A graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating and preparation method thereof

Abstract

The present invention discloses a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating and a preparation method thereof, which belongs to the technical field of water-based heavy-duty anticorrosion coatings and comprises the following raw materials: polyamine chelating agent, graphene oxide, acrylic acid and its derivatives, Ti(SO4)2, intrinsic graphene, silicon micropowder, and curing agent; the anticorrosion coating is prepared using the above materials, and the steps are: S1, preparing acrylic resin modified by graphene oxide; S2, preparing graphene-modified nano-silicon-titanium composite filler; S3, preparing graphene-modified nano-silicon-titanium water-based anticorrosion coating. The present invention adopts the above-mentioned graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating and a preparation method thereof to solve the dispersion problem when silicon-titanium is used as an anticorrosion material, and proposes an anticorrosion coating with excellent anticorrosion performance, strong adhesion, and good dispersion performance.

Description

Technical Field

[0001] The invention relates to the technical field of water-based heavy-duty anti-corrosion coatings, and in particular to a graphene-modified nano-silicon-titanium water-based heavy-duty anti-corrosion coating and a preparation method thereof. Background Art

[0002] Silicon (Si), titanium (Ti) and their alloys can be widely used in the field of corrosion protection due to their superior mechanical properties, good biocompatibility and corrosion resistance. However, their dispersion problem has been difficult to solve due to their surface inertness and nanometer size.

[0003] Graphene is a two-dimensional carbon nanomaterial composed of carbon atoms in a hexagonal honeycomb lattice with sp2 hybrid orbitals

[13] . Graphene has many excellent properties, such as the highest hardness, with a strength of 130GPa and an elastic modulus of 1Tpa. In addition, graphene's physical properties are also very superior, such as a conductivity of up to 6*105S / m, a thermal conductivity of 5000W / mK, and a surface area of ​​2600m2 / g. Graphene and graphene derivatives with a large surface area have good hydrophobicity, chemical resistance, stability and high mechanical strength, and can be used as good additives in anti-corrosion coatings.

[0004] However, in the prior art, there are two ways to composite nano-silicon titanium and carbon: one is through physical shearing, and the other is through high-temperature composite; both methods have certain disadvantages. Through physical shearing, the uniformity of the composite is difficult to ensure, while the high-temperature method has high energy consumption and cannot be mass-produced.

[0005] In order to solve the surface inertness and dispersion problems of silicon and titanium when used as anti-corrosion materials, and to improve the composite method of nano silicon titanium and carbon in the prior art, the present invention provides a graphene-modified nano silicon titanium water-based heavy-duty anti-corrosion coating and a preparation method thereof. Summary of the invention

[0006] The purpose of the present invention is to provide a graphene-modified nano-silicon-titanium water-based heavy-duty anti-corrosion coating and a preparation method thereof, so as to solve the dispersion problem when silicon-titanium is used as an anti-corrosion material, and to propose an anti-corrosion coating with excellent anti-corrosion performance, strong adhesion and good dispersion performance.

[0007] To achieve the above object, the present invention provides a graphene-modified nano-silicon-titanium water-based anti-corrosion coating, comprising the following raw materials:

[0008] Polyamine chelating agent, graphene oxide, acrylic acid and its derivatives, Ti(SO4)2, intrinsic graphene, silicon micropowder, and curing agent.

[0009] Preferably, the mass numbers of the polyamine chelating agent, the Ti(SO4)2 and the silicon powder are all 1-10 mass parts, and the mass number of the intrinsic graphene is 0.1-5 mass parts.

[0010] Preferably, the polyamine chelating agent is one or more of EDTA and DTPA.

[0011] Preferably, the graphene oxide refers to graphene with a C / O ratio of less than 0.8, 1-5 layers, and a flake size of 0.1-3 μm; the intrinsic graphene refers to graphene with a C / O ratio of greater than 40, 1-10 layers, and a flake size of 0.1-5 μm.

[0012] Preferably, the acrylic acid and its derivatives are one or more of acrylic acid, hydroxyacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and octyl acrylate.

