CN113278312A - Organic-inorganic hybrid water-based emulsion, preparation method thereof and super-anticorrosion coating - Google Patents
Organic-inorganic hybrid water-based emulsion, preparation method thereof and super-anticorrosion coating Download PDFInfo
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Abstract
The invention discloses an organic-inorganic hybrid aqueous emulsion, which comprises 100 parts of lithium potassium silicate solution, 1-3 parts of coupling agent and 10-30 parts of self-crosslinking aqueous emulsion by weight; wherein the modulus of the lithium potassium silicate solution is 4.0-5.0, and the ratio of lithium to potassium is 2: 0.8-1.2; the self-crosslinking aqueous emulsion contains epoxy phosphate. Also discloses a preparation method thereof and a super anticorrosive paint prepared by the same. By adopting the organic-inorganic hybrid water-based emulsion, the preparation method thereof and the super-anticorrosive coating, the coating finally has the advantages of organic materials and inorganic materials, and can effectively solve the problems that the existing coating is not high-temperature resistant and has insufficient anticorrosive performance.
Description
Technical Field
The invention relates to an organic-inorganic hybrid water-based emulsion, a preparation method thereof and a super anticorrosive coating, belonging to the technical field of anticorrosive coatings.
Background
With the development of advanced technology in modern industry, metal materials such as common alloy steel, heat-resistant steel and the like generate creep deformation due to overhigh temperature or are quickly corroded and peeled off due to the action of high-temperature airflow, the service life is shortened, and in order to eliminate or delay the occurrence of the phenomenon and improve the service life of equipment, high-temperature-resistant paint is often coated on the surface of the metal materials. Therefore, the use of high temperature resistant coatings is expanding.
The high-temperature resistant coating can be divided into two categories of organic high-temperature resistant coating and inorganic high-temperature resistant coating. The organic high-temperature resistant paint is a temperature resistant paint taking organic silicon as a film forming substance, and is usually prepared by taking silicon as a base material and matching with various high-temperature resistant pigments and fillers. Since the silicon Si-O bond has a high polarity, the bond is easily cleaved under the attack of electrophiles or nucleophiles. Therefore, the organic silicon high-temperature resistant coating has limited temperature resistance, and has poor mechanical strength, adhesive force and corrosion resistance. The inorganic high-temperature resistant coating is a protective coating taking silicate and silicon dioxide (SiO2) as film forming substances, and has the advantages of good temperature resistance, non-combustibility, excellent air permeability, environmental protection and the like. The coating is widely applied to the fields of building coatings and heat-insulating coatings, but when the coating and the coating are prepared by using a silicate aqueous solution alone, the coating has the defects of poor shielding effect, early water resistance, long curing time, easy cracking of a coating film and the like due to micro-porosity. Although the corrosion resistance can be improved by increasing the modulus of the silicate, the silicate is easy to gel when the modulus is higher, and the coating is unstable; the water resistance can also be improved by improving the polymerization degree through heating and curing, but the use condition is limited, and the wide use and popularization are not facilitated.
Therefore, the development of a high-temperature-resistant anticorrosive coating with high mechanical strength, adhesive force and corrosion resistance by chemically modifying the existing high-temperature-resistant material by adopting various functional materials has become a necessary trend in the development of water-based high-temperature-resistant coatings.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides an organic-inorganic hybrid water-based emulsion, a preparation method thereof and a super-anticorrosive coating, which can improve the early water resistance and flexibility of the silicate-based water-based inorganic coating, so that the coating finally has the advantages of organic materials and inorganic materials, and can effectively solve the problems of no high temperature resistance and insufficient anticorrosive performance of the existing coating.
The technical scheme adopted by the invention is as follows:
an organic-inorganic hybrid aqueous emulsion comprises, by weight, 100 parts of a lithium potassium silicate solution, 1-3 parts of a coupling agent, and 10-30 parts of a self-crosslinking aqueous emulsion; wherein the modulus of the lithium potassium silicate solution is 4.0-5.0, and the ratio of lithium to potassium is 2: 0.8-1.2; the self-crosslinking aqueous emulsion contains epoxy phosphate.
