CN111518451B - Epoxy micaceous iron intermediate paint - Google Patents
Epoxy micaceous iron intermediate paint Download PDFInfo
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- CN111518451B CN111518451B CN202010534519.3A CN202010534519A CN111518451B CN 111518451 B CN111518451 B CN 111518451B CN 202010534519 A CN202010534519 A CN 202010534519A CN 111518451 B CN111518451 B CN 111518451B
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention relates to an epoxy micaceous iron intermediate paint, which belongs to the technical field of coatings and comprises the following components in percentage by weight: 90-95% of the component A; 5-10% of the component B; wherein the component A comprises the following components in percentage by weight: 25-40% of carboxyl modified epoxy resin; 30-55% of mica iron oxide; 10-15% of additive; 10-15% of a mixed solvent A; wherein the component B comprises the following components in percentage by weight: 65-75% of polyamide curing agent; and B, 25-35% of mixed solvent. The invention has the advantage of better rust prevention protection for the matrix.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an epoxy micaceous iron intermediate paint.
Background
Epoxy mica iron oxide paint is one of the most widely applied heavy anti-corrosion coatings in the world at present, and has wide application in the aspects of ship protection, container protection, steel bridge towers, marine facilities and the like. The epoxy mica iron oxide paint is used as the intermediate layer of the composite coating, and the shielding effect of the flaky pigment is utilized to protect the metal substrate.
For example, chinese patent application publication No. CN105086751A discloses a quick-drying and quick-setting epoxy micaceous iron oxide antirust paint and a preparation method thereof, wherein the quick-drying and quick-setting epoxy micaceous iron oxide antirust paint is prepared from the following raw materials: 15-25 parts of epoxy resin liquid, 45-55 parts of griseofulvin, 3-4 parts of boron powder, 0.1-0.5 part of ethanol, 0.2-0.7 part of butanol, 22-23 parts of xylene, 7-8 parts of polyamide resin curing agent, 6-8 parts of auxiliary agent, 3-4 parts of aluminum powder slurry and 2-4 parts of solvent.
The above prior art solutions have the following drawbacks: in the technical scheme, because the epoxy resin is not modified at all, and the epoxy resin is used as a film forming component of a solvent type coating, the requirement of brushing is that a brushed substrate needs to be dried, and if the substrate is in a wet state, the adhesion force of the brushed and cured epoxy micaceous iron antirust paint is poor under the mutual repulsion action of polar groups and nonpolar groups, the brushed and cured epoxy micaceous iron antirust paint is easy to fall off. In the actual production process, the brushing of the primer is prone to have defects, and once the defects of the brushing of the primer cause the exposure of a wet substrate and the adhesion force of the micaceous iron intermediate paint on the wet substrate is poor, the final result is that the substrate cannot be effectively protected from rust, so that the epoxy micaceous iron intermediate paint capable of better protecting the substrate from rust is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the epoxy micaceous iron intermediate paint which has the advantage of better rust prevention protection on a substrate.
The above object of the present invention is achieved by the following technical solutions:
the epoxy micaceous iron intermediate paint comprises the following components in percentage by weight:
90-95% of the component A;
5-10% of the component B;
wherein the component A comprises the following components in percentage by weight:
25-40% of carboxyl modified epoxy resin;
30-55% of mica iron oxide;
10-25% of additive;
10-15% of a mixed solvent A;
wherein the component B comprises the following components in percentage by weight:
65-75% of polyamide curing agent;
and B, 25-35% of mixed solvent.
By adopting the technical scheme, the epoxy resin is subjected to carboxyl modification, carboxyl is introduced into the epoxy resin, and the existence of the carboxyl enables the original nonpolar epoxy resin to be changed into carboxyl modified epoxy resin and have certain amphipathy, namely, the carboxyl modified epoxy resin has certain dispersion effect. Therefore, the dispersion effect of the powder components in the epoxy micaceous iron oxide intermediate paint, such as micaceous iron oxide, is better, so that the overall performance of the epoxy micaceous iron oxide intermediate paint is improved. In addition, although carboxyl groups are partially reacted in the curing process of the micaceous iron oxide intermediate paint, the unreacted carboxyl groups enable the micaceous iron oxide intermediate paint to have certain polar adsorption capacity, so that the micaceous iron oxide intermediate paint not only has good adhesion capacity to a primer and a finish paint, but also has good adhesion capacity to a bare substrate and even a wet substrate, and the micaceous iron oxide intermediate paint is not easy to peel off, which means a better protection effect on the substrate.
