CN113025165A - Solvent-free epoxy heavy-duty anticorrosive paint and preparation method and application thereof - Google Patents
Solvent-free epoxy heavy-duty anticorrosive paint and preparation method and application thereof Download PDFInfo
- Publication number
- CN113025165A CN113025165A CN202110171042.1A CN202110171042A CN113025165A CN 113025165 A CN113025165 A CN 113025165A CN 202110171042 A CN202110171042 A CN 202110171042A CN 113025165 A CN113025165 A CN 113025165A
- Authority
- CN
- China
- Prior art keywords
- parts
- solvent
- epoxy resin
- agent
- duty anticorrosive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- 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
-
- 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
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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 solvent-free epoxy heavy-duty anticorrosive paint, and a preparation method and application thereof, and belongs to the technical field of paints. The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components in parts by weight: 30-60 parts of epoxy resin, 20-30 parts of polyamide resin, 5-10 parts of alkyd resin, 0.5-2 parts of dispersing agent, 0.5-2 parts of defoaming agent, 1-3 parts of flatting agent, 1-3 parts of anti-settling agent, 30-70 parts of filler, 1-2 parts of rheological additive and 10-20 parts of curing agent. The solvent-free epoxy heavy-duty anticorrosive coating combines the advantages of epoxy resin, polyamide resin and alkyd resin, has the characteristics of good film-forming property and high adhesive force of the epoxy resin, and has the characteristics of high viscosity and good gloss retention of the alkyd resin, good flexibility, wear resistance, oil resistance, water resistance and chemical corrosion resistance of the polyamide resin.
Description
Technical Field
The invention relates to a preparation method and application of a solvent-free epoxy heavy-duty anticorrosive paint, and belongs to the technical field of paints.
Background
Corrosion has always been one of the biggest challenges facing industries such as steel, metallurgy, construction, transportation, etc. There is data indicating that every second hand on a watch makes one and a half revolutions, 1 ton of steel is corroded to slag in the world. The loss caused by corrosion in 2015 years of China is as high as 3 trillion yuan RMB, and according to the calculation, if correct protection measures are taken, the corrosion loss of 7500-12000 trillion RMB can be reduced in China every year. Anticorrosive coatings are the most economical, most commonly used and most effective means of corrosion protection for metal or concrete materials today. The anticorrosive paint is generally divided into a conventional type and a heavy-duty anticorrosive type according to the corrosion resistance degree and the use requirement of a paint film layer. The conventional anticorrosive paint plays a role in corrosion resistance on metals and the like under general conditions, protects the service life of nonferrous metals, and mainly comprises red lead antirust paint, alkyd resin paint and the like; the heavy-duty anticorrosive coating is an anticorrosive coating which can be applied in a relatively severe corrosion environment compared with a conventional anticorrosive coating and has a longer protection period than the conventional anticorrosive coating, and mainly comprises an epoxy resin coating, a polyurethane coating, a fluorocarbon coating, a chlorinated rubber coating, an acrylic coating, an organic silicon resin coating, inorganic zinc silicate and the like. With the rapid development of the petroleum industry, railways, highway bridges, metallurgical industry, electric power and energy industry, machinery and textile industry, industrial product field, automobiles, ships, containers and other industries in China, continuous innovation of the technology of the anti-corrosive coating field is urgently needed.
The economic loss caused by corrosion is huge every year in the steel ocean engineering of ships, bridges, wharfs and the like all over the world. The antiseptic practice of each country proves that: the coating of the heavy-duty anticorrosive paint is the most effective and economic anticorrosive means for ocean engineering. Most heavy anticorrosive coatings in the existing market are solvent-based, cause the pollution to the environment, and have solvent detention risk during thick film coating, easily form pinhole and shrinkage cavity simultaneously for water and medium ion reach the substrate surface through diffusion and transmission very easily, produce corrosive substance and make the coating fracture after the inflation, finally cause the coating to drop, thereby lose the guard action. Patent 201811017758.0 reports a preparation method of epoxy pipeline anticorrosive paint, the main film forming substances of the patent are epoxy resin and acrylic resin, but the paint has low adhesion and requires high temperature in the reaction process; patent 201710989036.0 reports a moist epoxy anticorrosive paint which is easy to pollute due to organic solvent, although it can be applied on steel substrate with moisture.
