CN108822281B - Water-based epoxy resin curing agent and preparation method thereof - Google Patents
Water-based epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN108822281B CN108822281B CN201810599781.9A CN201810599781A CN108822281B CN 108822281 B CN108822281 B CN 108822281B CN 201810599781 A CN201810599781 A CN 201810599781A CN 108822281 B CN108822281 B CN 108822281B
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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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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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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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a waterborne epoxy resin curing agent and a preparation method thereof. The preparation method comprises the following steps: firstly, uniformly mixing fatty amine and polybasic organic acid, heating to 110-130 ℃, adding polyether amine, reacting for 1-3 h at constant temperature, adding epoxy resin, heating to 140-160 ℃, and reacting for 2-4 h at constant temperature to obtain the waterborne epoxy resin curing agent. The waterborne epoxy resin curing agent disclosed by the invention is good in dispersibility in water, good in compatibility with epoxy resin, free of volatile components, safe and environment-friendly, and a paint film obtained by curing the waterborne epoxy resin is high in hardness and good in toughness.
Description
Technical Field
The invention relates to a waterborne epoxy resin curing agent and a preparation method thereof.
Background
In recent years, with the increasing demands for environmental protection, aqueous epoxy systems free of volatile organic solvents or low volatile organic solvents (VOC) and free of harmful air pollutants (NHAP) have become a hot spot of current research. The method for modifying the epoxy curing agent by water-based modification is various, and amidation modification, polyamide modification, epoxy amine addition modification and the like are common. Currently, the curing agent most commonly used in the field of epoxy anticorrosive coatings is a polyamide-based epoxy curing agent, i.e., a polyamide-modified epoxy curing agent. However, the polyamide epoxy curing agent has poor hydrophilicity, poor compatibility with epoxy resin, short operation time, high curing speed and short application period when in use, and the prepared coating film has low strength, poor flexibility, poor impact property and brittle property, and cannot be applied to actual production in a large scale.
Disclosure of Invention
The invention aims to provide a water-based epoxy resin curing agent and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a water-based epoxy resin curing agent is prepared from fatty amine, polybasic organic acid, polyether amine and epoxy resin through condensation reaction.
The mass ratio of the fatty amine to the polybasic organic acid to the polyether amine to the epoxy resin is (30-40): (40-50): (5-10): (5-10).
The aliphatic amine is at least one of diethylenetriamine, triethylene tetramine, m-xylylenediamine and isophorone diamine.
The polyether amine is monoamino polyether.
The polybasic organic acid is industrial dimer acid.
The mass percentage of the dimer in the industrial dimer acid is 73-90%.
The epoxy resin is bisphenol A type epoxy resin.
The preparation method of the waterborne epoxy resin curing agent comprises the following steps: firstly, uniformly mixing fatty amine and polybasic organic acid, heating to 110-130 ℃, adding polyether amine, reacting for 1-3 h at constant temperature, adding epoxy resin, heating to 140-160 ℃, and reacting for 2-4 h at constant temperature to obtain the waterborne epoxy resin curing agent.
And adding the polyether amine in a dropwise manner, and finishing dropwise adding within 20-40 min.
The invention has the beneficial effects that: the waterborne epoxy resin curing agent disclosed by the invention is good in dispersibility in water, good in compatibility with epoxy resin, free of volatile components, safe and environment-friendly, and a paint film obtained by curing the waterborne epoxy resin is high in hardness and good in toughness.
1) Part of epoxy resin groups are introduced into the molecules of the waterborne epoxy resin curing agent, so that the compatibility of the curing agent and epoxy resin is improved;
2) the hardness of a paint film obtained by curing the waterborne epoxy resin by the waterborne epoxy resin curing agent can reach 3H-4H, and the paint film has good impact resistance and flexibility;
3) the waterborne epoxy resin curing agent disclosed by the invention is easy to obtain raw materials, low in production cost and wide in application range, and can be used in the fields of terrace, water conservancy facilities, bonding and repairing in a humid environment, underwater anticorrosive coatings and the like.
