CN112662276B - Bio-based fireproof salt-tolerant water-based epoxy resin coating and preparation method thereof - Google Patents
Bio-based fireproof salt-tolerant water-based epoxy resin coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bio-based fireproof salt-tolerant water-based epoxy resin coating and a preparation method thereof, wherein the bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following raw materials in parts by weight: 25-40 parts of a water-based epoxy resin emulsion curing agent, 40-80 parts of a water-based epoxy prepolymer solution, 0.3-1.2 parts of a defoaming agent, 0.3-1.8 parts of a flatting agent, 0.06-1.2 parts of a wetting dispersant and 1.3-9.6 parts of a curing accelerator. The invention has the advantages of simple and convenient synthesis process, small pollution, low toxicity, simple post-treatment, high yield and purity, and the obtained water-based epoxy resin coating has good processability, salt resistance and excellent fireproof effect. Compared with bisphenol A type waterborne epoxy resin coating, the tensile strength of the cured epoxy resin is improved to 8.3MPa, which is 319 percent of that of the bisphenol A epoxy resin in the comparative example, the epoxy resin is intrinsic flame retardant, the LOI value reaches 29.7 percent, the fire resistance temperature reaches 700 ℃, and the coating can resist salt corrosion.
Description
Technical Field
The invention relates to an epoxy resin coating, in particular to a bio-based fireproof salt-tolerant water-based epoxy resin coating and a preparation method thereof, belonging to the field of resin coatings.
Background
The fireproof and corrosion-resistant coating for steel is very important, the coating of the fireproof salt-resistant coating is an effective means for protecting steel, the water-based epoxy resin coating has great potential in the application aspect of steel coatings by virtue of the advantages of environmental friendliness, no VOC (volatile organic compounds) emission, simple operation process, good usability, good adhesion and the like, however, the fireproof performance of the epoxy resin is always poor, and the traditional water-based epoxy coating is obtained by introducing hydrophilic groups into bisphenol A epoxy resin through ring opening, so that the epoxy value is obviously reduced after water-based treatment due to the fact that the content of the epoxy groups in the molecules of the bisphenol A epoxy resin is less, the crosslinking degree of a cured product is low, and the mechanical property, particularly the rigidity and the corrosion resistance are further reduced.
The existing water-based epoxy resin paint is respectively brushed with the paint with fireproof and anticorrosive effects by a layered brushing method to obtain the fireproof and anticorrosive effects. The Chinese patent CN201110298461.8 discloses an environment-friendly steel structure building fireproof and anticorrosion composite coating, which is formed by compounding a fireproof coating and an anticorrosion coating, wherein the fireproof coating comprises the following materials in percentage by weight: 200-300 deionized water, 5-20 dispersing agents, 10-30 film-forming additives, 1-5 antifoaming agents, 20-70 titanium dioxide, 20-50 chlorinated paraffin at 70 ℃, 200-350 ammonium polyphosphate, 50-100 melamine, 50-100 dipentaerythritol, 30-100 expanded graphite and 200-300 acrylic emulsion. The special anticorrosive coating for the fireproof coating comprises the following materials in percentage by weight: 128 parts of deionized water, 1 part of dispersant, 48 parts of film forming additive, 7 parts of defoaming agent, 9.5 parts of propylene glycol, 5 parts of mildew preventive, 200 parts of titanium dioxide, 38 parts of sericite powder, 3.5 parts of precipitated barium sulfate and 615 parts of emulsion. The technology continuously coats the anticorrosive coating on the basis of the fireproof primer, and respectively achieves the effects of resisting fire for 90 minutes at 500 ℃ and resisting 3 wt% of saline for 120 hours. However, the problem of poor bonding force between the two coatings is caused by the difference of the surface tension of the water-based anticorrosive coating and the fireproof coating, and cracks or orange peel lines (Zhuyuan. preparation and performance research [ D ] 2016 ] of water-based intumescent steel structure fireproof coating) are generated on the surface of the anticorrosive coating which is coated subsequently under most conditions, so that the function of each coating is attenuated.
In recent years, techniques for improving the fire-retardant and corrosion-resistant properties of coatings by adding fire-retardant agents and corrosion-resistant agents have also appeared. The Chinese patent application CN201811534561.4 discloses a water-based anticorrosion and fireproof integrated coating, which comprises the following specific preparation steps: 1) mixing sodium tripolyphosphate, dimethylbenzene and a silane coupling agent, reacting, washing and drying to obtain modified sodium tripolyphosphate; 2) mixing modified sodium tripolyphosphate, graphene oxide and deionized water, reacting, washing and drying to obtain integrated sodium tripolyphosphate/graphene oxide; 3) mixing the integrated sodium tripolyphosphate/graphene oxide, deionized water and water-based epoxy resin to obtain mother liquor; 4) and mixing the mother solution and other auxiliary agents in proportion to obtain the water-based anticorrosive fireproof integrated coating. The technology is prepared by integrally adding graphene oxide and sodium tripolyphosphate into aqueous epoxy resin through a silane coupling agent, and in addition, the hollow microspheres and ceramic powder are added to improve the rigidity of the aqueous epoxy resin, so that the LOI value is increased to 23.1%, and the salt spray resistance is improved by 500 hours. However, the technology still uses various additives, and does not mention whether to avoid the problem that the blending compatibility of the additive and the waterborne epoxy resin matrix is poor, and the LOI value is 23.1 percent which is only 1.1 percent higher than that of flammable materials, so that the urgent requirement of fire resistance of steel at present is difficult to meet.
With the requirements of social sustainable development and environmental protection, the epoxy resin coating which is phosphorus-free, halogen-free, intrinsically fireproof and anticorrosive, especially the multifunctional coating with salt corrosion resistance, gradually becomes the most advanced research hotspot and difficulty because the multifunctional coating can be used in severe environment and reduce the corrosion of steel in seawater. The prior art does not have an effective material which can improve the rigidity of a coating by intrinsic fire prevention and salt corrosion resistance without adding inorganic additives on the premise of simultaneously achieving phosphorus and halogen free.
Disclosure of Invention
Aiming at the defects of the existing water-based epoxy resin coating, the invention aims to provide a bio-based fireproof salt-tolerant water-based epoxy resin coating which is phosphorus-free and halogen-free, has the fire resistance temperature of 700 ℃, improves the rigidity, resists 3.5 wt% of saline water to soak for more than 35 days, and a preparation method thereof, and solves the problems of poor compatibility of an additive and a substrate, poor multi-coating operability, poor fireproof and anticorrosion effects and the like in the prior art.