[0013] Preferably, the silicon powder has a particle size of 0.1-1 μm and a purity greater than 95%.

[0014] Preferably, the curing agent is a water-based curing agent, and the water-based curing agent is one or more of water-based methyl etherified amino resin, butyl etherified amino resin, or water-based TDI and HDI.

[0015] A method for preparing a graphene-modified nano-silicon-titanium water-based anticorrosive coating comprises the following steps:

[0016] S1. Preparation of graphene oxide modified acrylic resin:

[0017] S11, adding 1-10 parts of a polyamine chelating agent to a 1-5% by mass graphene oxide aqueous dispersion, stirring for 10-30 minutes, to obtain polyamino chelating agent modified graphene oxide;

[0018] S12, taking 1-20 parts by mass of a dispersion of polyamino chelating agent-modified graphene oxide, adding it to acrylic acid and its derivative monomers, stirring for 10-30 minutes, adding a certain amount of initiator, and obtaining graphene oxide-modified acrylic resin;

[0019] S2, preparing graphene-modified nano-silicon-titanium composite filler;

[0020] 1-10 parts by mass of Ti(SO4)2 is dissolved in 100 parts by mass of 1 mol / L sulfuric acid, 0.1-5 parts by mass of intrinsic graphene and 1-10 parts by mass of silicon powder are added, the pH is adjusted to 7 with ammonia water, stirring is continued for 30-60 minutes, and then washed with deionized water and dried to obtain a graphene-modified nano-silicon-titanium composite filler;

[0021] S3, preparing graphene-modified nano-silicon-titanium water-based anti-corrosion coating;

[0022] 1-50 parts by mass of graphene-modified nano-silicon-titanium composite filler, 20-50 parts by mass of graphene oxide-modified acrylic resin, dispersant, leveling agent, thickener, defoamer and curing agent are mixed, and stirred at 40-60° C. for 0.5-2h to obtain a graphene-modified nano-silicon-titanium water-based anticorrosive coating.

[0023] Preferably, the stirring rate in S2 is 100 r / min, and the initiator is a peroxide or an azo initiator.

[0024] Preferably, the dispersant is a surfactant with a benzene ring, and the dispersant is polystyrene sodium sulfate with a mass fraction of 0.05-1%; the leveling agent and defoamer are one or more of polydimethylsiloxane, alkyl-modified organic siloxane, and fluorine-modified acrylate, and their mass fractions are 0.1-1%; the thickener is one or more of an associative alkali swelling thickener or a polyurethane thickener, and their mass fractions are 0.1-2%; the curing agent is a water-based amino resin or a water-based isocyanate curing agent, and their mass fractions are 1%-10%.

[0025] Therefore, the present invention adopts the above-mentioned graphene-modified nano-silicon-titanium water-based heavy-duty anti-corrosion coating and its preparation method, which has the following beneficial effects:

[0026] (1) Excellent anti-corrosion performance: Graphene, as a two-dimensional material, has excellent anti-corrosion performance. The nano-silicon titanium composited on the surface of graphene increases the density of the coating, and it also has excellent anti-corrosion performance. After the acrylic resin and the curing agent are cross-linked, the mechanical properties and anti-corrosion performance of the coating are more superior, thus the corrosion resistance will be further enhanced compared with the single graphene heavy anti-corrosion coating.

[0027] (2) Excellent adhesion: First, the complexation between the chelate and the metal matrix will further increase the bonding strength between the coating and the matrix, so that the resulting coating is denser and has a stronger shielding effect. Secondly, when the corrosive medium conducts and corrodes the matrix, the metal ions that lose electrons are quickly complexed, preventing further corrosion of the substrate after being penetrated by water.

[0028] (3) Excellent dispersibility and stability: In this scheme, graphene oxide is grafted onto acrylic resin, which not only ensures the hydrophilic dispersibility of the coating, but also utilizes graphene oxide to disperse graphene, so that both graphene and graphene oxide have excellent dispersibility in the coating.

