CN113292926A - Water-based self-repairing epoxy anticorrosive paint and preparation method thereof - Google Patents
Water-based self-repairing epoxy anticorrosive paint and preparation method thereof Download PDFInfo
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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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- 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
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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
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- C08K2003/328—Phosphates of heavy metals
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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
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Abstract
A water-based self-repairing epoxy anticorrosive paint and a preparation method thereof are disclosed, and the water-based self-repairing epoxy anticorrosive paint comprises the following raw materials: modified epoxy resin, epoxy emulsifier, deionized water, modified zinc phosphate, water-based curing agent, anti-flash rust agent and defoaming agent. The modified epoxy resin is prepared by reacting bisphenol A epoxy resin, tertiary carbonic acid glycidyl ether and sulfydryl end-capped polysulfide rubber under the catalysis of triethylamine; the modified zinc phosphate is prepared by ball milling zinc phosphate and gamma-mercaptopropyl trimethoxy silane in a ball mill; the epoxy emulsifier is prepared by the reaction of sulfydryl end-capped polysulfide rubber, bisphenol A epoxy resin and polyethylene glycol under the catalysis of boron trifluoride diethyl etherate. And (3) placing the aqueous dispersion prepared from the raw materials in a sand mill to disperse until the fineness is less than 50 micrometers, discharging, and adding an aqueous curing agent to obtain the aqueous self-repairing epoxy anticorrosive paint. The invention has the advantages of strong self-repairing capability of the coating, capability of self-repairing at room temperature, high aging resistance and corrosion resistance, uniform prepared coating and the like.
Description
Technical Field
The invention relates to the technical field of water-based anticorrosive coatings, in particular to a water-based self-repairing epoxy anticorrosive coating and a preparation method thereof.
Background
The corrosion prevention of the coating is a main form of metal protection, and the method prevents water, oxygen and electrolyte from permeating by forming a uniform and compact physical shielding layer on the surface of a metal substrate to inhibit the electrochemical corrosion behavior. Epoxy resins have excellent mechanical properties, thermal stability and chemical resistance and are the preferred resins for the manufacture of anticorrosion primers. The epoxy resin is brittle and is in severe environments of high and low temperature alternation, high humidity, ultraviolet light aging and the like for a long time, fine cracks are easily formed in the resin, and the resin gradually accumulates and diffuses to cause failure of a coating. The self-repairing material can self-repair the microcracks by utilizing the stress capability of the material, and becomes a research hotspot in the field of materials in recent years. A variety of dynamic bonds or structures can be used to construct the self-healing material, including hydrogen bonding, Diels-Alder reactions, transesterification reactions, and disulfide bonds.
The disulfide bond self-repairing structure has the characteristics of low repairing temperature and repeated repairing, and has better application prospect. Chinese patent publication No. CN106753192A discloses a room-temperature self-repairing and high-elongation polysulfide sealant, which comprises a thiol-terminated liquid polysulfide rubber, epoxy resin, an aromatic epoxy glycidyl ether modified liquid polysulfide oligomer and 2,4, 6-tris (dimethylaminomethyl) phenol, wherein the cross sections of the sealant are contacted with each other at room temperature, and self-repairing can be completed after 12-72 hours.
Chinese patent publication No. CN105111689A discloses a self-repairing nano conductive polymer material and a preparation method thereof, wherein after liquid polysulfide rubber of thiol group, bisphenol A type epoxy resin and sodium hydroxide react, conductive nano particles, a curing agent, a catalyst and an initiator are added to prepare the self-repairing nano conductive polymer material, which can meet the self-repairing requirement of the conductive material.
Chinese patent publication No. CN111410907A discloses a self-repairing type temperature-resistant and wear-resistant polyaspartic acid ester coating and a preparation method thereof, and the method directly adds aliphatic polysulfide modified epoxy resins EPS15 and EPS25 of Hengtian Hengjiangkezhiyu limited company to the polyaspartic acid ester coating to prepare the self-repairing type coating. The copper brush marks on the surface of the coating can be repaired within 5 min.
