CN106957409B - Water-based epoxy resin curing agent - Google Patents
Water-based epoxy resin curing agent Download PDFInfo
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- CN106957409B CN106957409B CN201710222566.2A CN201710222566A CN106957409B CN 106957409 B CN106957409 B CN 106957409B CN 201710222566 A CN201710222566 A CN 201710222566A CN 106957409 B CN106957409 B CN 106957409B
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- epoxy resin
- curing agent
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- phenylenediamine
- diethanolamine
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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
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
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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
- C08G59/20—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 epoxy compounds used
-
- 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
- C08G59/5033—Amines aromatic
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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
- C08G59/56—Amines together with other curing agents
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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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a water-based epoxy resin curing agent, belonging to the field of coating chemical industry. The curing agent adopts aromatic para-substituted diamine as a main amine compound, and comprises the following components in percentage by mass: 20-30 wt% of p-phenylenediamine compounds, 10-15 wt% of epoxy resin, 5-10 wt% of epoxy active diluent AGE, 2-3 wt% of diethanolamine, 10-15 wt% of acetic acid and 40-50 wt% of deionized water. The waterborne epoxy curing agent is prepared by firstly carrying out ring opening on diethanol amine and epoxy resin to prepare modified epoxy resin, then carrying out addition reaction on the modified epoxy resin and p-phenylenediamine compounds, and dropwise adding deionized water for dispersion after neutralization. The invention has the advantages of simple operation, low reaction temperature, easy control of the reaction process, no discharge of VOCs (volatile organic compounds), low viscosity and short curing time.
Description
Technical Field
The invention relates to a strong-effect water-based epoxy resin curing agent, belonging to the field of coating chemical industry.
Background
The epoxy resin paint has excellent physical performance, mechanical performance, electric insulating performance, excellent adhering performance to various kinds of material and simple and flexible construction process, and may be used widely in paint. The solvent-based epoxy coating contains a large amount of Volatile Organic Compounds (VOCs), and the VOCs are the main causes of photochemical smog and can cause chronic respiratory diseases, damage to central nerves, irritation to mucous membranes, carcinogenesis and teratogenesis and the like, so that the control of the discharge amount of the VOCs is imperative. Therefore, the country has set a series of policy and regulation to limit the discharge of VOCs, and the water-based epoxy coating is a great trend in the development of the current coating.
The curing agent is one of the key factors affecting the performance of the waterborne epoxy coating. The traditional solvent-based curing agent is difficult to be miscible with the water-based epoxy coating, so the water-based epoxy system can be solved only by using the water-based epoxy curing agentAnd (5) problems are solved. The common aliphatic amine curing agent has great stimulation to human body and is easy to react with CO in the air2The reaction generates salt or absorbs moisture and whitens, so that the practically used waterborne epoxy curing agent is mostly an addition product of polyamine and epoxy resin. However, the modified amine curing agent still has various defects at present, and patent CN103788343A discloses a preparation method of a zero-VOCs waterborne epoxy curing agent, wherein polyether amine (which is volatile and toxic) is adopted as an epoxy resin modifier and is further grafted on an amine compound, and the curing agent has good stability, moderate viscosity, colorless and transparent cured product, but poor weather resistance, easy yellowing, and poor flexibility and adhesion.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a strong-effect water-based epoxy resin curing agent which takes water as a solvent and does not discharge VOCs.
The technical scheme adopted by the invention is as follows:
the water-based epoxy resin curing agent comprises the following components in percentage by mass: 10-15 wt% of epoxy resin, 5-10 wt% of epoxy active diluent AGE, 20-30 wt% of p-phenylenediamine compound, 2-3 wt% of diethanolamine, 10-15 wt% of acetic acid and 40-50 wt% of deionized water.
The waterborne epoxy curing agent is prepared by firstly carrying out ring opening on diethanol amine and epoxy resin to prepare modified epoxy resin, then carrying out addition reaction on the modified epoxy resin and p-phenylenediamine compounds, and dropwise adding deionized water for dispersion after neutralization.
The aqueous epoxy curing agent takes aromatic para-substituted diamine as a main amine compound, such as p-phenylenediamine, N-phenyl-p-phenylenediamine, N-dimethyl-p-phenylenediamine, N-isopropyl-N' -phenyl-p-phenylenediamine, N-ethyl-p-phenylenediamine and N, N-diethyl-p-phenylenediamine. More preferably p-phenylenediamine.
