CN109021213B - Water-based epoxy resin and preparation method thereof - Google Patents
Water-based epoxy resin and preparation method thereof Download PDFInfo
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- CN109021213B CN109021213B CN201810599854.4A CN201810599854A CN109021213B CN 109021213 B CN109021213 B CN 109021213B CN 201810599854 A CN201810599854 A CN 201810599854A CN 109021213 B CN109021213 B CN 109021213B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
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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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- Health & Medical Sciences (AREA)
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- Epoxy Resins (AREA)
Abstract
The invention discloses a water-based epoxy resin and a preparation method thereof. The preparation method of the waterborne epoxy resin comprises the following steps: firstly, reacting polyetheramine with a monoepoxy compound to prepare an intermediate, and then condensing the intermediate with epoxy resin to obtain the waterborne epoxy resin. The water-based epoxy resin has the advantages of no volatile component, no solvent addition, moderate viscosity, simple preparation method and wide application range, and the emulsion prepared by the water-based epoxy resin has good storage stability and small particle size, and the paint film prepared by mixing the water-based epoxy resin with a curing agent has good toughness.
Description
Technical Field
The invention relates to a water-based epoxy resin and a preparation method thereof.
Background
Epoxy resin is widely used in many fields such as coatings, adhesives, composite materials and the like because of its excellent physical and chemical properties. Most of the traditional epoxy resin coatings are insoluble in water and have high viscosity, and a large amount of organic solvent needs to be added for dilution during construction, so that the damage to the ecological environment and the physical health of constructors can be caused. In the last decade, the application field of the water-based epoxy resin is wider and wider, the water-based epoxy resin is substituted for the oil-based epoxy resin in some fields, and with the increasing attention of people on environmental protection, the water-based epoxy coating is likely to completely replace the solvent-based epoxy coating. Since the performance of the water-based epoxy resin has a decisive role in the overall performance of the water-based epoxy coating, the development of the water-based epoxy resin with excellent performance and environmental protection is critical.
At present, a plurality of methods for preparing epoxy resin into water are available, and the methods are roughly divided into an external emulsifier method, a chemical modification method and a curing agent emulsification method, but all have obvious defects. The emulsifier addition method needs to introduce an emulsifier into the whole system, and the emulsifier is remained in the final cured product, so that the physical and mechanical properties of the cured product can be influenced; the chemical modification method has complex operation and higher cost; although the curing agent emulsification method has a simpler process than the external emulsifier method, the problems of incomplete resin emulsification, large dispersion particle size, poor storage stability and the like exist. A certain amount of cosolvent is often added into the existing waterborne epoxy resin to reduce the viscosity and improve the emulsion stability, but the VOC content of a waterborne system is increased, and many ionic waterborne resins have the problems of poor coating toughness, poor storage stability and the like, and are difficult to meet the increasing practical requirements.
Therefore, there is a need to develop a waterborne epoxy resin with moderate viscosity, good storage stability, safety, environmental protection, good emulsion stability and good paint film toughness.
Disclosure of Invention
The invention aims to provide a water-based epoxy resin and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of the water-based epoxy resin comprises the following steps: firstly, reacting polyetheramine with a monoepoxy compound to prepare an intermediate, and then condensing the intermediate with epoxy resin to obtain the waterborne epoxy resin.
The polyether amine is polyether amine D230.
The monoepoxy compound is at least one of allyl glycidyl ether and glycidyl methacrylate.
The epoxy resin is bisphenol A type epoxy resin.
The polyether amine and the monoepoxy compound are in a molar ratio of (1-1.2): 1.
the mass ratio of the intermediate to the epoxy resin is 1: (3-10).
The invention has the beneficial effects that: the water-based epoxy resin has the advantages of no volatile component, no solvent addition, moderate viscosity, simple preparation method and wide application range, and the emulsion prepared by the water-based epoxy resin has good storage stability and small particle size, and the paint film prepared by mixing the water-based epoxy resin with a curing agent has good toughness.