The purpose of the invention is realized by the following technical scheme.
The bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following raw materials in parts by weight: 25-40 parts of a water-based epoxy resin emulsion curing agent, 40-80 parts of a water-based epoxy prepolymer solution, 0.3-1.2 parts of a defoaming agent, 0.3-1.8 parts of a flatting agent, 0.06-1.2 parts of a wetting dispersant and 1.3-9.6 parts of a curing accelerator;
the aqueous epoxy prepolymer solution is prepared by the following method: protocatechuic aldehyde and 4,4' -diaminodiphenylmethane are reacted to prepare Schiff base structural intermediate; dissolving the Schiff base structural intermediate and tetrabutylammonium bromide in epichlorohydrin, and reacting to prepare an epoxy prepolymer; the epoxy prepolymer and diethanol amine are dissolved and then react to prepare aqueous epoxy prepolymer solution.
To further achieve the object of the present invention, preferably, the preparation method of the aqueous epoxy prepolymer solution comprises the following steps:
1) preparation of Schiff base structural intermediate: dissolving protocatechualdehyde and 4,4' -diaminodiphenylmethane, heating to 40-70 ℃ under stirring, heating to 60-85 ℃, and reacting for 4-8 hours under the protection of nitrogen and condensation reflux; cooling, precipitating, filtering, washing and drying to obtain a Schiff base structural intermediate;
2) preparation of epoxy prepolymer: dissolving the Schiff base structural intermediate obtained in the step 1) and tetrabutylammonium bromide in epoxy chloropropane, heating to 100-110 ℃, reacting for 2-6 hours, cooling to room temperature, and dropwise adding a sodium hydroxide solution in an ice water bath; heating to 60-65 ℃ for reaction for 4-6 hours, allowing the solution to become turbid, standing for 6-12 hours, separating an oil layer product, washing, and performing rotary evaporation to obtain an epoxy prepolymer;
3) preparation of aqueous epoxy prepolymer solution: dissolving the epoxy prepolymer obtained in the step 2) and diethanolamine, heating to 65-85 ℃, reacting for 1.5-3 hours under stirring, dropwise adding glacial acetic acid, continuously stirring for 20-60 minutes to obtain a waterborne epoxy prepolymer, adding water, continuously stirring for reacting for 20-40 minutes, and ultrasonically vibrating at room temperature to prepare a waterborne epoxy prepolymer solution.
Preferably, the structure of the schiff base intermediate is:
the Schiff base intermediate is yellow powder at room temperature and is easy to absorb water.
Preferably, the structural formula of the epoxy prepolymer is:
the epoxy prepolymer is a tan viscous liquid at room temperature, and the epoxy value is 0.42-0.46 mol/100 g.
Preferably, the molar ratio of the protocatechualdehyde to the 4,4' -diaminodiphenylmethane is 2: 1-4: 1; the molar ratio of the Schiff base structural intermediate to the epichlorohydrin is 1: 8-1: 20, and the molar ratio of the tetrabutylammonium bromide to the Schiff base structural intermediate is 1: 8-1: 12; the molar ratio of the amino group of the diethanolamine to the epoxy group in the epoxy prepolymer is 4.5: 10-6.5: 10.
Preferably, in the step 1), the protocatechualdehyde and 4,4' -diaminodiphenylmethane are dissolved in a first solvent, wherein the first solvent is one of ethanol, dioxane, methanol and dimethylformamide, and the amount of the first solvent is 4-6 times of the mass of the protocatechualdehyde; the precipitate is precipitated by pouring the cooled product into a mixed solution of deionized water and ethanol with the volume ratio of 2: 1-4: 1; the drying is vacuum drying; the vacuum drying temperature is 90-110 ℃, and the drying time is 10-12 hours; the stirring speed is 200-250 r/min.
Preferably, in the step 2), the washing is repeatedly washing the oil layer product separated after standing by using a mixed solution of deionized water and dichloromethane, wherein the volume ratio of the deionized water to the dichloromethane is 1: 1-2: 1; the rotary evaporation is carried out for 2-4 hours at 85-95 ℃; the concentration of the sodium hydroxide solution is 25-40 wt%, and the molar ratio of the added sodium hydroxide to the Schiff base intermediate is 4: 1-6: 1;
in the step 2), before the Schiff base intermediate is used, vacuum drying is carried out for 12 hours at the temperature of 100-110 ℃; the reaction is carried out for 2-6 hours at 100-110 ℃ under stirring, and the stirring speed is 100-250 r/min; the reaction at 60-65 ℃ for 4-6 hours is carried out under stirring at a stirring speed of 150-250 r/min.
Preferably, in step 3), the epoxy prepolymer and the diethanolamine are dissolved by dissolving the epoxy prepolymer and the diethanolamine in a second solvent; the second solvent is one or more of ethanol, propanol, ethyl acetate, isopropanol, tetrahydrofuran and methyl isobutyl ketone; the dosage of the second solvent is 0.3-1.0 time of the total mass of the epoxy prepolymer; the dosage of the dropwise added glacial acetic acid is 0.5-1.0 time of the molar dosage of the diethanolamine; the ratio of the water to the total mass of the diethanolamine and the epoxy prepolymer is 3: 2-2: 3; the ultrasonic vibration time is 15-45 minutes; the power of the ultrasonic vibration is 100-480W; the stirring speed for reacting for 1.5-3 hours under stirring is 150-300 r/min; the stirring speed of the stirring reaction for 20-60 minutes is 150-300 r/min; the stirring speed of the stirring reaction for 20-40 minutes is 350-550 r/min.
Preferably, the defoaming agent is at least one of polydimethylsilane compound molecular defoaming agents Formstara10, Formstara12, Formstara34 and Formstara36 of Corning chemical Co., Ltd, or polysiloxane-polyether copolymer defoaming agents Foamex815, Foamex8030, Foamex Airex901W of Germany Yingchu high chemical Co., Ltd, or Deformer155 of Heihuan chemical engineering; the leveling agent is at least one of polyether modified polydimethylsiloxane copolymer BYK-333, BYK-330, BYK-358N, BYK-360 and SILCN333 of German Bike chemistry or Ciba-3580 leveling agent of Switzerland Ciba fine chemical engineering company; the wetting dispersant is at least one of polyether modified organic silicon wetting agents TEGOWet KL245, TEGOWet270, Miigao TSF4440 and TSF4458 of Germany Wingdi high chemistry company, or SKB-008 of Keningchemical company, or GreesolA04BC, GreesolA04DPM, Tujel FS-204PG and Tujel FS-204E of Yueyang Karman company.