Detailed Description
A water-based epoxy resin curing agent is prepared from fatty amine, polybasic organic acid, polyether amine and epoxy resin through condensation reaction.
Preferably, the mass ratio of the fatty amine, the polybasic organic acid, the polyether amine and the epoxy resin is (30-40): (40-50): (5-10): (5-10).
Preferably, the aliphatic amine is at least one of diethylenetriamine, triethylene tetramine, m-xylylenediamine and isophorone diamine.
Preferably, the polyether amine is monoamino polyether (one end of the polyether molecular chain contains amino groups, and the other end does not contain amino groups).
Preferably, the polybasic organic acid is an industrial dimer acid.
Preferably, the mass percentage of the dimer in the industrial dimer acid is 73-90%.
Preferably, the epoxy resin is a bisphenol a type epoxy resin.
The preparation method of the waterborne epoxy resin curing agent comprises the following steps: firstly, uniformly mixing fatty amine and polybasic organic acid, heating to 110-130 ℃, adding polyether amine, reacting for 1-3 h at constant temperature, adding epoxy resin, heating to 140-160 ℃, and reacting for 2-4 h at constant temperature to obtain the waterborne epoxy resin curing agent.
Preferably, the polyether amine is added in a dropwise manner, and the dropwise addition is completed within 20-40 min.
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
uniformly mixing 70g of m-xylylenediamine and 90g of industrial dimer acid, adding the mixture into a reaction vessel, dropwise adding 20g of monoamino polyether into the reaction vessel at 120 ℃, completing dropwise addition within 30min, reacting at constant temperature for 3h, adding 20g of epoxy resin E-51 into the reaction vessel, heating to 150 ℃, reacting at constant temperature for 3h, beginning to titrate the amine value, stopping the reaction after the amine value is stable, and obtaining the waterborne epoxy resin curing agent (the amine value is 211 mgKOH/g).
Example 2:
uniformly mixing 60g of diethylenetriamine and 100g of industrial dimer acid, adding the mixture into a reaction vessel, dropwise adding 15g of monoamino polyether into the reaction vessel at 120 ℃, completing the dropwise addition within 20min, reacting at constant temperature for 3h, adding 13g of epoxy resin E-51 into the reaction vessel, heating to 140 ℃, reacting at constant temperature for 4h, beginning to titrate the amine value, stopping the reaction after the amine value is stable, and obtaining the waterborne epoxy resin curing agent (the amine value is 237 mgKOH/g).
Example 3:
uniformly mixing 75g of isophorone diamine and 95g of industrial dimer acid, adding the mixture into a reaction vessel, dropwise adding 10g of monoamino polyether into the reaction vessel at 110 ℃, completing dropwise addition within 40min, reacting at constant temperature for 2h, adding 16g of epoxy resin E-51 into the reaction vessel, heating to 150 ℃, reacting at constant temperature for 3h, beginning to titrate the amine value, and stopping reaction after the amine value is stable to obtain the waterborne epoxy resin curing agent (the amine value is 189 mgKOH/g).
Example 4:
uniformly mixing 75g of triethylene tetramine and 85g of industrial dimer acid, adding the mixture into a reaction vessel, dropwise adding 13g of monoamino polyether into the reaction vessel at 120 ℃, completing dropwise addition within 30min, reacting at constant temperature for 2h, adding 20g of epoxy resin E-51 into the reaction vessel, heating to 160 ℃, reacting at constant temperature for 2h, beginning to titrate the amine value, stopping the reaction after the amine value is stable, and obtaining the waterborne epoxy resin curing agent (the amine value is 250 mgKOH/g).
Example 5:
uniformly mixing 80g of m-xylylenediamine and 86g of industrial dimer acid, adding the mixture into a reaction vessel, dropwise adding 17g of monoamino polyether into the reaction vessel at 130 ℃, completing dropwise addition within 30min, reacting at constant temperature for 3h, adding 15g of epoxy resin E-51 into the reaction vessel, heating to 150 ℃, reacting at constant temperature for 3h, beginning to titrate the amine value, stopping the reaction after the amine value is stable, and obtaining the waterborne epoxy resin curing agent (the amine value is 269 mgKOH/g).