In the invention, the inorganic silicate and the organic emulsion are subjected to composite modification to prepare the coating, so that the early water resistance and flexibility of the silicate-based water-based inorganic coating can be improved, and the coating finally has the advantages of both organic materials and inorganic materials; the silicate is modified by the coupling agent, and the hydrolysate of the coupling agent can be chemically bonded or physically adsorbed with Si-OH on the surface of the colloid in the silicate solution, so that the charge distribution on the surface of the colloid is changed, the steric hindrance effect can be achieved, the active Si-OH bonding probability is reduced, and the storage stability of the silicate is improved; the emulsifier has epoxy phosphate ester and can improve the adhesive force and the corrosion resistance of a paint film.
Preferably, the raw materials of the self-crosslinking aqueous emulsion comprise, by weight, 1.5-2.5 parts of an emulsifier, 10-30 parts of epoxy resin, 10-25 parts of a vinyl monomer, 1-3 parts of a functional monomer, 0.2-0.3 part of an initiator, 50-60 parts of deionized water, 0.2-0.7 part of sodium bicarbonate and 0.6-1.2 parts of adipic dihydrazide; the emulsifier contains epoxy phosphate.
In the scheme, the self-crosslinking aqueous emulsion contains epoxy groups, and the alkaline environment of the lithium potassium silicate solution can open the ring of the epoxy groups in the curing process so as to improve the adhesive force of the coating.
Preferably, the raw materials of the emulsifier comprise, by weight, 40-80% of polyethylene glycol monomethyl ether, 1-15% of epoxy resin, 3-12% of glycidyl ester, 50-150ppm of p-hydroxyanisole, 0.3-1% of boron trifluoride diethyl etherate, 0.5-3% of phosphoric acid solution, 1-5% of neutralizing agent and 10-20% of water.
In the scheme, the prepared emulsifier is a reactive emulsifier, so that the emulsifier can be prevented from migrating to the surface of a paint film, and the influence of the emulsifier on the performances of corrosion resistance, water resistance and the like of the synthetic emulsion is reduced; the epoxy resin reacts with phosphoric acid to ensure that the emulsifier has epoxy phosphate ester which can improve the adhesive force and the corrosion resistance of a paint film; the emulsifier molecule has both ionic group and non-ionic group, and can control the size of the emulsion well and raise the stability of the emulsion.
Preferably, the coupling agent is an epoxy hydrocarbyl silane coupling agent, and the self-crosslinking aqueous emulsion contains adipic dihydrazide.
In the scheme, the coupling agent has an epoxy group, and can be matched with a functional monomer and adipyl in the aqueous emulsion to form a cross-linked structure with an interpenetrating network in the drying film-forming process of the coating, so that the compactness of the coating film and the water resistance, acid resistance and alkali resistance are improved.
A preparation method of organic-inorganic hybrid aqueous emulsion comprises the following steps:
step a, mixing an emulsifier and deionized water, then adding epoxy resin, a functional monomer, a vinyl monomer, an initiator and sodium bicarbonate, and uniformly stirring to obtain a pre-emulsion;
step b, mixing the emulsifier and the deionized water, uniformly stirring, heating to 75-85 ℃, adding 5-10% of pre-emulsion, and reacting to obtain seed emulsion;
step c, heating the seed emulsion to 76-86 ℃, then adding the rest pre-emulsion, heating to 85-90 ℃ after finishing dropwise adding, preserving heat, then cooling, adjusting the pH, and adding adipic dihydrazide to obtain a self-crosslinking aqueous emulsion;
and d, stirring potassium silicate, lithium silicate and deionized water at 25-45 ℃, slowly dripping alkaline silica sol, keeping the temperature and continuously stirring until the solution is clear, preparing a lithium potassium silicate solution with the lithium potassium ratio of 2:0.8-1.2 and the modulus of 4.0-5.0, slowly dripping a coupling agent, keeping the temperature at 20-35 ℃ for 0.5-1h, finally adding a self-crosslinking aqueous emulsion with the weight of 10-30% of that of the lithium potassium silicate solution, and stirring to obtain the organic-inorganic hybrid aqueous emulsion.
In the invention, the self-crosslinking aqueous emulsion is prepared firstly and is subjected to organic-inorganic hybridization with the lithium potassium silicate solution, the preparation method is simple, and the process control can be facilitated.
Preferably, the alkaline silica sol has a particle size of 10-15nm and a silica content of 30%.
Preferably, the modulus of the lithium silicate is 3.2 to 5.2 and the modulus of the potassium silicate is 2.4 to 4.0.