[0029] (4) Excellent thermal conductivity: The graphene in this preparation method comes from the acrylic resin on the one hand, and the other part comes from the later addition. In this way, the graphene grafted resin can be used to effectively disperse the later added graphene, thereby improving the thermal conductivity and anti-corrosion properties of the coating.

[0030] (5) Excellent bactericidal performance: Due to the electronic effects of C=O double bonds and ππ conjugation of graphene oxide, the antibacterial effect of the surface of the water-retaining coating is further enhanced.

[0031] The technical solution of the present invention is further described in detail below through embodiments. DETAILED DESCRIPTION

[0032] The technical solution of the present invention is further illustrated by the following examples.

[0033] Example 1

[0034] A method for preparing a graphene-modified nano-silicon-titanium water-based anticorrosive coating comprises the following steps:

[0035] S1. Preparation of graphene oxide modified acrylic resin:

[0036] S11, adding 10 parts of EDTA to a graphene oxide aqueous dispersion having a mass fraction of 1-5%, stirring for 30 minutes to obtain EDTA-modified graphene oxide;

[0037] S12, taking 10 parts by mass of the dispersion of EDTA-modified graphene oxide, adding it to the acrylic acid monomer, stirring for 30 minutes, adding a certain amount of diisopropyl peroxydicarbonate, and obtaining graphene oxide-modified acrylic resin.

[0038] S2, preparing graphene-modified nano-silicon-titanium composite filler;

[0039] Take 10 parts by mass of Ti(SO4)2 and dissolve it in 100 parts of 1 mol / L sulfuric acid, add 5 parts by mass of intrinsic graphene and 10 parts by mass of silicon powder, adjust the pH to 7 with ammonia water and continue stirring for 50 minutes, then wash with deionized water and dry to obtain graphene-modified nano-silicon-titanium composite filler.

[0040] S3, preparing graphene-modified nano-silicon-titanium water-based anti-corrosion coating;

[0041] Take 50 parts by mass of graphene-modified nano-silicon-titanium composite filler, 50 parts by mass of graphene oxide-modified acrylic resin, 0.1% by mass of polystyrene sodium sulfate, 0.2% by mass of polydimethylsiloxane, 0.1% by mass of polyurethane thickener, and 5% by mass of aqueous isocyanate, mix them, stir at 60°C for 2h, and obtain a graphene-modified nano-silicon-titanium water-based anti-corrosion coating.

[0042] Example 2

[0043] A method for preparing a graphene-modified nano-silicon-titanium water-based anticorrosive coating comprises the following steps:

[0044] S1. Preparation of graphene oxide modified acrylic resin:

[0045] S11, adding 1 part of EDTA to a graphene oxide aqueous dispersion having a mass fraction of 1-5%, stirring for 10 minutes to obtain EDTA-modified graphene oxide;

[0046] S12, taking 1 part by mass of the dispersion of EDTA-modified graphene oxide, adding it to the acrylic acid monomer, stirring for 10 minutes, adding a certain amount of diisopropyl peroxydicarbonate, and obtaining graphene oxide-modified acrylic resin.

[0047] S2, preparing graphene-modified nano-silicon-titanium composite filler;

[0048] Take 1 mass part of Ti(SO4)2 and dissolve it in 100 parts of 1 mol / L sulfuric acid, add 0.1 mass part of intrinsic graphene and 1 mass part of silicon powder, adjust the pH to 7 with ammonia water and continue stirring for 30 minutes, then wash with deionized water and dry to obtain graphene-modified nano-silicon-titanium composite filler.

[0049] S3, preparing graphene-modified nano-silicon-titanium water-based anti-corrosion coating;

[0050] Take 5 parts by mass of graphene-modified nano-silicon-titanium composite filler, 20 parts by mass of graphene oxide-modified acrylic resin, 0.1% by mass of polystyrene sodium sulfate, 0.2% by mass of polydimethylsiloxane, 0.1% by mass of polyurethane thickener, and 8% by mass of water-based amino resin, mix them, stir at 60°C for 1 hour, and obtain a graphene-modified nano-silicon-titanium water-based anti-corrosion coating.