Preferably, the curing accelerator is one of 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30 and K-54;
the waterborne epoxy resin emulsion curing agent is BC919 (active hydrogen content is 0.403mol/100g) of Guangzhou limited company of the science and technology of the solid new material, H228B (active hydrogen content is 0.255mol/100g) of northwest Yongxin coating limited company or PLR736 (active hydrogen content is 1.13mol/100g) of northwest Yongxin coating limited company.
The preparation method of the bio-based fireproof salt-resistant water-based epoxy resin coating comprises the following steps: and at normal temperature, adding a water-based epoxy resin emulsion curing agent, a flatting agent, a wetting dispersant, a defoaming agent and a curing accelerator into a water-based epoxy prepolymer solution under stirring, stirring at the speed of 350-550 r/min for 5-20 minutes to obtain the bio-based fireproof salt-tolerant water-based epoxy resin coating.
The invention adopts protocatechuic aldehyde to synthesize the polyepoxy epoxy prepolymer and the waterborne epoxy condensate with higher crosslinking degree by an environment-friendly synthesis method. Protocatechualdehyde is a bio-based phenolic compound containing two phenolic hydroxyl groups and an aldehyde group, and can be prepared into a Schiff base structure containing phenyl
The carbon-nitrogen six-membered ring can be generated at high temperature by the C ═ N double bond in the structure of the epoxy prepolymer, and the polymer forms a stable crosslinking network by the six-membered ring structure, so that the material is endowed with good fire resistance. Meanwhile, N-element lone-pair electrons and pi-electron clouds can be formed by C-N in the molecules of the Schiff base and the metal surface, so that the Schiff base is adsorbed on the metal surface, and the corrosion caused by redox reaction of metal in salt solution is reduced, thereby simultaneously endowing the water-based epoxy resin with intrinsic fireproof and anticorrosion functions. In addition, the traditional waterborne epoxy resin generally needs to be added with a rigidity additive to make up the defects of low rigidity and difficult scratch resistance, and the rigidity can be enhanced by utilizing the rigid structure of the protocatechuic aldehyde with a plurality of benzene rings.
The invention designs and synthesizes the bio-based water-based epoxy prepolymer containing Schiff base structure and multi-epoxy functional group to obtain the water-based epoxy condensate with higher crosslinking density, and the Schiff base has the characteristics of fire prevention and corrosion prevention and is environment-friendly. At present, the research on the aspect is little at home and abroad, so the development of the intrinsic anticorrosion fireproof water-based epoxy resin is urgently needed, and the research and development significance is great.
In the invention, 4 phenolic hydroxyl groups of the Schiff base intermediate can react with epichlorohydrin to generate epoxy prepolymer with 4 epoxy groups. 4 epoxy groups of the epoxy prepolymer can be subjected to ring-opening hydration reaction with diethanol amine, and the ring-opening amount of the reaction is controlled to generate the waterborne epoxy prepolymer still having a plurality of epoxy groups.
Compared with the prior art, the formula of the invention has the following advantages:
1. the epoxy resin cured coating obtained by the invention has the characteristics of intrinsic fire resistance and salt corrosion resistance, is phosphorus-free, halogen-free, environment-friendly and safe, avoids the operation of respectively coating fire-proof paint and anticorrosive paint, can realize good fire resistance and salt corrosion resistance, and has strong operability.
2. The epoxy resin cured film obtained by the invention has intrinsic fire resistance, the LOI value is 29.7%, the LOI value is increased by 6.6 units (invention CN201811534561.4) compared with an additive-type fire-proof salt-resistant coating, the fire resistance temperature is increased to 700 ℃ compared with the traditional bisphenol A-type epoxy resin coating, the rigidity is improved, the epoxy resin cured film can resist 3.5 wt% saline water for more than 35 days, and the epoxy resin cured film can be stably used in a harsh environment.
3. The water-based anticorrosion and fireproof integrated coating prepared by the preparation method disclosed by the invention is good in dispersibility, high in anticorrosion performance, good in flame retardant effect, convenient and fast to construct and free of interlayer shedding.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of Schiff base structural intermediate (PH-DDM) obtained in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of an epoxy Prepolymer (PDE) obtained in example 1 of the present invention.
FIG. 3 is a FTIR spectrum of the Schiff base structural intermediate, the epoxy prepolymer and the aqueous epoxy prepolymer (WPDE) obtained in example 1 of the present invention.
FIG. 4(a) is a graph showing the residual condition of a sample after the test by a cone calorimeter in comparative example 1 of the present invention.
FIG. 4(b) is a sample residue after the cone calorimeter test of example 1 of the present invention.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following drawings and examples, but the present invention is not limited thereto.
Example 1
A preparation method of a bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following steps:
(1) preparation of Schiff base structural intermediate:dissolving 41g of protocatechualdehyde and 20g of 4,4' -diaminodiphenylmethane in 200g of dimethylformamide, adding the mixture into a three-neck flask, heating the mixture to 70 ℃ under stirring, mechanically stirring the mixture at 200r/min under the action of nitrogen protection and condensation reflux, and reacting the mixture for 4 hours at 80 ℃; after the reaction is finished, precipitating by using a blending solution of deionized water and ethanol in a volume ratio of 3:1 to obtain a precipitation product, carrying out suction filtration for 5 times, washing by using deionized water to remove a solvent, and drying the product at 90 ℃ in vacuum to obtain the Schiff base structural intermediate PH-DDM. Dissolving a small amount of the product in a dimethyl sulfoxide deuterated reagent (DMSO), and performing1H NMR measurements, the results are shown in FIG. 1, where the chemical shifts are-OH (H) at 9.58ppm and 9.30ppm1And H2) The peak at the chemical shift of 8.39ppm is the Schiff base structure-CH- ═ N- (H)6) And the peak at 7.40-6.83 ppm is proton (H) on benzene ring3-5，H7，H8). The product was subjected to FTIR test at the same time, and as shown in fig. 3, PH-DDM showed an absorption peak (1627 cm) of schiff base (C ═ N) structure-1) And phenolic hydroxyl absorption peak (3501 cm)-1，1393cm-1) The successful synthesis of an intermediate (PH-DDM) containing a Schiff base structure is shown in the following formula.
