CN109280521B - Epoxy structural adhesive curing agent and preparation method and application thereof - Google Patents
Epoxy structural adhesive curing agent and preparation method and application thereof Download PDFInfo
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- CN109280521B CN109280521B CN201811162731.0A CN201811162731A CN109280521B CN 109280521 B CN109280521 B CN 109280521B CN 201811162731 A CN201811162731 A CN 201811162731A CN 109280521 B CN109280521 B CN 109280521B
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to an epoxy structural adhesive curing agent, a preparation method and application thereof, wherein the curing agent is prepared from the following raw materials in parts by weight: 10-20 parts of E51 type epoxy resin, 5-10 parts of 692 epoxy resin active diluent, 20-30 parts of isophorone diamine, 10-20 parts of diethylenetriamine and 30-40 parts of benzyl alcohol; the curing agent has the advantages of low viscosity, low amine value, excellent water resistance, difficult color change and the like.
Description
Technical Field
The invention relates to the field of epoxy structural adhesive, and particularly relates to an epoxy structural adhesive curing agent and a preparation method and application thereof.
Background
The epoxy structural adhesive is a solvent-free liquid epoxy resin adhesive and can be cured at normal temperature or under heating. The cured adhesive layer has a moderate hardness so as to withstand an extremely strong impact and vibration, and has good mechanical properties, good electrical insulation, and can withstand temperature variations and flexural peel stress. The paint has no corrosiveness, and has good adhesion to metal, ceramic, vulcanized rubber, glass fiber finished products, carbon fiber finished products and the like; high resistance to high temp and oil.
The epoxy structural adhesive comprises a main agent and a curing agent, wherein the curing agent comprises aliphatic amine, cyclic amine, aromatic amine and the like; however, the existing curing agent has the defects of high amine value, high viscosity, poor water resistance and easy color change.
Epoxy resin structural adhesives have high strength, water resistance, weather resistance and other properties, and are therefore widely used in the construction field. At present, the market of epoxy resin structural adhesives is more and more occupied, however, the strength, water resistance and other properties of the low-end adhesives cannot be effectively guaranteed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an epoxy structural adhesive curing agent which has the advantages of low viscosity, low amine value, excellent water resistance, no color change and the like.
The second purpose of the invention is to provide a preparation method of the epoxy structural adhesive curing agent, and the curing agent prepared by the method has excellent comprehensive performance, wide sources of preparation raw materials and is beneficial to large-scale production.
The third purpose of the invention is to provide an epoxy structural adhesive which has excellent tensile-shear strength, compression-shear strength, flexural modulus of elasticity and impact toughness, is significantly higher than the industrial standard, and expands the application range of the epoxy structural adhesive.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides an epoxy structural adhesive curing agent, which is prepared from the following raw materials in parts by weight:
10-20 parts of E51 type epoxy resin, 5-10 parts of 692 epoxy resin active diluent, 20-30 parts of isophorone diamine, 10-20 parts of diethylenetriamine and 30-40 parts of benzyl alcohol.
Through the specific selection of the raw materials and the dosage thereof, the curing agent has the advantages of low viscosity, low amine value, excellent water resistance, difficult color change and the like; wherein, the E51 type epoxy resin and 692 epoxy resin reactive diluent can reduce the amine value of the curing agent by reacting with low molecular weight isophorone diamine and diethylenetriamine; in addition, the viscosity of the curing agent can be adjusted by adding benzyl alcohol; the comprehensive performance of the curing agent is improved.
The viscosity of the curing agent prepared by the raw materials with the specific dosage is less than 900mPa.s, preferably 640-870 mPa.s; an amine value of 340mgKOH/g or less; preferably 295-340 mgKOH/g.
Further, the curing agent is prepared from the following raw materials in parts by weight:
18-19 parts of E51 type epoxy resin, 8-10 parts of 692 epoxy resin reactive diluent, 21-22 parts of isophorone diamine, 14-15 parts of diethylenetriamine and 35-36 parts of benzyl alcohol;
furthermore, the curing agent is prepared from the following raw materials in parts by weight:
19 parts of E51 type epoxy resin, 10 parts of 692 epoxy resin reactive diluent, 21 parts of isophorone diamine, 15 parts of diethylenetriamine and 35 parts of benzyl alcohol.