1) The waterborne epoxy resin has no volatile component, no solvent addition and moderate viscosity, and completely meets the national requirements on environmental protection;
2) the emulsion prepared by mixing the water-based epoxy resin and water has good centrifugal stability, and can be stably stored for more than 6 months at normal temperature;
3) the self-emulsifying effect of the water-based epoxy resin is excellent, the particle size distribution of the emulsion is concentrated, the particle size of the emulsion is less than 500 mu m, and the emulsion has blue light;
4) the waterborne epoxy resin molecule of the invention contains longer polyether chain segment, which improves the flexibility of the molecule, and the paint film prepared by mixing the waterborne epoxy resin molecule and the curing agent has good impact resistance and flexibility;
5) the water-based epoxy resin can be used in the fields of adhesion, repair, underwater anticorrosive paint and the like of terraces, water conservancy facilities and humid environments.
Detailed Description
A preparation method of the water-based epoxy resin comprises the following steps: firstly, reacting polyetheramine with a monoepoxy compound to prepare an intermediate, and then condensing the intermediate with epoxy resin to obtain the waterborne epoxy resin.
Preferably, the preparation method of the water-based epoxy resin comprises the following steps: firstly, mixing polyetheramine and a monoepoxy compound, reacting for 2-3 hours at 45-55 ℃ to obtain an intermediate, then dropwise adding the intermediate into epoxy resin, and reacting for 2-4 hours at 80-110 ℃ after dropwise adding to obtain the water-based epoxy resin.
Preferably, the polyetheramine is polyetheramine D230 with the structural formula
x≈2.5。
Preferably, the monoepoxy compound is at least one of allyl glycidyl ether and glycidyl methacrylate.
Preferably, the epoxy resin is a bisphenol a type epoxy resin.
More preferably, the epoxy resin is prepared from epoxy resin E-51 and epoxy resin E-20 according to a mass ratio of 1: (0.2-0.5) by compounding.
Still more preferably, the epoxy resin is prepared from epoxy resin E-51 and epoxy resin E-20 according to a mass ratio of 1: (0.4-0.5) by compounding.
Preferably, the molar ratio of the polyether amine to the monoepoxy compound is (1-1.2): 1.
preferably, the mass ratio of the intermediate to the epoxy resin is 1: (3-10).
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
23g of polyetheramine D230 and 11.4g of allyl glycidyl ether are mixed, the temperature is raised to 50 ℃, the mixture is reacted for 2 hours at constant temperature, an intermediate is obtained, 59.5g of epoxy resin E-51 and 25.5g of epoxy resin E-20 are mixed, the temperature is raised to 80 ℃, 15g of the intermediate is dripped after the epoxy resin is completely melted, and the intermediate is reacted for 2 hours at constant temperature after the intermediate is dripped, so that the waterborne epoxy resin is obtained.
Example 2:
mixing 23g of polyetheramine D230 and 11.8g of glycidyl methacrylate, heating to 50 ℃, reacting at constant temperature for 2.5 hours to obtain an intermediate, mixing 60g of epoxy resin E-51 with 27g of epoxy resin E-20, heating to 90 ℃, dropwise adding 10g of the intermediate after the epoxy resin is completely melted, and reacting at constant temperature for 3 hours after the intermediate is completely dropwise added to obtain the waterborne epoxy resin.
Example 3:
firstly, mixing 22g of polyetheramine D230 and 10g of allyl glycidyl ether, heating to 50 ℃, reacting at constant temperature for 3 hours to obtain an intermediate, then mixing 50g of epoxy resin E-51 and 24g of epoxy resin E-20, heating to 100 ℃, dropwise adding 20g of the intermediate after the epoxy resin is completely melted, and reacting at constant temperature for 3.5 hours after the intermediate is dropwise added to obtain the waterborne epoxy resin.