(2) Preparation of aqueous epoxy prepolymer: dissolving 20g of the Schiff base structural intermediate PH-DDM and 1.42g of tetrabutylammonium bromide in 45g of epichlorohydrin, adding the solution into a three-neck flask, reacting at 105 ℃ for 4 hours under mechanical stirring at 250r/min, then cooling, dropwise adding 28g of sodium hydroxide solution (NaOH) with the mass fraction of 25 wt% into an ice water bath, continuing to react for 3 hours at 60 ℃ and 250r/min to obtain a product turbid solution, standing the product turbid solution in a separating funnel for 12 hours for liquid separation, taking an oil phase, washing residual salt by using a deionized water and dichloromethane mixed solution (the volume ratio is 2:1), washing for 5 times by using deionized water to remove a small amount of salt impurities in the oil phase, taking the oil phase by using liquid separation, and carrying out rotary evaporation at 90 ℃ for 2 hours to prepare the epoxy prepolymer PDE.1H NMR and FTIR resultsAs shown in fig. 2 and 3. Wherein, the peak with the chemical shift of 2.5-2.8 ppm corresponds to the epoxy group-CHOCH- (H)1And H2) The peak with chemical shift of 8.43-8.57 ppm can be assigned as proton (H) on Schiff base structure (-CH ═ N-)7，H7’) (ii) a Can be seen in the FTIR spectrum of PDE, at 910cm-1A characteristic absorption peak of an epoxy group appeared in the vicinity of the region and was located at 3501cm-1，1393cm-1And the peak sum of phenolic hydroxyl groups of (1) is located at 1210cm-1The C-O characteristic peak of (A) disappeared, indicating that the conversion of the PH-DDM into an epoxy Prepolymer (PDE) was successful as shown in the following formula.
(3) Preparation of aqueous epoxy prepolymer solution: 12g of the epoxy prepolymer and 2.64g of Diethanolamine (DEA) were dissolved in 12g of absolute ethanol (EtOH), the mixture was added to a three-necked flask, and reacted at 80 ℃ for 2 hours at 300r/min, 1.13g of glacial acetic acid (AcOH) was slowly added dropwise thereto and the reaction was continued at 300r/min for 30 minutes, at which time the product was a waterborne epoxy prepolymer (WPDE) and detected by FTIR, as shown in FIG. 3, the WPDE appeared at 3620cm-1The obvious peak of the alcoholic hydroxyl group indicates that the hydration is successful. Continuously adding 9.76g of water, mechanically stirring at 550r/min for 30 minutes, then ultrasonically vibrating for 30 minutes at the power of 100W to prepare the aqueous epoxy prepolymer solution.
(4) Preparing the fireproof salt-resistant water-based epoxy resin coating: and (2) mixing 40g of BC919 curing agent (Banco 919 long-chain aliphatic amine curing agent) with the aqueous epoxy resin solution according to the mass ratio of 1:2.544, sequentially adding 1g of Formstara10 defoaming agent, 1.53g of BYK-333 leveling agent, 0.77g of SKB-008 wetting agent and 2g of 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30 curing accelerator during rotation at the rotating speed of 550r/min, and stirring for 5 minutes to obtain the bio-based fireproof salt-resistant aqueous epoxy resin coating.
Example 2
A preparation method of a bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following steps:
(1) preparation of Schiff base structural intermediate: dissolving 55.2g of protocatechualdehyde and 20g of 4,4' -diaminodiphenylmethane in 240g of dimethylformamide, adding the solution into a three-neck flask, heating the solution to 70 ℃ under stirring, mechanically stirring the solution at 250r/min under the action of nitrogen protection and condensation reflux, and reacting the solution for 8 hours at 85 ℃; after the reaction is finished, precipitating by using a blending solution of deionized water and ethanol in a volume ratio of 2:1 to obtain a precipitation product, carrying out suction filtration for 5 times, washing by using deionized water to remove a solvent, and drying the product in vacuum at 110 ℃ to obtain the Schiff base structural intermediate PH-DDM. The resulting PH-DDM was structurally identical to FIG. 1.
(2) Preparation of aqueous epoxy prepolymer: dissolving 20g of the Schiff base structural intermediate PH-DDM and 1.77g of tetrabutylammonium bromide in 80g of epichlorohydrin, adding the solution into a three-neck flask, reacting at 110 ℃ for 4 hours under mechanical stirring at 250r/min, then cooling, dropwise adding 26g of sodium hydroxide solution (NaOH) with the mass fraction of 40 wt% into an ice water bath, continuing to react for 6 hours at 65 ℃ and 250r/min to obtain a product turbid solution, standing the product turbid solution in a separating funnel for 12 hours for liquid separation, taking an oil phase, washing for 5 times by using a deionized water and dichloromethane mixed solution (the volume ratio is 1:1) to remove a small amount of salt impurities in the oil phase, taking the oil phase by liquid separation, and performing rotary evaporation at 85 ℃ for 3 hours to prepare the aqueous epoxy prepolymer PDE. The PDE structures obtained are essentially in accordance with fig. 2.
(3) Preparation of aqueous epoxy prepolymer solution: 12g of the above epoxy prepolymer and 3.05g of Diethanolamine (DEA) were dissolved in 4.5g of isopropyl alcohol (IPA), the resulting solution was put into a three-necked flask, reacted at 65 ℃ for 3 hours at 250r/min, and 1.74g of glacial acetic acid (AcOH) was slowly added dropwise thereto, and the reaction was continued at 250r/min for 30 minutes, whereby the FTIR of the resulting waterborne epoxy prepolymer was substantially in agreement with FIG. 3, and the peak ratio of hydroxyl groups was slightly increased due to the increase in the degree of hydration. 22.57g of water is added continuously, the mixture is stirred for 20 minutes at 500r/min and then is subjected to ultrasonic vibration for 15 minutes, and the ultrasonic vibration power is 480W, so that the aqueous epoxy prepolymer solution is prepared.
(4) Preparing the fireproof salt-resistant water-based epoxy resin coating: 40g of BC919 curing agent (a Banco919 long-chain aliphatic amine curing agent) is mixed with the aqueous epoxy resin solution according to the mass ratio of 1:2.544, 1g of Formstara12 antifoaming agent, 1.53g of BYK-330 leveling agent, 0.77g of TEGOWET KL245 wetting agent and 2g of 2,4, 6-tri (dimethylaminomethyl) phenol K-54 curing accelerator are sequentially added in the rotation process at the rotating speed of 350r/min, and the mixture is stirred for 15 minutes to obtain the bio-based fireproof salt-tolerant aqueous epoxy resin coating.