By further limiting the amounts of the above-mentioned raw materials, the amine value and viscosity of the curing agent can be improved more effectively.
The second aspect of the present invention provides a preparation method of the above curing agent, which comprises the following steps:
(1) uniformly mixing E51 type epoxy resin and 692 epoxy resin reactive diluent to obtain a mixture, and uniformly dividing the mixture into 3 parts;
(2) mixing isophorone diamine and diethylenetriamine and pouring the mixture into a reaction kettle;
(3) placing benzyl alcohol into a reaction kettle and starting stirring;
(4) placing the 3-component mixture in the step (1) into a reaction kettle at intervals for reaction;
(5) and (3) after the mixture in the step (1) is completely placed into the reaction kettle, continuously stirring until the temperature is kept constant, and obtaining the epoxy structural adhesive curing agent.
The preparation method can fully promote the reaction among the raw materials, improves the comprehensive performance of the prepared curing agent, has wide sources of the raw materials and is beneficial to large-scale production.
The control parameters in the preparation method of the invention are not strictly limited, and preferably, in the step (4), the control interval time is 25-35 min; controlling the reaction temperature to be less than or equal to 70 ℃; more preferably, the reaction temperature is controlled to be 50-70 ℃. Through the limitation of the parameters, the uniformity and the full reaction of the raw materials can be facilitated, the reaction speed is controlled through temperature control, violent reaction is avoided, the performance of the prepared curing agent is reduced, and the curing agent is prevented from yellowing.
The third aspect of the invention provides an epoxy structural adhesive, which is prepared from the curing agent or the curing agent prepared by the preparation method.
The specific composition of the epoxy structural adhesive is not strictly limited, and preferably, the epoxy structural adhesive is prepared from a component A and a component B according to the ratio of 1: 1;
wherein, the component A comprises: 30-35 parts of E51 type epoxy resin, 1-3 parts of benzyl alcohol and 60-70 parts of activated calcium carbonate;
the component B comprises: 20-25 parts of curing agent, 1-3 parts of benzyl alcohol and 70-80 parts of activated calcium carbonate.
The epoxy structural adhesive prepared from the raw materials with the specific dosage has excellent comprehensive performance, particularly higher strength, and the tensile and shear strength of the epoxy structural adhesive is more than 16 MPa; the compression shear strength is more than 18 MPa; flexural modulus of elasticity of 3800MPa or more; the impact toughness is more than 3J/c square meter.
Compared with the prior art, the invention has the beneficial effects that at least:
(1) the epoxy structural adhesive curing agent has the advantages of low viscosity, low amine value, excellent water resistance, difficult color change and the like.
(2) The curing agent prepared by the preparation method of the epoxy structural adhesive curing agent has excellent comprehensive performance, and the preparation raw materials are wide in source and beneficial to large-scale production.
(3) The epoxy structural adhesive has excellent tensile and shear strength, compression and shear strength, bending elastic modulus and impact toughness, is obviously higher than the industrial standard, and expands the application range of the epoxy structural adhesive.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by manufacturers, and are all conventional products available on the market.
Example 1
Curing agent for epoxy structural adhesive
The epoxy structural adhesive curing agent is prepared from the following raw materials in parts by weight:
20 parts of E51 type epoxy resin, 10 parts of 692 epoxy resin reactive diluent, 20 parts of isophorone diamine, 20 parts of diethylenetriamine and 30 parts of benzyl alcohol.
Second, preparation method
The preparation method of the epoxy structural adhesive curing agent comprises the following steps:
(1) uniformly mixing E51 type epoxy resin and 692 epoxy resin reactive diluent to obtain a mixture, and uniformly dividing the mixture into 3 parts;
(2) mixing isophorone diamine and diethylenetriamine and pouring the mixture into a reaction kettle;
(3) placing benzyl alcohol into a reaction kettle and starting stirring;
(4) placing the 3-component mixture obtained in the step (1) into a reaction kettle at intervals for reaction, wherein the interval time is 25min, and the reaction temperature is 50 ℃;
(5) and (3) after the mixture in the step (1) is completely placed into the reaction kettle, continuously stirring until the temperature is kept constant, and obtaining the epoxy structural adhesive curing agent.
