CN111072995B - Water-based epoxy emulsion, water-based epoxy coating and preparation method thereof - Google Patents
Water-based epoxy emulsion, water-based epoxy coating and preparation method thereof Download PDFInfo
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- CN111072995B CN111072995B CN201911422109.3A CN201911422109A CN111072995B CN 111072995 B CN111072995 B CN 111072995B CN 201911422109 A CN201911422109 A CN 201911422109A CN 111072995 B CN111072995 B CN 111072995B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The invention provides a water-based epoxy emulsion, a water-based epoxy coating and a preparation method thereof. The water-based epoxy emulsion comprises the following components in percentage by mass: 40-50% of E20 epoxy resin, 3-5% of emulsifier, 2-10% of hydrophobic modifier, 4-5% of cosolvent and the balance of water; the hydrophobic modifier is one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized castor oil, dimer acid diglycidyl ester and cardanol glycidyl ether; the emulsifier is an epoxide-polyethylene glycol-epoxide type emulsifier. The waterborne epoxy emulsion has better stability, and after the waterborne epoxy emulsion is applied to waterborne epoxy coating, a paint film formed by the waterborne epoxy emulsion has better water resistance.
Description
Technical Field
The invention relates to the technical field of epoxy coatings, and in particular relates to a water-based epoxy emulsion, a water-based epoxy coating and a preparation method thereof.
Background
The traditional solvent-based coating contains a large amount of organic solvents, which causes great harm to the global environment. In recent years, with the enhancement of environmental protection awareness and ecological protection awareness, the share of the water-based paint in the market is increasing, and the water-based epoxy resin paint also becomes the focus of research and development. In the water-based epoxy resin coating, the epoxy resin has good chemical properties and physical properties and is widely applied to the field of coatings.
When the epoxy resin is used for preparing the waterborne epoxy emulsion, an emulsifier is required to be added in order to ensure the stability of the waterborne epoxy emulsion, and more hydrophilic groups are contained in the system, so that the waterborne epoxy resin coating is poor in water resistance after being formed into a film and is easy to foam and peel. The researchers improve the emulsifier, and the prior art (chinese patent CN 1415680A) discloses a method for preparing a waterborne epoxy emulsion by using an amphiphilic emulsifier, wherein although the stability of the obtained waterborne epoxy emulsion is good, the reaction degree of the emulsifier is difficult to control, and unreacted primary hydroxyl groups can cause low crosslinking density of a paint film and finally cause poor water resistance of the paint film.
In this regard, there is a need to develop an aqueous epoxy emulsion having good stability and good water resistance.
Disclosure of Invention
Aiming at the problem of poor water resistance of the existing water-based epoxy emulsion due to an emulsifier, the invention provides the water-based epoxy emulsion which has good stability and can form a paint film with better water resistance after being applied to a water-based epoxy coating.
Another object of the present invention is to provide a method for preparing the aqueous epoxy emulsion.
It is a further object of the present invention to provide a waterborne epoxy coating.
In order to solve the technical problems, the invention adopts the technical scheme that:
the water-based epoxy emulsion comprises the following components in percentage by mass:
40-50% of E20 epoxy resin, 3-5% of emulsifier, 2-10% of hydrophobic modifier, 4-5% of cosolvent and the balance of water; the hydrophobic modifier is one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized castor oil, dimer acid diglycidyl ester and cardanol glycidyl ether; the emulsifier is an epoxide-polyethylene glycol-epoxide type emulsifier (EP-PEG-EP).
The inventor of the application discovers through creative experiments that the obtained water-based epoxy emulsion has better stability by selecting a specific water-based epoxy emulsion system and adding epoxidized vegetable oil serving as a hydrophobic modifier into the water-based epoxy emulsion system, and a paint film formed by the water-based epoxy emulsion has better water resistance after the water-based epoxy emulsion is applied to a water-based epoxy paint.