Example 3
A preparation method of a bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following steps:
(1) preparation of Schiff base structural intermediate: dissolving 55.2g of protocatechualdehyde and 20g of 4,4' -diaminodiphenylmethane in 300g of ethanol, adding the mixture into a three-neck flask, heating the mixture to 60 ℃ under stirring, mechanically stirring the mixture at 250r/min under the action of nitrogen protection and condensation reflux, and reacting the mixture for 8 hours at 70 ℃; after the reaction is finished, precipitating by using a blending solution of deionized water and ethanol in a volume ratio of 4:1 to obtain a precipitation product, carrying out suction filtration for 5 times, washing by using deionized water to remove a solvent, and drying the product in vacuum at 100 ℃ to obtain the Schiff base structural intermediate PH-DDM. The resulting PH-DDM was structurally identical to FIG. 1.
(2) Preparation of aqueous epoxy prepolymer: dissolving 20g of the Schiff base structural intermediate PH-DDM and 1.57g of tetrabutylammonium bromide in 65g of epichlorohydrin, adding the solution into a three-neck flask, reacting at 110 ℃ for 6 hours under mechanical stirring at 150r/min, then cooling, dropwise adding 26g of sodium hydroxide solution (NaOH) with the mass fraction of 40 wt% into an ice water bath, continuing to react for 6 hours at 65 ℃ and 200r/min to obtain a product turbid solution, standing the product turbid solution in a separating funnel for 12 hours for liquid separation, taking an oil phase, washing for 5 times by using a deionized water and dichloromethane mixed solution (the volume ratio is 1.5:1) to remove a small amount of salt impurities in the oil phase, taking the oil phase by liquid separation, and performing rotary evaporation at 90 ℃ for 2 hours to prepare the aqueous epoxy PDE prepolymer. The PDE structures obtained are essentially in accordance with fig. 2.
(3) Preparation of aqueous epoxy prepolymer solution: 12g of the above epoxy prepolymer and 2.49g of Diethanolamine (DEA) were dissolved in 10.5g of Propanol (PA), and the mixture was put into a three-necked flask, reacted at 75 ℃ for 2.5 hours at 150r/min, and slowly added dropwise with 1.28g of glacial acetic acid (AcOH) and further reacted at 150r/min for 40 minutes, whereby FTIR of the resulting waterborne epoxy prepolymer was substantially in accordance with FIG. 3. Adding 9.67g of water, stirring for 30 minutes at 450r/min, and then ultrasonically vibrating for 15 minutes at the ultrasonic vibration power of 300W to prepare the aqueous epoxy prepolymer solution.
(4) Preparing the fireproof salt-resistant water-based epoxy resin coating: 40g H228B curing agent (polyether modified epoxy amine adduct curing agent, northwest Yongxin paint Co., Ltd.) and the aqueous epoxy resin solution described in example 1 are mixed according to the mass ratio of 1:2.1, 1.76g of Formex815 defoaming agent, 1.17g of BYK-358N flatting agent, 1.17g of Michiji TSF4440 wetting agent and 5.86g of 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30 curing accelerator are sequentially added in a rotating process at the rotating speed of 550r/min, and the mixture is stirred for 10 minutes to obtain the paint.
Example 4
A preparation method of a bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following steps:
(1) preparation of Schiff base structural intermediate: dissolving 27.2g of protocatechualdehyde and 20g of 4,4' -diaminodiphenylmethane in 163g of methanol, adding the mixture into a three-neck flask, heating the mixture to 40 ℃ under stirring, mechanically stirring the mixture at 200r/min under the action of nitrogen protection and condensation reflux, and reacting the mixture for 6 hours at 60 ℃; after the reaction is finished, precipitating by using a blending solution of deionized water and ethanol in a volume ratio of 2:1 to obtain a precipitation product, carrying out suction filtration for 5 times, washing by using deionized water to remove a solvent, and drying the product in vacuum at 95 ℃ to obtain the Schiff base structural intermediate PH-DDM. The resulting PH-DDM was structurally identical to FIG. 1.
(2) Preparation of aqueous epoxy prepolymer: dissolving 20g of the Schiff base structural intermediate PH-DDM and 1.29g of tetrabutylammonium bromide in 35g of epichlorohydrin, adding the solution into a three-neck flask, reacting at 110 ℃ for 6 hours under mechanical stirring at 100r/min, then cooling, dropwise adding 26g of sodium hydroxide solution (NaOH) with the mass fraction of 40 wt% into an ice water bath, continuing to react for 4 hours at 60 ℃ and 200r/min to obtain a product turbid solution, standing the product turbid solution in a separating funnel for 12 hours, separating, taking an oil phase, washing for 5 times by using a deionized water and dichloromethane mixed solution (the volume ratio is 1.5:1) to remove a small amount of salt impurities in the oil phase, taking the oil phase by separating, and carrying out rotary evaporation at 95 ℃ for 2 hours to prepare the aqueous epoxy PDE prepolymer. The PDE structures obtained are essentially in accordance with fig. 2.
(3) Preparation of aqueous epoxy prepolymer solution: 12g of the above epoxy prepolymer and 3.33g of Diethanolamine (DEA) were dissolved in 7.6g of tetrahydrofuran (PA), and the mixture was put into a three-necked flask, reacted at 65 ℃ for 3 hours at 200r/min, and slowly added dropwise with 1.52g of glacial acetic acid (AcOH) and reacted at 200r/min for further 25 minutes, whereby FTIR of the resulting waterborne epoxy prepolymer was substantially in accordance with FIG. 3. The degree of hydration is increased, and the peak ratio of hydroxyl groups is slightly increased. 10.22g of water is added continuously, the mixture is stirred for 20 minutes at 400r/min and then is subjected to ultrasonic vibration for 15 minutes, and the ultrasonic vibration power is 250W, so that the aqueous epoxy prepolymer solution is prepared.
(4) Preparing the fireproof salt-resistant water-based epoxy resin coating: 40g of PLR736 curing agent (polyether modified epoxy amine adduct curing agent, North West Yongxin paint Co., Ltd.) and the aqueous epoxy resin solution described in example 1 are mixed according to the mass ratio of 1:7. 83, 5.73g of Formex Airex901W defoaming agent, 3.82g of BYK-360 leveling agent, 3.82g of Mimex TSF4458 wetting agent and 19.1g of 2,4, 6-tris (dimethylaminomethyl) phenol K-54 curing accelerator are sequentially added in the rotation process at the rotating speed of 550r/min, and the mixture is stirred for 15 minutes to obtain the paint.