Solvent-free coatings, also known as reactive solvent coatings, are not completely solvent-free, but rather refer to the solvent that ultimately becomes a component of the coating film and does not emit VOCs into the atmosphere during the curing to form a film. The solvent-free coating only contains a very small amount of volatile organic solvent, so that only few shrinkage cavities and pinholes are generated after the coating is cured, and the compactness of the coating effectively increases the barrier property and the permeation resistance of the anticorrosive coating. However, the solvent-free coating in the current market is limited by the material properties and the process, the corrosion protection effect on metal and concrete matrixes is not ideal, the cost of the solvent-free coating with prominent individual performance is high, and the cost performance of the coating is reduced. The prior art reports a solvent-free epoxy steel structure anticorrosive paint, but the acid resistance, alkali resistance and salt spray resistance of the paint are not ideal. Patent 201710323891.8 reports a solvent-free anticorrosive paint, but the paint contains a seal coat and a top coat, and the thickness of a single film is thinner, so that the times of construction are increased, and the anticorrosive effect of the coating is influenced. Therefore, the solvent-free anticorrosive paint with high performance and environmental protection under the harsh environment of ocean engineering is developed, and has huge application prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method and application of a solvent-free heavy-duty anticorrosive coating with high adhesion, one-time construction film forming, high thickness and good chemical corrosion resistance.
In order to achieve the purpose, the invention adopts the technical scheme that: a solvent-free epoxy heavy-duty anticorrosive paint comprises the following components in parts by weight: 30-60 parts of epoxy resin, 20-30 parts of polyamide resin, 5-10 parts of alkyd resin, 0.5-2 parts of dispersing agent, 0.5-2 parts of defoaming agent, 1-3 parts of flatting agent, 1-3 parts of anti-settling agent, 30-70 parts of filler, 1-2 parts of rheological additive and 10-20 parts of curing agent.
The epoxy resin is a thermosetting resin containing two or more epoxy groups per molecule on average. The ether bond and the hydroxyl contained in the molecular structure of the epoxy resin are strong polar groups, and the groups can generate strong adhesive force between the epoxy resin molecules and the surface of a substrate, particularly a metal surface, and the excellent adhesive force is the most basic condition for a good coating. After the epoxy resin is cured to form a film, the molecular structure is compact because the molecules contain stable ether bonds of benzene rings, so that the stability of the epoxy resin to chemical media is better. The alkyd resin has the characteristics of high viscosity, good gloss retention, good flexibility, wear resistance, oil resistance, water resistance and chemical corrosion resistance of the polyamide resin, and excellent mechanical and corrosion resistance. The solvent-free epoxy heavy-duty anticorrosive paint disclosed by the invention combines the advantages of epoxy resin, polyamide resin and alkyd resin. The solvent-free epoxy heavy-duty anticorrosive coating is a thick paste type coating, and a defoaming agent is required to be added to eliminate bubbles entering a coating system in the stirring process; the dispersant can improve the stability of the coating dispersion system, can be adsorbed on the surface of the filler, and prevents the dispersed filler from forming harmful flocculation again.
As a preferable embodiment of the solvent-free epoxy heavy-duty anticorrosive coating, the epoxy resin is 40-60 parts by weight, and the curing agent is 13.7-20 parts by weight. More preferably, the epoxy resin is 50 parts by weight and the curing agent is 16.7 parts by weight. The adhesive force of the solvent-free epoxy heavy anti-corrosion coating is influenced by the using amount of the epoxy resin, and researches show that when the epoxy resin accounts for 40-60 parts by weight and the curing agent accounts for 13.7-20 parts by weight, the adhesive force of the solvent-free epoxy heavy anti-corrosion coating is better, and particularly when the epoxy resin accounts for 50 parts by weight and the curing agent accounts for 16.7 parts by weight, the adhesive force of the solvent-free epoxy heavy anti-corrosion coating is optimal.
Preferably, the epoxy resin is polysilane modified bisphenol A epoxy resin, because the siloxane bond has high bond energy, the polymer molecular chain has high crimpability, gamma-aminopropyl triethoxysilane (KH-550) is used as a modifier to modify the bisphenol A epoxy resin, and the KH-550 and the bisphenol A epoxy resin are subjected to crosslinking to form the siloxane-siloxane bond, so that the molecular weight is improved, and the mechanical properties, the water resistance, the weather resistance and the like of the resin are improved.
Preferably, the volume ratio of the KH-550 to the bisphenol A epoxy resin is 1: 10-1: 15. the volume ratio of KH-550 to bisphenol a epoxy resin affects the transparency, viscosity, stability of the polysilane-modified bisphenol a epoxy resin of the present invention. When the addition amount of KH-550 is too small, the transparency of the polysilane-modified bisphenol A epoxy resin is poor; when the KH-550 is added in an excessive amount, KH550 will further react with bisphenol A epoxy resin, and the system will easily gel.