The present invention in a preferred example may be further configured to: the carboxyl modified epoxy resin comprises the following components in percentage by weight:
93-97% of epoxy resin;
2-6% of acrylic monomers;
1-2% of dibenzoyl peroxide.
By adopting the technical scheme, the epoxy resin and the acrylic monomer are mixed, and the acrylic monomer is grafted to the epoxy resin under the condition that dibenzoyl peroxide is used as an accelerating agent, so that carboxyl is introduced to the epoxy resin. In addition, because the introduction of carboxyl makes the epoxy resin have certain hydrophilicity, once the grafting rate of the carboxyl is too high, the whole formula system of the epoxy resin is affected, and the grafting rate of the carboxyl is too low, which easily causes the amphipathy to be weak. Therefore, it is necessary to control the grafting ratio of the carboxyl groups on the epoxy resin. By controlling the amount of the acrylic monomer, the grafting rate of the carboxyl can be controlled, so that the problem that the coating is not suitable for an organic solvent system due to the fact that the hydrophilicity of the coating is too strong because the grafting rate of the carboxyl is too high is solved. We have found that controlling the acrylic monomer to within the range of 2 to 6% by weight enables the carboxyl modified epoxy resin to have a certain amphiphilicity while being suitable for use in organic solvent systems.
The present invention in a preferred example may be further configured to: the acrylic monomer comprises the following components in percentage by weight:
20-30% of methacrylic acid;
70-80% of acrylic acid.
By adopting the technical scheme, both methacrylic acid and acrylic acid are common industrial raw materials, so that the production difficulty and the production cost are reduced.
The present invention in a preferred example may be further configured to: the preparation process of the carboxyl modified epoxy resin specifically comprises the following process steps:
s1: dissolving epoxy resin in a modified mixed solvent, heating in a water bath to 110 ℃ under the protection of nitrogen to obtain a mixture A;
s2: mixing the acrylic monomer and the dibenzoyl peroxide according to the proportion to obtain a mixture B, then dropwise adding the mixture B into the mixture A obtained in the step S1, and carrying out heat preservation reaction at the temperature of 100-110 ℃ for 1-2 hours to obtain the carboxyl modified epoxy resin.
By adopting the technical scheme, the epoxy resin is simple in modification process conditions and short in process flow, so that the epoxy resin is suitable for modifying the epoxy resin on a large scale, the production adaptability is improved, and the production efficiency is improved.
Furthermore, we have found that the carboxyl modified epoxy resin has a certain hydrophilicity by introducing carboxyl while maintaining its lipophilicity and has a small influence on the overall solvent system and performance thereof when the reaction time is maintained between 1 and 2 hours. At the moment, the carboxyl modified epoxy resin can be used as a film forming component, and the amphipathy of the carboxyl modified epoxy resin also enables the carboxyl modified epoxy resin to have a certain dispersion effect, so that various powder materials are not easy to agglomerate, the uniformity of the prepared epoxy micaceous iron oxide intermediate paint is improved, the possibility of sedimentation of various materials can be reduced, the compatibility of each component can be improved, and the fracture strength among interfaces of each component is improved.
The present invention in a preferred example may be further configured to: the modified mixed solvent in the step S1 comprises the following components in percentage by weight:
20-30% of n-butyl alcohol;
70-80% of ethylene glycol butyl ether.
By adopting the technical scheme, the n-butyl alcohol and the ethylene glycol butyl ether are common solvents of the epoxy resin, and the epoxy resin can be well dissolved.
The present invention in a preferred example may be further configured to: the additive comprises the following components in percentage by weight:
10-13% of an auxiliary agent;
30-35% of an antirust agent;
30-35% of filler;
20-26% of organic bentonite.
By adopting the technical scheme, the organic bentonite not only can be used as a rheological agent to improve the rheological property of the epoxy micaceous iron intermediate paint, but also can be used as an anti-settling agent to reduce the possibility of material settling. And the additionally added antirust agent can further improve the protection effect of the epoxy micaceous iron intermediate paint on the matrix. In addition, through the synergy of the organic bentonite and the epoxy resin with certain amphiphilic effect, the organic bentonite has good dispersion effect, and the anti-settling effect and the rheological effect of the organic bentonite are also improved.