The structural formula of the water-based epoxy resin curing agent is shown as the following formula (I):
wherein R is1、R2、R3、R4Comprising at least one H and one (II)
The preparation method of the waterborne epoxy resin curing agent comprises the following steps:
the method comprises the following steps: preparation of modified epoxy resin
(1) Diluting: diluting the epoxy resin and an active diluent AGE according to the mass ratio until the epoxy resin and the active diluent AGE are uniform and transparent;
(2) modification: and controlling the temperature to be 80-85 ℃, dropwise adding diethanolamine under the stirring state, controlling the molar ratio of the diethanolamine to the epoxy resin to be 0.3-0.5, and reacting at constant temperature for 1-2 h to obtain the modified epoxy resin.
Step two: preparation of the curing agent
(1) Dissolving: adding the amine compound and propylene glycol methyl ether into a flask with a protective gas, a condenser pipe and a stirring device according to the mass ratio, and dissolving the mixture at 100-150 ℃ to obtain a dark red uniform transparent liquid;
(2) reaction: slowly dropwise adding the modified epoxy resin in the step one, cooling to 90 ℃, and reacting for 3-5 h;
(3) and (3) distillation: adding acetic acid, reacting at constant temperature for 30min, and distilling out propylene glycol methyl ether and redundant acetic acid neutralizer under reduced pressure;
(4) diluting: slowly dripping deionized water under the stirring state, diluting until the solid content is 50%, and dispersing for 30min at room temperature to obtain the strong-effect water-based epoxy curing agent.
Compared with the prior art, the invention has the following advantages:
the invention has simple operation, low reaction temperature and easy control of reaction process, the curing agent takes water as solvent, no VOCs is discharged, the viscosity is low (18 ℃, 200 mPa.s), the curing time is short (surface drying time is less than 30min, and full drying time is less than 3 h), the flexibility is good (less than or equal to 1 grade), and the adhesive force is good (less than or equal to 1 grade).
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
a water-based epoxy resin curing agent is prepared by the following steps:
the method comprises the following steps: preparation of modified epoxy resin
(1) Diluting 100g of epoxy resin E-44 and 80 g of epoxy reactive diluent AGE for 30min to be uniform and transparent;
(2) controlling the temperature at 80-85 ℃, dropwise adding 14 g of diethanolamine, and reacting for 1-1.5 h;
step two: preparation of the curing agent
(1) Dissolving 100g of p-phenylenediamine and 20 g of propylene glycol methyl ether in a flask with a protective gas, a condenser and a stirring device at 100 ℃ to obtain a uniform and transparent liquid;
(2) slowly dripping 115 g of the modified epoxy resin in the step one, and reacting for 3-5 h at 90 ℃;
(3) adding 75 g of glacial acetic acid, reacting at constant temperature for 30min, and distilling under reduced pressure to obtain propylene glycol monomethyl ether and redundant organic acid neutralizer;
(4) and slowly dripping 215 g of deionized water under the stirring state, and dispersing for 30min at room temperature to obtain the zero-VOCs strong waterborne epoxy resin curing agent.
The appearance of the waterborne epoxy resin curing agent is dark red liquid; the solid content is 50 percent; active hydrogen equivalent (mol/100 g): 0.546; viscosity (18 ℃): less than or equal to 200 mPa.s; centrifuge stability (3000 r/min,30 min): no delamination occurred.
Example 2:
the preparation process of the waterborne epoxy resin curing agent comprises the following steps:
the method comprises the following steps: preparation of modified epoxy resin
(1) Diluting 100g of epoxy resin E-51 and 100g of epoxy reactive diluent AGE to be uniform and transparent;
(2) controlling the temperature at 80-90 ℃, dropwise adding 16 g of diethanolamine, and reacting for 1-1.5 h;
step two: preparation of the curing agent
(1) Dissolving 150 g of N-phenyl-p-phenylenediamine and 30 g of propylene glycol methyl ether in a flask with a protective gas, a condenser and a stirring device at 150 ℃ to obtain a dark red uniform transparent liquid;
(2) slowly dropwise adding 100g of the modified epoxy resin in the step one, and reacting for 3-5 h at 80 ℃;
(3) adding 50 g of glacial acetic acid, reacting at constant temperature for 30min, and distilling under reduced pressure to obtain propylene glycol monomethyl ether and redundant organic acid neutralizer;
(4) slowly dripping 250 g of deionized water under the stirring state, and dispersing for 30min at room temperature to obtain the zero-VOCs strong waterborne epoxy resin curing agent.