Preferably, the filler consists of bentonite, titanium dioxide and barium sulfate. The filler can affect the internal stress generated in the curing process of the coating film, and the internal stress is an important factor influencing the adhesive force of the coating. Different fillers and amounts added can affect the corrosion resistance of the coating and the physical properties of the coating base. Titanium dioxide is a white pigment, has high whiteness, strong covering power and high weather resistance. The barium sulfate has excellent acid and alkali resistance and lower oil absorption value, and the weather resistance and the acid and alkali resistance of the coating can be improved by adding the barium sulfate. The bentonite can improve the sagging resistance and the film forming thickness of the epoxy resin in the brushing process.
Preferably, the mass ratio of the bentonite to the titanium dioxide to the barium sulfate is that the mass ratio of the bentonite to the titanium dioxide to the barium sulfate is: titanium dioxide: barium sulfate 1: 1: 1-1: 3: 3. the stability, acid and alkali resistance and weather resistance of the solvent-free epoxy heavy-duty anticorrosive coating are influenced by the addition amount of the filler, and researches show that the mass ratio of bentonite, titanium dioxide and barium sulfate is bentonite: titanium dioxide: barium sulfate 1: 1: 1-1: 3: 3, the acid-base resistance and stability of the present invention are better.
As a preferred embodiment of the solvent-free epoxy heavy-duty anticorrosive coating, the curing agent is triethylene tetramine.
The solvent-free epoxy coating requires that a coating formed by the curing agent and the resin component has good performance of resisting external mechanical abrasion and chemical corrosion for a long time, so the key of the performance of the coating is determined by the curing agent and the crosslinking curing effect. The products of the crosslinking of epoxy resins with different curing agents vary widely. The triethylene tetramine has low toxicity, can be quickly cured with epoxy resin to form a film at normal temperature, and has high crosslinking density.
In addition, the invention also provides a preparation method of the solvent-free epoxy heavy-duty anticorrosive paint, which comprises the following steps: mixing and stirring epoxy resin, polyamide resin, alkyd resin, a dispersing agent, a defoaming agent, a flatting agent and an anti-settling agent for 0.5-1h, and then adding a filler and stirring for 1-2 h; and adding a rheological additive, stirring, and finally adding a curing agent, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive paint.
In addition, the invention also provides application of the solvent-free epoxy heavy-duty anticorrosive paint in the field of steel structure and concrete surface corrosion prevention in marine environment.
Compared with the prior art, the invention has the beneficial effects that: the invention uniformly disperses a plurality of resins to prepare the solvent-free epoxy heavy-duty anticorrosive paint. The coating has the advantages of high adhesive force, high hardness, excellent salt spray resistance, good impact resistance, good flexibility, excellent acid and alkali resistance and high chloride ion permeability resistance; the solid content of the coating is more than 99%, volatile organic compounds are not generated, the process is simple, the paint film is three-in-one in bottom and middle surface, the single film forming thickness can reach 500 mu m, the coating times are reduced, the energy is saved, the environment is protected, and the coating is suitable for large-scale production.
Drawings
FIG. 1 is a graph showing the effect of example 1 before and after 3000h of salt spray resistance.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components: 50 parts of epoxy resin, 25 parts of polyamide resin, 7 parts of alkyd resin, 1 part of dispersing agent, 1 part of defoaming agent, 2 parts of flatting agent, 2 parts of anti-settling agent, 40 parts of filler, 1 part of rheological additive and 16.7 parts of curing agent.
The preparation method of the solvent-free epoxy heavy-duty anticorrosive paint comprises the following steps:
(1) preparation of bisphenol A type epoxy resin
A500 mL three-necked flask was equipped with a stirrer, a reflux condenser and a thermometer. 12.3 parts of bisphenol A, 41 parts of epichlorohydrin and 4.1 parts of NaOH are added and mixed and stirred. Then slowly heating to 80 ℃, and finishing the reaction after reacting for 3 hours. The reaction solution was filtered to remove the by-product NaCl, and the excess epichlorohydrin was distilled off under reduced pressure (recovered) (60-70 ℃ C.). Then, distillation was stopped, and the residue was poured into a small beaker while it was hot to obtain a pale yellow, transparent and viscous bisphenol A type epoxy resin.
(2) Preparation of polysilane modified bisphenol A type epoxy resin
Mixing a silane coupling agent KH-550 and bisphenol A epoxy resin according to a volume ratio of 1: 10, and stirring at 1000rpm for 1h to obtain the polysilane modified bisphenol A epoxy resin.