The present invention in a preferred example may be further configured to: the auxiliary agent comprises the following components in percentage by weight:
30-40% of defoaming agent;
50-60% of a dispersant;
10-20% of antibacterial agent.
Wherein the antibacterial agent is sodium benzoate.
By adopting the technical scheme, the sodium benzoate is used as a broad-spectrum antibacterial agent and has good sterilization and bacteriostasis effects under an acidic condition. Before curing, the carboxyl modified epoxy resin is acidic, so that the sodium benzoate can reduce the possibility of putrefaction of the epoxy micaceous iron intermediate paint. After solidification, the existing outside rainfall is always acidic, so that the epoxy micaceous iron oxide intermediate paint has certain antibacterial capacity and can reduce the corrosion of bacteria to a matrix to a certain extent.
The present invention in a preferred example may be further configured to: the antirust agent is sodium gluconate.
By adopting the technical scheme, as the sodium gluconate has good chelating performance, when iron serving as an anode is corroded and loses electrons to become ferrous ions or ferric ions, the iron can react with the sodium gluconate to generate a complex, and an insoluble precipitation film is generated on the surface of a substrate to prevent further corrosion, so that the antirust effect is achieved.
In addition, sodium benzoate is added into the epoxy micaceous iron intermediate paint, and when the sodium benzoate is used as an antibacterial agent, benzoate ions of the epoxy micaceous iron intermediate paint can compete with chloride ions and the like for adsorption, so that the adsorption of corrosive chloride ions and the like on a substrate interface is weakened, and the adsorption quantity of sodium gluconate on the substrate interface is increased. Therefore, the sodium gluconate can better form a protective film on the surface of the substrate. That is, the sodium benzoate can cooperate with the sodium gluconate to further improve the protection effect on the matrix and reduce the possibility of rusting the matrix.
The present invention in a preferred example may be further configured to: the filler comprises the following components in percentage by weight:
50-60% of MOF-5 material loaded with zinc phosphate;
40-50% of ferrophosphorus powder.
By adopting the technical scheme, the conductivity of the ferrophosphorus powder can be increased, so that the cathode protection effect of the epoxy micaceous iron intermediate paint is increased, and the antirust effect on a matrix is improved. In addition, the MOF-5 material is a common organic-inorganic hybrid material at present, is constructed by organic coordination and inorganic metal units, and has the characteristics of large specific surface area, large pore volume, good thermal stability, light weight and the like. The organic ligand in the MOF-5 material can improve the affinity of the polymer component in the micaceous iron oxide intermediate paint and the MOF-5 material, so that the compatibility of the polymer component and the MOF-5 material is improved; the affinity of the MOF-5 material and inorganic components in the epoxy micaceous iron intermediate paint can be improved by the inorganic metal units, so that the internal connection force of the epoxy micaceous iron intermediate paint can be improved by adding the MOF-5 material, and various physical properties of the epoxy micaceous iron intermediate paint can be improved.
However, MOF-5 materials suffer from the disadvantage that the MOF-5 material is susceptible to structural collapse in a humid environment. It is determined that the MOF-5 material absorbed with zinc phosphate is added into the epoxy micaceous iron oxide intermediate paint to ensure that the epoxy micaceous iron oxide intermediate paint has higher stability in the production process because the epoxy micaceous iron oxide intermediate paint is an organic solvent system. In the using process, a finish paint is generally coated outside the micaceous iron oxide intermediate paint, only when the coating cracks, the MOF-5 material in the micaceous iron oxide intermediate paint can be contacted with precipitation, and after the micaceous iron oxide intermediate paint is cured into a film, once the micaceous iron oxide intermediate paint is contacted with the precipitation, the MOF-5 material can be contacted with water to collapse the structure, so that the zinc phosphate adsorbed in the micaceous iron oxide intermediate paint is released.
