CN112080190A

CN112080190A - Heavy-duty anticorrosive and antifouling paint with ultrahigh barrier and shielding properties and preparation method thereof

Info

Publication number: CN112080190A
Application number: CN202010983755.3A
Authority: CN
Inventors: 慕雷
Original assignee: BEIJING MUCHEN FIREPROOF HEAT INSULATION SPECIAL MATERIALS CO LTD
Current assignee: BEIJING MUCHEN FIREPROOF HEAT INSULATION SPECIAL MATERIALS CO LTD
Priority date: 2020-09-18
Filing date: 2020-09-18
Publication date: 2020-12-15
Also published as: WO2022057165A1

Abstract

A heavy-duty anticorrosive antifouling coating with ultrahigh barrier property and shielding property and a preparation method thereof are A, B bi-component systems, wherein the component A comprises resin, active diluent, a composite magnetic two-dimensional graphene nano sheet guided by magnetic field magnetization, anticorrosive pigment, wetting agent, defoaming agent and dispersing agent, and the mass ratio of each component is as follows: 10-30: 10-20: 5-10: 5-10: 1-2: 1-2: 1-2, the component B is a curing agent, and the ratio of the A, B components is 1.8-2.2: 1. The graphene magnetized by the magnetic field of the magnetic substance is adopted, and the material is guided by the magnetic field on the molecular scale. Due to the realization of the orientation of the flake graphene, the characteristic of graphene barrier shielding can be realized, the function of a labyrinth effect can be provided, the magnetic graphene can be fully applied to various application environments with the product requirements of prevention, protection, shielding, separation, resistance and shielding, and the barrier shielding of the material added with the magnetic graphene on moisture, adverse factors of a moisture environment and microbial bacteria is greatly improved.

Description

Heavy-duty anticorrosive and antifouling paint with ultrahigh barrier and shielding properties and preparation method thereof

Technical Field

The invention relates to a coating, in particular to a coating used in an extreme environment.

Background

At present, the global demand for corrosion prevention and decontamination (biology) of materials in special environments and extreme environments is higher and higher, and in addition, the demand for wear resistance and weather resistance protection of extremely fast and deep appliance and equipment materials is also high.

Graphene and MXene are two-dimensional nanoscale sheets, excellent mechanical, electrical, electrochemical and thermodynamic properties of the graphene and MXene are used for various products at present, and after the graphene and MXene are combined with materials, the distribution of the graphene and MXene in molecular sizes is Random and uncontrollable and non-directional, so that the high-efficiency barrier property and shielding property cannot be realized, and the performance of the graphene and MXene on weather resistance still cannot meet the requirements of extreme environments.

Disclosure of Invention

In order to solve the use problem of the coating in an extreme environment, the invention provides a heavy-duty anticorrosive antifouling coating of magnetostrictive guiding graphene with ultrahigh barrier shielding property and a preparation method thereof.

The technical scheme of the invention is as follows:

the heavy-duty anticorrosive antifouling paint with ultrahigh barrier property and shielding property is characterized in that the paint is an A, B bi-component system, the component A comprises resin, active diluent, a composite magnetic two-dimensional graphene nano sheet guided by magnetic field magnetization, anticorrosive pigment, wetting agent, defoaming agent and dispersing agent, and the mass ratio of each component is as follows: 10-30: 10-20: 5-10: 5-10: 1-2: 1-2: 1-2, wherein the component B is a curing agent, the composite magnetic two-dimensional graphene nano sheet is a composite material of an OMMT montmorillonite nano material and graphene, the mass fraction of the graphene is 0.08-0.12%, the mass fraction of the OMMT montmorillonite nano material is 99.92-99.88, and the ratio of the components A, B is 1.8-2.2: 1.

Preferably, the graphene is RGO.

Preferred such resins are (bisphenol a) epoxy resins, alkyd resins, polyurethane and/or acrylic resins.

Further preferred is that the resin is a solventless (bisphenol a) epoxy resin.