Preferably, in the step a, the epoxy resin is one or more of bisphenol A epoxy resin with an epoxy value of 0.2-0.45 and bisphenol F epoxy resin with an epoxy value of 0.52-0.56; the functional monomer is one or more of diacetone acrylamide, isobutoxy methacrylamide, ethyl acetoacetate methacrylate and glycidyl methacrylate; the vinyl monomer is one or more of acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, butyl methacrylate, isobornyl acrylate and styrene; the initiator is one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
Preferably, the raw materials of the emulsifier comprise, by weight, 40-80% of polyethylene glycol monomethyl ether, 1-15% of epoxy resin, 3-12% of glycidyl ester, 50-150ppm of p-hydroxyanisole, 0.3-1% of boron trifluoride diethyl etherate, 0.5-3% of phosphoric acid solution, 1-5% of neutralizing agent and 10-20% of water.
Preferably, the preparation method of the emulsifier comprises the following steps:
step 1: heating polyethylene glycol monomethyl ether to 70-80 ℃, simultaneously dripping a mixture of glycidyl ester, epoxy resin and p-hydroxyanisole and boron trifluoride diethyl etherate, and keeping the temperature for 3-4h after dripping.
Step 2: heating to 90-110 deg.C, adding 85% phosphoric acid solution dropwise, and keeping the temperature for 2-3 h.
And step 3: cooling, adding neutralizing agent and water to obtain the emulsifier.
Preferably, in step 1, the epoxy resin is one or more of bisphenol A epoxy resin with an epoxy value of 0.44-0.51 and bisphenol F epoxy resin with an epoxy value of 0.52-0.56; the glycidyl ester is glycidyl methacrylate and/or diglycidyl tetrahydrophthalate; the neutralizing agent is one or more of triethylamine, dimethylethanolamine, dimethylisopropanolamine and sodium hydroxide.
Preferably, the molecular weight of the polyethylene glycol monomethyl ether is 600-2000.
The super anticorrosive paint comprises, by weight, 45-65 parts of organic-inorganic hybrid aqueous emulsion, 10-25 parts of deionized water, 0.1-0.3 part of wetting dispersant, 0.05-0.1 part of defoamer, 0.1-0.2 part of pH regulator, 0.3-0.5 part of rheological additive, 10-25 parts of high temperature resistant powder and 5-25 parts of weather-resistant pigment.
Preferably, the defoaming agent is polysiloxane, the rheological agent is acrylic acid, the wetting dispersant is sodium polyacrylate, and the pH regulator is amine.
Preferably, the high-temperature resistant powder is one or more of boride, carbide, nitride and silicide.
Preferably, the preparation method of the super anticorrosive paint comprises the following steps: uniformly mixing deionized water, a wetting dispersant, a defoaming agent, high-temperature-resistant powder and a weather-resistant pigment, grinding to the fineness of 20-40 mu m, adding an organic-inorganic nano hybrid high-temperature-resistant emulsion and a pH regulator, uniformly mixing, and then adding a rheological additive to prepare the super anticorrosive coating.
The super-anticorrosion paint disclosed by the invention has excellent high temperature resistance and acid and alkali resistance, when the ambient temperature is 120 ℃, the super-anticorrosion paint of the product can be stabilized in 38% HCl solution for 48H, and H is obtained under the condition that the pH value is 12SO4The stability time in the solution can reach 15 days, and the stability time in the NaOH solution with the mass fraction of 40% is more than 40 days.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. through the coupling agent modified silicate, the hydrolysate of the coupling agent can be chemically bonded or physically adsorbed with Si-OH on the surface of colloid in silicate solution, so that the charge distribution on the surface of the colloid is changed, the steric hindrance effect can be achieved, the active Si-OH bonding probability is reduced, and the storage stability of the silicate is improved.
2. The epoxy group introduced by the coupling agent is matched with the functional monomer and the adipyl hydrazine in the modified acrylic emulsion, so that a cross-linked structure with an interpenetrating network can be formed in the polymer drying film-forming process, and the compactness of a coating film and the water resistance, the acid resistance and the alkali resistance are improved.
3. The reactive emulsifier is adopted, so that the emulsifier can be prevented from migrating to the surface of the paint film; the influence of the emulsifier on the performances of corrosion resistance, water resistance and the like of the synthetic emulsion is reduced; the epoxy phosphate on the emulsifier is beneficial to the adhesion and corrosion resistance of a paint film; the emulsifier molecule has both ionic group and non-ionic group, and the size of the particle can be well controlled in emulsion preparation, and the stability is good.
