CN112225879B - Modified amine curing agent and preparation method thereof - Google Patents
Modified amine curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN112225879B CN112225879B CN202011115748.8A CN202011115748A CN112225879B CN 112225879 B CN112225879 B CN 112225879B CN 202011115748 A CN202011115748 A CN 202011115748A CN 112225879 B CN112225879 B CN 112225879B
- Authority
- CN
- China
- Prior art keywords
- curing agent
- amine curing
- modified amine
- polyamine
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a modified amine curing agent and a preparation method thereof, wherein the modified amine curing agent contains the following molecular structure:
or
One or two of (a) and (b), wherein P is 1 Is a difunctional epoxy resin or a monoepoxy compound, P 2 Is an acrylic ester monomer containing alkyl substituent groups,
is polyamine. The modified amine curing agent prepared by the invention has low viscosity, and can reduce the construction difficulty and make the construction modes of the coating diverse after being used in the coating, and can be sprayed, blade-coated and roll-coated; the prepared modified amine curing agent does not contain any solvent, has zero content of volatile organic matters, is harmless to the environment, constructors and the like, improves the compatibility of the curing agent and epoxy resin by epoxy modification of the curing agent, increases the hydrophobicity of a coating by steric hindrance and shielding effect generated by alkyl substituent groups, protects weak chemical bonds in the coating, and improves the resistance of the coating to various corrosive media.
Description
Technical Field
The invention belongs to the technical field of environment-friendly coatings, and particularly relates to a modified amine curing agent and a preparation method thereof.
Background
In the coating field in the current Chinese market, the main market is still occupied by the oil coating. In order to achieve a workable viscosity during the use of the oil based paint, a large amount of organic solvent is usually added, so that the paint contains a large amount of VOC (volatile organic compounds), which adversely affects the health of constructors and the environment during the curing process of the paint. And peculiar smell exists in the construction area within a period of time after construction. In recent years, laws and regulations are successively issued by various countries around the world to limit the use of oil-based coatings, and the research on environment-friendly coatings is more and more focused. The currently developed and applied environment-friendly coatings still have various problems, some of which are harsh in construction conditions and some of which are too high in cost. The water-based paint in the environment-friendly paint on the market is convenient to construct, energy-saving and environment-friendly and is widely accepted. However, the water-based paint has high corrosion to coating equipment, and the chemical resistance of the water-based paint is far lower than that of an oil-based paint, so that the water-based paint is difficult to meet the harsh requirements of people. In addition, the performance of the aqueous coating material deteriorates when stored or used in a low-temperature environment, and bacteria easily grow in the presence of water in the coating material.
The curing agent used in the coating has important influence on the coating construction condition and the coating property, and the amine curing agent commonly used in the current market adds a plurality of solvents to improve the performance of the amine curing agent, but simultaneously causes high content of Volatile Organic Compounds (VOC) and causes certain influence on the environment; the curing agent contains water, so that the obtained coating is easy to breed bacteria; the curing agent has strong volatility, high polarity and poor chemical resistance, and is difficult to meet the requirements of people; and the curing agent has high viscosity, which causes the problems of large construction difficulty, short construction time and the like. Therefore, it is highly desirable to develop an amine curing agent that is solvent-free, has low viscosity, and has strong chemical resistance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified amine curing agent and a preparation method thereof, and the defects of short construction time, strong volatility, high polarity and the like of an unmodified amine curing agent are overcome by modifying the amine curing agent. Meanwhile, the prepared curing agent has low viscosity, does not contain Volatile Organic Compounds (VOC) and water, is environment-friendly, stable in storage and easy to construct; the molecular structure of the coating contains alkyl substituent groups, the structure has stronger hydrophobicity and larger steric hindrance, and the shielding effect can provide protection for weak bonds in the curing agent, thereby increasing the chemical resistance of the coating.
The invention adopts one of the technical schemes: a modified amine curing agent contains the following molecular structure:
one or two of (a) and (b), wherein P is 1 Is a difunctional epoxy resin or a monoepoxy compound, P 2 Is an acrylic ester monomer containing alkyl substituent groups,
is polyamine.
Further, said P 1 Is one or more of bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-54, sanmu SM-828, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tertiary carbonic acid glycidyl ester, butyl glycidyl ether, long-chain alkane glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether and o-tolyl glycidyl ether.