Further preferably, the reactive diluent is a monofunctional or polyfunctional amine or glyceryl ether organic molecule reactive diluent.

Preferably, the composite magnetic two-dimensional graphene nano-sheet is a functionalized graphene composite material intercalated by iron ions and guided in a magnetic field.

Further preferred said functionalization is activation with the surfactants KH-550, 560, Tween 80, Triton-100 and/or SDBS.

Further preferably, the curing agent comprises one or more of aliphatic polyamine, alicyclic polyamine, low molecular weight polyamide, polyether polyol and modified aromatic amine.

The preferable anticorrosive pigment is one or more of zinc phosphate, white phosphate, iron oxide red, zinc oxide, mica iron oxide and zinc powder.

The preparation method of the coating is characterized by firstly preparing a composite magnetic two-dimensional graphene nano sheet with magnetic orientation and functionalization, utilizing an iron ion solution to intercalate iron ions into the graphene, realizing magnetic orientation through magnetic field induction, then adding a surfactant to activate the graphene, and mixing the graphene with OMMT;

then uniformly mixing resin, reactive diluent, the magnetic field magnetization-oriented composite magnetic two-dimensional graphene nano sheet, anticorrosive pigment, wetting agent, defoaming agent and dispersing agent;

and mixing the AB component at normal temperature for curing.

The invention has the following technical effects:

the invention adopts the functionalized graphene magnetized by the magnetic field of the magnetic substance, and the material is provided with orientation on the molecular scale by the magnetic field. Due to the realization of the orientation of the flake graphene, the characteristic of graphene barrier shielding can be realized, the function of a labyrinth effect can be provided, the magnetic graphene can be fully applied to various application environments with the product requirements of prevention, protection, shielding, separation, resistance and shielding, and the barrier shielding of the material added with the magnetic graphene on moisture, adverse factors of a moisture environment and microbial bacteria is greatly improved. The functional filler OMMT active montmorillonite is supplemented, is a nano-sheet material and can play a labyrinth role. Magnetic graphene (directional) and OMMT (random direction) are shared in the coating, so that a high-barrier and high-shielding labyrinth effect can be achieved, the anti-corrosion effect is further improved, the stability and dispersion of a system are guaranteed by using the magnetic graphene as a matrix, and the graphene can be prevented from agglomerating under the proportion of the invention. The RGO reduced graphene oxide system was chosen to be the most stable and the best results.

In addition, the magnetized graphene sheets are added with the anticorrosive coating, the conductivity of the anticorrosive coating and the barrier property of a labyrinth formed by the same orientation greatly improve the anticorrosive effect of the material.

The reactive diluent added may be a dilute coating system to adjust consistency.

In addition, the original organic small molecules also participate in the curing reaction to improve the crosslinking degree.

Drawings

Fig. 1 is a comparison of before and after the orientation of graphene platelet sheets;

FIG. 2 is a polarization curve of graphene composite coatings with different contents in a 3.5% NaCl solution;

fig. 3 is an ac impedance curve of graphene composite coatings with different contents in 3.5% NaCl solution.

Examples

For a better understanding of the present invention, the present invention is further explained below with reference to specific embodiments.

Example 1

Preparation of component A

Firstly, preparing graphene with magnetic orientation and functionalization, intercalating iron ions into RGO graphene by utilizing ferric chloride and the like, realizing magnetic orientation through magnetic field induction, and then adding a surfactant KH-550 to activate the graphene. Magnetic field guidance before and after as shown in fig. 1, the maximum magnetic field of 30mTSA, perpendicular to the direction of penetration, was then mixed with OMMT.

Then 25 parts of bisphenol A epoxy resin, 12 parts of alcohol acid glycidyl ether serving as an active diluent, 10 parts of composite magnetic two-dimensional graphene nano-sheets (graphene: OMMT, 0.1% of graphene and 99.9% of OMMT) guided by magnetic field magnetization, 10 parts of anti-corrosion pigment zinc oxide and 5 parts of defoaming, wetting and dispersing aids are mixed uniformly by a batch double-slurry mixer. Dispersing agent, wetting agent and defoaming agent are all materials used in common commercial coating.

Component B

Low molecular weight polyamides.

The AB component is mixed and cured at normal temperature according to the mass fraction of 2:1 to obtain a product, and the product has excellent benefits of corrosion resistance and biological pollution resistance.

Example 2

Preparation of component A

The procedure for preparing the magnetically oriented and functionalized graphene is similar to example 1.

25 parts of MDI, 18 parts of alcohol acid glycidyl ether serving as an active diluent, 8 parts of composite magnetic two-dimensional graphene nano sheets (graphene: OMMT, 0.1% of graphene and 99.9% of OMMT) guided by magnetic field magnetization, 10 parts of zinc phosphate serving as an anticorrosive pigment, 2 parts of an antifoaming agent, 1 part of a wetting agent and 2 parts of an antifoaming agent, which are put in batches and uniformly mixed. Dispersing agent, wetting agent and defoaming agent are all materials used in common commercial coating.

Component B

Polyether polyol PEG-400.

Comparative example

The method is different from the method in that the graphene in the magnetic field magnetization-oriented composite magnetic two-dimensional graphene nanosheets is 0, 0.05%, 0.15%, 0 and 2%.

The corrosion resistance test is carried out by adopting the embodiment and the comparative example, the comparative example with the addition of 0.05 percent of graphene has the most serious corrosion of the coating, a large amount of corrosion marks exist at the scratch, and the corrosion degree is more serious than that of the coating before the modification of the graphene. The fact that when a small amount of graphene is added, the graphene is not enough to form a physical isolation layer in a coating, the corrosion is serious, and the corrosion of a substrate can be even accelerated. With the addition of 0.1% of the coating of the example, the coating also has corrosion phenomena, but the corrosion degree is light, the corrosion spread degree at the gap is small, and the coating does not warp or bubble integrally. Probably because the content of the graphene is increased at the moment, the physical barrier effect of the graphene in the coating is increased, an effective physical barrier layer is formed, and the corrosion is slowed down. The coatings of the comparative examples, which are 0.15% and 0.2%, are added, the area of the corrosion expanding to the periphery is large at the scratch, the rust spots are also formed at the scratch, and the coating is tilted, which shows that the coating is thick due to the excessively high addition of graphene, the graphene is easy to disperse in the coating, the mechanical property of part of the area of the paint film is reduced, the adhesion between the coating and the substrate is reduced, and the corrosion expanding is serious.

FIG. 2 is a 1cm view²And soaking the thermal reduction graphene composite coatings with different contents in 3.5% NaCl solution at 27 +/-2 ℃ to obtain a Tafel polarization curve. Table 1 shows the calculation results of the polarization curves of the graphene composite coatings with different contents. As can be seen from fig. 2, compared with the composite coating before graphene modification, the corrosion resistance of the coating after graphene addition is enhanced. The corrosion potential of the composite coating without the added graphene is-1.50V, after the added graphene, the corrosion potential of the composite coating gradually rises, when RGO is added by 0.1%, the self-corrosion potential of the composite coating is-0.90V, compared with the coating without the added graphene, the self-corrosion potential of the coating is improved by 0.60V, and when RGO is-0%, the self-corrosion current of the composite coating is 0.79 muA/cm 2, when 0.1% RGO is added, the corrosion current density of the composite coating is reduced to 0.07 muA/cm 2, and the corrosion current density is reduced by nearly 12 times compared with the coating without the added graphene, so that the corrosion resistance of the coating can be greatly improved by adding a small amount of graphene. When the amount of graphene added is 0.15%, the self-corrosion potential of the coating does not change much as compared with RGO-0.1%, but the corrosion current density of the coating changes greatly at this time, and the corrosion resistance of the coating is lowered. Therefore, when the content of graphene in the composite coating is 0.1%, the corrosion resistance is optimal.