4. The super-anticorrosive paint controls the temperature resistance, adhesive force and corrosion resistance of emulsion by adjusting high-temperature-resistant powder and modified silicate solution; combines the continuous film forming property, initial water resistance and flexibility of the organic emulsion and the high temperature resistance, corrosion resistance, high hardness, scratch resistance and other properties of the inorganic temperature-resistant coating.
5. The super-anticorrosive paint contains no fluorine, so that no fluorine-containing wastewater is generated in the production process, and the harm and pollution to human bodies and the environment can be effectively avoided; the prepared coating is a single-component coating, can be cured at normal temperature, simplifies the operation process, saves the use cost and is beneficial to popularization and application.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
The preparation method of the organic-inorganic hybrid aqueous emulsion of the embodiment comprises the following steps:
step a, mixing 1.1 parts of emulsifier and 17.5 parts of deionized water, then adding 17 parts of epoxy resin E51, 15.6 parts of methyl methacrylate, 3 parts of isobornyl methacrylate, 0.5 part of methacrylic acid, 3.5 parts of butyl acrylate, 0.5 part of glycidyl methacrylate, 0.8 part of diacetone acrylamide, 0.3 part of sodium persulfate and 0.5 part of sodium bicarbonate, and uniformly stirring at a high speed to obtain a pre-emulsion;
step b, mixing 0.9 part of emulsifier and 38 parts of deionized water, uniformly stirring, heating to 85 ℃, adding a part of 10% pre-emulsion, and reacting to obtain seed emulsion;
step c, heating the seed emulsion to 86 ℃, then adding the rest pre-emulsion, after dropwise adding is completed for 5 hours, heating to 90 ℃, preserving heat for 1 hour, then cooling to below 40 ℃, adjusting the pH to 7.5, and adding 0.8 part of adipic dihydrazide to obtain a self-crosslinking aqueous emulsion;
and d, putting the potassium silicate with the modulus of 2.6, the lithium silicate with the modulus of 5.2 and deionized water into a kettle, heating to 45 ℃, stirring, slowly dropping alkaline silica sol, keeping the temperature, continuously stirring until the solution is clear, preparing a lithium potassium silicate solution with the lithium potassium ratio of 2:1.2 and the modulus of 5.0, slowly dropping 1.5% of a coupling agent KH560, keeping the temperature at 35 ℃ for 0.5h, finally adding a self-crosslinking aqueous emulsion with the weight of 17% of the lithium potassium silicate solution, and stirring to obtain the organic-inorganic hybrid aqueous emulsion.
The preparation process of the emulsifier comprises the following steps:
step 1: heating 80 parts of 2000 molecular weight polyethylene glycol monomethyl ether to 80 ℃, simultaneously dropwise adding a mixture of 4.8 parts of glycidyl methacrylate, 2.4 parts of epoxy resin E44, 70ppm of p-hydroxyanisole and 0.6 part of boron trifluoride diethyl etherate, and preserving heat for 4 hours after dropwise adding;
step 2: heating to 110 ℃, dropwise adding 1.2 parts of 85% phosphoric acid solution, and keeping the temperature for 2 hours after dropwise adding;
and step 3: and cooling, and adding 2.3 parts of dimethyl isopropanolamine and 11 parts of purified water to prepare the emulsifier.
Example 2
The preparation method of the organic-inorganic hybrid aqueous emulsion of the embodiment comprises the following steps:
step a, mixing 0.9 part of emulsifier and 20 parts of deionized water, then adding 30 parts of epoxy resin E51, 8.1 parts of methyl methacrylate, 1.5 parts of butyl acrylate, 0.4 part of methacrylic acid, 1.4 parts of isobutoxy methacrylamide, 1.6 parts of diacetone acrylamide, 0.3 part of sodium persulfate and 0.55 part of sodium bicarbonate, and uniformly stirring at a high speed to obtain a pre-emulsion;
step b, mixing 0.6 part of emulsifier and 40 parts of deionized water, uniformly stirring, heating to 80 ℃, adding part of 7.5% pre-emulsion, and reacting for 0.5h to obtain seed emulsion;
step c, heating the seed emulsion to 81 ℃, then adding the rest pre-emulsion, heating to 88 ℃ after dropwise adding is completed for 4.5 hours, keeping the temperature for 1 hour, then cooling to below 40 ℃, adjusting the pH to 7.5, and adding 0.6 part of adipic dihydrazide to obtain a self-crosslinking aqueous emulsion;
and d, putting the potassium silicate with the modulus of 2.6, the lithium silicate with the modulus of 5.2 and deionized water into a kettle, heating to 35 ℃, stirring, slowly dropping alkaline silica sol, keeping the temperature, continuously stirring until the solution is clear, preparing a lithium potassium silicate solution with the lithium potassium ratio of 2:1 and the modulus of 4.5, slowly dropping 1% of a coupling agent KH560, keeping the temperature at 30 ℃ for 0.5h, finally adding a self-crosslinking aqueous emulsion with the weight of 10% of the lithium potassium silicate solution, and stirring to obtain the organic-inorganic hybrid aqueous emulsion.