Further, the viscosity of the difunctional epoxy resin is less than 200mpa.s.
Further, said P 2 Is one or more of isopropyl acrylate, isobutyl acrylate, isoamyl acrylate, isononyl acrylate, isooctyl acrylate, isodecyl acrylate and 2-ethylbutyl acrylate.
Further, the polyamine is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, polyethylene polyamine, m-xylylenediamine, isophorone diamine and 1, 3-cyclohexane dimethylamine.
The second technical scheme of the invention is as follows: the preparation method of the modified amine curing agent comprises the following steps:
adding P into polyamine at 45-70 deg.C 1 Keeping the temperature to react for 1 to 1.5 hours, then raising the temperature to 75 to 90 ℃, and reacting for 1.5 to 3 hours; cooling to 55-60 deg.C, adding P 2 Keeping the temperature for reaction for 1-1.5h, then raising the temperature to 90-130 ℃ and reacting for 3-5h.
Further, P 1 、P 2 The molar ratio to polyamine is 1: (0.8-2): (1-3)。
Further, P 1 The polyamine is added dropwise.
In the preparation process of the invention, P 1 The epoxide group of (A) and the amine hydrogen of the polyamine undergo a ring-opening reaction, P 2 The double bond of the acrylate monomer and the amine hydrogen of the polyamine generate addition reaction to form the modified amine curing agent.
The invention has the beneficial effects that:
1. the modified p-amine curing agent is prepared by reacting the epoxy resin or the monoepoxy compound, the acrylate monomer and the amine curing agent, so that the defects of short construction time, strong volatility, high polarity and the like of the unmodified amine curing agent are overcome, and meanwhile, the preparation process is simple, the prepared modified amine curing agent does not contain any solvent (including water), has zero content of VOC (volatile organic compounds), and is harmless to the environment, constructors and the like;
2. the modified amine curing agent prepared by the invention has low viscosity and high solid content, can reduce the construction difficulty after being used in the coating, enables the coating to have various construction modes, and can be sprayed, blade-coated and roll-coated;
3. the modified amine curing agent prepared by the invention contains a multi-substituted structure, and the steric hindrance shielding effect of the modified amine curing agent has super-strong resistance to water and various corrosive solutions.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below.
FIG. 1 is a graph showing an unappressed sample of the paint film obtained in example 5, wherein (a) is the unappressed sample, and (b) is the content of H in 10wt% 2 SO 4 In 1300H, in (c) in 10wt% in HCl for 1300H, in (d) in 10wt% in NaOH for 1300H, in (e) in 10wt% in NaCl for 1300H, in (f) in 120# in gasoline for 1300H, in (g) in H # in gasoline 2 And soaking the sample in O for 1300 hours.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
Example 1
The synthesis of the modified amine curing agent comprises the following steps:
(1) Adding 14.2g of 1, 3-cyclohexanedimethylamine into a three-neck flask;
(2) Slowly dripping 34.32g of polypropylene glycol diglycidyl ether with the viscosity of 30-70mpa.s into a three-neck flask at the temperature of 70 ℃, stirring while dripping to uniformly mix the mixture, finishing dripping for 5min, keeping the temperature of 70 ℃ for reacting for 1h, and heating to 85 ℃ for reacting for 2h;
(3) Reducing the temperature to 60 ℃;
(4) Adding 17.82g of isononyl acrylate into a three-neck flask, and carrying out heat preservation reaction for 1 hour;
(5) And raising the temperature to 125 ℃ for reaction for 4 hours, and taking out to obtain the modified amine curing agent.
Example 2
The synthesis of the modified amine curing agent comprises the following steps:
(1) Adding 13.6g of m-xylylenediamine into a three-necked flask;
(2) Slowly dripping 22.8g of tertiary carbonic acid glycidyl ester into a three-neck flask at the temperature of 55 ℃, stirring while dripping to uniformly mix the tertiary carbonic acid glycidyl ester, finishing dripping for 5min, keeping the temperature of 55 ℃ for reacting for 1.5h, and heating to 80 ℃ for reacting for 3h;
(3) Reducing the temperature to 60 ℃;
(4) Adding 29.7g of isooctyl acrylate into a three-neck flask, and keeping the temperature to react for 1.5h;
(5) And raising the temperature to 120 ℃ for reaction for 3 hours, and taking out to obtain the modified amine curing agent.