Detecting the amine value and the viscosity of the epoxy structural adhesive curing agent by adopting an acid-base titration method and a rotational viscometer, wherein the detected viscosity is 870 mPa.s; the amine value was 340 mgKOH/g.
Example 2
Curing agent for epoxy structural adhesive
The epoxy structural adhesive curing agent is prepared from the following raw materials in parts by weight:
10 parts of E51 type epoxy resin, 5 parts of 692 epoxy resin reactive diluent, 20 parts of isophorone diamine, 10 parts of diethylenetriamine and 40 parts of benzyl alcohol.
Second, preparation method
The preparation method of the epoxy structural adhesive curing agent comprises the following steps:
(1) uniformly mixing E51 type epoxy resin and 692 epoxy resin reactive diluent to obtain a mixture, and uniformly dividing the mixture into 3 parts;
(2) mixing isophorone diamine and diethylenetriamine and pouring the mixture into a reaction kettle;
(3) placing benzyl alcohol into a reaction kettle and starting stirring;
(4) placing the 3-component mixture obtained in the step (1) into a reaction kettle at intervals for reaction, wherein the interval time is 35min, and the reaction temperature is 70 ℃;
(5) and (3) after the mixture in the step (1) is completely placed into the reaction kettle, continuously stirring until the temperature is kept constant, and obtaining the epoxy structural adhesive curing agent.
Detecting the amine value and the viscosity of the epoxy structural adhesive curing agent by adopting an acid-base titration method and a rotational viscometer, wherein the detected viscosity is 640 mPa.s; the amine value was 310 mgKOH/g.
Example 3
Curing agent for epoxy structural adhesive
The epoxy structural adhesive curing agent is prepared from the following raw materials in parts by weight:
19 parts of E51 type epoxy resin, 10 parts of 692 epoxy resin reactive diluent, 21 parts of isophorone diamine, 15 parts of diethylenetriamine and 35 parts of benzyl alcohol.
Second, preparation method
The preparation method of the epoxy structural adhesive curing agent comprises the following steps:
(1) uniformly mixing E51 type epoxy resin and 692 epoxy resin reactive diluent to obtain a mixture, and uniformly dividing the mixture into 3 parts;
(2) mixing isophorone diamine and diethylenetriamine and pouring the mixture into a reaction kettle;
(3) placing benzyl alcohol into a reaction kettle and starting stirring;
(4) placing the 3-component mixture obtained in the step (1) into a reaction kettle at intervals for reaction, wherein the interval time is 30min, and the reaction temperature is 60 ℃;
(5) and (3) after the mixture in the step (1) is completely placed into the reaction kettle, continuously stirring until the temperature is kept constant, and obtaining the epoxy structural adhesive curing agent.
Detecting the amine value and the viscosity of the epoxy structural adhesive curing agent by adopting an acid-base titration method and a rotational viscometer, wherein the detected viscosity is 850 mPa.s; the amine value was 295 mgKOH/g.
Example 4
The embodiment is an epoxy structural adhesive which is prepared from a component A and a component B according to the ratio of 1: 1;
wherein, the component A comprises: 33 parts of E51 type epoxy resin, 2 parts of benzyl alcohol and 65 parts of activated calcium carbonate;
the component B comprises: 22 parts of epoxy structural adhesive curing agent prepared in example 3, 2 parts of benzyl alcohol and 76 parts of activated calcium carbonate.
The strength of the epoxy structural adhesive was measured according to JC887-2001, and the results are shown in Table 1.
Comparative example 1
The comparative example is an epoxy structural adhesive curing agent, which is prepared from the following raw materials in parts by weight:
29 parts of E51 type epoxy resin, 21 parts of isophorone diamine, 15 parts of diethylenetriamine and 35 parts of benzyl alcohol.
