a composite graphene microcapsule, which comprises the following steps:
the method comprises the following steps: dissolving urea into formaldehyde, adjusting the pH value to be alkaline, and heating and stirring to obtain a prepolymer; according to the invention, triethanolamine is adopted to adjust the pH value to 7-8, the mixture is heated to 50-100 ℃ in water bath, and after reaction is carried out for 0.5-3 h, a prepolymer is prepared, wherein the mass ratio of formaldehyde to urea is 1-8: 1;
step two: adding graphene into epoxy resin, and uniformly mixing to prepare a core material, wherein the method specifically comprises the following steps: adding graphene into epoxy resin, and performing ball milling by using a ball mill at the ball milling speed of 200-800 rpm for 0.5-3 h to prepare a core material;
step three: dissolving the corrosion inhibitor in ultrapure water, adding the core material, and uniformly mixing to prepare the composite emulsion, wherein the preparation method specifically comprises the following steps: dissolving a corrosion inhibitor in ultrapure water, adding a core material, uniformly mixing at a stirring speed of 300-1000 rpm for 0.5-3 h to prepare a composite emulsion; the corrosion inhibitor comprises one or more of sodium tungstate, sodium molybdate, potassium chromate, sodium nitrite, benzimidazole, sodium polyphosphate, benzothiazole or sodium dodecyl benzene sulfonate, but is not limited to the above;
step four: respectively adding the prepolymer, the curing agent and the reaction accelerator into the composite emulsion, uniformly mixing to obtain a microcapsule pre-synthesis emulsion system, heating the system to 30-80 ℃, wherein the heating time is 0.5-2 h, adjusting the pH to 2-5 by adopting hydrochloric acid, and reacting for 1-8 h to obtain a microcapsule product. It should be noted that, the curing agent may be resorcinol, and the reaction promoter may be ammonium chloride, but the invention is not limited thereto;
step five: and filtering, washing and drying the microcapsule product to obtain the composite graphene microcapsule.
In some embodiments, the method further comprises adding an emulsifier, wherein the graphene is added in 0.1-2% by mass, the epoxy resin is added in 1-10%, the corrosion inhibitor is added in 0.01-1%, and the emulsifier is added in 0.1-10%, preferably, the emulsifier can be one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, OP-10 or Tween 80.
The invention also provides a composite graphene microcapsule prepared by the preparation method. The composite graphene microcapsule can be applied to steel coatings by those skilled in the art.
The composite graphene microcapsule is applied to the steel coating by loading graphene and a corrosion inhibitor by utilizing a microcapsule technology, and is used for improving the corrosion resistance of the damaged steel of the coating and prolonging the service life of the steel in a high-acid, high-alkali and high-salt environment, so that the service life of a base material is prolonged, and the using amount of a coating is reduced.
The composite graphene microcapsule of the present invention, and the preparation method and the application thereof are described in detail below with specific embodiments.
The experimental methods used in the following examples are not specifically described, and the materials, reagents and the like used in the following examples are generally commercially available under the usual conditions unless otherwise specified.
Comparative example 1
(1) Preparation of a prepolymer: dissolving 8.64 g of urea into 25.12 g of formaldehyde, adding 2 drops of triethanolamine, adjusting the pH value to 7, and stirring for 1h in a water bath at 60 ℃ to prepare a prepolymer;
(2) preparation of a core material: adding 0.05 g of graphene into 5 g of epoxy resin, and performing ball milling for 1.5 h by using a ball mill at the speed of 400 rpm to obtain a core material;
(3) preparing a composite emulsion: uniformly dissolving 1.2 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 100 mL of ultrapure water, then adding the core material, and stirring at 500 rpm for 1h to obtain a composite emulsion;
(4) preparation of microcapsule product: slowly titrating the prepolymer, resorcinol and ammonium chloride into the composite emulsion by using a burette, uniformly mixing, slowly heating the composite emulsion system to 60 ℃ within 1h, then adjusting the pH to 4 by using hydrochloric acid, and reacting for 4 h;
(5) preparing a composite graphene microcapsule: and filtering the microcapsule product, washing the filtered product with clear water and alcohol for three times respectively, and drying the product to obtain the pure graphene microcapsule # 1.
Example 1
(1) Preparation of a prepolymer: dissolving 10.04 g of urea into 25.12 g of formaldehyde, adding 3 drops of triethanolamine, adjusting the pH value to 7.8, and stirring for 1 hour in a 70 ℃ water bath to prepare a prepolymer;
(2) preparation of a core material: adding 0.05 g of graphene and 0.025 g of sodium tungstate into 5 g of epoxy resin, and performing ball milling for 1 hour by using a ball mill at the speed of 300 rpm to obtain a core material;
(3) preparing a composite emulsion: uniformly dissolving 1 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 100 mL of ultrapure water, then adding the core material, and stirring at 600 rpm for 1h to obtain a composite emulsion;
(4) preparation of microcapsule product: slowly titrating the prepolymer, resorcinol and ammonium chloride into the composite emulsion by using a burette, uniformly mixing, slowly heating the composite emulsion system to 55 ℃ within 1h, then adjusting the pH to 3.5 by using hydrochloric acid, and reacting for 4 h;
(5) preparing a composite graphene microcapsule: and filtering the microcapsule product, washing the filtered product with clear water and alcohol for three times respectively, and drying the product to obtain the pure composite (graphene and sodium tungstate) graphene microcapsule 2 #.
Comparative example 2
(1) Preparation of a prepolymer: dissolving 8.64 g of urea into 25.12 g of formaldehyde, adding 2 drops of triethanolamine, adjusting the pH value to 7.5, and stirring for 1h in water bath at 60 ℃ to prepare a prepolymer;
(2) preparation of a core material: adding 0.05 g of graphene into 5 g of epoxy resin, and performing ball milling for 1.5 h by using a ball mill at the speed of 200 rpm to obtain a core material;
(3) preparing a composite emulsion: uniformly dissolving 1.2 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 100 mL of ultrapure water, then adding the core material, and stirring at 600 rpm for 1h to obtain a composite emulsion;
(4) preparation of microcapsule product: slowly titrating the prepolymer, resorcinol and ammonium chloride into the composite emulsion by using a burette, uniformly mixing, slowly heating the composite emulsion system to 60 ℃ within 1h, then adjusting the pH to 2.5 by using hydrochloric acid, and reacting for 4 h;
(5) preparing a composite graphene microcapsule: and filtering the microcapsule product, washing the filtered product with clear water and alcohol for three times respectively, and drying the product to obtain the pure graphene microcapsule # 3.
Example 2
(1) Preparation of a prepolymer: dissolving 10.04 g of urea into 28.26 g of formaldehyde, adding 2 drops of triethanolamine, adjusting the pH value to 8, and stirring for 1h in water bath at 85 ℃ to prepare a prepolymer;
(2) preparation of a core material: adding 0.05 g of graphene and 0.03g of sodium tungstate into 5 g of epoxy resin, and performing ball milling for 1 hour by using a ball mill at the speed of 300 rpm to obtain a core material;
(3) preparing a composite emulsion: uniformly dissolving 1 g of Sodium Dodecyl Benzene Sulfonate (SDBS) in 100 mL of ultrapure water, then adding the core material, and stirring at 700 rpm for 1h to obtain a composite emulsion;
(4) preparation of microcapsule product: slowly titrating the prepolymer, resorcinol and ammonium chloride into the composite emulsion by using a burette, uniformly mixing, slowly heating the composite emulsion system to 55 ℃ within 1h, then adjusting the pH to 3.5 by using hydrochloric acid, and reacting for 4 h;
(5) preparing a composite graphene microcapsule: and filtering the microcapsule product, washing the filtered product with clear water and alcohol for three times respectively, and drying the product to obtain the pure composite (graphene and sodium tungstate) graphene microcapsule 4 #.