First, Zn in zinc phosphate2+，PO4-Reacting with iron to form Fe-Zn-P2O5Phosphating of films ofThe surface of the metal substrate is passivated to generate Zn with approximate molecular formula2Fe(PO4)2·4H20 of a phosphating compound. In addition, various intermediate products generated in the hydrolysis process of the zinc phosphate also react with corrosion on the surface of the metal to form an insoluble complex so as to form an isolation region between the metal and a corrosion product, so that not only can the further invasion of a corrosion medium be prevented, but also a cathode protection effect is realized, and a substrate is protected.
In the corrosion process, the metal surface can also generate oxygen absorption reaction, the oxygen absorption reaction can generate more hydroxide ions, and the hydroxide ions can be combined with zinc ions to generate zinc hydroxide slightly soluble in water, so that a more complete protective film is further formed, and the antirust effect is further improved.
In addition, the epoxy resin has certain hydroxyl, and after carboxyl is introduced into the carboxyl modified epoxy resin, partial carboxyl still exists even after the epoxy resin is cured, namely, partial carboxyl and hydroxyl still exist in the cured micaceous iron oxide intermediate paint. Then, two crystal water in the zinc phosphate can react with carboxyl and hydroxyl to generate gel, and the gel can fill and repair micro cracks generated by the epoxy micaceous iron intermediate paint to isolate precipitation from further corroding a substrate, so that the self-repairing of the epoxy micaceous iron intermediate paint is realized.
The present invention in a preferred example may be further configured to: the A mixed solvent comprises the following components in percentage by weight:
60-70% of dimethylbenzene;
30-40% of butyl acetate;
the mixed solvent B comprises the following components in percentage by weight:
60-70% of dimethylbenzene;
30-40% of n-butanol.
By adopting the technical scheme, the mixed solvent A and the mixed solvent B are common solvent systems and are easy to obtain and produce.
In summary, the invention includes at least one of the following beneficial technical effects:
1. by modifying the epoxy resin with carboxyl, the original nonpolar epoxy resin has certain amphipathy, namely, the epoxy resin has certain dispersion effect; in addition, the introduction of carboxyl enables the coating to have certain polar adsorption capacity, so that the coating can be better adsorbed on the substrate to better protect the substrate;
2. the grafting time of carboxyl on the epoxy resin and the addition amount of acrylic monomers are controlled, and the grafting rate of the carboxyl is controlled, so that the adhesive capacity and the dispersibility of the coating are improved on the premise of reducing the influence on a solvent system and the performance;
3. the antibacterial ability of the coating before and after curing can be improved by adding the sodium benzoate antibacterial agent, the protective effect of the coating on the substrate can be improved by adding the sodium gluconate antirust agent, and the protective effect of the coating on the substrate can be synergistically improved by adding the sodium benzoate and the sodium gluconate;
4. the MOF-5 material loaded with zinc phosphate is added, the MOF-5 material serving as a filler can improve the compatibility of each component in the coating, and the zinc phosphate has a certain corrosion inhibition effect, so that the protection of the coating on a matrix is further improved.
Detailed Description
The invention discloses an epoxy micaceous iron intermediate paint which comprises the following components in percentage by weight:
90% of the component A;
and 10% of the component B.
Wherein the component A comprises the following components in percentage by weight:
40% of carboxyl modified epoxy resin;
30% of mica iron oxide;
15% of an additive;
and 15% of A mixed solvent.
Wherein the mica iron oxide is 800 mesh mica iron oxide ash produced by Dudu chemical industry.
Wherein the carboxyl modified epoxy resin comprises the following components in percentage by weight:
97% of epoxy resin;
2% of acrylic monomer;
1% of dibenzoyl peroxide.
Wherein the epoxy resin is E51 epoxy resin produced by Xinye Hao chemical industry.
Wherein the acrylic monomer comprises the following components in percentage by weight:
30% of methacrylic acid;
acrylic acid 70%.
The preparation process of the carboxyl modified epoxy resin specifically comprises the following process steps:
s1: dissolving epoxy resin in a modified mixed solvent, and heating in a water bath to 100 ℃ under the protection of nitrogen to obtain a mixture A;
s2: and (3) mixing the acrylic monomer and the dibenzoyl peroxide according to the proportion to obtain a mixture B, then dropwise adding the mixture B into the mixture A obtained in the step S1, and carrying out heat preservation reaction at the temperature of 100 ℃ for 1.5 hours to obtain the carboxyl modified epoxy resin.