The above patent discloses the use of thiol-terminated polysulfide rubber or polysulfide rubber modified epoxy resin in self-repairing type packaging adhesives and solvent-based coatings. But the self-repairing technology is not popularized in a water-based system, especially a water-based preservative system on a large scale. The reason is that resin particles in the water-based paint need to break through steric shielding of the surfactant to complete particle interface contact and fusion, and the surfactant naturally forms stress cracking points and corrosion leakage points of the cured material. In order to solve the technical problems, two types of self-repairing structures are introduced into a hydrophilic interface contacted by particles, and are combined with polysulfide rubber modified epoxy resin to jointly prepare the self-repairing epoxy anticorrosive paint with higher self-repairing efficiency and anticorrosive capability. The disulfide bond modified epoxy emulsifier in the method can break through the steric hindrance of polyethylene glycol at a hydrophilic interface to form a self-repairing-S-S-structure, and the structural strength and the self-repairing capability of the cured waterborne epoxy coating are improved; the mercapto-modified zinc phosphate antirust pigment can reduce the self-repairing activation energy and provide good corrosion inhibition and passivation capability for the anticorrosive coating.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems, the invention provides the water-based self-repairing epoxy anticorrosive coating and the preparation method thereof, and the coating has the advantages of strong self-repairing capability, room-temperature self-repairing capability, high aging resistance and anticorrosive capability, uniform prepared coating and the like.
The technical scheme is as follows: the water-based self-repairing epoxy anticorrosive paint comprises the following raw materials in parts by mass: 100 parts of modified epoxy resin, 15-30 parts of epoxy emulsifier, 100 parts of deionized water, 150 parts of modified zinc phosphate, 20-40 parts of modified zinc phosphate, 50-80 parts of aqueous curing agent, 1-3 parts of flash rust inhibitor and 0.5-1.5 parts of defoaming agent;
the modified epoxy resin is prepared by reacting bisphenol A epoxy resin, tertiary carbonic acid glycidyl ether and sulfydryl end-capped polysulfide rubber under the catalysis of triethylamine;
the modified zinc phosphate is prepared by ball milling zinc phosphate and gamma-mercaptopropyl trimethoxy silane in a ball mill;
the epoxy emulsifier is prepared by reacting bisphenol A epoxy resin, sulfydryl end-capped polysulfide rubber and polyethylene glycol under the catalysis of boron trifluoride diethyl etherate.
Preferably, the mercapto-terminated polysulfide rubber is a liquid polysulfide rubber of type LP-3 from eastern japan company.
Preferably, the bisphenol a type epoxy resin is one of E20, E44, and E51.
Preferably, the polyethylene glycol is one of PEG-1500, PEG-4000 and PEG-6000.
Preferably, the aqueous curing agent is one of Hensmai Aradur 38-1, Dow WB 8001 and Barring petrochemical CYDHD-220; the flash rust inhibitor is a sodium nitrite aqueous solution with the mass fraction of 15%; the defoamer is one of TEGO FOAMEX 1488, BYK 024 and TEGO AIREX 901W.
Preferably, the modified epoxy resin comprises the raw materials of bisphenol A epoxy resin, tertiary carbonic acid glycidyl ether, sulfydryl end-capped polysulfide rubber and triethylamine in a mass ratio of 1: (0.1-0.3): (0.5-0.8): (0.02-0.05).
Preferably, the epoxy emulsifier is prepared from bisphenol A epoxy resin, mercapto-terminated polysulfide rubber, polyethylene glycol and boron trifluoride diethyl etherate in a mass ratio of 1: (0.6-1.5): (1.5-2): (0.02-0.05).
Preferably, the modified zinc phosphate comprises the raw materials of zinc phosphate and gamma-mercaptopropyltrimethoxysilane in a mass ratio of 1: (0.1-0.3).