The preparation process of the emulsifier comprises the following steps:
step 1: heating 57 parts of polyethylene glycol monomethyl ether with the molecular weight of 600 to 75 ℃, simultaneously dropwise adding a mixture of 10.8 parts of glycidyl methacrylate, 8.7 parts of epoxy resin E44, 70ppm of p-hydroxyanisole and 0.6 part of boron trifluoride diethyl etherate, and preserving heat for 3.5 hours after dropwise adding;
step 2: heating to 100 ℃, dropwise adding 1.14 parts of 85% phosphoric acid solution, and keeping the temperature for 2.5h after dropwise adding;
and step 3: and cooling, and adding 0.85 part of sodium hydroxide and 20 parts of purified water to prepare the emulsifier.
Example 3
The preparation method of the organic-inorganic hybrid aqueous emulsion of the embodiment comprises the following steps:
step a, mixing 1.6 parts of emulsifier and 15 parts of deionized water, then adding 10 parts of bisphenol F epoxy resin with an epoxy value of 0.52, 17.6 parts of methyl methacrylate, 7 parts of butyl acrylate, 0.4 part of methacrylic acid, 0.1 part of ethyl acetoacetate methacrylate, 1 part of diacetone acrylamide, 0.2 part of potassium persulfate and 0.7 part of sodium bicarbonate, and uniformly stirring at a high speed to obtain a pre-emulsion;
step b, mixing 0.9 part of emulsifier and 35 parts of deionized water, uniformly stirring, heating to 80 ℃, adding part of 5% pre-emulsion, and reacting for 0.5h to obtain seed emulsion;
step c, heating the seed emulsion to 83 ℃, then adding the rest pre-emulsion, heating to 88 ℃ after dropwise adding is completed for 4.5 hours, keeping the temperature for 1 hour, then cooling to below 40 ℃, adjusting the pH to 7.5, and adding 1.2 parts of adipic dihydrazide to obtain a self-crosslinking aqueous emulsion;
and d, putting the potassium silicate with the modulus of 4.0, the lithium silicate with the modulus of 5.2 and deionized water into a kettle, heating to 30 ℃, stirring, slowly dropping alkaline silica sol, keeping the temperature, continuously stirring until the solution is clear, preparing a lithium potassium silicate solution with the lithium potassium ratio of 2:1 and the modulus of 5, slowly dropping 1% of a coupling agent KH561, keeping the temperature at 32 ℃ for 0.5h, finally adding a self-crosslinking aqueous emulsion with the weight of 20% of the lithium potassium silicate solution, and stirring to obtain the organic-inorganic hybrid aqueous emulsion.
The preparation process of the emulsifier comprises the following steps:
step 1: heating 40 parts of polyethylene glycol monomethyl ether with the molecular weight of 1600 to 75 ℃, simultaneously dropwise adding a mixture of 3 parts of glycidyl methacrylate, 2.4 parts of epoxy resin E44, 5.3 parts of tetrahydrophthalic acid diglycidyl ester, 50ppm of p-hydroxyanisole and 0.4 part of boron trifluoride diethyl etherate, and keeping the temperature for 3.5 hours after dropwise adding;
step 2: heating to 100 ℃, dropwise adding 2.16 parts of 85% phosphoric acid solution, and keeping the temperature for 2.5 hours after dropwise adding;
and step 3: and 3.9 parts of triethylamine and 20 parts of purified water are added into the mixture after the temperature is reduced, and the emulsifier is prepared.