Example 5
A preparation method of a bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following steps:
(1) preparation of Schiff base structural intermediate: dissolving 55.2g of protocatechualdehyde and 20g of 4,4 '-diaminodiphenylmethane in 200g of dioxane, adding the protocatechualdehyde and the 4,4' -diaminodiphenylmethane into a three-neck flask, heating to 65 ℃ under stirring, mechanically stirring at 200r/min under the action of nitrogen protection and condensation reflux, and reacting for 6 hours at 85 ℃; after the reaction is finished, precipitating by using a blending solution of deionized water and ethanol in a volume ratio of 3:1 to obtain a precipitation product, carrying out suction filtration for 5 times, washing by using deionized water to remove a solvent, and drying the product in vacuum at 95 ℃ to obtain the Schiff base structural intermediate PH-DDM. The resulting PH-DDM was structurally identical to FIG. 1.
(2) Preparation of aqueous epoxy prepolymer: dissolving 20g of the Schiff base structural intermediate PH-DDM and 1.18g of tetrabutylammonium bromide in 75g of epichlorohydrin, adding the solution into a three-neck flask, reacting at 105 ℃ for 5 hours under mechanical stirring at 200r/min, then cooling, dropwise adding 17.5g of sodium hydroxide solution (NaOH) with the mass fraction of 40 wt% into an ice water bath, continuing to react for 5 hours at 60 ℃ and 250r/min to obtain a product turbid solution, standing the product turbid solution in a separating funnel for 12 hours for liquid separation, taking an oil phase, washing for 5 times by using a deionized water and dichloromethane mixed solution (the volume ratio is 2:1) to remove a small amount of salt impurities in the oil phase, taking the oil phase by liquid separation, and performing rotary evaporation at 85 ℃ for 3 hours to prepare the aqueous epoxy PDE prepolymer. The PDE structures obtained are essentially in accordance with fig. 2.
(3) Preparation of aqueous epoxy prepolymer solution: 12g of the above epoxy prepolymer and 2.77g of Diethanolamine (DEA) were dissolved in 14.7g of ethanol (EtOH), the mixture was charged into a three-necked flask, reacted at 75 ℃ for 1.5 hours at 200r/min, and slowly added dropwise with 1.19g of glacial acetic acid (AcOH) and reacted at 200r/min for 40 minutes, whereby FTIR of the resulting waterborne epoxy prepolymer was substantially in accordance with FIG. 3. Adding 9.85g of water, stirring for 30 minutes at 450r/min, and then ultrasonically vibrating for 45 minutes at the ultrasonic vibration power of 200W to prepare the aqueous epoxy prepolymer solution.
(4) Preparing the fireproof salt-resistant water-based epoxy resin coating: a curing agent 40g H228B (northwest Yongxin paint Co., Ltd., polyether modified epoxy amine adduct curing agent) was mixed with the aqueous epoxy resin solution described in example 2 in a mass ratio of 1: 2.15, adding 1.89g of Deformer155 antifoaming agent, 1.26g of SILCN333 leveling agent, 1.01g of GreesolA04BC wetting agent and 10.08g of 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30 curing accelerator in sequence during rotation at the rotating speed of 350r/min, and stirring for 10 minutes to obtain the coating.
Example 6
A preparation method of a bio-based fireproof salt-tolerant water-based epoxy resin coating comprises the following steps:
(1) preparation of Schiff base structural intermediate: dissolving 41g of protocatechualdehyde and 20g of 4,4 '-diaminodiphenylmethane in 240g of dioxane, adding the protocatechualdehyde and the 4,4' -diaminodiphenylmethane into a three-neck flask, heating to 50 ℃ under stirring, mechanically stirring at 250r/min under the action of nitrogen protection and condensation reflux, and reacting for 6 hours at 85 ℃; after the reaction is finished, precipitating by using a blending solution of deionized water and ethanol in a volume ratio of 4:1 to obtain a precipitation product, carrying out suction filtration for 5 times, washing by using deionized water to remove a solvent, and drying the product at 98 ℃ in vacuum to obtain the Schiff base structural intermediate PH-DDM. The resulting PH-DDM was structurally identical to FIG. 1.
(2) Preparation of aqueous epoxy prepolymer: dissolving 20g of the Schiff base structural intermediate PH-DDM and 1.57g of tetrabutylammonium bromide in 60g of epichlorohydrin, adding the solution into a three-neck flask, reacting at 105 ℃ for 5 hours under mechanical stirring at 200r/min, then cooling, dropwise adding 42.5g of sodium hydroxide solution (NaOH) with the mass fraction of 25 wt% into an ice water bath, continuing to react for 6 hours at 60 ℃ and 250r/min to obtain a product turbid solution, standing the product turbid solution in a separating funnel for 12 hours for liquid separation, taking an oil phase, washing for 5 times by using a deionized water and dichloromethane mixed solution (the volume ratio is 1.5:1) to remove a small amount of salt impurities in the oil phase, taking the oil phase by liquid separation, and performing rotary evaporation at 90 ℃ for 2 hours to prepare the aqueous epoxy prepolymer PDE. The PDE structures obtained are essentially in accordance with fig. 2.
(3) Preparation of aqueous epoxy prepolymer solution: 12g of the above epoxy prepolymer and 2.49g of Diethanolamine (DEA) were dissolved in 4.5g of ethanol (EtOH), the mixture was put into a three-necked flask, reacted at 65 ℃ for 3 hours at 150r/min, and slowly added dropwise with 0.71g of glacial acetic acid (AcOH) and reacted at 250r/min for further 30 minutes, whereby FTIR of the resulting waterborne epoxy prepolymer was substantially in accordance with FIG. 3. Adding 14.5g of water, stirring at 550r/min for 30 minutes, and then ultrasonically vibrating for 20 minutes at 480W to prepare the aqueous epoxy prepolymer solution.
(4) Preparing an anticorrosion fireproof integrated waterborne epoxy resin coating: 40g of PLR736 curing agent, (northwest Yongxin paint Co., Ltd., polyether modified epoxy amine adduct) and the aqueous epoxy resin solution described in example 2 were mixed according to the mass ratio of 1:9.51, and 6.31g of Formex8030 defoamer, 4.20g of Ciba-3580 leveling agent, 3.15g of scribble Happy FS-204PG wetting agent and 33.6g of 2.4.6-tris (dimethylaminomethyl) phenol K-54 curing accelerator were sequentially added during rotation at a rotation speed of 550r/min, and then stirred for 20 minutes to obtain a paint.
Comparative example
(1) Preparation of bisphenol a waterborne epoxy prepolymer: 15g of epoxy prepolymer (E51, Balin division, China petrochemical Co., Ltd.) and 3.22g of Diethanolamine (DEA) are dissolved in 7g of absolute ethanol (EtOH) and added into a three-neck flask, the mixture is reacted for 2 hours at 70 ℃ under the condition of stirring at 250r/min, 1.37g of glacial acetic acid (AcOH) is slowly dropped into the mixture to continue the reaction for 30 minutes, 12g of water is added, mechanical stirring is carried out at 500r/min, then ultrasonic vibration is carried out for 30 minutes, the power is 100W, and the aqueous epoxy resin solution is prepared.
(2) Preparation of bisphenol A waterborne epoxy resin coating: and mixing 40g of BC919 curing agent with the aqueous epoxy resin solution according to the ratio of 1:2.19, sequentially adding 0.64g of Formstara10 leveling agent, 0.38g of BK-333 defoaming agent, 1.28g of SKB-008 wetting agent and 2g of 2,4, 6-tris (dimethylaminomethyl) phenol curing accelerator during rotation at the rotating speed of 550r/min, and stirring for 5 minutes at the rotating speed of 550r/min to obtain the coating.
Pouring the prepared paint on a clean tetrafluoroethylene plate, sequentially coating the paint on the clean tetrafluoroethylene plate from 100 micrometers, 200 micrometers and 300 micrometers to 600 micrometers by using a four-side coater, drying and curing at room temperature for 24 hours, then transferring the paint into an oven, drying at 70 ℃ for 12 hours, curing at 23 ℃ and 50% humidity for 7 hours, separating the paint from the tetrafluoroethylene plate by using a scraper to obtain a complete water-based epoxy film, measuring the thickness of the film, and testing the mechanical properties, namely tensile modulus, tensile strength and elongation at break of the paint by using No. 5967 tensile mode of an ASTM D882-12 material testing system. LOI testing was performed according to ASTM D2863-97 standard (sample size 150X 6.5X 3.2mm) using FTA-SC48 oxygen index apparatus (LOI, FTT, UK). According to ISO5660 (the size of a test sample is 100X 5mm), CONE calorimetric test is carried out by using a CONE CONE calorimeter (FTT, UK), fire resistance test is carried out by simulating a large-plate combustion method device according to GB14907-2002 'general technical conditions of fire-retardant coating for steel structure', the vertical distance between the position of an alcohol flame thrower and the coating surface of the test sample is 70mm, and the temperature of the back fire surface of the steel plate when a coating charring layer is still complete is measured. The prepared paint is coated on a Q235 steel plate with the thickness of about 200 mu m, the volume of about 2/3 of the steel plate is immersed in 3.5 wt% of sodium chloride solution, whether the sample plate has the phenomena of peeling, bubbling, rusting, discoloring, light loss and the like is observed at intervals, and the longest time that the coated steel plate does not change is taken as the performance index. Adhesion testing the coatings prepared were tested according to ASTM D4541 in the weight range of 0.6kg/m2The dosage of the rust removing agent is coated on a steel plate, the material quality of the steel plate meets the standard GB/T9271, the rust removing grade reaches the GB/T8923 specified Sa2.5 grade through sand blasting treatment, and the surface roughnessThe test is carried out after reaching the middle grade specified in GB/T13288.1 and curing for 7 days at 23 +/-2 ℃ and 50 +/-5% humidity. The pencil hardness refers to the national standard GB/6739-. The test results of examples 1-6 and comparative example are shown in table 1.
From the above table 1, the bio-based material protocatechuic aldehyde (PH) is adopted to design and synthesize the bio-based waterborne epoxy prepolymer containing the schiff base structure and the polyepoxy functional group, and the prepared waterborne epoxy cured material coating has higher crosslinking density and is endowed with the intrinsic fire-proof salt-resistant property and the environmental friendliness. The tensile strength of the film reaches 8.3MPa, the tensile modulus reaches 245.6MPa, and the tensile strength is respectively 5.7MPa and 163.3MPa higher than that of the traditional bisphenol A waterborne epoxy resin film used in the comparison. The fire-resistant temperature can reach 500-700 ℃, and the self-extinguishing function is realized. Compared with the traditional bisphenol A type waterborne epoxy resin coating of the comparative example, the limit oxygen index can reach 29.7 percent at most, and is increased by 11 percent.
TABLE 1 Properties of aqueous epoxy resin films obtained in examples and comparative examples
As shown in the attached figure 4, compared with the appearance that the combustion of the comparative example is almost finished, the residual quantity of the film of the waterborne epoxy cured coating prepared by the invention is compact, compact and continuous in expansion type structure after combustion, and the structure can be used as a protective layer to well isolate the transmission of heat and gas between a combustion area and the interior of an epoxy matrix in the combustion process. Compared with the existing additive type fireproof anticorrosive coatings (CN 201110298461.8 and CN201811534561.4), the intrinsic fireproof and salt-tolerant coating is realized, the highest fireproof temperature is increased by 200 ℃, the LOI value is increased by 6.6 percent, the salt-tolerant time is longer than 30 days, the excellent mechanical property is also considered, and the coating has better practical application value.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The bio-based fireproof salt-tolerant water-based epoxy resin coating is characterized by comprising the following raw materials in parts by weight: 25-40 parts of a water-based epoxy resin emulsion curing agent, 40-80 parts of a water-based epoxy prepolymer solution, 0.3-1.2 parts of a defoaming agent, 0.3-1.8 parts of a flatting agent, 0.06-1.2 parts of a wetting dispersant and 1.3-9.6 parts of a curing accelerator;
the aqueous epoxy prepolymer solution is prepared by the following method: protocatechuic aldehyde and 4,4' -diaminodiphenylmethane are reacted to prepare Schiff base structural intermediate; dissolving the Schiff base structural intermediate and tetrabutylammonium bromide in epichlorohydrin, and reacting to prepare an epoxy prepolymer; the epoxy prepolymer and diethanol amine are dissolved and then react to prepare aqueous epoxy prepolymer solution.