The preparation method of the waterborne self-repairing epoxy anticorrosive paint comprises the following steps:
(1) preparation of modified epoxy resin: adding bisphenol A epoxy resin, tertiary carbonic acid glycidyl ether, sulfydryl terminated polysulfide rubber and triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature;
(2) preparation of epoxy emulsifier: adding toluene, sulfydryl-terminated polysulfide rubber, bisphenol A epoxy resin and polyethylene glycol into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding boron trifluoride diethyl etherate, reacting for 5 hours, and then decompressing and steaming out the toluene, wherein the mass ratio of the toluene to the bisphenol A epoxy resin is 5: 1;
(3) preparation of modified zinc phosphate: zinc phosphate and gamma-mercaptopropyl-trimethoxysilane are subjected to ball milling in a ball mill for 2 hours;
(4) preparing a water-based self-repairing epoxy anticorrosive paint: adding the modified epoxy resin and the epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding deionized water for dispersing for 0.5 hour to obtain aqueous dispersion resin, adding the modified zinc phosphate, the anti-flash rust agent and the defoaming agent into the dispersion, placing the dispersion into a sand mill for dispersing until the fineness is less than 50 microns, discharging, and adding the aqueous curing agent to obtain the aqueous self-repairing epoxy anticorrosive paint.
The intrinsic self-repairing mechanism of the high polymer material follows a mobile phase model, and the process can be divided into the following four steps: the material is damaged to generate damage → the material itself or the damage is stimulated by the external environment to generate a 'mobile phase' → 'mobile phase', the physical and chemical reaction is generated after the diffusion and fusion of the mobile phase at the damage → the repair reaction is followed by the 'mobile phase' to finally fill up and repair the damage. The disulfide self-repairing structure has the advantages of low glass transition temperature, good microcosmic fluidity and low self-repairing temperature, and is more suitable for the self-repairing requirement of a large-area anticorrosive coating. The invention takes the terminal sulfydryl polysulfide rubber as a modified structure of the epoxy resin, and can endow the epoxy resin with high anticorrosion capability with self-repairing performance. However, the pure disulfide structure still has a self-repairing temperature of about 50 ℃, and cannot meet the technical requirement of room temperature self-repairing. To solve this problem, the present invention introduces thiols or thiolates as a vehicle. The mechanism is that sulfur negative ions attack disulfide bonds, so that the disulfide bonds are rearranged after the disulfide bonds are broken, the activation energy of rearrangement is reduced, and the self-repairing temperature is reduced to room temperature. Referring to fig. 1, the invention uses gamma-mercaptopropyl-trimethoxysilane as a mercapto source and is adhered to the surface of the zinc phosphate antirust pigment by virtue of silane coupling effect, thereby not only avoiding the odor of free mercaptan, but also improving the anticorrosion capability of the composite coating by utilizing the passivation function of zinc phosphate. According to the invention, a disulfide bond structure is simultaneously introduced into the modified epoxy resin and the emulsifier structure, and the stable water-based self-repairing epoxy anticorrosive paint is innovatively prepared by virtue of a similar compatibility principle.
Has the advantages that: (1) according to the invention, by means of the ring-opening reaction of sulfydryl and epoxy, polysulfide rubber is introduced into an epoxy resin system to endow the epoxy resin with self-repairing capability, and the tertiary carbonic acid glycidyl ether is introduced in the modification process, so that the aging resistance and the corrosion resistance of the epoxy resin are improved by using the tertiary carbonic acid long carbon chain.
(2) The introduction of sulfydryl terminated polysulfide rubber into the hydrophobic end of the epoxy emulsifier is beneficial to improving the emulsifying capacity of the emulsifier on the modified epoxy resin. When the water-based resin is cured into a film, the disulfide bond structure with the self-repairing capability is simultaneously distributed in the resin particles and the particle fusion interface, so that the uniformity and the self-repairing capability of the coating are improved.