Test example:
respectively mixing the curing agents prepared in examples 1-5 with waterborne epoxy resin (with the solid content of 30-40%) according to the mass ratio of 40:100 to prepare epoxy resin varnish paint films (samples 1-5), simultaneously mixing m-xylylenediamine with the waterborne epoxy resin according to the stoichiometric ratio to prepare epoxy resin varnish paint films (comparative samples), standing the epoxy resin varnish paint films at normal temperature for 30min, then putting the varnish paint films into a 70 ℃ oven for curing for 1h, naturally cooling, and then carrying out performance tests, wherein the test results are shown in the following table:
TABLE 1 Performance test results for epoxy varnish films
Note:
the test method for each performance index in the table is as follows:
1) 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-;
2) 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;
3) 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;
4) 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 (5)
1. A waterborne epoxy resin curing agent is characterized in that: the epoxy resin is obtained by condensation reaction of fatty amine, polybasic organic acid, polyether amine and epoxy resin; the mass ratio of the fatty amine to the polybasic organic acid to the polyether amine to the epoxy resin is (30-40): (40-50): (5-10): (5-10); the aliphatic amine is at least one of diethylenetriamine, triethylene tetramine, m-xylylenediamine and isophorone diamine; the polybasic organic acid is industrial dimer acid; the polyether amine is monoamino polyether; the preparation method of the waterborne epoxy resin curing agent comprises the following steps: firstly, uniformly mixing fatty amine and polybasic organic acid, then heating to 110-130 ℃, adding polyether amine, reacting for 1-3 h at constant temperature, then adding epoxy resin, heating to 140-160 ℃, and reacting for 2-4 h at constant temperature.
2. The aqueous epoxy resin curing agent according to claim 1, characterized in that: the mass percentage of the dimer in the industrial dimer acid is 73-90%.
3. The aqueous epoxy resin curing agent according to claim 1, characterized in that: the epoxy resin is bisphenol A type epoxy resin.
4. The method for preparing the aqueous epoxy resin curing agent according to claim 1, wherein: the method comprises the following steps: firstly, uniformly mixing fatty amine and polybasic organic acid, heating to 110-130 ℃, adding polyether amine, reacting for 1-3 h at constant temperature, adding epoxy resin, heating to 140-160 ℃, and reacting for 2-4 h at constant temperature to obtain the waterborne epoxy resin curing agent.
5. The method of claim 4, wherein: and adding the polyether amine in a dropwise manner, and finishing dropwise adding within 20-40 min.
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| CN109627692A (en) * | 2018-12-14 | 2019-04-16 | 中国林业科学研究院林产化学工业研究所 | A kind of self-emulsifying, flexible fat-based aqueous epoxy resins and preparation method thereof |
| CN110078897A (en) * | 2019-05-24 | 2019-08-02 | 上海瀚岱化学有限公司 | A kind of stain resistant aqueous epoxy hardener and its preparation process |
| CN111718483B (en) * | 2019-06-08 | 2024-06-11 | 山东德源环氧科技有限公司 | Synthesis method of low molecular polyamide curing agent |
| CN115746265A (en) * | 2022-11-21 | 2023-03-07 | 江苏富琪森新材料有限公司 | Water-based epoxy curing agent for zinc-rich epoxy coating and preparation method thereof |
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| US9862798B2 (en) * | 2013-09-30 | 2018-01-09 | Evonik Degussa Gmbh | Epoxy liquid curing agent compositions |
| CN103788343B (en) * | 2014-01-26 | 2016-02-17 | 浙江环达漆业集团有限公司 | A kind of Diamond Search aqueous epoxy curing agent |
| CN104231232A (en) * | 2014-10-11 | 2014-12-24 | 安徽工程大学 | Polyether amine modified waterborne epoxy floor hardener and preparation method thereof |
| CN105504296B (en) * | 2015-12-29 | 2018-10-16 | 江苏丰彩新型建材有限公司 | A kind of nonionic waterborne epoxy curing agent and preparation method thereof |
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