[0051] Example 3

[0052] A method for preparing a graphene-modified nano-silicon-titanium water-based anticorrosive coating comprises the following steps:

[0053] S1. Preparation of graphene oxide modified acrylic resin:

[0054] S11, adding 5 parts of EDTA to a graphene oxide aqueous dispersion having a mass fraction of 1-5%, stirring for 30 minutes to obtain EDTA-modified graphene oxide;

[0055] S12, taking 5 parts by mass of the dispersion of EDTA-modified graphene oxide, adding it to the acrylic acid monomer, stirring for 30 minutes, adding a certain amount of diisopropyl peroxydicarbonate, and obtaining graphene oxide-modified acrylic resin.

[0056] S2, preparing graphene-modified nano-silicon-titanium composite filler;

[0057] Take 5 parts by mass of Ti(SO4)2 and dissolve it in 100 parts of 1 mol / L sulfuric acid, add 3 parts by mass of intrinsic graphene and 5 parts by mass of silicon powder, adjust the pH to 7 with ammonia water and continue stirring for 60 minutes, then wash with deionized water and dry to obtain graphene-modified nano-silicon-titanium composite filler.

[0058] S3, preparing graphene-modified nano-silicon-titanium water-based anti-corrosion coating;

[0059] Take 20 parts by mass of graphene-modified nano-silicon-titanium composite filler, 20 parts by mass of graphene oxide-modified acrylic resin, 0.1% by mass of polystyrene sodium sulfate, 0.2% by mass of polydimethylsiloxane, 0.1% by mass of polyurethane thickener, and 8% by mass of water-based amino resin, mix them, stir at 60°C for 1.5h, and obtain a graphene-modified nano-silicon-titanium water-based anti-corrosion coating.

[0060] Example 4

[0061] A method for preparing a graphene-modified nano-silicon-titanium water-based anticorrosive coating comprises the following steps:

[0062] S1. Preparation of graphene oxide modified acrylic resin:

[0063] S11, adding 10 parts of EDTA to a graphene oxide aqueous dispersion having a mass fraction of 1-5%, stirring for 20 minutes to obtain EDTA-modified graphene oxide;

[0064] S12, taking 10 parts by mass of the dispersion of EDTA-modified graphene oxide, adding it to the acrylic acid monomer, stirring for 20 minutes, adding a certain amount of diisopropyl peroxydicarbonate, and obtaining graphene oxide-modified acrylic resin.

[0065] S2, preparing graphene-modified nano-silicon-titanium composite filler;

[0066] Take 8 parts by mass of Ti(SO4)2 and dissolve it in 100 parts of 1 mol / L sulfuric acid, add 4 parts by mass of intrinsic graphene and 8 parts by mass of silicon powder, adjust the pH to 7 with ammonia water and continue stirring for 60 minutes, then wash with deionized water and dry to obtain graphene-modified nano-silicon-titanium composite filler.

[0067] S3, preparing graphene-modified nano-silicon-titanium water-based anti-corrosion coating;

[0068] Take 30 parts by mass of graphene-modified nano-silicon-titanium composite filler, 30 parts by mass of graphene oxide-modified acrylic resin, 0.1% by mass of polystyrene sodium sulfate, 0.2% by mass of polydimethylsiloxane, 0.1% by mass of polyurethane thickener, 5% by mass of water-based amino resin and 3% by mass of isocyanate, mix them, stir at 50°C for 2h, and obtain a graphene-modified nano-silicon-titanium water-based anti-corrosion coating.

[0069] The above embodiments are compared, and the experimental results are shown in the following table:

[0070]

[0071] The graphene in the technical solution protected by the present invention comes from the resin on the one hand, and the other part comes from later addition, so that the graphene added later can be effectively dispersed by using the graphene grafted resin, thereby improving the thermal conductivity and anti-corrosion properties of the coating; in addition, it grafts graphene oxide onto the acrylic resin, which not only ensures the hydrophilic dispersion performance of the coating, but also uses graphene oxide to disperse the graphene, so that both graphene and graphene oxide have excellent dispersion properties in the coating.