(3) The mercapto-modified zinc phosphate is introduced as an antirust pigment, so that the corrosion resistance of the coating can be improved by using the passivation capability of the zinc phosphate, and the activation energy of disulfide bond rearrangement can be reduced by using the mercapto group on the surface of the zinc phosphate, thereby realizing the room temperature repair capability.
Drawings
FIG. 1 is a schematic diagram of a self-repair process of a modified epoxy coating.
Detailed Description
The invention is further described with reference to specific examples. The epoxy resins E20, E44, E51 used in the examples and comparative examples were purchased from Nantong star plastics, Inc.; polyethylene glycol PEG-1500, PEG-4000 and PEG-6000 are available from Oakk GmbH of Liaoyang; zinc phosphate was purchased from Yaozhou Fine chemical Co., Ltd; the tertiary carbonic acid glycidyl ether is purchased from Henan Hansen, and all other raw materials are industrial-grade commodities.
Example 1
Preparation of modified epoxy resin: adding 100kg of E44 type epoxy resin, 20kg of tertiary carbonic acid glycidyl ether, 65kg of LP-3 type polysulfide rubber and 4kg of triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature.
Preparation of epoxy emulsifier: adding 500kg of toluene, 100kg of E44 epoxy resin, 110kg of LP-3 type polysulfide rubber, 180kg of polyethylene glycol PEG-4000 into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding 3kg of boron trifluoride diethyl etherate, reacting for 5 hours, and decompressing and distilling out the toluene.
Preparation of modified zinc phosphate: ball-milling 100kg of zinc phosphate and 20kg of gamma-mercaptopropyl-trimethoxysilane in a ball mill for 2 hours;
preparing a water-based self-repairing epoxy anticorrosive paint: adding 100kg of modified epoxy resin and 20kg of epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding 120kg of deionized water, dispersing for 0.5 hour to obtain a resin aqueous dispersion, adding 30kg of modified zinc phosphate, 2kg of 15 wt.% sodium nitrite aqueous solution and 1kg of TEGO FMAMEX 1488 defoaming agent into the dispersion, placing the dispersion into a sand mill, dispersing until the fineness is less than 50 micrometers, discharging, and adding 65kg of Dow WB 8001 curing agent to obtain the water-based self-repairing epoxy anticorrosive paint.
Comparative example 1
The difference from example 1 is that no LP-3 type polysulfide rubber is added in the preparation of the epoxy emulsifier. The method comprises the following specific steps:
preparation of modified epoxy resin: adding 100kg of E44 type epoxy resin, 20kg of tertiary carbonic acid glycidyl ether, 65kg of LP-3 type polysulfide rubber and 4kg of triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature.
Preparation of epoxy emulsifier: adding 500kg of toluene, 100kg of E44 type epoxy resin and 180kg of polyethylene glycol PEG-4000 into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding 3kg of boron trifluoride diethyl etherate, reacting for 5 hours, and decompressing and distilling out the toluene.
Preparation of modified zinc phosphate: ball-milling 100kg of zinc phosphate and 20kg of gamma-mercaptopropyl-trimethoxysilane in a ball mill for 2 hours;
preparing a water-based self-repairing epoxy anticorrosive paint: adding 100kg of modified epoxy resin and 20kg of epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding 120kg of deionized water, dispersing for 0.5 hour to obtain a resin aqueous dispersion, adding 30kg of modified zinc phosphate, 2kg of 15 wt.% sodium nitrite aqueous solution and 1kg of TEGO FMAMEX 1488 defoaming agent into the dispersion, placing the dispersion into a sand mill, dispersing until the fineness is less than 50 micrometers, discharging, and adding 65kg of Dow WB 8001 curing agent to obtain the water-based self-repairing epoxy anticorrosive paint.