Example 4:
firstly, mixing 27.5g of polyetheramine D230 and 16.2g of glycidyl methacrylate, heating to 50 ℃, reacting at constant temperature for 3 hours to obtain an intermediate, then mixing 54g of epoxy resin E-51 and 27g of epoxy resin E-20, heating to 110 ℃, dropwise adding 10g of the intermediate after the epoxy resin is completely melted, and reacting at constant temperature for 4 hours after the intermediate is completely dropwise added to obtain the waterborne epoxy resin.
Example 5:
firstly, mixing 27.5g of polyetheramine D230 and 11.4g of allyl glycidyl ether, heating to 50 ℃, reacting at constant temperature for 2.5 hours to obtain an intermediate, then mixing 54g of epoxy resin E-51 and 27g of epoxy resin E-20, heating to 95 ℃, dropwise adding 10g of the intermediate after the epoxy resin is completely melted, and reacting at constant temperature for 4 hours after the intermediate is completely dropwise added to obtain the waterborne epoxy resin.
Test example:
1) the aqueous epoxy resin prepared in the embodiments 1 to 5 is heated to 50 ℃, the distilled water is slowly added, the viscosity of the whole system tends to increase firstly and then decrease, the adding speed of the distilled water is increased when the viscosity begins to decrease until the solid content reaches 60 percent, the aqueous emulsion 1 to 5 is obtained, and then the performance test is carried out on the aqueous emulsion, wherein the test results are shown in the following table:
TABLE 1 Performance test results for aqueous emulsions 1-5
Note:
the test method for each performance index in the table is as follows:
centrifugal stability: adding the aqueous emulsion into a centrifuge, adjusting the rotating speed to 3000r/min, centrifuging for 30min, and observing whether the emulsion has the phenomena of layering, flocculation precipitation and the like;
storage stability: and (3) standing the aqueous emulsion at normal temperature for 6 months, and observing whether the emulsion has the phenomena of sedimentation, layering and the like.
2) Mixing the water-based emulsion 1-5 with a water-based curing agent to prepare varnish, preparing an epoxy resin varnish paint film (paint film samples 1-5), standing the varnish paint film for 30min at normal temperature, curing the varnish paint film in a 70 ℃ oven for 1h, naturally cooling, and performing performance test, wherein the test results are shown in the following table:
TABLE 2 Performance test results for paint film samples 1-5
Note:
the test method for each performance index in the table is as follows:
pencil hardness: the pencil with a certain hardness mark is arranged on a pencil hardness tester, the pencil is scratched on a coating film, whether the pencil lead scratches on the coating film or not is carefully observed, the hardness of the coating film pencil is represented by the hardest pencil mark which does not cause the damage of the coating film, according to the regulation of GB/T6739-;
adhesion (cross-hatch method): and scribing square cross grid patterns with equal intervals on the coating by using a grid scribing knife, wherein the grid interval is 1mm, the scratch needs to penetrate through the coating film until reaching the substrate, a 3M adhesive tape is pasted on the grid scribing area, the adhesive tape is lightly pressed by fingers to be fully contacted with the coating film of the grid scribing area, then the adhesive tape is rapidly pulled open, and whether the coating is adhered to the substrate in the grid scribing area or not is observed. The measurement results can be classified according to GB/T9286-1998 grid test for paint films of colored paint and varnish, the adhesion of the coating is classified into six grades from 0 grade to 5 grade, the 0 grade shows that the cutting edge is completely smooth and has no drop, and the 5 grade shows that more than 65 percent of the area coating drops;
flexibility (bending test of mandrel): the prepared coated test plate is placed on a circular shaft with a known diameter to be bent, and the cracking or breaking condition of the coating is observed. According to the regulations of GB/T6742-86 paint film bending test (cylindrical shaft), the flexibility of the coating film is expressed by the minimum shaft rod diameter which does not cause the coating film to be damaged;
impact resistance height: the determination is carried out according to GB/T1732-93 & lt determination method for impact resistance of paint film & gt. Placing the iron plate of the coating film on an anvil, placing the coating film upwards, placing a heavy hammer with fixed mass at a certain height right above the coating film, enabling the heavy hammer to fall freely and impact on the coating film and the iron plate, observing whether the paint film has cracks or peeling phenomena by using a magnifying lens, and expressing the impact resistance of the paint film by the maximum height of the heavy hammer without causing the damage of the paint film.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart 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 (3)
1. A preparation method of water-based epoxy resin is characterized by comprising the following steps: the method comprises the following steps: mixing polyetheramine and a monoepoxy compound, reacting for 2-3 hours at 45-55 ℃ to obtain an intermediate, dropwise adding the intermediate into epoxy resin, and reacting for 2-4 hours at 80-110 ℃ after dropwise adding to obtain water-based epoxy resin;
the polyether amine is polyether amine D230;
the monoepoxy compound is at least one of allyl glycidyl ether and glycidyl methacrylate;
the epoxy resin is prepared from epoxy resin E-51 and epoxy resin E-20 according to the mass ratio of 1: (0.2-0.5) compounding;
the polyether amine and the monoepoxy compound are in a molar ratio of (1-1.2): 1;
the mass ratio of the intermediate to the epoxy resin is 1: (3-10).