Example 4
The preparation method of the organic-inorganic hybrid aqueous emulsion of the embodiment comprises the following steps:
step a, mixing 1.5 parts of emulsifier and 17.5 parts of deionized water, then adding 25 parts of epoxy resin E51, 13.5 parts of methyl methacrylate, 2 parts of isobornyl acrylate, 0.55 part of acrylic acid, 1 part of diacetone acrylamide, 0.25 part of sodium persulfate and 0.5 part of sodium bicarbonate, and uniformly stirring at a high speed to obtain a pre-emulsion;
step b, mixing 0.7 part of emulsifier and 37 parts of deionized water, uniformly stirring, heating to 75 ℃, adding part of 5% pre-emulsion, and reacting to obtain seed emulsion;
step c, heating the seed emulsion to 76 ℃, then adding the rest pre-emulsion, heating to 85 ℃ after dropwise adding is completed for 4 hours, keeping the temperature for 0.5 hour, then cooling to below 40 ℃, adjusting the pH to 7.5, and adding 1 part of adipic dihydrazide to obtain a self-crosslinking aqueous emulsion;
and d, putting the potassium silicate with the modulus of 2.6, the lithium silicate with the modulus of 4.3 and deionized water into a kettle, heating to 25 ℃, stirring, slowly dropping alkaline silica sol, keeping the temperature, continuously stirring until the solution is clear, preparing a lithium potassium silicate solution with the lithium potassium ratio of 2:0.8 and the modulus of 4.0, slowly dropping 1.5% of a coupling agent KH560, keeping the temperature at 20 ℃ for 1h, finally adding a self-crosslinking aqueous emulsion with the weight of 15% of the lithium potassium silicate solution, and stirring to obtain the organic-inorganic hybrid aqueous emulsion.
The preparation process of the emulsifier comprises the following steps:
step 1: heating 64 parts of polyethylene glycol monomethyl ether with the molecular weight of 1600 to 70 ℃, simultaneously dropwise adding a mixture of 2.6 parts of glycidyl methacrylate, 8.4 parts of epoxy resin E51, 50ppm of p-hydroxyanisole and 0.4 part of boron trifluoride diethyl etherate, and preserving heat for 4 hours after dropwise adding;
step 2: heating to 90 ℃, dropwise adding 2.46 parts of 85% phosphoric acid solution, and keeping the temperature for 3 hours after dropwise adding;
and step 3: and 3.9 parts of dimethylethanolamine and 18.2 parts of purified water are added after the temperature is reduced to prepare the emulsifier.
Comparative example 1
This comparative example differs from example 4 in that the emulsifier used was a conventional emulsifier and did not contain epoxy phosphate.
Comparative example 2
The difference between the comparative example and the example 4 is that potassium silicate with the modulus of 4.0, lithium silicate with the modulus of 5.2 and deionized water are put into a kettle and heated to be stirred at the temperature of 30 ℃, alkaline silica sol is slowly dripped, the solution is kept warm and is continuously stirred until the solution is clear, a lithium potassium silicate solution with the lithium potassium ratio of 2:1 and the modulus of 5 is prepared, 1 percent of coupling agent KH561 is slowly dripped, the solution is kept warm at the temperature of 32 ℃ for 0.5h, and finally common commercial water-based emulsion with the weight of 20 percent of the lithium potassium silicate solution is added, and the organic-inorganic hybrid water-based emulsion is obtained by stirring.
Comparative example 3
This comparative example differs from example 4 in that a conventional non-epoxy hydrocarbyl silane coupling agent is used as the coupling agent.
Comparative example 4
This comparative example differs from example 4 in that no adipic dihydrazide was added in the preparation of the aqueous emulsion.
Comparative example 5
This comparative example differs from example 4 in that the coupling agent used was a conventional non-epoxy hydrocarbyl silane coupling agent and no adipic dihydrazide was added in the preparation of the aqueous emulsion.
Based on the above examples and comparative examples, the same coatings were made according to the following formulation and the coating properties were compared: 45-65 parts of organic-inorganic hybrid aqueous emulsion, 10-25 parts of deionized water, 0.1-0.3 part of wetting dispersant, 0.05-0.1 part of defoaming agent, 0.1-0.2 part of pH regulator, 0.3-0.5 part of rheological additive, 10-25 parts of high-temperature resistant powder and 5-25 parts of weather-resistant pigment.