Comparative example 2
The difference from example 1 is that the modified zinc phosphate was replaced with commercially available zinc phosphate. The method comprises the following specific steps:
preparation of modified epoxy resin: adding 100kg of E44 type epoxy resin, 20kg of tertiary carbonic acid glycidyl ether, 65kg of LP-3 type polysulfide rubber and 4kg of triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature.
Preparation of epoxy emulsifier: adding 500kg of toluene, 100kg of E44 epoxy resin, 110kg of LP-3 type polysulfide rubber, 180kg of polyethylene glycol PEG-4000 into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding 3kg of boron trifluoride diethyl etherate, reacting for 5 hours, and decompressing and distilling out the toluene.
Preparing a water-based self-repairing epoxy anticorrosive paint: adding 100kg of modified epoxy resin and 20kg of epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding 120kg of deionized water, dispersing for 0.5 hour to obtain a resin aqueous dispersion, adding 30kg of commercially available zinc phosphate, 2kg of 15wt% sodium nitrite aqueous solution and 1kg of TEGO FMAMEX 1488 defoaming agent into the dispersion, placing the dispersion into a sand mill, dispersing until the fineness is less than 50 micrometers, discharging, and adding 65kg of Dow WB 8001 curing agent to obtain the water-based self-repairing epoxy anticorrosive paint.
Comparative example 3
The difference from example 1 is that no LP-3 type polysulfide rubber is added to prepare the epoxy emulsifier; the modified zinc phosphate was replaced with a commercially available zinc phosphate. The method comprises the following specific steps:
preparation of modified epoxy resin: adding 100kg of E44 type epoxy resin, 20kg of tertiary carbonic acid glycidyl ether, 65kg of LP-3 type polysulfide rubber and 4kg of triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature.
Preparation of epoxy emulsifier: adding 500kg of toluene, 100kg of E44 type epoxy resin and 180kg of polyethylene glycol PEG-4000 into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding 3kg of boron trifluoride diethyl etherate, reacting for 5 hours, and decompressing and distilling out the toluene.
Preparing a water-based self-repairing epoxy anticorrosive paint: adding 100kg of modified epoxy resin and 20kg of epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding 120kg of deionized water, dispersing for 0.5 hour to obtain a resin aqueous dispersion, adding 30kg of commercially available zinc phosphate, 2kg of 15wt% sodium nitrite aqueous solution and 1kg of TEGO FMAMEX 1488 defoaming agent into the dispersion, placing the dispersion into a sand mill, dispersing until the fineness is less than 50 micrometers, discharging, and adding 65kg of Dow WB 8001 curing agent to obtain the water-based self-repairing epoxy anticorrosive paint.
Example 2
Preparation of modified epoxy resin: adding 100kg of E20 type epoxy resin, 30kg of tertiary carbonic acid glycidyl ether, 80kg of LP-3 type polysulfide rubber and 5kg of triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature.
Preparation of epoxy emulsifier: adding 500kg of toluene, 100kg of E20 type epoxy resin, 150kg of LP-3 type polysulfide rubber, 200kg of polyethylene glycol PEG-6000 into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding 5kg of boron trifluoride diethyl etherate, reacting for 5 hours, and decompressing and distilling out the toluene.
Preparation of modified zinc phosphate: ball-milling 100kg of zinc phosphate and 30kg of gamma-mercaptopropyl-trimethoxysilane in a ball mill for 2 hours;
preparing a water-based self-repairing epoxy anticorrosive paint: adding 100kg of modified epoxy resin and 30kg of epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding 150kg of deionized water, dispersing for 0.5 hour to obtain a resin aqueous dispersion, adding 40kg of modified zinc phosphate, 3kg of 15wt% sodium nitrite aqueous solution and 1.5kg of TEGO AIREX 901W defoaming agent into the dispersion, placing the dispersion into a sand mill, dispersing until the fineness is less than 50 microns, discharging, and adding 80kg of Henmi ARADR 38-1 curing agent to obtain the water-based self-repairing epoxy anticorrosive paint.