The appearance of the waterborne epoxy resin curing agent is dark red liquid; the solid content is 50 percent; active hydrogen equivalent (mol/100 g): 0.546; viscosity (18 ℃): less than or equal to 200 mPa.s; centrifuge stability (3000 r/min,30 min): no delamination occurred.
Claims (1)
1. A waterborne epoxy resin curing agent is characterized in that: the structural formula of the water-based epoxy resin curing agent is shown as the following formula (I):
wherein R1, R2, R3 and R4 at least comprise one H and one (II)
The water-based epoxy resin curing agent comprises the following raw materials in percentage by mass:
10-15 wt% of epoxy resin, 5-10 wt% of epoxy active diluent AGE, 20-30 wt% of p-phenylenediamine compound, 2-3 wt% of diethanolamine, 10-15 wt% of acetic acid and 40-50 wt% of deionized water;
the preparation method of the waterborne epoxy resin curing agent comprises the following steps:
the method comprises the following steps: preparation of modified epoxy resin
Diluting the epoxy resin and an active diluent AGE according to the mass ratio until the epoxy resin and the active diluent AGE are uniform and transparent; heating the temperature to 85 ℃, dropwise adding diethanolamine under the stirring state, controlling the molar ratio of the diethanolamine to the epoxy resin to be 0.3-0.5, and reacting at constant temperature for 1-2 h to obtain modified epoxy resin;
step two: preparation of the curing agent
(1) Dissolving: adding the amine compound and propylene glycol methyl ether into a flask with a protective gas, a condenser pipe and a stirring device according to the mass ratio, and dissolving the mixture at 100-150 ℃ to obtain a dark red uniform transparent liquid;
(2) reaction: slowly dropwise adding the modified epoxy resin in the step one, cooling to 90 ℃, and reacting for 3-5 h;
(3) and (3) distillation: adding acetic acid, reacting at constant temperature for 30min, and distilling out propylene glycol methyl ether and redundant acetic acid neutralizer under reduced pressure;
(4) diluting: slowly dripping deionized water under the stirring state, diluting until the solid content is 50%, and dispersing for 30min at room temperature to obtain the water-based epoxy curing agent;
the p-phenylenediamine compound is p-phenylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710222566.2A CN106957409B (en) | 2017-04-07 | 2017-04-07 | Water-based epoxy resin curing agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710222566.2A CN106957409B (en) | 2017-04-07 | 2017-04-07 | Water-based epoxy resin curing agent |
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| CN106957409A CN106957409A (en) | 2017-07-18 |
| CN106957409B true CN106957409B (en) | 2020-04-10 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108956366A (en) * | 2018-07-19 | 2018-12-07 | 浩力森化学科技（江苏）有限公司 | A kind of aqueous amine epoxy hardener solid part detection method |
| CN110330863A (en) * | 2019-07-22 | 2019-10-15 | 福建省澳龙环保新材料有限公司 | A kind of aqueous salt spray resistance polishes and preparation method thereof |
| CN110396175B (en) * | 2019-07-24 | 2021-12-28 | 浙江农林大学 | Self-emulsifying antibacterial water-based epoxy resin and application thereof in wood and bamboo protection |
| CN111500157A (en) * | 2020-06-24 | 2020-08-07 | 南通晶锐新型碳材料科技有限公司 | Preparation method of water-based graphene epoxy zinc-rich coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085898A (en) * | 2007-07-17 | 2007-12-12 | 马鞍山采石矶涂料有限公司 | Environment-friendly type normal temperature solidifying water epoxy resin coating and preparation method thereof |
| CN102250321A (en) * | 2011-05-13 | 2011-11-23 | 湖南大学 | Quick-drying room temperature curing waterborne epoxy resin curing agent and preparation method thereof |
| CN102268214A (en) * | 2011-08-29 | 2011-12-07 | 华南理工大学 | Preparation method of aqueous epoxy resin paint |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3641765B2 (en) * | 1996-04-24 | 2005-04-27 | 東都化成株式会社 | Epoxy resin and curable composition containing the epoxy resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085898A (en) * | 2007-07-17 | 2007-12-12 | 马鞍山采石矶涂料有限公司 | Environment-friendly type normal temperature solidifying water epoxy resin coating and preparation method thereof |
| CN102250321A (en) * | 2011-05-13 | 2011-11-23 | 湖南大学 | Quick-drying room temperature curing waterborne epoxy resin curing agent and preparation method thereof |
| CN102268214A (en) * | 2011-08-29 | 2011-12-07 | 华南理工大学 | Preparation method of aqueous epoxy resin paint |
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