(3) Preparation of solvent-free epoxy heavy-duty anticorrosive paint
50 parts of polysilane modified bisphenol A type epoxy resin in the step (2), 25 parts of polyamide resin, 7 parts of alkyd resin, 1 part of dispersing agent 6212, 2 parts of leveling agent BYK346, 1 part of defoaming agent SRE 2122 and 2 parts of anti-settling agent carboxymethyl cellulose are mixed and stirred for 1 hour, and then 10 parts of bentonite, 15 parts of titanium dioxide and 15 parts of barium sulfate are added at 1000rpm and stirred for 1 hour; and adding 1 part of rheological additive, stirring at 2500rpm for 40min, and finally adding 16.7 parts of tetraethylenetriamine, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive paint.
Example 2
The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components: 60 parts of epoxy resin, 30 parts of polyamide resin, 10 parts of alkyd resin, 1 part of dispersing agent, 1 part of defoaming agent, 2 parts of flatting agent, 2 parts of anti-settling agent, 70 parts of filler, 1 part of rheological additive and 20 parts of curing agent.
The preparation method of the solvent-free epoxy heavy-duty anticorrosive paint comprises the following steps:
(1) preparation of bisphenol A type epoxy resin
A500 mL three-necked flask was equipped with a stirrer, a reflux condenser and a thermometer. 12.6 parts of bisphenol A, 42 parts of epichlorohydrin and 4.2 parts of NaOH are added and mixed and stirred. Then slowly heating to 80 ℃, and finishing the reaction after reacting for 3 hours. The reaction solution was filtered to remove the by-product NaCl, and the excess epichlorohydrin was distilled off under reduced pressure (recovered) (60-70 ℃ C.). The distillation was stopped and the residue was poured hot into a small beaker to give a pale yellow, transparent, viscous bisphenol A epoxy resin.
(2) Preparation of polysilane modified bisphenol A type epoxy resin
Mixing a silane coupling agent KH-550 and bisphenol A epoxy resin according to a volume ratio of 1: 12, and stirring the mixture at 1000rpm for 1 hour to obtain the polysilane modified bisphenol A epoxy resin.
(3) Preparation of solvent-free epoxy heavy-duty anticorrosive paint
60 parts of polysilane modified bisphenol A type epoxy resin in the step (2), 30 parts of polyamide resin, 10 parts of alkyd resin, 1 part of dispersing agent 6212, 2 parts of leveling agent BYK346, 1 part of defoaming agent SRE 2122 and 2 parts of anti-settling agent carboxymethyl cellulose are mixed and stirred for 1 hour, and then 10 parts of bentonite, 30 parts of titanium dioxide and 30 parts of barium sulfate are added at 1000rpm and stirred for 2 hours; and adding 1 part of rheological additive, stirring for 40min at 2500rpm, and finally adding 20 parts of tetraethylenetriamine, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive coating.
Example 3
The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components: 40 parts of epoxy resin, 20 parts of polyamide resin, 5 parts of alkyd resin, 1 part of dispersing agent, 1 part of defoaming agent, 2 parts of flatting agent, 2 parts of anti-settling agent, 35 parts of filler, 1 part of rheological additive and 13.7 parts of curing agent.
The preparation method of the solvent-free epoxy heavy-duty anticorrosive paint comprises the following steps:
(1) preparation of bisphenol A type epoxy resin
A500 mL three-necked flask was equipped with a stirrer, a reflux condenser and a thermometer. Adding 11.4 parts of bisphenol A, 38 parts of epichlorohydrin and 3.8 parts of NaOH, mixing and stirring, slowly heating to 80 ℃, and reacting for 3 hours to finish the reaction. The reaction solution was filtered to remove the by-product NaCl, and the excess epichlorohydrin was distilled off under reduced pressure (recovered) (60-70 ℃ C.). The distillation was stopped and the residue was poured hot into a small beaker to give a pale yellow, transparent, viscous bisphenol A epoxy resin.
(2) Preparation of polysilane modified bisphenol A type epoxy resin
Mixing a silane coupling agent KH-550 and bisphenol A epoxy resin according to a volume ratio of 1: 15 and stirring at 1000rpm for 1h to obtain the polysilane modified bisphenol A epoxy resin.
(3) Preparation of solvent-free epoxy heavy-duty anticorrosive paint
Mixing and stirring 40 parts of polysilane modified bisphenol A epoxy resin in the step (2), 20 parts of polyamide resin, 5 parts of alkyd resin, 1 part of dispersing agent 6212, 2 parts of leveling agent BYK346, 1 part of defoaming agent SRE 2122 and 2 parts of anti-settling agent carboxymethyl cellulose for 0.5h, and then adding 10 parts of bentonite, 15 parts of titanium dioxide and 10 parts of barium sulfate at 1000rpm and stirring for 1 h; and adding 1 part of rheological additive, stirring at 2500rpm for 40min, and finally adding 13.7 parts of tetraethylenetriamine, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive paint.
Example 4
The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components: 60 parts of epoxy resin, 30 parts of polyamide resin, 10 parts of alkyd resin, 0.5 part of dispersing agent, 0.5 part of defoaming agent, 1 part of flatting agent, 1 part of anti-settling agent, 30 parts of filler, 1.5 parts of rheological additive and 20 parts of curing agent.
The preparation method of the solvent-free epoxy heavy-duty anticorrosive paint comprises the following steps:
(1) preparation of bisphenol A type epoxy resin
A500 mL three-necked flask was equipped with a stirrer, a reflux condenser and a thermometer. 12.6 parts of bisphenol A, 42 parts of epichlorohydrin and 4.2 parts of NaOH are added and mixed and stirred. Then slowly heating to 80 ℃, and finishing the reaction after reacting for 3 hours. The reaction solution was filtered to remove the by-product NaCl, and the excess epichlorohydrin was distilled off under reduced pressure (recovered) (60-70 ℃ C.). The distillation was stopped and the residue was poured hot into a small beaker to give a pale yellow, transparent, viscous bisphenol A epoxy resin.
(2) Preparation of polysilane modified bisphenol A type epoxy resin
Mixing a silane coupling agent KH-550 and bisphenol A epoxy resin according to a volume ratio of 1: 12 and stirring at 1000rpm for 0.8h to obtain the polysilane modified bisphenol A epoxy resin.
(3) Preparation of solvent-free epoxy heavy-duty anticorrosive paint
Mixing 60 parts of polysilane modified bisphenol A type epoxy resin in the step (2), 30 parts of polyamide resin, 10 parts of alkyd resin, 0.5 part of dispersing agent 6212, 1 part of leveling agent BYK346, 0.5 part of defoaming agent SRE 2122 and 1 part of anti-settling agent carboxymethyl cellulose, stirring for 1 hour, then adding 10 parts of bentonite, 10 parts of titanium dioxide and 10 parts of barium sulfate at 1000rpm, and stirring for 1.5 hours; and then adding 1.5 parts of rheological additive, stirring for 40min at 2500rpm, and finally adding 20 parts of tetraethylenetriamine, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive paint.
Example 5
The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components: 60 parts of epoxy resin, 30 parts of polyamide resin, 10 parts of alkyd resin, 2 parts of dispersing agent, 2 parts of defoaming agent, 3 parts of flatting agent, 3 parts of anti-settling agent, 70 parts of filler, 2 parts of rheological additive and 20 parts of curing agent.
The preparation method of the solvent-free epoxy heavy-duty anticorrosive paint comprises the following steps:
(1) preparation of bisphenol A type epoxy resin
A500 mL three-necked flask was equipped with a stirrer, a reflux condenser and a thermometer. 12.6 parts of bisphenol A, 42 parts of epichlorohydrin and 4.2 parts of NaOH are added and mixed and stirred. Then slowly heating to 80 ℃, and finishing the reaction after reacting for 3 hours. The reaction solution was filtered to remove the by-product NaCl, and the excess epichlorohydrin was distilled off under reduced pressure (recovered) (60-70 ℃ C.). The distillation was stopped and the residue was poured hot into a small beaker to give a pale yellow, transparent, viscous bisphenol A epoxy resin.
(2) Preparation of polysilane modified bisphenol A type epoxy resin
Mixing a silane coupling agent KH-550 and bisphenol A epoxy resin according to a volume ratio of 1: 12 and stirring at 1000rpm for 0.8h to obtain the polysilane modified bisphenol A epoxy resin.
(3) Preparation of solvent-free epoxy heavy-duty anticorrosive paint
60 parts of polysilane modified bisphenol A type epoxy resin in the step (2), 30 parts of polyamide resin, 10 parts of alkyd resin, 2 parts of dispersing agent 6212, 3 parts of flatting agent BYK346, 2 parts of defoaming agent SRE 2122 and 3 parts of anti-settling agent carboxymethyl cellulose are mixed and stirred for 1 hour, and then 10 parts of bentonite, 30 parts of titanium dioxide and 30 parts of barium sulfate are added at 1000rpm and stirred for 1.5 hours; and then adding 2 parts of rheological additive, stirring for 40min at 2500rpm, and finally adding 20 parts of tetraethylenetriamine, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive coating.
Example 6
The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components: 30 parts of epoxy resin, 20 parts of polyamide resin, 10 parts of alkyd resin, 1 part of dispersing agent, 1 part of defoaming agent, 2 parts of flatting agent, 2 parts of anti-settling agent, 70 parts of filler, 1 part of rheological additive and 10 parts of curing agent.
The preparation method of the solvent-free epoxy heavy-duty anticorrosive paint comprises the following steps:
(1) preparation of bisphenol A type epoxy resin
A500 mL three-necked flask was equipped with a stirrer, a reflux condenser and a thermometer. 12.6 parts of bisphenol A, 42 parts of epichlorohydrin and 4.2 parts of NaOH are added and mixed and stirred. Then slowly heating to 80 ℃, and finishing the reaction after reacting for 3 hours. The reaction solution was filtered to remove the by-product NaCl, and the excess epichlorohydrin was distilled off under reduced pressure (recovered) (60-70 ℃ C.). The distillation was stopped and the residue was poured hot into a small beaker to give a pale yellow, transparent, viscous bisphenol A epoxy resin.
(2) Preparation of polysilane modified bisphenol A type epoxy resin
Mixing a silane coupling agent KH-550 and bisphenol A epoxy resin according to a volume ratio of 1: 12 and stirring at 1000rpm for 0.8h to obtain the polysilane modified bisphenol A epoxy resin.
(3) Preparation of solvent-free epoxy heavy-duty anticorrosive paint
Mixing and stirring 30 parts of polysilane modified bisphenol A type epoxy resin in the step (2), 20 parts of polyamide resin, 10 parts of alkyd resin, 1 part of dispersing agent 6212, 2 parts of leveling agent BYK346, 1 part of defoaming agent SRE 2122 and 2 parts of anti-settling agent carboxymethyl cellulose for 1 hour, and then adding 10 parts of bentonite, 10 parts of titanium dioxide and 10 parts of barium sulfate at 1000rpm and stirring for 1.5 hours; and adding 1 part of rheological additive, stirring for 40min at 2500rpm, and finally adding 10 parts of tetraethylenetriamine, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive coating.
Comparative example 1
The solvent-free epoxy heavy-duty anticorrosive paint comprises the following components: 50 parts of epoxy resin, 25 parts of polyamide resin, 7 parts of alkyd resin, 1 part of dispersing agent, 1 part of defoaming agent, 2 parts of flatting agent, 2 parts of anti-settling agent, 40 parts of filler, 1 part of rheological additive and 16.7 parts of curing agent.
The preparation method of the solvent-free epoxy heavy-duty anticorrosive paint comprises the following steps:
(1) preparation of bisphenol A type epoxy resin
A500 mL three-necked flask was equipped with a stirrer, a reflux condenser and a thermometer. 12.3 parts of bisphenol A, 41 parts of epichlorohydrin and 4.1 parts of NaOH are added and mixed and stirred. Then slowly heating to 80 ℃, and finishing the reaction after reacting for 3 hours. The reaction solution was filtered to remove the by-product NaCl, and the excess epichlorohydrin was distilled off under reduced pressure (recovered) (60-70 ℃ C.). Then, distillation was stopped, and the residue was poured into a small beaker while it was hot to obtain a pale yellow, transparent and viscous bisphenol A type epoxy resin.
(2) Preparation of solvent-free epoxy heavy-duty anticorrosive paint
50 parts of polysilane modified bisphenol A type epoxy resin in the step (1), 25 parts of polyamide resin, 7 parts of alkyd resin, 1 part of dispersing agent 6212, 2 parts of leveling agent BYK346, 1 part of defoaming agent SRE 2122 and 2 parts of anti-settling agent carboxymethyl cellulose are mixed and stirred for 1 hour, and then 10 parts of bentonite, 15 parts of titanium dioxide and 15 parts of barium sulfate are added at 1000rpm and stirred for 1 hour; and adding 1 part of rheological additive, stirring at 2500rpm for 40min, and finally adding 16.7 parts of tetraethylenetriamine, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive paint.
Examples of effects
The performances of examples 1 to 6 and comparative example 1 were measured according to the following test methods, and the test results are shown in table 1.