Example 3
The synthesis of the modified amine curing agent comprises the following steps:
(1) Adding 20.6g of diethylenetriamine into a three-neck flask;
(2) Slowly dripping 13.12g of o-tolyl glycidyl ether into a three-neck flask at the temperature of 45 ℃, stirring while dripping to uniformly mix the o-tolyl glycidyl ether, finishing dripping for 10min, keeping the temperature of 45 ℃ for reacting for 1.5h, and heating to 75 ℃ for reacting for 1.5h;
(3) Reducing the temperature to 60 ℃;
(4) Adding 24.96g of acrylic acid-2-ethyl butyl ester into a three-neck flask, and carrying out heat preservation reaction for 1 hour;
(5) And raising the temperature to 100 ℃ for reaction for 4 hours, and taking out the reaction product to obtain the modified amine curing agent.
Example 4
The synthesis of the modified amine curing agent comprises the following steps:
(1) Adding 27.2g of triethylene tetramine into a three-neck flask;
(2) Slowly dripping 30.3g of benzyl glycidyl ether into a three-neck flask at the temperature of 50 ℃, stirring while dripping to uniformly mix the benzyl glycidyl ether, finishing dripping within 10min, then keeping the temperature of 50 ℃ for reacting for 1h, and heating to 80 ℃ for reacting for 2h;
(3) Reducing the temperature to 60 ℃;
(4) Adding 44.67g of isoamyl acrylate into a three-neck flask, and carrying out heat preservation reaction for 1 hour;
(5) And (3) raising the temperature to 110 ℃ for reaction for 5 hours, and taking out to obtain the modified amine curing agent.
Example 5
The synthesis of the modified amine curing agent comprises the following steps:
(1) Adding 34.04g of isophorone diamine into a three-neck flask;
(2) Mixing 10.1g of polyethylene glycol diglycidyl ether with 1.64g of bisphenol A epoxy resin E-51, slowly adding the mixture dropwise into a three-neck flask at the temperature of 60 ℃ while stirring to uniformly mix the mixture, finishing the dropwise addition for 8min, keeping the temperature of 60 ℃ for reacting for 1h, and heating to 80 ℃ for reacting for 2h;
(3) Reducing the temperature to 60 ℃;
(4) Adding 20.45g of isooctyl acrylate into a three-neck flask, and carrying out heat preservation reaction for 1h;
(5) And (3) heating the temperature to 110 ℃ for reaction for 4 hours, and taking out the product to obtain the modified amine curing agent.
Effect verification example 1:
the curing agents prepared in examples 1 to 5 were tested for viscosity and solid content, respectively, with the test standards and results shown in tables 1 and 2, respectively.
TABLE 1
| Detecting items | Detection standard |
| Viscosity of the oil | GB/T 1723-93 |
| Solid content | GB/T 1725-2007 |
TABLE 2
Effect verification example 2:
respectively mixing the curing agent prepared in the examples 1-5 with a defoaming agent BYK-A530, a wetting agent TEGO Wet KL 245 and a flatting agent BYK333 as a component A according to the mass ratio of 99.4; 95-100wt% of bisphenol A epoxy resin E-51 and 5-0wt% of epoxy reactive diluent AGE are mixed to form a component B, wherein the total amount of the bisphenol A epoxy resin E-51 and the epoxy reactive diluent AGE is 100wt%; and preparing the component A and the component B into varnish according to the molar ratio of active hydrogen to epoxy group 1 (1-1.1), coating the varnish on a tin plate through a wire rod, and curing at room temperature. And (3) after the paint film is completely cured, detecting the performance of the paint film, wherein the detection standard of the detection item is shown in a table 3, and the detection result is shown in a table 4.
TABLE 3
| Detecting items | Detection standard |
| Adhesion force | GB 1720-79(89) |
| Hardness of pencil | GB/T 6739-1996 |
| Resistance to water and chemicals | GB 1763-79(89) |
TABLE 4
FIG. 1 is a sample of an un-soaked sample of paint film prepared using the modified curing agent of example 5 and samples tested for water and chemical resistance.