Performance testing
The graphene microcapsules 1# and the composite graphene microcapsules 2# prepared in comparative example 1 and example 1 were subjected to a scanning electron microscope test.
Scanning Electron Microscope (SEM) images of the graphene microcapsule 1# can be obtained through SEM experiments, and as shown in fig. 1, it can be seen that the graphene microcapsule 1# is in a relatively regular spherical shape, has a relatively uniform size, and has a clear boundary. As shown in fig. 2, a Scanning Electron Microscope (SEM) picture of the composite graphene microcapsule 2# also shows that the composite graphene microcapsule 2# is relatively regular spherical, uniform in size and clear in boundary. As can be understood by those skilled in the art, the scanning electron microscope images of the graphene microcapsule 1# and the composite graphene microcapsule 2# are not very different.
Application testing
In the present invention, the application test of the graphene microcapsule 1# and the composite type graphene microcapsule 2# in the above comparative example 1 and example 1 is performed to study the application effect of the composite type graphene microcapsule, specifically, the test steps are as follows:
step 1: substrate pretreatment
Taking one bottom surface of a 316 steel cylinder with the diameter of 18 mm as a substrate, polishing the coating surface from coarse to fine by using 80-1200 mesh abrasive paper to remove oxides on the surface of the steel, wiping the steel substrate by using alcohol-soaked absorbent cotton, and cleaning the steel substrate by using ultrasonic waves. The other surface and the side surface of the steel cylinder are sealed by epoxy resin;
and 2, step: respectively adding the graphene microcapsule 1# and the composite graphene microcapsule 2# into an epoxy resin coating according to the content of 2 wt%, and ultrasonically dispersing for 5 min to remove air bubbles in the coating to respectively prepare the coating containing the graphene microcapsule 1# and the composite graphene microcapsule 2 #;
and 3, step 3: and (2) uniformly coating the prepared coating containing the graphene microcapsule 1# and the coating containing the composite graphene microcapsule 2# on the bottom surface of the steel cylinder obtained in the step (1) by using a four-side coating device, and simultaneously, uniformly coating the coating not containing the composite graphene microcapsule on the bottom surface of the steel cylinder obtained in the step (1) to be used as a blank experiment, so as to prepare a coating with the thickness of 80 +/-5 micrometers, and drying the coating for two days at room temperature.
After the drying is finishedThen, the substrate containing the coating layer of the graphene microcapsule 1# is soaked, and the soaking resistance is shown in fig. 4, and as can be seen from fig. 4, the initial resistance of the coating layer reaches 8.97 × 108 Ω·cm2In the subsequent soaking process, the graphene has good barrier effect once, so that the impedance is 1.47 multiplied by 108 Ω·cm2Is lifted to 4.62 multiplied by 108 Ω·cm2In the blank experiment, when the coating not containing the composite graphene microcapsules is also uniformly coated on the bottom surface of the steel cylinder as a blank coating, the impedance is 6.52 × 107 Ω·cm2And the service life of the paint containing the composite graphene microcapsule No. 1 is about 2.5 times of that of a blank coating.
Similarly, the substrate coated with the composite graphene microcapsule 2# containing graphene and sodium tungstate is soaked, and the soaking impedance is shown in fig. 5, and as can be seen from fig. 5, the initial impedance of the coating is as high as 3.56 × 109 Ω·cm2In the 20-60 d process, the impedance of the coating of the composite graphene microcapsule 2# coating containing graphene and sodium tungstate is raised to 10 DEG8And thus extends the coating life. The service life of the paint after the paint is added is about 4 times of that of a blank coating.
The invention carries out performance measurement on the composite type graphene microcapsule 2# so as to research the synthesis effect of the composite type graphene microcapsule 2#, and the Raman spectra are shown in figure 3, and can be seen from the figure and are respectively positioned at 1350 cm-1And 1580 cm-1There are two characteristic peaks of graphene, indicating that the graphene sheets are successfully encapsulated in the microcapsules.