(1) Adhesion force: test Standard GB/T1720-
(2) Hardness: test standard GB/T6739-
(3) Impact resistance: test Standard GB/T1732-1993
(4) Flexibility: test Standard GB/T1731-1993
(5) Salt water resistance: normal temperature brine method for testing standard GB/T1763-89
(6) Gasoline resistance: test standard GB/T1734 + 1993 gasoline immersion method
(7) Salt spray resistance: test standard GB/T1771-91
(8) Acid and alkali resistance: test standard GB/T1763-89
(9) Moisture and heat resistance: test Standard GB/T1740-
(10) Resistance to chloride ion permeability: test Standard JTJ 275-
TABLE 1
As can be seen from Table 1, the solvent-free epoxy heavy-duty anticorrosive coating disclosed by the invention has the advantages that the adhesive force can reach 12Mpa, the hardness can reach 5H, the salt spray resistance exceeds 4000H, the impact resistance is 50cm, the flexibility can reach 1mm, and the 10% H resistance2SO4960h, 960h for resisting 10 percent NaOH, 720h for resisting 3 percent NaCl, 600h for resisting 93# gasoline and 0.8X10 for resisting chloride ion permeability-3mg/(cm2.d)。
FIG. 1 is a graph showing the effects of example 1 before and after 3000h of salt spray resistance, wherein the upper part of FIG. 1 is a photograph of example 1 before 3000h of salt spray resistance, and the lower part of FIG. 1 is a photograph of example 1 after 3000h of salt spray resistance. Comparing the upper part and the lower part, the method shows that no obvious difference exists before and after the salt fog resistance of the embodiment, which shows that the solvent-free epoxy heavy-duty anticorrosive coating has excellent salt fog resistance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The solvent-free epoxy heavy-duty anticorrosive paint is characterized by comprising the following components in parts by weight: 30-60 parts of epoxy resin, 20-30 parts of polyamide resin, 5-10 parts of alkyd resin, 0.5-2 parts of dispersing agent, 0.5-2 parts of defoaming agent, 1-3 parts of flatting agent, 1-3 parts of anti-settling agent, 30-70 parts of filler, 1-2 parts of rheological additive and 10-20 parts of curing agent.
2. The solvent-free epoxy heavy duty anticorrosive paint according to claim 1, wherein the epoxy resin is 40 to 60 parts by weight, and the curing agent is 13.7 to 20 parts by weight.
3. The solvent-free epoxy heavy duty anticorrosive paint according to claim 1, wherein the epoxy resin is 50 parts by weight, and the curing agent is 16.7 parts by weight.
4. The solvent-free epoxy heavy duty anticorrosive coating according to any one of claims 1 to 3, wherein the epoxy resin is a polysilane-modified bisphenol A type epoxy resin.
5. The solvent-free epoxy heavy duty anticorrosive coating according to claim 4, wherein the polysilane-modified bisphenol A type epoxy resin is prepared by the following steps: gamma-aminopropyltriethoxysilane and bisphenol a type epoxy resin were mixed in a 1: 10-1: 15, and stirring to obtain the polysilane modified bisphenol A epoxy resin.
6. The solvent-free epoxy heavy duty anticorrosive coating of claim 1, wherein the filler consists of bentonite, titanium dioxide and barium sulfate.
7. The solvent-free epoxy heavy-duty anticorrosive paint according to claim 6, wherein the mass ratio of bentonite, titanium dioxide and barium sulfate is bentonite: titanium dioxide: barium sulfate 1: 1: 1-1: 3: 3.
8. the solvent-free epoxy heavy duty anticorrosive coating according to any one of claims 1 to 3, wherein the curing agent is triethylene tetramine.
9. The method for preparing the solvent-free epoxy heavy duty anticorrosive paint according to any one of claims 1 to 8, characterized by comprising the steps of: mixing and stirring epoxy resin, polyamide resin, alkyd resin, a dispersing agent, a defoaming agent, a flatting agent and an anti-settling agent for 0.5-1h, and then adding a filler and stirring for 1-2 h; and adding the rheological additive, stirring for 40min, and finally adding the curing agent, stirring and mixing to obtain the solvent-free epoxy heavy-duty anticorrosive paint.
10. The use of the solvent-free epoxy heavy duty coating of any one of claims 1-8 in the field of corrosion protection of steel structures and concrete surfaces in marine environments.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110171042.1A CN113025165A (en) | 2021-02-08 | 2021-02-08 | Solvent-free epoxy heavy-duty anticorrosive paint and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110171042.1A CN113025165A (en) | 2021-02-08 | 2021-02-08 | Solvent-free epoxy heavy-duty anticorrosive paint and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113025165A true CN113025165A (en) | 2021-06-25 |
Family
ID=76460628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110171042.1A Pending CN113025165A (en) | 2021-02-08 | 2021-02-08 | Solvent-free epoxy heavy-duty anticorrosive paint and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113025165A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044880A (en) * | 2021-09-28 | 2022-02-15 | 昆明国松特种涂料有限公司 | Polycarbonate epoxy resin, solvent-free anticorrosive paint and application |