Preferably, the aqueous epoxy emulsion comprises the following components in percentage by mass: 45 to 50 percent of E20 epoxy resin, 3.4 to 4.1 percent of emulsifier, 2.4 to 9.2 percent of hydrophobic modifier, 4 to 4.5 percent of cosolvent and the balance of water.
Preferably, the aqueous epoxy emulsion comprises the following components in percentage by mass: 45-50% of E20 epoxy resin, 3.4-3.6% of emulsifier, 2.4-3.4% of hydrophobic modifier, 4-4.5% of cosolvent and the balance of water; the hydrophobic modifier is one or two of epoxidized soybean oil and epoxidized fatty acid methyl ester.
Preferably, the aqueous epoxy emulsion comprises the following components in percentage by mass: 45-50% of E20 epoxy resin, 3.8-4.1% of emulsifier, 5-9.2% of hydrophobic modifier, 4-4.5% of cosolvent and the balance of water; the hydrophobic modifier is one or more of epoxy castor oil, dimer acid diglycidyl ester and cardanol glycidyl ether. The inventor of the application finds that the epoxy castor oil, the dimer acid diglycidyl ester and the cardanol glycidyl ether can participate in curing, the using amount of the epoxy castor oil, the dimer acid diglycidyl ester and the cardanol glycidyl ether can be further increased, and the water resistance of the water-based epoxy emulsion can be further improved within the range of the using amount of the scheme.
In the aqueous epoxy emulsion, the epoxide-polyethylene glycol-epoxide emulsifier is prepared by the reaction of E51 epoxy resin and polyethylene glycol 6000 (PEG 6000), wherein the dosage ratio of the E51 epoxy resin to the polyethylene glycol 6000 is 2mol:1mol.
Specifically, the preparation method comprises the following steps: mixing E51 epoxy resin and polyethylene glycol 6000, heating the mixture under the protection of nitrogen until the mixture is completely melted, uniformly stirring the mixture, adding a catalyst at the temperature of not higher than 75 ℃, and then carrying out heat preservation reaction at the temperature of 70 ℃ under the protection of nitrogen.
In the waterborne epoxy emulsion, the cosolvent is one or more of propylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol ethyl ether.
The preparation method of the waterborne epoxy emulsion comprises the following steps: e20 epoxy resin, emulsifier, hydrophobic modifier, cosolvent and adhesion promoter are put into an emulsifying kettle to be heated and dissolved uniformly, dispersed, added with 1/3 to 1/2 of water, continuously dispersed, dropwise added with the rest 1/2 to 2/3 of water after the viscosity rises, and then cooled to normal temperature. In the emulsification process of the epoxy resin, the hydrophobic modifier is brought into emulsion particles, and then the water resistance of a paint film is improved through the hydrophobicity of the hydrophobic modifier when the water-based epoxy paint is cured.
And further, putting the E20 epoxy resin, the emulsifier, the hydrophobic modifier and the cosolvent into an emulsifying kettle, heating and dissolving uniformly, dispersing, adding 1/3 of water, continuing to disperse, dropwise adding the rest 2/3 of water after the viscosity rises obviously, dripping for 1 hour, and cooling to the normal temperature.
In the preparation method of the water-based epoxy emulsion, the heating temperature is 80 ℃. The dispersion is carried out by a high-speed dispersion machine at 2000 r/min. The cooling is normal temperature water cooling.
The invention also provides a water-based epoxy coating, which comprises the water-based epoxy emulsion.
Preferably, the waterborne epoxy coating comprises an A component and a B component; the component A comprises the waterborne epoxy emulsion; the component B comprises a curing agent.
More preferably, the water-based epoxy coating comprises the following components in parts by weight:
the component A comprises: 100 parts of the waterborne epoxy emulsion;
and B component: 10 parts of curing agent and 10 parts of water.