The coatings prepared in examples 1 to 4 and comparative examples 1 to 4 were examined, respectively:
| high temperature detection | HCl resistance | H-resistance2SO4 | NaOH-resistant | Adhesion force | |
| Example 1 | 803 | 55 | 370 | 984 | Level 0 |
| Example 2 | 820 | 64 | 390 | 960 | Level 0 |
| Example 3 | 835 | 60 | 375 | 972 | Level 0 |
| Example 4 | 828 | 52 | 360 | 1020 | Level 0 |
| Comparative example 1 | 795 | 43 | 306 | 846 | Stage 2 |
| Comparative example 2 | 815 | 45 | 311 | 854 | Stage 2 |
| Comparative example 3 | 820 | 49 | 348 | 973 | Level 0 |
| Comparative example 4 | 819 | 49 | 350 | 980 | Level 0 |
| Comparative example 5 | 814 | 47 | 340 | 962 | Level 0 |
| Standard of merit | / | GB/T 9274 | GB/T 9274 | GB/T 9274 | GB/T 9286 |
The above is a test performance comparison table, wherein the high temperature detection method comprises the following steps: selecting a 1mm steel plate as a detection sample base material, carrying out oil and rust removal treatment, and then spraying or brushing to prepare a sample plate (coating is coated on two sides and the periphery), wherein the thickness of the coating after curing is 15-20 mu m; and (3) taking a muffle furnace or other high-temperature equipment (with the temperature range of 0-1000 ℃) with a temperature display as a heat source, putting the cured sample plate into the high-temperature equipment at normal temperature, starting the equipment, heating to 120 ℃, preserving the temperature until bubbles appear on the surface of the coating and fall off, taking out the sample plate, and recording the time.
The data units for the high temperature test, acid and base salt resistance, were hours, with 38% HCl as hydrochloric acid and H at pH 1 as sulfuric acid2SO4And the sodium hydroxide is 40% NaOH.
The coatings prepared in the embodiments 1-4 of the invention have better high temperature resistance and acid, alkali and salt corrosion resistance.
In comparative example 1, the emulsifier was a simple ionic emulsifier or a nonionic emulsifier, and as a result, there was a case where particles were not uniform in the aqueous emulsion obtained; in examples 1 to 4, the resulting aqueous emulsions were uniform in particle size.
The comparison shows that the emulsifier in the comparative example 1 does not contain epoxy phosphate, and the emulsifier in the comparative example 2 is a common water-based emulsion, so that the adhesive force and the acid and alkali corrosion resistance of the final coating are greatly reduced; of these, comparative example 1 is much worse because the emulsion particles produced in comparative example 1 are not uniform, which affects the final properties of the coating.
Comparative example 3 coupling agent used common non-epoxy hydrocarbyl silane coupling agent, comparative example 4 did not add adipyl, comparative example 5 coupling agent used common non-epoxy hydrocarbyl silane coupling agent and did not add adipyl, adhesion and acid and alkali corrosion resistance of final coating also reduced. The reason is that the adipic dihydrazide and the epoxy group in the coupling agent can form a cross-linked structure with an interpenetrating network in the process of drying and film forming of the polymer, so that the compactness of the coating film and the water resistance, acid resistance and alkali resistance are improved.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (10)
1. An organic-inorganic hybrid aqueous emulsion characterized in that: by weight, 100 parts of lithium potassium silicate solution, 1-3 parts of coupling agent and 10-30 parts of self-crosslinking aqueous emulsion are included; wherein the modulus of the lithium potassium silicate solution is 4.0-5.0, and the ratio of lithium to potassium is 2: 0.8-1.2; the self-crosslinking aqueous emulsion contains epoxy phosphate.
2. The organic-inorganic hybrid aqueous emulsion according to claim 1, characterized in that: the raw materials of the self-crosslinking aqueous emulsion comprise, by weight, 1.5-2.5 parts of an emulsifier, 10-30 parts of epoxy resin, 10-25 parts of a vinyl monomer, 1-3 parts of a functional monomer, 0.2-0.3 part of an initiator, 50-60 parts of deionized water, 0.2-0.7 part of sodium bicarbonate and 0.6-1.2 parts of adipic dihydrazide; the emulsifier contains epoxy phosphate.