The preparation method of the epoxy structural adhesive curing agent adopts the preparation method in the embodiment 3.
Detecting the amine value and the viscosity of the epoxy structural adhesive curing agent by adopting an acid-base titration method and a rotational viscometer, wherein the detected viscosity is 1100 mPa.s; the amine value was 320 mgKOH/g.
Comparative example 2
The comparative example is an epoxy structural adhesive curing agent, which is prepared from the following raw materials in parts by weight:
19 parts of E51 type epoxy resin, 10 parts of 692 epoxy resin reactive diluent, 36 parts of isophorone diamine and 35 parts of benzyl alcohol.
The preparation method of the epoxy structural adhesive curing agent is generally the preparation method in example 3.
Detecting the amine value and the viscosity of the epoxy structural adhesive curing agent by adopting an acid-base titration method and a rotary viscometer, wherein the detected viscosity is 1050 mPa.s; the amine value was 245 mgKOH/g.
Comparative example 3
The comparative example is an epoxy structural adhesive curing agent, and the preparation raw materials of the epoxy structural adhesive curing agent are basically the same as those of the epoxy structural adhesive curing agent in example 3, except that E51 epoxy resin is replaced by E44 epoxy resin with equal parts. The preparation method of the epoxy structural adhesive curing agent is the same as that in example 3.
Detecting the amine value and the viscosity of the epoxy structural adhesive curing agent by adopting an acid-base titration method and a rotational viscometer, wherein the detected viscosity is 1400 mPa.s; the amine value was 310 mgKOH/g.
Comparative example 4
The comparative example is an epoxy structural adhesive, which is basically the same as the epoxy structural adhesive in example 4, and the difference is that the epoxy structural adhesive curing agent prepared in example 3 is replaced by the epoxy structural adhesive curing agent prepared in comparative example 1.
The strength of the epoxy structural adhesive was measured according to JC887-2001, and the results are shown in Table 1.
Comparative example 5
The comparative example is an epoxy structural adhesive, which is basically the same as the epoxy structural adhesive in example 4, and the difference is that the epoxy structural adhesive curing agent prepared in example 3 is replaced by the epoxy structural adhesive curing agent prepared in comparative example 2.
The strength of the epoxy structural adhesive was measured according to JC887-2001, and the results are shown in Table 1.
Comparative example 6
The comparative example is an epoxy structural adhesive, which is basically the same as the epoxy structural adhesive in example 4, and the difference is that the epoxy structural adhesive curing agent prepared in example 3 is replaced by the epoxy structural adhesive curing agent prepared in comparative example 3.
The strength of the epoxy structural adhesive was measured according to JC887-2001, and the results are shown in Table 1.
TABLE 1
From Table 1, it can be seen that
The epoxy structural adhesive obtained by the curing agent in the technical scheme has excellent tensile shear strength, compression shear strength, bending elastic modulus and impact toughness.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. An epoxy structural adhesive is characterized in that,
the epoxy structural adhesive is prepared from a component A and a component B according to the ratio of 1: 1; wherein:
the component A comprises: 30-35 parts of E51 type epoxy resin, 1-3 parts of benzyl alcohol and 60-70 parts of activated calcium carbonate;
the component B comprises: 20-25 parts of curing agent, 1-3 parts of benzyl alcohol and 70-80 parts of active calcium carbonate;
the tensile-shear strength of the epoxy structural adhesive is more than 16 MPa; the compression shear strength is more than 18 MPa; flexural modulus of elasticity of 3800MPa or more; the impact toughness is more than 3J/c square meter;
the curing agent is prepared from the following raw materials in parts by weight:
18-19 parts of E51 type epoxy resin, 8-10 parts of 692 epoxy resin reactive diluent, 21-22 parts of isophorone diamine, 14-15 parts of diethylenetriamine and 35-36 parts of benzyl alcohol;
the viscosity of the curing agent is less than 900 mPa.s;
the amine value of the curing agent is below 340 mgKOH/g.
2. The epoxy structural adhesive of claim 1, wherein the curing agent is prepared from the following raw materials in parts by weight:
19 parts of E51 type epoxy resin, 10 parts of 692 epoxy resin reactive diluent, 21 parts of isophorone diamine, 15 parts of diethylenetriamine and 35 parts of benzyl alcohol.