TABLE 1 calculation results of polarization curves of graphene composite coatings with different contents

FIG. 3 is an area of 1cm²The sample was immersed in NaCl of 3.5% concentration, and an ac impedance graph of the sample was measured using the sample as a working electrode, a platinum electrode as an auxiliary electrode, and a saturated calomel electrode as a reference electrode. As can be seen from the figure, each coating presents a single capacitive arc which can represent the electrode proceeding process in the system, and in the initial stage, the coating is in a dry state and has a high water absorption rate, so that the capacitance increase amplitude is high, and the coating is saturated and the capacitance change is gentle. The radius of the curve (c) in the figure is the largest, indicating that the corrosion resistance of the composite coating is the largest when the graphene addition amount is 0.1%. The graphene is added into the composite coating within a certain range, so that the corrosion resistance of the coating can be improved to a great extent, when the addition amount of the graphene is less than 0.1%, the corrosion resistance of the composite coating is improved along with the increase of the content of the graphene, but when the addition amount of the graphene is 0.15%, the corrosion resistance of the composite coating is greatly reduced, probably because the graphene is agglomerated, the surface of the coating has defects, corrosive ions can quickly reach a substrate, and the metal surface is corroded. It can be seen that the ac impedance spectrum results are consistent with those obtained from tafel polarization curves.

It is pointed out here that the above description is helpful for the person skilled in the art to understand the content of the invention, but does not limit the scope of protection of the invention. Any such equivalents, modifications and/or omissions as may be made without departing from the spirit and scope of the invention may be resorted to.

Claims

1. The heavy-duty anticorrosive antifouling paint with ultrahigh barrier property and shielding property is characterized by being an A, B bi-component system, wherein the component A comprises resin, active diluent, a composite magnetic two-dimensional graphene nano sheet guided by magnetic field magnetization, anticorrosive pigment, a wetting agent, a defoaming agent and a dispersing agent, and the mass ratio of the components is as follows: 10-30: 10-20: 5-10: 5-10: 1-2: 1-2: 1-2, wherein the component B is a curing agent, the composite magnetic two-dimensional graphene nano sheet is a composite material of an OMMT montmorillonite nano material and graphene, the mass fraction of the graphene is 0.08-0.12%, the mass fraction of the OMMT montmorillonite nano material is 99.92-99.88, and the ratio of the components A, B is 1.8-2.2: 1.

2. The coating according to claim 1, characterized in that the resin is a bisphenol a epoxy resin, an alkyd resin, a polyurethane and/or an acrylic resin.

3. The coating according to claim 2, characterized in that the resin is a solventless bisphenol a epoxy resin.

4. The coating according to claim 1, characterized in that the reactive diluent is a monofunctional or polyfunctional amine, or a glycerol ether-based organic molecular reactive diluent.

5. The coating according to claim 1, characterized in that the composite magnetic two-dimensional graphene nanosheets are functionalized graphene composites oriented in a magnetic field via intercalation of iron ions.

6. The coating according to claim 5, characterized in that the functionalization is activated using the surfactants KH-550, 560, Tween 80, Triton-100 and/or SDBS.

7. The coating of claim 1, wherein the curing agent comprises one or more of aliphatic polyamines, cycloaliphatic polyamines, low molecular weight polyamides, polyether polyols, and modified aromatic amines.

8. The paint of claim 1, wherein the anticorrosive pigment is one or more of zinc phosphate, white phosphate, iron oxide red, zinc oxide, mica iron oxide and zinc powder.

9. The coating according to claim 1, characterized in that the graphene employs RGO.

10. The preparation method of the coating material according to any one of claims 1 to 9, characterized in that a magnetically oriented and functionalized composite magnetic two-dimensional graphene nanosheet is first prepared, a solution of iron ions is used to intercalate iron ions into graphene, magnetic orientation is achieved by magnetic field induction, then a surfactant is added to activate graphene, and then the graphene is mixed with OMMT;

and mixing the AB component at normal temperature for curing.