| CN115093768A (en) * | 2022-06-14 | 2022-09-23 | 中山大学 | Solvent-free modified epoxy anticorrosive coating and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016017102A (en) * | 2014-07-07 | 2016-02-01 | 日立化成株式会社 | Heat-resistant resin composition |
| CN109370365A (en) * | 2018-08-03 | 2019-02-22 | 中山大学 | A kind of ship anticorrosion and antifouling dual-function paint |
| WO2019070146A1 (en) * | 2017-10-04 | 2019-04-11 | Общество С Ограниченной Ответственностью "Рустек" | Varnish-paint composition for obtaining thin coatings by cathodic electrodeposition method |
| CN110903739A (en) * | 2019-12-11 | 2020-03-24 | 薛彦高 | Graphene high-temperature-resistant anticorrosive paint |
| CN111303729A (en) * | 2020-05-06 | 2020-06-19 | 佛山湘潭大学绿色智造研究院 | Solvent-free anticorrosive paint and preparation method thereof |
-
2021
- 2021-02-08 CN CN202110171042.1A patent/CN113025165A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016017102A (en) * | 2014-07-07 | 2016-02-01 | 日立化成株式会社 | Heat-resistant resin composition |
| WO2019070146A1 (en) * | 2017-10-04 | 2019-04-11 | Общество С Ограниченной Ответственностью "Рустек" | Varnish-paint composition for obtaining thin coatings by cathodic electrodeposition method |
| CN109370365A (en) * | 2018-08-03 | 2019-02-22 | 中山大学 | A kind of ship anticorrosion and antifouling dual-function paint |
| CN110903739A (en) * | 2019-12-11 | 2020-03-24 | 薛彦高 | Graphene high-temperature-resistant anticorrosive paint |
| CN111303729A (en) * | 2020-05-06 | 2020-06-19 | 佛山湘潭大学绿色智造研究院 | Solvent-free anticorrosive paint and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 潘少川等: "《实验应力分析》", 31 October 1988 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044880A (en) * | 2021-09-28 | 2022-02-15 | 昆明国松特种涂料有限公司 | Polycarbonate epoxy resin, solvent-free anticorrosive paint and application |
| CN114044880B (en) * | 2021-09-28 | 2024-01-09 | 昆明国松特种涂料有限公司 | Polycarbonate epoxy resin, solvent-free anticorrosive paint and application |
| CN115093768A (en) * | 2022-06-14 | 2022-09-23 | 中山大学 | Solvent-free modified epoxy anticorrosive coating and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110484095B (en) | Thick-coating underwater curing long-acting anticorrosive coating and preparation method thereof | |
| CN109370364B (en) | Nano anticorrosive paint for metal surface in acid-related environment and preparation method thereof | |
| CN101643615B (en) | Polyaniline modified glass flake heavy-duty anti-corrosive coating and preparation method thereof | |
| CN113025165A (en) | Solvent-free epoxy heavy-duty anticorrosive paint and preparation method and application thereof | |
| CN101747691B (en) | Single-component modified high chlorinated polyethylene weathering resistant residual rust painting | |
| CN103333607A (en) | Corrosion-resistant high-temperature insulation paint | |
| CN109306226B (en) | Long-acting anticorrosion primer for metal substrate and preparation method thereof | |
| KR102199316B1 (en) | Eco-friendly steel structure concrete protective epoxy composition containing modified graphene and steel structure repair method using the same | |
| CN111303729B (en) | Solvent-free anticorrosive paint and preparation method thereof | |
| CN107603423A (en) | A kind of underwater curing ocean steel construction durably anticorrosion paint and preparation method thereof | |
| CN111004557A (en) | Nano modified epoxy heavy-duty anticorrosive paint | |
| CN112375463A (en) | Environment-friendly high-solid-content heavy-duty anticorrosive paint for inner wall of storage tank and preparation method thereof | |
| CN113444383A (en) | Emulsion modified inorganic zinc-rich silicate anticorrosive paint and preparation method thereof | |
| CN110343443A (en) | A kind of graphene coating and preparation method thereof | |
| CN112194916A (en) | Water-based silica sol gel inorganic zinc-rich primer and preparation method thereof | |
| CN113025185A (en) | Graphene super-hydrophobic anticorrosive paint and preparation method thereof | |
| CN1752160A (en) | Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof | |
| CN109988442B (en) | Graphene water-based zinc silicate coating, application thereof and anticorrosive coating | |
| CN115286767A (en) | Antibacterial fluorine modified epoxy vinyl ester resin, preparation method thereof and multi-mechanism synergetic universal anticorrosive coating | |
| CN112029382B (en) | Long-acting anticorrosion solvent-free universal epoxy coating and preparation method thereof | |
| CN110105848B (en) | Water-based epoxy asphalt anticorrosive paint and processing technology thereof | |
| CN115386280B (en) | Heavy-duty anticorrosive paint and preparation method thereof | |
| CN114149729B (en) | Anti-corrosion static-conductive solvent-free polyurea coating and preparation method and application thereof | |
| CN115011213A (en) | Solvent-free heavy-duty anticorrosive paint capable of being coated with water and rust and preparation method thereof | |
| CN115466557A (en) | Anti-rust and anti-corrosion primer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210625 |