Dissolving urea into formaldehyde, adjusting the pH value to be alkaline, and heating and stirring to obtain a prepolymer; adding graphene into epoxy resin, and uniformly mixing to obtain a core material; dissolving the corrosion inhibitor in ultrapure water, adding the core material, and uniformly mixing to prepare a composite emulsion; respectively adding a prepolymer, a curing agent and a reaction accelerator into the composite emulsion, uniformly mixing to obtain a microcapsule pre-synthesized emulsion system, heating the system and adjusting the pH value, and obtaining a microcapsule product after the reaction is finished; and filtering, washing and drying the microcapsule product to obtain the composite graphene microcapsule. The preparation method is simple and low in cost.
The composite graphene microcapsule is applied to the steel coating by loading graphene and a corrosion inhibitor by utilizing a microcapsule technology, and is used for improving the corrosion resistance of the damaged steel of the coating and prolonging the service life of the steel in a high-acid, high-alkali and high-salt environment, so that the service life of a base material is prolonged, and the using amount of a coating is reduced.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a composite graphene microcapsule is characterized by comprising the following steps:
dissolving urea into formaldehyde, adjusting the pH value to be alkaline, and heating and stirring to obtain a prepolymer;
adding graphene into epoxy resin, and uniformly mixing to obtain a core material;
dissolving the corrosion inhibitor in ultrapure water, adding the core material, and uniformly mixing to prepare a composite emulsion;
respectively adding a prepolymer, a curing agent and a reaction promoter into the composite emulsion, uniformly mixing to obtain a microcapsule pre-synthesized emulsion system, heating the system and adjusting the pH, and obtaining a microcapsule product after the reaction is finished;
and filtering, washing and drying the microcapsule product to obtain the composite graphene microcapsule.
2. The preparation method of the composite graphene microcapsule according to claim 1, wherein the step of obtaining a prepolymer comprises: dissolving urea into formaldehyde, adjusting the pH value to 7-8 by using triethanolamine, heating to 50-100 ℃ by using water bath, and reacting for 0.5-3 h to obtain a prepolymer, wherein the mass ratio of the formaldehyde to the urea is 1-8: 1.
3. The preparation method of the composite graphene microcapsule according to claim 1, wherein the step of adding graphene into epoxy resin and uniformly mixing to prepare the core material comprises: adding graphene into epoxy resin, and performing ball milling by using a ball mill at the ball milling speed of 200-800 rpm for 0.5-3 h to obtain the core material.
4. The preparation method of the composite graphene microcapsule according to claim 1, wherein the step of preparing the composite emulsion comprises: dissolving the corrosion inhibitor in ultrapure water, adding the core material, uniformly mixing at the stirring speed of 300-1000 rpm for 0.5-3 h to obtain the composite emulsion.
5. The method for preparing composite graphene microcapsules according to claim 1, wherein the step of obtaining a microcapsule product comprises: and (3) heating the system to 30-80 ℃, wherein the heating time is 0.5-2 h, adjusting the pH to 2-5 by adopting hydrochloric acid, and reacting for 1-8 h to obtain a microcapsule product.
6. The method for preparing the composite graphene microcapsule according to claim 1, wherein the step of preparing the core material comprises: and adding graphene and sodium tungstate into epoxy resin, and performing ball milling by using a ball mill at the ball milling speed of 200-800 rpm for 0.5-3 h to obtain the core material.
7. The preparation method of the composite graphene microcapsule according to claim 1, wherein the corrosion inhibitor comprises one or more of sodium tungstate, sodium molybdate, potassium chromate, sodium nitrite, benzimidazole, sodium polyphosphate, benzothiazole or sodium dodecyl benzene sulfonate.
8. A method for preparing composite graphene microcapsules according to claim 1, wherein the curing agent comprises resorcinol, and the reaction promoter comprises ammonium chloride.
9. A composite graphene microcapsule prepared by the preparation method of any one of claims 1 to 8.
10. The use of the composite graphene microcapsules of claim 9 in steel coatings.
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