The curing agent for the aqueous epoxy coating material of the present invention is preferably a polyamide curing agent, such as a commercially available 651 type polyamide curing agent.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a specific water-based epoxy emulsion system is selected, epoxidized vegetable oil is used as a hydrophobic modifier and added into the water-based epoxy emulsion system, so that the obtained water-based epoxy emulsion has better stability, and after the water-based epoxy emulsion is applied to a water-based epoxy coating, a paint film formed by the water-based epoxy emulsion has better water resistance.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The starting materials in the examples are all commercially available; the reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Wherein the emulsifier is epoxide-polyethylene glycol-epoxide type emulsifier (EP-PEG-EP) available from HJ-8124 of sea Polymer materials science and technology (Hydraer, inc.).
Or prepared according to the following method: weighing E51 epoxy resin and polyethylene glycol 6000 (PEG 6000), wherein the dosage ratio of the E51 epoxy resin to the polyethylene glycol 6000 is 2mol:1mol, mixing, heating to 70 ℃ under the protection of nitrogen until the mixture is completely melted, and stirring uniformly. Then slowly adding boron trifluoride diethyl etherate at the temperature of not higher than 75 ℃, and then keeping the temperature of 70 ℃ under the protection of nitrogen for 4 hours of reaction to obtain waxy emulsified EP-PEG-EP.
Examples and comparative examples
An aqueous epoxy emulsion comprising the following components: e20 epoxy resin, an emulsifier, a hydrophobic modifier, a cosolvent and water; wherein the hydrophobic modifier is one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized castor oil, dimer acid diglycidyl ester and cardanol glycidyl ether, and the emulsifier is the above-mentioned epoxide-polyethylene glycol-epoxide type emulsifier.
The preparation method of the waterborne epoxy emulsion comprises the following steps: e20 epoxy resin, an emulsifier, a hydrophobic modifier and a cosolvent are put into an emulsifying kettle and heated at 80 ℃ to be dissolved uniformly, a high-speed dispersion machine is used for carrying out 2000r/min dispersion, 1/3 of water is added, the dispersion is continued for 0.5h, after the viscosity rises obviously, the rest 2/3 of water is dripped, the dripping is finished within 1 h, and normal-temperature water is used for cooling to normal temperature.
The ingredients and specific amounts for each example are shown in table 1:
TABLE 1
The ingredients and specific amounts for each ratio are shown in table 2:
TABLE 2
Testing
The aqueous epoxy emulsion prepared above was subjected to a stability test, and the results are shown in tables 3 and 4:
TABLE 3
TABLE 4
The aqueous epoxy emulsions obtained in the above examples and comparative examples were respectively prepared into aqueous epoxy coatings for testing. The water-based epoxy coating comprises the following components in parts by weight: the component A comprises: 100 parts of the prepared waterborne epoxy emulsion; and B component: 10 parts of curing agent and 10 parts of water; wherein the curing agent is commercially available 651 type polyamide curing agent.
And respectively testing each performance index of the prepared water-based epoxy coating, wherein each test standard is as follows: bending test: GB/T6742-2007; and (3) impact resistance test: GB/T1732-1993; and (3) grid drawing test: GB/T9286-1998; water resistance: GB/T1733-1993.
The test results are shown in tables 5 and 6 below:
TABLE 5
TABLE 6
| Performance index | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Bending test (mm) | ≤2 | ≤2 | ≤2 | ≤2 | ≤2 | ≤2 |
| Impact resistance test (cm) | 50 | 50 | 50 | 50 | 50 | 50 |
| Lattice test | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 |
| Water resistance test (h) | 65 | 70 | 280 | 75 | 70 | 80 |
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. The water-based epoxy emulsion is characterized by comprising the following components in percentage by mass:
40-50% of E20 epoxy resin, 3-5% of emulsifier, 2-10% of hydrophobic modifier, 4-5% of cosolvent and the balance of water;
the hydrophobic modifier is one or more of epoxidized soybean oil, epoxidized fatty acid methyl ester, epoxidized castor oil, dimer acid diglycidyl ester and cardanol glycidyl ether;
the emulsifier is an epoxide-polyethylene glycol-epoxide type emulsifier; the epoxide-polyethylene glycol-epoxide emulsifier is prepared by the reaction of E51 epoxy resin and polyethylene glycol 6000, wherein the dosage ratio of the E51 epoxy resin to the polyethylene glycol 6000 is 2mol:1mol of the active component;
the cosolvent is one or more of propylene glycol methyl ether, ethylene glycol ethyl ether or propylene glycol ethyl ether.