3. The epoxy structural adhesive as claimed in claim 1 or 2, wherein the curing agent has a viscosity of 640-870 mpa.s.
4. The epoxy structural adhesive as claimed in claim 1 or 2, wherein the amine value of the curing agent is 295-340 mgKOH/g.
5. The method for preparing the epoxy structural adhesive as claimed in any one of claims 1 to 4, wherein the method for preparing the curing agent comprises the following steps:
(1) uniformly mixing E51 type epoxy resin and 692 epoxy resin reactive diluent to obtain a mixture, and uniformly dividing the mixture into 3 parts;
(2) mixing isophorone diamine and diethylenetriamine and pouring the mixture into a reaction kettle;
(3) placing benzyl alcohol into a reaction kettle and starting stirring;
(4) placing 3 parts of the mixture obtained in the step (1) into a reaction kettle at intervals for reaction;
(5) and (3) after the mixture in the step (1) is completely placed into the reaction kettle, continuously stirring until the temperature is kept constant, and obtaining the epoxy structural adhesive curing agent.
6. The method for preparing the epoxy structural adhesive according to claim 5, wherein in the step (4), the interval time is 25-35 min; the reaction temperature is less than or equal to 70 ℃.
7. The method for preparing the epoxy structural adhesive according to claim 6, wherein in the step (4), the reaction temperature is controlled to be 50-70 ℃.
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| CN201811162731.0A CN109280521B (en) | 2018-09-30 | 2018-09-30 | Epoxy structural adhesive curing agent and preparation method and application thereof |
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| CN201811162731.0A CN109280521B (en) | 2018-09-30 | 2018-09-30 | Epoxy structural adhesive curing agent and preparation method and application thereof |
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| CN109280521B true CN109280521B (en) | 2021-06-01 |
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| CN113527636A (en) * | 2021-07-20 | 2021-10-22 | 福州七彩居建材有限公司 | Preparation method of low-viscosity environment-friendly high-toughness epoxy curing agent |
| CN117384467B (en) * | 2023-10-13 | 2024-05-14 | 今程粘胶(惠州)有限公司 | Heat-resistant epoxy resin composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460689A (en) * | 2003-05-16 | 2003-12-10 | 广州秀珀化工有限公司 | Modified alicyclic amine solidifying agent and its preparation method |
| EP2092018A1 (en) * | 2006-12-15 | 2009-08-26 | Ashland Licensing and Intellectual Property LLC | Low odor, fast cure, toughened epoxy adhesive |
| CN103554439A (en) * | 2013-10-12 | 2014-02-05 | 瑞奇化工（松滋）有限公司 | Low-odor epoxy curing agent and preparation method thereof |
| CN105837797A (en) * | 2016-04-08 | 2016-08-10 | 苏州圣杰特种树脂有限公司 | A water-based epoxy resin curing agent |
| CN106893451A (en) * | 2017-03-09 | 2017-06-27 | 烟台大学 | A kind of epoxy paste paint and its preparation application method without nonyl phenol |
-
2018
- 2018-09-30 CN CN201811162731.0A patent/CN109280521B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460689A (en) * | 2003-05-16 | 2003-12-10 | 广州秀珀化工有限公司 | Modified alicyclic amine solidifying agent and its preparation method |
| EP2092018A1 (en) * | 2006-12-15 | 2009-08-26 | Ashland Licensing and Intellectual Property LLC | Low odor, fast cure, toughened epoxy adhesive |
| CN103554439A (en) * | 2013-10-12 | 2014-02-05 | 瑞奇化工（松滋）有限公司 | Low-odor epoxy curing agent and preparation method thereof |
| CN105837797A (en) * | 2016-04-08 | 2016-08-10 | 苏州圣杰特种树脂有限公司 | A water-based epoxy resin curing agent |
| CN106893451A (en) * | 2017-03-09 | 2017-06-27 | 烟台大学 | A kind of epoxy paste paint and its preparation application method without nonyl phenol |
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