2. The aqueous epoxy resin prepared by the method of claim 1.
3. The application of the water-based epoxy resin in the fields of water-based floor paint and water-based anticorrosive paint of claim 2.
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| CN109021213B true CN109021213B (en) | 2020-12-15 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021237556A1 (en) * | 2020-05-28 | 2021-12-02 | 江苏扬农锦湖化工有限公司 | Waterborne epoxy floor paint and preparation method therefor |
| CN114686069B (en) * | 2020-12-28 | 2023-03-31 | 中海油常州涂料化工研究院有限公司 | Polyacrylate resin modified waterborne epoxy emulsion and preparation method thereof |
| CN112680105A (en) * | 2020-12-28 | 2021-04-20 | 大连油漆有限公司 | Environment-friendly anticorrosive paint, hyperbranched epoxy resin and preparation method thereof |
| WO2023121073A1 (en) * | 2021-12-20 | 2023-06-29 | 한국화학연구원 | Gemini-type epoxy resin emulsifier and method for preparing same |
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|---|---|---|---|---|
| WO2011024014A1 (en) * | 2009-08-27 | 2011-03-03 | Polinvent Kft. | Amine-epoxy adducts and their use for preparing polyurea and polyurea-polyurethane coatings |
| CN102633989A (en) * | 2012-03-27 | 2012-08-15 | 广东新劲刚超硬材料有限公司 | Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method |
| CN106987194A (en) * | 2017-04-14 | 2017-07-28 | 华南理工大学 | A kind of non-ion aqueous epoxy resin latex and nonionic waterborne epoxy curing agent and its preparation method and aqueous epoxy resins varnish |
| CN108003755A (en) * | 2017-12-25 | 2018-05-08 | 昆明国松特种涂料有限公司 | A kind of non-solvent epoxy drinking-water white paint and preparation method thereof |
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- 2018-06-12 CN CN201810599854.4A patent/CN109021213B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011024014A1 (en) * | 2009-08-27 | 2011-03-03 | Polinvent Kft. | Amine-epoxy adducts and their use for preparing polyurea and polyurea-polyurethane coatings |
| CN102633989A (en) * | 2012-03-27 | 2012-08-15 | 广东新劲刚超硬材料有限公司 | Non-ionic active epoxy emulsifier preparation method and waterborne epoxy resin preparation method |
| CN106987194A (en) * | 2017-04-14 | 2017-07-28 | 华南理工大学 | A kind of non-ion aqueous epoxy resin latex and nonionic waterborne epoxy curing agent and its preparation method and aqueous epoxy resins varnish |
| CN108003755A (en) * | 2017-12-25 | 2018-05-08 | 昆明国松特种涂料有限公司 | A kind of non-solvent epoxy drinking-water white paint and preparation method thereof |
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