2. The aqueous epoxy emulsion of claim 1, comprising the following components in percent by mass: 45 to 50 percent of E20 epoxy resin, 3.4 to 4.1 percent of emulsifier, 2.4 to 9.2 percent of hydrophobic modifier, 4 to 4.5 percent of cosolvent and the balance of water.
3. The aqueous epoxy emulsion of claim 1, comprising the following components in mass percent: 45 to 50 percent of the E20 epoxy resin, 3.4 to 3.6 percent of emulsifier, 2.4 to 3.4 percent of hydrophobic modifier, 4 to 4.5 percent of cosolvent and the balance of water;
the hydrophobic modifier is one or two of epoxidized soybean oil and epoxidized fatty acid methyl ester.
4. The aqueous epoxy emulsion of claim 1, comprising the following components in percent by mass: 45 to 50 percent of the E20 epoxy resin, 3.8 to 4.1 percent of emulsifier, 5 to 9.2 percent of hydrophobic modifier, 4 to 4.5 percent of cosolvent and the balance of water;
the hydrophobic modifier is one or more of epoxy castor oil, dimer acid diglycidyl ester and cardanol glycidyl ether.
5. The method for preparing the aqueous epoxy emulsion according to any one of claims 1 to 4, comprising the steps of: e20 epoxy resin, an emulsifier, a hydrophobic modifier and a cosolvent are put into an emulsifying kettle to be heated and dissolved uniformly, dispersed, added with 1/3 to 1/2 of water to be dispersed continuously, dropwise added with the rest 1/2 to 2/3 of water after the viscosity rises, and then cooled to the normal temperature.
6. An aqueous epoxy paint, characterized by comprising the aqueous epoxy emulsion according to any one of claims 1 to 4.
7. The waterborne epoxy coating of claim 6, comprising an A-side and a B-side; the component A comprises the aqueous epoxy emulsion of any one of claims 1 to 4; the component B comprises a curing agent.
8. The waterborne epoxy coating of claim 7, comprising the following components in parts by weight:
and (2) component A: 100 parts of the aqueous epoxy emulsion according to any one of claims 1 to 4;
and the component B comprises: 10 parts of curing agent and 10 parts of water.
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| EP1495068B1 (en) * | 2002-04-15 | 2005-11-09 | The Coca-Cola Company | Coating composition containing an epoxide additive and structures coated therewith |
| DE60309853T2 (en) * | 2002-04-25 | 2007-09-20 | Ashland Licensing and Intellectual Property LLC, Dublin | SURFACE IMPROVERS FOR REINFORCED COMPOSITE COMPOSITIONS |
| CN105238227B (en) * | 2015-11-25 | 2018-03-27 | 湖南沃特邦恩新材料有限公司 | A kind of water-base epoxy impregnated insulating paint and preparation method thereof |
| CN106366854A (en) * | 2016-08-31 | 2017-02-01 | 中国科学院兰州化学物理研究所 | High-water-resistance self-emulsified double-component water-borne epoxy glass baking lacquer as well as preparation method and application thereof |
| CN107033739B (en) * | 2017-05-09 | 2020-03-10 | 重庆交通大学 | Nonionic water-based epoxy emulsion with adjustable coating flexibility and preparation method thereof |
| CN107522873A (en) * | 2017-08-23 | 2017-12-29 | 佛山市高明同德化工有限公司 | A kind of Diamond Search aqueous epoxy emulsion and preparation method thereof |
| CN107916049A (en) * | 2017-12-06 | 2018-04-17 | 陕西宝塔山油漆股份有限公司 | A kind of preparation method of the soybean oil modified epoxy-ester anticorrosive paint of water-base epoxy |
| CN109251575A (en) * | 2018-09-17 | 2019-01-22 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of the water-fast aqueous enamel paint of high adhesion force |
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