Example 3
Preparation of modified epoxy resin: adding 100kg of E51 type epoxy resin, 10kg of tertiary carbonic acid glycidyl ether, 50kg of LP-3 type polysulfide rubber and 2kg of triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature.
Preparation of epoxy emulsifier: adding 500kg of toluene, 100kg of E51 type epoxy resin, 60kg of LP-3 type polysulfide rubber and 150kg of polyethylene glycol PEG-1500 into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding 2kg of boron trifluoride diethyl etherate, reacting for 5 hours, and decompressing and distilling out the toluene.
Preparation of modified zinc phosphate: ball-milling 100kg of zinc phosphate and 10kg of gamma-mercaptopropyl-trimethoxysilane in a ball mill for 2 hours;
preparing a water-based self-repairing epoxy anticorrosive paint: adding 100kg of modified epoxy resin and 15kg of epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding 100kg of deionized water, dispersing for 0.5 hour to obtain a resin aqueous dispersion, adding 20kg of modified zinc phosphate, 1kg of 15wt% sodium nitrite aqueous solution and 0.5kg of BYK 024 defoaming agent into the dispersion, placing the dispersion into a sand mill, dispersing until the fineness is less than 50 microns, discharging, and adding 50kg of ba ling petrochemical CYDHD-220 curing agent to obtain the self-repairing waterborne epoxy anticorrosive paint.
The waterborne self-repairing epoxy anticorrosive coatings prepared in the examples and the comparative examples are placed in a tetrafluoroethylene mold, demolding is carried out after curing at room temperature for 7 days, dumbbell-shaped tensile samples are prepared according to IOS527-2:2012, and the tensile strength and the elongation at break are tested according to GB/T1040 standard. Cutting the dumbbell piece into two halves in the middle, aligning and attaching the section, repairing for 24 hours at room temperature, and repeatedly circulating for 5 times and then testing the tensile strength and the elongation at break.
The water-based self-repairing epoxy anticorrosive coatings prepared in the examples and the comparative examples are blade-coated on the surface of a cold-rolled steel test plate by using a wire bar coater, dried at room temperature for 7 days, edge-sealed by using a polyvinyl chloride adhesive tape, and then various performance tests are carried out according to national standards, and the results are shown in table 1.
TABLE 1 Performance test results of waterborne self-repairing epoxy anticorrosive coatings
As can be seen from table 1, the epoxy emulsifier in comparative example 1 does not contain a disulfide bond structure, and cannot provide a self-repairing capability for the fused interface of the epoxy particles, and the unfused region between the particles forms a stress cracking point, resulting in a significant decrease in tensile strength and elongation at break; in comparative example 2, an epoxy emulsifier with a disulfide bond structure is used, but the zinc phosphate surface is not modified by sulfydryl, so that the self-repairing temperature is greatly increased, and the self-repairing efficiency is reduced due to the increase of the difficulty of opening the disulfide bond and secondary connection. Comparative example 3 using an EP-PEG type epoxy emulsifier having no self-healing ability and zinc phosphate without mercapto modification, it hardly exerted a self-healing effect only by virtue of the disulfide bond of the resin itself. Compared with the water-based self-repairing epoxy anticorrosive coating prepared in the embodiment 1-3, the coating has better coating hardness, adhesive force and anticorrosive performance, and the self-repairing efficiency is still more than 98% after 5 times of cyclic failure tests.
Claims (9)
1. The water-based self-repairing epoxy anticorrosive paint is characterized by comprising the following raw materials in parts by mass: 100 parts of modified epoxy resin, 15-30 parts of epoxy emulsifier, 100 parts of deionized water, 150 parts of modified zinc phosphate, 20-40 parts of modified zinc phosphate, 50-80 parts of aqueous curing agent, 1-3 parts of flash rust inhibitor and 0.5-1.5 parts of defoaming agent;
the modified epoxy resin is prepared by reacting bisphenol A epoxy resin, tertiary carbonic acid glycidyl ether and sulfydryl end-capped polysulfide rubber under the catalysis of triethylamine;
the modified zinc phosphate is prepared by ball milling zinc phosphate and gamma-mercaptopropyl trimethoxy silane in a ball mill;
the epoxy emulsifier is prepared by reacting bisphenol A epoxy resin, sulfydryl end-capped polysulfide rubber and polyethylene glycol under the catalysis of boron trifluoride diethyl etherate.