The modified mixed solvent in the step S1 comprises the following components in percentage by weight:
20% of n-butyl alcohol;
ethylene glycol butyl ether 80%.
Wherein, the additive in the component A comprises the following components in percentage by weight:
10% of an auxiliary agent;
35% of antirust agent;
30% of filler;
and 25% of organic bentonite.
Wherein, the auxiliary agent comprises the following components in percentage by weight:
40% of defoaming agent;
50% of a dispersant;
10 percent of antibacterial agent.
Wherein the antifoaming agent is 2550 antifoaming agent produced by basf.
Wherein, the dispersant is PX4585 dispersant produced by Pasteur.
Wherein the antibacterial agent is sodium benzoate.
Wherein the antirust agent is sodium gluconate.
Wherein the organic bentonite is produced by Tianlong organic bentonite GmbH.
Wherein, the filler comprises the following components in percentage by weight:
50% of MOF-5 material loaded with zinc phosphate;
50% of ferrophosphorus powder;
wherein the ferrophosphorus powder is produced by Limited liability company of the four-ring pigment in Anhui province.
The preparation process of the MOF-5 material loaded with zinc phosphate specifically comprises the following steps:
a: mixing zinc phosphate powder with acetone to prepare a suspension of 20 wt%;
b: taking 100 parts by weight of the suspension in the step A, adding 50 parts by weight of MOF-5 material, and oscillating on a shaking table for 12 hours to obtain a primary adsorption mixture;
c: and D, taking the preliminary adsorption mixture obtained in the step C, carrying out suction filtration, and drying at the temperature of 50 ℃ for 2 hours to obtain the MOF-5 material loaded with zinc phosphate.
Wherein the MOF-5 material is produced by Xian Qiyue biotechnology limited company.
Wherein the zinc phosphate is produced by Shijiazhuan Xinsheng chemical industry Co.
Wherein the component A mixed solvent comprises the following components in percentage by weight:
60% of dimethylbenzene;
and 40% of butyl acetate.
Wherein the component B specifically comprises the following components in percentage by weight:
65% of polyamide curing agent;
and 35% of a mixed solvent B.
Wherein the polyamide curing agent is CV115 polyamide curing agent produced by France Craiverley corporation.
The mixed solvent B comprises the following components in percentage by weight:
60% of dimethylbenzene;
40 percent of n-butyl alcohol.
Examples 2-5 differ from example 1 in that the weight percentages of the a and B components are as follows:
examples 6-12 differ from example 1 in that the weight percentages of the components in the a component are as follows:
examples 13-17 differ from example 1 in that the weight percentages of the components in the carboxy modified resin are as follows:
examples 18 to 21 differ from example 1 in that the weight percentages of the components in the carboxy-modified resin are as follows:
examples 22 to 25 differ from example 1 in that the carboxyl-modified epoxy resin was prepared in the process as follows:
examples 26 to 29 are different from example 1 in that the weight percentages of the components in the modified mixed solvent in step S1 are as follows:
examples 30-36 differ from example 1 in that the weight percentages of the components in the additive are as follows:
examples 37 to 43 differ from example 1 in that the weight percentages of the components in the auxiliary are given in the following table:
examples 44-47 differ from example 1 in that the weight percentages of the components in the filler are as follows:
examples 48 to 51 differ from example 1 in that the weight percentages of the components in the B component are as follows:
examples 52-55 differ from example 1 in that the weight percentages of the components in the solvent mixture a are as follows:
examples 56-59 differ from example 1 in that the weight percentages of the components in the B mixed solvent are as follows:
comparative example
Comparative example 1 is different from example 1 in that the carboxyl-modified epoxy resin in the a component is changed to E51 epoxy resin.
Comparative example 2 is different from example 1 in that the carboxyl group-modified epoxy resin contains 85% by weight of the epoxy resin, 14% by weight of the acrylic monomer, and 1% by weight of dibenzoyl peroxide.
Comparative example 3 is different from example 1 in that the reaction time of the heat-retaining in step S2 is 3 hours in the process for preparing a carboxyl group-modified epoxy resin.
Comparative example 4 is different from example 1 in that the antibacterial agent was JDTKS-012, from Geneva nanotechnology (Xiamen) Co., Ltd., rather than sodium benzoate.
Comparative example 5 differs from example 1 in that the rust inhibitor is aluminum paste, not sodium gluconate.
Comparative example 6 differs from example 1 in that the filler comprises 50% calcium carbonate, 50% ferrophosphorus powder.
Detection method
1. The acid mist resistance test is carried out according to the requirement of GB/T1771;
2. the test for 3% saline resistance is carried out according to the requirements of GB/T10834;
3. the adhesion test is carried out according to the requirements of GB/T5210;
4. the flexibility test is carried out according to the requirements of GB/T1731;
5. the artificial accelerated ageing test is carried out according to the requirements of GB/T1865.
The test results are given in the following table
Conclusion
It can be seen from the data of comparative example 1 and comparative example 1 that since the resin of comparative example 1 is not modified with carboxyl groups, the coating does not have polar groups, and accordingly, the adhesion of the coating to a polar substrate is reduced. In addition, the carboxyl modified epoxy resin has a certain dispersion effect, so that the dispersibility and compatibility of each component in the coating can be improved; although the dispersant is added in the comparative example 1, the conventional E51 epoxy resin does not have the dispersing effect, and as a result, the performance of the coating in the comparative example 1 is reduced. In addition, because the carboxyl content in the coating is low, even if the MOF-5 material is disintegrated after rainfall, the zinc phosphate is not easy to form gel after being released, and then the coating in the comparative example 1 has no self-repairing capability, so that the ageing resistance and the corrosion resistance of the coating in the comparative example 1 are reduced.
As can be understood from the data of comparative example 1 and comparative example 2, the grafting ratio of carboxyl groups is an important factor affecting the properties of the final carboxyl-modified epoxy resin when carboxyl groups are subjected to carboxyl modification. In comparative example 2, too much acrylic monomer is added, which results in too high grafting ratio of carboxyl group on epoxy resin, and too much carboxyl group results in too strong hydrophilicity of carboxyl group modified epoxy resin, so the compatibility of the epoxy resin in organic solvent system is reduced, and the performance of the coating in comparative example 2 is poor.
It can be seen from the data of comparative example 1 and comparative example 3 that, similar to comparative example 2, the reaction time of the heat preservation is too long during the preparation of the carboxyl-modified epoxy resin, so that the acrylic monomer is more sufficiently grafted to the epoxy resin, and similarly, the grafting ratio of the carboxyl group on the epoxy resin is too high, and finally, the performance of the coating in comparative example 3 is poor.
It can be understood from the data of comparative example 1 and comparative example 4 that the replacement of the antibacterial agent results in the disappearance of the synergistic rust inhibitive effect of the antibacterial agent and the rust inhibitive agent, and then the rust inhibitive effect of the coating in comparative example 4 is correspondingly reduced.
It can be understood from the data of comparative example 1 and comparative example 5 that although the aluminum paste also has the rust inhibitive effect and the rust inhibitive oil effect is good, the rust inhibitive effect in comparative example 5 is slightly lowered due to the lack of the synergistic rust inhibitive effect with the antibacterial agent.
It can be seen from the data of comparative example 1 and comparative example 6 that, in the absence of zinc phosphate, the microcracks are not self-repaired when the coating cracks, resulting in a decrease in the aging and corrosion resistance of the coating of comparative example 6. In addition, MOF-5 has a certain amphiphilicity, i.e., a certain dispersion effect, while calcium carbonate is not amphiphilic, which results in a decrease in the dispersibility of the components of the coating in comparative example 6, and a decrease in the properties of the coating in comparative example 6. Moreover, calcium carbonate does not have a synergistic rust inhibitive effect similar to that of zinc phosphate, and finally, the rust inhibitive effect of the coating in comparative example 6 is lowered.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (4)
1. An epoxy micaceous iron intermediate paint is characterized in that: comprises the following components in percentage by weight:
90-95% of the component A;
5-10% of the component B;
wherein the component A comprises the following components in percentage by weight:
25-40% of carboxyl modified epoxy resin;
30-55% of mica iron oxide;
10-15% of additive;
10-15% of a mixed solvent A;
wherein the component B comprises the following components in percentage by weight:
65-75% of polyamide curing agent;
25-35% of mixed solvent B;
the additive comprises the following components in percentage by weight:
10-13% of an auxiliary agent;
30-35% of an antirust agent;
30-35% of filler;
20-26% of organic bentonite;
the auxiliary agent comprises the following components in percentage by weight:
30-40% of defoaming agent;
50-60% of a dispersant;
10-20% of antibacterial agent;
wherein the antibacterial agent is sodium benzoate;
the antirust agent is sodium gluconate;
the carboxyl modified epoxy resin comprises the following components in percentage by weight:
93-97% of epoxy resin;
2-6% of acrylic monomers;
1-2% of dibenzoyl peroxide;
the acrylic monomer comprises the following components in percentage by weight:
20-30% of methacrylic acid;
70-80% of acrylic acid;
the filler comprises the following components in percentage by weight:
50-60% of MOF-5 material loaded with zinc phosphate;
40-50% of ferrophosphorus powder.