2. The bio-based fire-proof salt-tolerant aqueous epoxy resin coating as claimed in claim 1, wherein the preparation method of the aqueous epoxy prepolymer solution comprises the following steps:
1) preparation of Schiff base structural intermediate: dissolving protocatechualdehyde and 4,4' -diaminodiphenylmethane, heating to 40-70 ℃ under stirring, heating to 60-85 ℃, and reacting for 4-8 hours under the protection of nitrogen and condensation reflux; cooling, precipitating, filtering, washing and drying to obtain a Schiff base structural intermediate;
2) preparation of epoxy prepolymer: dissolving the Schiff base structural intermediate obtained in the step 1) and tetrabutylammonium bromide in epoxy chloropropane, heating to 100-110 ℃, reacting for 2-6 hours, cooling to room temperature, and dropwise adding a sodium hydroxide solution in an ice water bath; heating to 60-65 ℃ for reaction for 4-6 hours, allowing the solution to become turbid, standing for 6-12 hours, separating an oil layer product, washing, and performing rotary evaporation to obtain an epoxy prepolymer;
3) preparation of aqueous epoxy prepolymer solution: dissolving the epoxy prepolymer obtained in the step 2) and diethanolamine, heating to 65-85 ℃, reacting for 1.5-3 hours under stirring, dropwise adding glacial acetic acid, continuously stirring for 20-60 minutes to obtain a waterborne epoxy prepolymer, adding water, continuously stirring for reacting for 20-40 minutes, and ultrasonically vibrating at room temperature to prepare a waterborne epoxy prepolymer solution.
3. The bio-based fire-retardant salt-tolerant aqueous epoxy resin coating as claimed in claim 2, wherein the structure of the Schiff base intermediate is as follows:
the Schiff base intermediate is yellow powder at room temperature and is easy to absorb water;
the structural formula of the epoxy prepolymer is as follows:
the epoxy prepolymer is a tan viscous liquid at room temperature, and the epoxy value is 0.42-0.46 mol/100 g.
4. The bio-based fireproof and salt-tolerant water-based epoxy resin coating as claimed in claim 2, wherein the molar ratio of the protocatechuic aldehyde to the 4,4' -diaminodiphenylmethane is 2: 1-4: 1; the molar ratio of the Schiff base structural intermediate to the epichlorohydrin is 1: 8-1: 20, and the molar ratio of the tetrabutylammonium bromide to the Schiff base structural intermediate is 1: 8-1: 12; the molar ratio of the amino group of the diethanolamine to the epoxy group in the epoxy prepolymer is 4.5: 10-6.5: 10.
5. The bio-based fireproof and salt-tolerant water-based epoxy resin coating according to claim 2, wherein in the step 1), protocatechuic aldehyde and 4,4' -diaminodiphenylmethane are dissolved in a first solvent, wherein the first solvent is one of ethanol, dioxane, methanol and dimethylformamide, and the amount of the first solvent is 4-6 times of the mass of protocatechuic aldehyde; the precipitate is precipitated by pouring the cooled product into a mixed solution of deionized water and ethanol with the volume ratio of 2: 1-4: 1; the drying is vacuum drying; the vacuum drying temperature is 90-110 ℃, and the drying time is 10-12 hours; the stirring speed is 200-250 r/min.
6. The bio-based fireproof and salt-tolerant water-based epoxy resin coating as claimed in claim 2, wherein in the step 2), the oil layer product separated after standing is repeatedly washed by a mixed solution of deionized water and dichloromethane, and the volume ratio of the deionized water to the dichloromethane is 1: 1-2: 1; the rotary evaporation is carried out for 2-4 hours at 85-95 ℃; the concentration of the sodium hydroxide solution is 25-40 wt%, and the molar ratio of sodium hydroxide to the Schiff base intermediate in the sodium hydroxide solution is 4: 1-6: 1;
in the step 2), before the Schiff base intermediate is used, vacuum drying is carried out for 12 hours at the temperature of 100-110 ℃; the reaction is carried out for 2-6 hours at 100-110 ℃ under stirring, and the stirring speed is 100-250 r/min; the reaction at 60-65 ℃ for 4-6 hours is carried out under stirring at a stirring speed of 150-250 r/min.
7. The bio-based fire-proof salt-tolerant aqueous epoxy resin coating as claimed in claim 2, wherein in the step 3), the epoxy prepolymer and the diethanolamine are dissolved in a second solvent; the second solvent is one or more of ethanol, propanol, ethyl acetate, isopropanol, tetrahydrofuran and methyl isobutyl ketone; the dosage of the second solvent is 0.3-1.0 time of the total mass of the epoxy prepolymer; the dosage of the dropwise added glacial acetic acid is 0.5-1.0 time of the molar dosage of the diethanolamine; the ratio of the water to the total mass of the diethanolamine and the epoxy prepolymer is 3: 2-2: 3; the ultrasonic vibration time is 15-45 minutes; the power of the ultrasonic vibration is 100-480W; the stirring speed for reacting for 1.5-3 hours under stirring is 150-300 r/min; the stirring speed of the stirring reaction for 20-60 minutes is 150-300 r/min; the stirring speed of the stirring reaction for 20-40 minutes is 350-550 r/min.
8. The bio-based fireproof and salt-resistant water-based epoxy resin coating as claimed in claim 1, wherein the defoamer is at least one of polydimethylsiloxane compound molecular defoamer Formstabr 10, Formstabr 12, Formstabr 34 of Corning chemical Co., Ltd, or polysiloxane-polyether copolymer defoamer Foamex815, Foamex8030, Foamex Airex901W of Germany winning creative chemical Co., Ltd, or Deformer155 of Hichwa chemical engineering; the leveling agent is at least one of polyether modified polydimethylsiloxane copolymer BYK-333, BYK-330, BYK-358N, BYK-360 and SILCN333 of German Bike chemistry or Ciba-3580 leveling agent of Switzerland Ciba fine chemical engineering company; the wetting dispersant is at least one of polyether modified organic silicon wetting agents TEGOWet KL245, TEGOWet270, My chart TSF4440 or GreesolA04BC, GreesolA04DPM, Mylar FS-204PG and Mylar FS-204E of Yueyanggdaidi high chemistry company; the curing accelerator is one of 2,4, 6-tri (dimethylaminomethyl) phenol DMP-30 and K-54.
9. The preparation method of the bio-based fire-retardant salt-tolerant aqueous epoxy resin coating according to any one of claims 1 to 8, characterized in that: and adding a waterborne epoxy resin emulsion curing agent, a flatting agent, a wetting dispersant, a defoaming agent and a curing accelerator into a waterborne epoxy prepolymer solution at normal temperature under stirring, and stirring to obtain the bio-based fireproof salt-tolerant waterborne epoxy resin coating.
10. The preparation method of the bio-based fireproof and salt-tolerant water-based epoxy resin coating as claimed in claim 9, wherein the stirring speed is 350-550 r/min, and the stirring time is 5-20 minutes.
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