As can be seen from tables 2 and 4 and FIG. 1, the modified amine curing agent prepared by the technical scheme of the invention has low viscosity and high solid content, and after the modified amine curing agent is prepared into a paint film, the obtained paint film has high hardness and strong water resistance and corrosion resistance.
The varnish prepared by the modified amine curing agents prepared in the embodiments 1 to 5 according to the method is coated on a tin plate by adopting a spraying and blade coating mode, the varnish is cured at room temperature, and the performances of the varnish are detected after the varnish is completely cured, so that the varnish has the characteristics of high hardness, strong water resistance and corrosion resistance, and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (4)
1. The modified amine curing agent is characterized by comprising the following molecular structure:
one or two of (a) and (b), wherein P is 1 Is a difunctional epoxy resin or a monoepoxy compound, P 2 Is an acrylic ester monomer containing alkyl substituent groups,
is a polyamine;
the preparation method of the modified amine curing agent comprises the following steps:
adding P into polyamine at 45-70 deg.C 1 Keeping the temperature to react for 1 to 1.5 hours, then raising the temperature to 75 to 90 ℃, and reacting for 1.5 to 3 hours; cooling to 55-60 deg.C, adding P 2 Keeping the temperature to react for 1 to 1.5 hours, then raising the temperature to 90 to 130 ℃, and reacting for 3 to 5 hours;
P 1 、P 2 the molar ratio of the polyamine to the polyamine is 1: (0.8-2): (1-3);
the viscosity of the difunctional epoxy resin is less than 200mpa.s;
the P is 2 Is one or more of isopropyl acrylate, isobutyl acrylate, isoamyl acrylate, isononyl acrylate, isooctyl acrylate, isodecyl acrylate and 2-ethylbutyl acrylate;
the prepared modified amine curing agent does not contain any solvent.
2. The modified amine curing agent of claim 1, wherein P is selected from the group consisting of 1 Is one or more of bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-54, sanmu SM-828, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tertiary carbonic acid glycidyl ester, butyl glycidyl ether, long-chain alkane glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether and o-tolyl glycidyl ether.
3. The modified amine curing agent of claim 1, wherein the polyamine is one or more selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, m-xylylenediamine, isophoronediamine, and 1, 3-cyclohexyldimethylamine.
4. The modified amine curing agent of claim 1, wherein P is P 1 The polyamine is added dropwise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011115748.8A CN112225879B (en) | 2020-10-19 | 2020-10-19 | Modified amine curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011115748.8A CN112225879B (en) | 2020-10-19 | 2020-10-19 | Modified amine curing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112225879A CN112225879A (en) | 2021-01-15 |
| CN112225879B true CN112225879B (en) | 2023-03-10 |
Family
ID=74117884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011115748.8A Active CN112225879B (en) | 2020-10-19 | 2020-10-19 | Modified amine curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112225879B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337235B (en) * | 2021-07-09 | 2023-03-17 | 成都硅宝科技股份有限公司 | Fast-curing epoxy true porcelain adhesive for interior decoration and preparation method thereof |
| CN115321879B (en) * | 2022-08-31 | 2023-08-22 | 思特博恩(常州)新材料科技有限公司 | High-strength mineral lathe bed composite material and preparation method thereof |
| CN115785783B (en) * | 2022-12-05 | 2024-01-30 | 上海正欧实业有限公司 | Weather-resistant floor paint and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281759A (en) * | 1999-04-01 | 2000-10-10 | Mitsui Chemicals Inc | Latent epoxy hardener and one-component epoxy resin composition containing the same |
| JP2006131661A (en) * | 2004-11-02 | 2006-05-25 | Japan Epoxy Resin Kk | Epoxy resin composition and epoxy resin-cured material |
| CN1958639A (en) * | 2006-11-27 | 2007-05-09 | 华南理工大学 | Solidifying agent for aqueous epoxy resin, and preparation method |
| CN104558529A (en) * | 2014-12-26 | 2015-04-29 | 江苏苏博特新材料股份有限公司 | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent |
| CN105368241A (en) * | 2015-10-12 | 2016-03-02 | 江苏科技大学 | Anticorrosive paint composition containing self-emulsifying curing agent and preparation method of anticorrosive paint |
| CN107254030A (en) * | 2017-06-28 | 2017-10-17 | 绵阳惠利环氧工程有限公司 | It is a kind of to possess acrylate ended aqueous epoxy curing agent of self-defoaming ability and preparation method thereof |
| CN108192079A (en) * | 2017-12-28 | 2018-06-22 | 中科院广州化学有限公司 | A kind of high strength epoxy resin water phase curing agent and its preparation method and application |
| CN108864412A (en) * | 2018-07-11 | 2018-11-23 | 华南理工大学 | High-solid low-viscosity epoxy curing agent for waterborne epoxy self-leveling terrace and preparation method thereof |
-
2020
- 2020-10-19 CN CN202011115748.8A patent/CN112225879B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281759A (en) * | 1999-04-01 | 2000-10-10 | Mitsui Chemicals Inc | Latent epoxy hardener and one-component epoxy resin composition containing the same |
| JP2006131661A (en) * | 2004-11-02 | 2006-05-25 | Japan Epoxy Resin Kk | Epoxy resin composition and epoxy resin-cured material |
| CN1958639A (en) * | 2006-11-27 | 2007-05-09 | 华南理工大学 | Solidifying agent for aqueous epoxy resin, and preparation method |
| CN104558529A (en) * | 2014-12-26 | 2015-04-29 | 江苏苏博特新材料股份有限公司 | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent |
| CN105368241A (en) * | 2015-10-12 | 2016-03-02 | 江苏科技大学 | Anticorrosive paint composition containing self-emulsifying curing agent and preparation method of anticorrosive paint |
| CN107254030A (en) * | 2017-06-28 | 2017-10-17 | 绵阳惠利环氧工程有限公司 | It is a kind of to possess acrylate ended aqueous epoxy curing agent of self-defoaming ability and preparation method thereof |
| CN108192079A (en) * | 2017-12-28 | 2018-06-22 | 中科院广州化学有限公司 | A kind of high strength epoxy resin water phase curing agent and its preparation method and application |
| CN108864412A (en) * | 2018-07-11 | 2018-11-23 | 华南理工大学 | High-solid low-viscosity epoxy curing agent for waterborne epoxy self-leveling terrace and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112225879A (en) | 2021-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112225879B (en) | Modified amine curing agent and preparation method thereof | |
| US11597796B2 (en) | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof | |
| CN105601785B (en) | A kind of acrylic resin modified aqueous dispersion of epoxy active diluent | |
| CN108341928B (en) | Preparation method of water-based epoxy curing agent | |
| CN110746578B (en) | Water-based epoxy curing agent based on castor oil triglycidyl ether and preparation method thereof | |
| WO2009076609A2 (en) | Glycidyl carbamate coatings having improved corrosion resistance | |
| JP2016522851A (en) | Epoxy resin composition | |
| JP2014012837A (en) | Curing agent for epoxy functional compound | |
| EP2545121B1 (en) | Storage stable water based epoxy-amine curable systems | |
| CN109370384B (en) | Preparation method of self-emulsifying nonionic water-based epoxy curing agent | |
| JP2008247958A (en) | Aqueous epoxy resin composition | |
| CN110511356A (en) | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof | |
| CN114605616B (en) | Quick-drying nonionic water-based epoxy curing agent, and preparation method and application thereof | |
| KR20150079620A (en) | Weatherable coatings | |
| JP2007002250A (en) | Curing agent for coating composition | |
| CN109824837B (en) | High-strength high-toughness water-based antifouling metal baking paint and preparation method thereof | |
| JP6704344B2 (en) | Cationic alkyd resin | |
| CN111777922B (en) | Anticorrosion and mildewproof waterborne epoxy curing agent and preparation method thereof | |
| CN111826055A (en) | Waterborne epoxy zinc-rich primer curing agent and preparation method thereof | |
| CN114591492A (en) | Water-based epoxy curing agent and preparation method and application thereof | |
| CN112625216A (en) | Aqueous epoxy resin dispersion for weather-resistant finish paint and coating composition containing same | |
| US3129198A (en) | Quaternary monoimidazoline salts as thermosetting catalysts for resinous blends comprising polyepoxide polymers and acrylic polymers having a plurality of carboxyl groups therein | |
| JP5511544B2 (en) | Clean room painting method | |
| US2967172A (en) | Catalyzed epoxy coatings and articles coated therewith | |
| WO2022165729A1 (en) | Epoxy curing agents and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |