CN110229588B - Graphene composite nano-alloy underwater heavy-duty coating and preparation method thereof - Google Patents
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- 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
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- 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
- C09D5/10—Anti-corrosive paints containing metal dust
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a graphene composite nano alloy underwater heavy-duty coating which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 4 (1-2); the component A is prepared from the following raw materials in parts by weight: 110-40 parts of epoxy resin, 20-10 parts of epoxy resin, 30-10 parts of epoxy resin, 0-5 parts of toughening agent, 0 is excluded, 10-20 parts of graphene composite nano alloy base material, 0-5 parts of nano base material, 10-30 parts of filler, 0-5 parts of pigment, 0 is excluded, 0-2 parts of thixotropic agent, 0 is excluded, 0-1 part of functional assistant and 0 is excluded; the component B is prepared from the following raw materials in parts by weight: 20-25 parts of curing agent, 0-1 part of thixotropic agent and 0 part of thixotropic agent; 0-1 part of coupling agent, and 0 is not included. The anticorrosive coating disclosed by the invention is environment-friendly, has a good anticorrosive effect and is long in service life.
Description
Technical Field
The invention belongs to the field of anticorrosive materials, and particularly relates to a graphene composite nano-alloy underwater heavy-duty anticorrosive coating and a preparation method thereof.
Background
Along with the continuous development of economy, various domestic port docks, hydroelectric power station and the continuous development of boats and ships industry, port dock, the power station, large-scale sewage treatment plant, the mine, the tunnel, the swimming pool, underwater environment such as tank all need carry out the underwater repair to water, and the traditional material is under water the restoration back service life limit is extremely short, cause the engineering restoration volume to all increase every year, and the material that contains VOCS and heavy metal ion is introduced mostly to the material restoration under water in the preparation process to tradition, can produce the material that has harm to the environment in messenger's whole production process and the use, environmental protection not enough. Therefore, the development of an environment-friendly heavy-duty anticorrosive material for underwater repair with long service life has important significance.
Disclosure of Invention
In view of the above, the invention aims to provide an environment-friendly graphene composite nano alloy underwater heavy-duty coating with heavy duty and long service life and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the graphene composite nano-alloy underwater heavy-duty coating comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 4 (1-2);
the component A is prepared from the following raw materials in parts by weight:
the component B is prepared from the following raw materials in parts by weight:
20-25 parts of a curing agent,
0-1 part of thixotropic agent, excluding 0;
0-1 part of coupling agent, and 0 is not included.
Further, the epoxy value of the epoxy resin 1 is 0.41-0.47, the epoxy value of the epoxy resin 2 is 0.48-0.54, and the epoxy value of the epoxy resin 3 is 0.18-0.22.
Further, the graphene composite nano alloy base material is prepared by the method comprising the following steps:
a. mixing graphene powder, metal alloy powder, epoxy resin 1, a coupling agent and acetone according to a mass ratio of 20: firstly, ultrasonically mixing in a closed ultrasonic stirrer in a ratio of 20:59.6:0.4: 100;
b. b, introducing the mixed solution obtained in the step a into a nano grinder for grinding;
c. and d, removing the acetone in the mixed solution obtained in the step b to obtain the graphene composite nano alloy base material.
Further, the metal alloy powder in the step a is a mixture of more than two of silver, zirconium and titanium, and is subjected to ultrasonic mixing for 6 hours;
the fineness of the grinding in the step b is less than or equal to 20 mu m;
and c, vacuumizing at 60 ℃ for 60min to-0.8 Pa under the condition of removing the acetone in the step c.
Further, the coupling agent in the step a is GF 9.
Furthermore, the particle size of the graphene powder is 5-30 nm.
Further, the silver, the zirconium and the titanium are mixed according to the mass ratio of 1:1 (2-3).
Further, in the component A, the toughening agent is one or a mixture of two of DOP or DBP;
the nano base material is one or a mixture of two of nano titanium dioxide or nano zinc oxide;
the filler is one or a mixture of more than two of kaolin, precipitated barium sulfate, mica powder or zinc phosphate;
the pigment is one of titanium dioxide or iron oxide black;
the thixotropic agent is one or a mixture of more than two of white carbon black, gas-phase white carbon black or organic bentonite.
Further, the DOP and DBP are mixed in a ratio of 1: (2-5) mixing in a mass ratio;
the ratio of the nano titanium dioxide to the nano zinc oxide is 1: (1-2) mixing in a mass ratio;
mixing the kaolin, the precipitated barium sulfate, the mica powder and the zinc phosphate according to the mass ratio of 1:5:1.5: 1;
the white carbon black, the gas-phase white carbon black and the organic bentonite are mixed according to the mass ratio of 1:3: 1.
Further, the functional assistant is a coupling agent KH 550: dispersant BYK 104: the defoaming agent BYK054 is obtained by mixing according to the mass ratio of 2:1: 1.
Further, in the component B, the curing agent is one or two of JA-1S and MA according to the mass ratio of 1: (1-4) mixing; the thixotropic agent is TS 720; the coupling agent is GF 95.
The invention also provides a preparation method of the graphene composite nano alloy underwater heavy-duty coating, which comprises the following steps:
A. preparing a component A:
(1) heating and mixing all the epoxy resins in the formula, and then cooling to normal temperature for later use;
(2) sequentially adding other materials into the epoxy resin liquid according to the formula sequence, and dispersing by using a stirrer in a vacuum state to obtain a component A;
B. preparing a component B:
stirring, mixing and dispersing the three components of the formula until the components are uniform and have no particles;
C. and mixing the component A and the component B according to the formula proportion to obtain the anticorrosive paint.
Further, in the preparation method of the component A, the temperature in the step (1) is raised to 90-100 ℃, and the mixture is mixed for 1 hour; the stirring speed in the step (2) can be written as 800-.
Further, in the preparation method of the component B, the stirring speed is 400-600 r/min.
Compared with the prior art, the graphene composite nano alloy underwater heavy-duty coating and the preparation method thereof have the following advantages:
(1) the graphene composite nano alloy underwater heavy-duty coating is prepared by grafting and modifying main resin of the material by using graphene and a nano alloy material on the basis of a traditional underwater anticorrosive material, mainly chemically modifying the material by using the graphene and the nano composite alloy, and synthesizing the material by using high-solid raw materials because of considering the special requirement of the current society on environmental protection, wherein the material does not introduce any raw material containing VOCS and heavy metal ions, so that the non-environmental protection property of the traditional underwater anticorrosive material is completely broken through; meanwhile, the heavy-duty anticorrosive waterproof material system is applied to various underwater anticorrosive projects to prolong the service life of the heavy-duty anticorrosive waterproof material system, prevent various corrosion caused by external environments, reduce the cost of underwater repair projects and save social resources.
(2) The graphene is a high-quality material with the particle size of 5-30nm, and is compounded with the nanoscale alloy base material through a chemical bridging means, so that the obtained alloy base material has a nanometer material size effect, the modified alloy base material and main resin of the coating can be well bridged by utilizing a nanometer grinding technology and an ultrasonic mixing technology in the production process of the coating, and finally the underwater application property, the heavy corrosion resistance, the long-acting service life and other properties of the coating prepared through the reaction of the curing agent are 3-5 times higher than those of the traditional epoxy anticorrosive coating.
(3) The epoxy resin 1 is main resin, so that the basic corrosion resistance of the coating is ensured; the viscosity of the epoxy resin 2 is low, and the viscosity of a resin system can be properly adjusted; the epoxy resin 3 has good corrosion resistance and can also improve the bonding property of the coating; therefore, the coating is prepared by compounding three kinds of epoxy resin, so that the comprehensive performance of the coating is improved.
(4) The addition of the nano base material mainly utilizes the size effect of the nano material, so that the aging resistance and the corrosion resistance of the coating are improved, and the service life and the corrosion resistance of the coating are further improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail with reference to examples.
Example 1
The graphene composite nano-alloy underwater heavy-duty coating comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 4: 1;
the component A is prepared from the following raw materials in parts by weight:
| name of raw and auxiliary materials | Amount (parts by mass)) |
| Epoxy resin 1(E44) | 38 |
| Epoxy resin 2(E51) | 5 |
| Epoxy resin 3(E20) | 1 |
| Flexibilizer DOP | 5 |
| Graphene composite nano alloy base material | 12 |
| Nano base material nano titanium dioxide | 5 |
| Filler kaolin | 26.7 |
| Pigment titanium white powder | 5 |
| White carbon black thixotropic agent | 1.5 |
| Functional auxiliary agent | 0.8 |
The component B is prepared from the following raw materials in parts by weight:
the graphene composite nano alloy base material is prepared by the following steps:
a. graphene powder with the particle size of 10nm, metal alloy powder of silver and zirconium with the mass ratio of 1:1, epoxy resin 1, a coupling agent GF9 and acetone are mixed according to the mass ratio of 20: ultrasonically mixing for 6 hours in a closed ultrasonic stirrer in a ratio of 20:59.6:0.4: 100;
b. b, introducing the mixed solution obtained in the step a into a nano grinder to grind until the fineness is less than or equal to 20 microns;
c. and (c) vacuumizing the mixed solution obtained in the step (b) at the temperature of 60 ℃ for 60min to-0.8 Pa, and removing the acetone in the mixed solution to obtain the graphene composite nano alloy base material.
The functional assistant is coupling agent KH 550: dispersant BYK 104: the defoaming agent BYK054 is obtained by mixing according to the mass ratio of 2:1: 1.
Example 2
The graphene composite nano-alloy underwater heavy-duty anticorrosive paint comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 4: 1.5;
the component A is prepared from the following raw materials in parts by weight:
the component B is prepared from the following raw materials in parts by weight:
the graphene composite nano alloy base material is prepared by the following steps:
a. graphene powder with the particle size of 10nm, metal alloy powder of zirconium and titanium with the mass ratio of 1:2, epoxy resin 1, a coupling agent GF9 and acetone according to the mass ratio of 20: ultrasonically mixing for 6 hours in a closed ultrasonic stirrer in a ratio of 20:59.6:0.4: 100;
b. b, introducing the mixed solution obtained in the step a into a nano grinder to grind until the fineness is less than or equal to 20 microns;
c. and (c) vacuumizing the mixed solution obtained in the step (b) at the temperature of 60 ℃ for 60min to-0.8 Pa, and removing the acetone in the mixed solution to obtain the graphene composite nano alloy base material.
The functional assistant is coupling agent KH 550: dispersant BYK 104: the defoaming agent BYK054 is obtained by mixing according to the mass ratio of 2:1: 1.
Example 3
The graphene composite nano-alloy underwater heavy-duty anticorrosive paint comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2: 1;
the component A is prepared from the following raw materials in parts by weight:
the component B is prepared from the following raw materials in parts by weight:
| name of raw and auxiliary materials | Dosage (parts by mass) |
| Curing agent MA | 25 |
| Thixotropic agent TS720 | 1 |
| Coupling agent GF95 | 1 |
The graphene composite nano alloy base material is prepared by the following steps:
a. graphene powder with the particle size of 10nm, metal alloy powder of silver, zirconium and titanium with the mass ratio of 1:1:2, epoxy resin 1, coupling agent GF9 and acetone according to the mass ratio of 20: ultrasonically mixing for 6 hours in a closed ultrasonic stirrer in a ratio of 20:59.6:0.4: 100;
b. b, introducing the mixed solution obtained in the step a into a nano grinder to grind until the fineness is less than or equal to 20 microns;
c. and (c) vacuumizing the mixed solution obtained in the step (b) at the temperature of 60 ℃ for 60min to-0.8 Pa, and removing the acetone in the mixed solution to obtain the graphene composite nano alloy base material.
The functional assistant is coupling agent KH 550: dispersant BYK 104: the defoaming agent BYK054 is obtained by mixing according to the mass ratio of 2:1: 1.
The preparation method of the graphene composite nano-alloy underwater heavy-duty coating described in embodiments 1 to 3 includes the following steps:
A. preparing a component A:
(1) heating all the epoxy resin in the formula to 90-100 ℃, mixing for 1 hour, and then cooling to normal temperature for later use;
(2) sequentially adding other materials into the epoxy resin liquid according to the formula sequence, and stirring and dispersing for 2-3 hours at 1200r/min by using a planetary stirrer in a vacuum state to obtain a component A;
B. preparing a component B:
the three components of the formula are stirred and mixed at 500r/min until the components are uniform and have no particles.
C. And mixing the component A and the component B according to the formula proportion to obtain the anticorrosive paint.
The 3 materials obtained in examples 1-3 were coated in a standard environment to a film thickness of 0.65mm, and the coatings obtained were cured in a standard environment for 168 hours and were characterized as follows in tables 1-3.
Table 1 test properties of anticorrosive coatings obtained in example 1
Table 2 test properties of anticorrosive coatings obtained in example 2
Table 3 test properties of anticorrosive coatings obtained in example 3
Comparative example
On the basis of the above example 1, no graphene composite nano alloy base material was added to the component a, and the finally obtained material was subjected to a performance test, as shown in the following table.