[0072] Therefore, the present invention adopts a graphene-modified nano-silicon-titanium water-based heavy-duty anti-corrosion coating and a preparation method thereof to solve the dispersion problem when silicon-titanium is used as an anti-corrosion material, and proposes an anti-corrosion coating with excellent anti-corrosion performance, strong adhesion and good dispersion performance.

[0073] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anti-corrosion coating, characterized in that: Including the following ingredients: Polyamino chelating agent, graphene oxide, acrylic acid and its derivatives, Ti (SO4) 2, intrinsic graphene, silicon powder, curing agent; The preparation method of graphene-modified nano-silicon-titanium water-based heavy-duty anti-corrosion coating comprises the following steps: S1. Preparation of graphene oxide modified acrylic resin: S11, adding 1-10 parts by mass of a polyamino chelating agent to a 1-5% by mass aqueous dispersion of graphene oxide, stirring for 10-30 minutes, to obtain polyamino chelating agent modified graphene oxide; S12, taking 1-20 parts by mass of a dispersion of polyamino chelating agent-modified graphene oxide, adding it to acrylic acid and its derivative monomers, stirring for 10-30 minutes, adding a certain amount of initiator, and obtaining graphene oxide-modified acrylic resin; S2, preparing graphene-modified nano-silicon-titanium composite filler; 1-10 parts by mass of Ti(SO4)2 is dissolved in 100 parts by mass of 1 mol / L sulfuric acid, 0.1-5 parts by mass of intrinsic graphene and 1-10 parts by mass of silicon powder are added, the pH is adjusted to 7 with ammonia water and stirring is continued for 30-60 minutes, and then washed with deionized water and dried to obtain a graphene-modified nano-silicon-titanium composite filler; S3, preparing graphene-modified nano-silicon-titanium water-based heavy-duty anti-corrosion coating; 1-50 parts by mass of graphene-modified nano-silicon-titanium composite filler, 20-50 parts by mass of graphene oxide-modified acrylic resin, dispersant, leveling agent, thickener, defoamer, and curing agent are mixed, and stirred at 40-60° C. for 0.5-2 h to obtain a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating; The dispersant is a surfactant with a benzene ring, and the dispersant is polystyrene sodium sulfate with a mass fraction of 0.05-1%; the leveling agent and defoamer are one or more of polydimethylsiloxane, alkyl-modified organic siloxane, and fluorine-modified acrylate, and the mass fraction thereof is 0.1-1%; the thickener is one or more of an associative alkali swelling thickener or a polyurethane thickener, and the mass fraction thereof is 0.1-2%; the curing agent is a water-based amino resin or a water-based isocyanate curing agent, and the mass fraction thereof is 1%-10%.

2. The method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating according to claim 1, characterized in that: The mass numbers of the polyamino chelating agent, the Ti(SO4)2 and the silicon powder are all 1-10 mass parts, and the mass number of the intrinsic graphene is 0.1-5 mass parts.

3. The method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating according to claim 2, characterized in that: The polyamino chelating agent is one or more of EDTA and DTPA.

4. The method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating according to claim 3, characterized in that: The graphene oxide refers to graphene with a C / O ratio of less than 0.8, 1-5 layers, and a sheet size of 0.1-3 μm; the intrinsic graphene refers to graphene with a C / O ratio of greater than 40, 1-10 layers, and a sheet size of 0.1-5 μm.

5. The method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating according to claim 4, characterized in that: The acrylic acid and its derivatives are one or more of acrylic acid, hydroxy acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and octyl acrylate.

6. The method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating according to claim 5, characterized in that: The size of the silicon micropowder is 0.1-1 μm, and the purity is greater than 95%.

7. The method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating according to claim 6, characterized in that: The curing agent is a water-based curing agent, and the water-based curing agent is one or more of water-based methyl etherified amino resin, butyl etherified amino resin, or water-based TDI and HDI.

8. The method for preparing a graphene-modified nano-silicon-titanium water-based heavy-duty anticorrosion coating according to claim 1, characterized in that: The stirring rate in S2 is 100 r / min, and the initiator is a peroxide or an azo initiator.

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