3. The organic-inorganic hybrid aqueous emulsion according to claim 1, characterized in that: the raw materials of the emulsifier comprise, by weight, 40-80% of polyethylene glycol monomethyl ether, 1-15% of epoxy resin, 3-12% of glycidyl ester, 50-150ppm of p-hydroxyanisole, 0.3-1% of boron trifluoride diethyl etherate, 0.5-3% of phosphoric acid solution, 1-5% of neutralizing agent and 10-20% of water.
4. The organic-inorganic hybrid aqueous emulsion according to claim 1, characterized in that: the coupling agent is an epoxy hydrocarbyl silane coupling agent.
5. A preparation method of organic-inorganic hybrid aqueous emulsion is characterized by comprising the following steps: the method comprises the following steps:
step a, mixing an emulsifier and deionized water, then adding epoxy resin, a functional monomer, a vinyl monomer, an initiator and sodium bicarbonate, and uniformly stirring to obtain a pre-emulsion;
step b, mixing the emulsifier and the deionized water, uniformly stirring, heating to 75-85 ℃, adding 5-10% of pre-emulsion, and reacting to obtain seed emulsion;
step c, heating the seed emulsion to 76-86 ℃, then adding the rest pre-emulsion, heating to 85-90 ℃ after finishing dropwise adding, preserving heat, then cooling, adjusting the pH, and adding adipic dihydrazide to obtain a self-crosslinking aqueous emulsion;
and d, stirring potassium silicate, lithium silicate and deionized water at 25-45 ℃, slowly dripping alkaline silica sol, keeping the temperature and continuously stirring until the solution is clear, preparing a lithium potassium silicate solution with the lithium potassium ratio of 2:0.8-1.2 and the modulus of 4.0-5.0, slowly dripping a coupling agent, keeping the temperature at 20-35 ℃ for 0.5-1h, finally adding a self-crosslinking aqueous emulsion with the weight of 10-30% of that of the lithium potassium silicate solution, and stirring to obtain the organic-inorganic hybrid aqueous emulsion.
6. The method for preparing an organic-inorganic hybrid aqueous emulsion according to claim 5, wherein: in the step a, the epoxy resin is one or more of bisphenol A epoxy resin with an epoxy value of 0.2-0.45 and bisphenol F epoxy resin with an epoxy value of 0.52-0.56; the functional monomer is one or more of diacetone acrylamide, isobutoxy methacrylamide, ethyl acetoacetate methacrylate and glycidyl methacrylate; the vinyl monomer is one or more of acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, butyl methacrylate, isobornyl acrylate and styrene; the initiator is one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
7. The method for preparing an organic-inorganic hybrid aqueous emulsion according to claim 5, wherein: the preparation method of the emulsifier comprises the following steps:
step 1: heating polyethylene glycol monomethyl ether to 70-80 ℃, simultaneously dripping a mixture of glycidyl ester, epoxy resin and p-hydroxyanisole and boron trifluoride diethyl etherate, and keeping the temperature for 3-4h after dripping;
step 2: heating to 90-110 ℃, dropwise adding 85% phosphoric acid solution, and keeping the temperature for 2-3h after dropwise adding;
and step 3: cooling, adding neutralizing agent and water to obtain the emulsifier.
8. The method for preparing an organic-inorganic hybrid aqueous emulsion according to claim 5, wherein: in the step 1, the epoxy resin is one or more of bisphenol A epoxy resin with an epoxy value of 0.44-0.51 and bisphenol F epoxy resin with an epoxy value of 0.52-0.56; the glycidyl ester is glycidyl methacrylate and/or diglycidyl tetrahydrophthalate; the neutralizing agent is one or more of triethylamine, dimethylethanolamine, dimethylisopropanolamine and sodium hydroxide.
9. The method for producing an organic-inorganic hybrid aqueous emulsion according to claim 7 or 8, characterized in that: the molecular weight of the polyethylene glycol monomethyl ether is 600-2000.
10. A super anticorrosive paint using the organic-inorganic hybrid aqueous emulsion according to claim 1, characterized in that: according to the weight portion, 45-65 portions of organic-inorganic hybrid water-based emulsion, 10-25 portions of deionized water, 0.1-0.3 portion of wetting dispersant, 0.05-0.1 portion of defoaming agent, 0.1-0.2 portion of pH regulator, 0.3-0.5 portion of rheological additive, 10-25 portions of high temperature resistant powder and 5-25 portions of weather resistant pigment.
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