2. The epoxy micaceous iron intermediate paint as claimed in claim 1, wherein: the preparation process of the carboxyl modified epoxy resin specifically comprises the following process steps:
s1: dissolving epoxy resin in a modified mixed solvent, heating in a water bath to 110 ℃ under the protection of nitrogen to obtain a mixture A;
s2: mixing the acrylic monomer and the dibenzoyl peroxide according to the proportion to obtain a mixture B, then dropwise adding the mixture B into the mixture A obtained in the step S1, and carrying out heat preservation reaction at the temperature of 100-110 ℃ for 1-2 hours to obtain the carboxyl modified epoxy resin.
3. The epoxy micaceous iron intermediate paint as claimed in claim 2, characterized in that: the modified mixed solvent in the step S1 comprises the following components in percentage by weight:
20-30% of n-butyl alcohol;
70-80% of ethylene glycol butyl ether.
4. The epoxy micaceous iron intermediate paint as claimed in claim 1, wherein: the A mixed solvent comprises the following components in percentage by weight:
60-70% of dimethylbenzene;
30-40% of butyl acetate;
the mixed solvent B comprises the following components in percentage by weight:
60-70% of dimethylbenzene;
30-40% of n-butanol.
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| CN112570240A (en) * | 2020-12-18 | 2021-03-30 | 淮北工业建筑设计院有限责任公司 | Anticorrosion process for mine transportation trestle |
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| CN102337067A (en) * | 2011-07-06 | 2012-02-01 | 江苏金陵特种涂料有限公司 | Aqueous epoxy antirust paint |
| CN104140736A (en) * | 2014-03-23 | 2014-11-12 | 成都拜迪新材料有限公司 | Preparation method of composite layer paint used for bottom, middle part and surface of railway support |
| CN104762000A (en) * | 2015-04-21 | 2015-07-08 | 沈阳德奥司科技有限公司 | Salt-spray resistant water-borne container and environment-friendly metallic paint thereof |
| CN111004561A (en) * | 2019-12-25 | 2020-04-14 | 湖南航天三丰科工有限公司 | High-weather-resistance water-based epoxy intermediate paint |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337067A (en) * | 2011-07-06 | 2012-02-01 | 江苏金陵特种涂料有限公司 | Aqueous epoxy antirust paint |
| CN104140736A (en) * | 2014-03-23 | 2014-11-12 | 成都拜迪新材料有限公司 | Preparation method of composite layer paint used for bottom, middle part and surface of railway support |
| CN104762000A (en) * | 2015-04-21 | 2015-07-08 | 沈阳德奥司科技有限公司 | Salt-spray resistant water-borne container and environment-friendly metallic paint thereof |
| CN111004561A (en) * | 2019-12-25 | 2020-04-14 | 湖南航天三丰科工有限公司 | High-weather-resistance water-based epoxy intermediate paint |
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Denomination of invention: An epoxy micaceous iron intermediate paint Effective date of registration: 20220711 Granted publication date: 20211026 Pledgee: Zhejiang Zhuji Rural Commercial Bank Co.,Ltd. Pledgor: Zhejiang Zhonghong New Material Technology Co.,Ltd. Registration number: Y2022980010211 |
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Denomination of invention: An epoxy mica iron intermediate paint Effective date of registration: 20230713 Granted publication date: 20211026 Pledgee: Zhejiang Zhuji Rural Commercial Bank Co.,Ltd. Pledgor: Zhejiang Zhonghong New Material Technology Co.,Ltd. Registration number: Y2023980048275 |