TABLE 4 test Properties of anticorrosive coatings obtained in comparative examples
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The graphene composite nano alloy underwater heavy-duty coating is characterized by comprising the following components in parts by weight: comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 4 (1-2);
the component A is prepared from the following raw materials in parts by weight:
the component B is prepared from the following raw materials in parts by weight:
20-25 parts of a curing agent,
0-1 part of thixotropic agent, excluding 0;
0-1 part of coupling agent, and 0 is not included;
the graphene composite nano alloy base material is prepared by the method comprising the following steps:
a. mixing graphene powder, metal alloy powder, epoxy resin 1, a coupling agent and acetone according to a mass ratio of 20: firstly, ultrasonically mixing in a closed ultrasonic stirrer in a ratio of 20:59.6:0.4: 100;
b. b, introducing the mixed solution obtained in the step A into a nano grinder for grinding;
c. removing the acetone in the mixed solution obtained in the step B to obtain the graphene composite nano alloy base material;
the metal alloy powder in the step a is a mixture of more than two of silver, zirconium and titanium, and is subjected to ultrasonic mixing for 6 hours; the fineness of the grinding in the step b is less than or equal to 20 mu m; the condition for removing the acetone in the step c is that the vacuum pumping is carried out for 60min at the temperature of 60 ℃ to-0.8 Pa;
the particle size of the graphene powder is 5-30 nm;
the nano base material is one or a mixture of two of nano titanium dioxide or nano zinc oxide.
2. The graphene composite nano-alloy underwater heavy-duty coating as claimed in claim 1, wherein: the epoxy value of the epoxy resin 1 is 0.41-0.47, the epoxy value of the epoxy resin 2 is 0.48-0.54, and the epoxy value of the epoxy resin 3 is 0.18-0.22.
3. The graphene composite nano-alloy underwater heavy-duty coating as claimed in claim 1, wherein: in the component A, the toughening agent is one or a mixture of two of DOP or DBP; the filler is one or a mixture of more than two of kaolin, precipitated barium sulfate, mica powder or zinc phosphate; the pigment is one of titanium dioxide or iron oxide black; the thixotropic agent is one or a mixture of more than two of white carbon black, gas-phase white carbon black or organic bentonite.
4. The graphene composite nano-alloy underwater heavy-duty coating as claimed in claim 1, wherein: the functional assistant is coupling agent KH 550: dispersant BYK 104: the defoaming agent BYK054 is obtained by mixing according to the mass ratio of 2:1: 1.
5. The graphene composite nano-alloy underwater heavy-duty coating as claimed in claim 1, wherein: in the component B, the curing agent is one or two of JA-1S and MA according to the mass ratio of 1: (1-4) mixing; the thixotropic agent is TS 720; the coupling agent is GF 95.
6. The preparation method of the graphene composite nano-alloy underwater heavy-duty coating as claimed in any one of claims 1 to 5, characterized in that: the method comprises the following steps:
A. preparing a component A:
(1) heating and mixing all the epoxy resins in the formula, and then cooling to normal temperature for later use;
(2) sequentially adding other materials into the epoxy resin liquid according to the formula sequence, and dispersing by using a stirrer in a vacuum state to obtain a component A;
B. preparing a component B:
stirring, mixing and dispersing the three components of the formula until the components are uniform and have no particles;
C. and mixing the component A and the component B according to the formula proportion to obtain the anticorrosive paint.
7. The preparation method of the graphene composite nano-alloy underwater heavy-duty coating according to claim 6, characterized in that: in the preparation method of the component A, the temperature in the step (1) is raised to 90-100 ℃, and the mixture is mixed for 1 hour; the stirring speed in the step (2) is 800-.
8. The preparation method of the graphene composite nano-alloy underwater heavy-duty coating according to claim 6, characterized in that: in the preparation method of the component B, the stirring speed is 400-600 r/min.
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| CN110643267A (en) * | 2019-11-11 | 2020-01-03 | 厦门双瑞船舶涂料有限公司 | Thin-coating heavy-duty anticorrosive coating and preparation method thereof |
| CN113652147A (en) * | 2021-09-24 | 2021-11-16 | 肇庆市海特复合材料技术研究院 | Graphene composite anticorrosive paint |
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Effective date of registration: 20191213 Address after: 301600 Jinhai Road 5, Jinghai Economic Development Zone, Jinghai District, Tianjin. Applicant after: Tianjin Chang new material science and Technology Development Co Ltd Applicant after: Tianjin Qian Feng corrosion-resistant thermal insulation Engineering Co., Ltd Address before: No.5, jinhaidao, Jinghai Economic Development Zone, Tianjin 301600 Applicant before: Tianjin Chang new material science and Technology Development Co Ltd |
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