2. The waterborne self-repairing epoxy anticorrosive paint of claim 1, wherein the mercapto-terminated polysulfide rubber is liquid polysulfide rubber model LP-3 of Dongli corporation of Japan.
3. The waterborne self-repairing epoxy anticorrosive paint of claim 1, wherein the bisphenol A epoxy resin is one of E20, E44 and E51.
4. The waterborne self-repairing epoxy anticorrosive paint of claim 1, wherein the polyethylene glycol is one of PEG-1500, PEG-4000 and PEG-6000.
5. The waterborne self-healing epoxy anticorrosive coating according to claim 1, wherein the waterborne curing agent is one of hensmyru ARADUR 38-1, dow WB 8001 and barlington cymene CYDHD-220; the flash rust inhibitor is a sodium nitrite aqueous solution with the mass fraction of 15%; the defoamer is one of TEGO FOAMEX 1488, BYK 024 and TEGO AIREX 901W.
6. The water-based self-repairing epoxy anticorrosive paint as claimed in claim 1, wherein the modified epoxy resin comprises bisphenol A epoxy resin, glycidyl versatate, mercapto-terminated polysulfide rubber and triethylamine in a mass ratio of 1: (0.1-0.3): (0.5-0.8): (0.02-0.05).
7. The water-based self-repairing epoxy anticorrosive paint as claimed in claim 1, wherein the epoxy emulsifier comprises bisphenol A epoxy resin, mercapto-terminated polysulfide rubber, polyethylene glycol and boron trifluoride diethyl etherate in a mass ratio of 1: (0.6-1.5): (1.5-2): (0.02-0.05).
8. The water-based self-repairing epoxy anticorrosive paint of claim 1, wherein the modified zinc phosphate comprises zinc phosphate and gamma-mercaptopropyl-trimethoxysilane in a mass ratio of 1: (0.1-0.3).
9. The preparation method of the water-based self-repairing epoxy anticorrosive paint disclosed by any one of claims 1 to 8 is characterized by comprising the following steps:
(1) preparation of modified epoxy resin: adding bisphenol A epoxy resin, tertiary carbonic acid glycidyl ether, sulfydryl terminated polysulfide rubber and triethylamine into a reaction kettle, heating to 60 ℃, reacting for 8 hours, and cooling to room temperature;
(2) preparation of epoxy emulsifier: adding toluene, sulfydryl-terminated polysulfide rubber, bisphenol A epoxy resin and polyethylene glycol into a reactor with an oil-water separator, refluxing and dehydrating for 2 hours, cooling to 80 ℃, adding boron trifluoride diethyl etherate, reacting for 5 hours, and then decompressing and steaming out the toluene, wherein the mass ratio of the toluene to the bisphenol A epoxy resin is 5: 1;
(3) preparation of modified zinc phosphate: zinc phosphate and gamma-mercaptopropyl-trimethoxysilane are subjected to ball milling in a ball mill for 2 hours;
(4) preparing a water-based self-repairing epoxy anticorrosive paint: adding the modified epoxy resin and the epoxy emulsifier into a reaction kettle, heating to 60 ℃, adding deionized water for dispersing for 0.5 hour to obtain aqueous dispersion resin, adding the modified zinc phosphate, the anti-flash rust agent and the defoaming agent into the dispersion, placing the dispersion into a sand mill for dispersing until the fineness is less than 50 microns, discharging, and adding the aqueous curing agent to obtain the aqueous self-repairing epoxy anticorrosive paint.
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