CN112724370B - Preparation method of epoxy resin curing agent - Google Patents
Preparation method of epoxy resin curing agent Download PDFInfo
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- CN112724370B CN112724370B CN202011587258.8A CN202011587258A CN112724370B CN 112724370 B CN112724370 B CN 112724370B CN 202011587258 A CN202011587258 A CN 202011587258A CN 112724370 B CN112724370 B CN 112724370B
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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
- C08G59/621—Phenols
- C08G59/623—Aminophenols
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a preparation method of a novel epoxy resin curing agent, wherein the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent; the preparation method of the novel epoxy resin curing agent comprises the following steps: (1) Heating alkylphenol to 50-60 ℃, then adding formaldehyde solution with the mass concentration of 37-40%, and reacting for 4-5 hours to obtain a first mixture; (2) And adding polyamine into the first mixture, reacting for 6-8 hours, heating the first mixture to 100 ℃, adding a blocking agent into the first mixture, and reacting for 9-10 hours to obtain the novel epoxy resin curing agent. The novel water-type epoxy resin curing agent can rapidly cure epoxy resin at a lower temperature and is suitable for curing reaction under the condition of water.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to a preparation method of a novel epoxy resin curing agent.
Background
Epoxy resin is used as a common resin material and is widely applied to the fields of automobiles, ships, electronic power, buildings, packaging and the like, however, the pure epoxy resin has little practical value, and only is changed into a three-dimensional network structure through modification, a series of excellent performances can be presented, a curing agent is often used for modifying the epoxy resin, and the epoxy resin is changed into the three-dimensional network structure through direct curing reaction with the epoxy resin, so that the structure and the quality of the curing agent are very important, and the application effect of the epoxy resin is directly influenced.
At present, the epoxy resin curing agents commonly used mainly comprise fatty amine curing agents, anhydride curing agents, phenolic amine curing agents and the like, and the consumption of the fatty amine curing agents is large, but the brittleness, impact resistance and weather resistance of the epoxy resin curing agents are poor, and the toxicity of the epoxy resin curing agents is relatively large, so that the application of the epoxy resin curing agents is limited to a certain extent. Anhydride-based curing agents have long pot lives, storage stability, but chemical modification is difficult, curing time is long, and moisture resistance is poor. Phenolic amine curing agents are generally prepared from phenol, formaldehyde and polyamine through Mannich addition reaction, the curing agents have relatively good reaction activity, and can be used for curing epoxy resin in normal-temperature environment and environment with relatively high humidity, but the curing agents still have relatively short service life, insufficient elasticity or toughness, water resistance and sea water resistance and are still unsatisfactory.
Aiming at the defects of the existing curing agent, the preparation method is environment-friendly, can realize the rapid curing of the epoxy resin at a lower temperature, and is very urgent for curing agents suitable for conditions of water and seawater.
Disclosure of Invention
The invention aims to overcome and supplement the defects in the prior art and provide a preparation method of a novel epoxy resin curing agent, which can rapidly cure epoxy resin at a lower temperature and is suitable for curing reaction under the condition of water. The technical scheme adopted by the invention is as follows:
a method for preparing a novel epoxy resin curing agent, wherein: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the novel epoxy resin curing agent specifically comprises the following steps:
(1) Heating alkylphenol to 50-60 ℃, then adding formaldehyde solution with the mass concentration of 37-40%, and reacting for 4-5 hours to obtain a first mixture;
(2) And adding polyamine into the first mixture, reacting for 6-8 hours, heating the first mixture to 100 ℃, adding a blocking agent into the first mixture, and reacting for 9-10 hours to obtain the novel epoxy resin curing agent.
Preferably, the preparation method of the novel epoxy resin curing agent comprises the following steps: the alkylphenol in the step (1) is any one or a mixture of two of cardanol, carvacrol and dodecylphenol.
Preferably, the preparation method of the novel epoxy resin curing agent comprises the following steps: the molar ratio of the alkylphenol to formaldehyde in the step (1) is 1:0.9-1.1.
Preferably, the preparation method of the novel epoxy resin curing agent comprises the following steps: the polyamine in the step (2) is any one or a mixture of two of dodecyl dipropylene triamine, diethylenetriamine and N-oil-based-1, 3-propylene diamine.
Preferably, the preparation method of the novel epoxy resin curing agent comprises the following steps: the end capping agent in the step (2) is any one or a mixture of two of glycidyl butyl ether, glycidyl allyl ether and glycidyl phenyl ether.
Preferably, the preparation method of the novel epoxy resin curing agent comprises the following steps: the mol ratio of the alkylphenol to the polyamine is 1:1-1.5, and the mol ratio of the alkylphenol to the end capping agent is 1:0.5-1.
The invention has the advantages that: the novel water-type epoxy resin curing agent disclosed by the invention can be used for rapidly curing epoxy resin at a lower temperature, is suitable for curing reaction under a water-containing condition, is simple in preparation process, easy to obtain raw materials, convenient to popularize, environment-friendly, capable of rapidly curing epoxy resin in a low-temperature environment of 0 ℃, and capable of rapidly curing epoxy resin under a water-containing condition.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1:
a method for preparing a novel epoxy resin curing agent, wherein: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the novel epoxy resin curing agent comprises the following steps:
putting 1mol of cardanol into a reaction kettle, heating to 50 ℃, adding 0.9mol of formaldehyde solution with the concentration of 37%, reacting for 4 hours to obtain a first mixture, dropwise adding 1mol of diethylenetriamine into the first mixture, reacting for 6 hours, then raising the temperature of the first mixture to 90 ℃, adding 0.5mol of glycidyl butyl ether, and reacting for 9 hours to obtain the curing agent.
Example 2:
a method for preparing a novel epoxy resin curing agent, wherein: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the novel epoxy resin curing agent comprises the following steps:
putting 1mol of carvacrol into a reaction kettle, heating to 60 ℃, adding 1.1mol of 40% formaldehyde solution, reacting for 5 hours to obtain a first mixture, dropwise adding 1.5mol of dodecyl dipropylene triamine into the first mixture, and reacting for 8 hours. Then the temperature of the first mixture is raised to 100 ℃, 1mol of glycidol allyl ether is added for reaction for 10 hours, and the curing agent is obtained.
Example 3:
a method for preparing a novel epoxy resin curing agent, wherein: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the novel epoxy resin curing agent comprises the following steps:
putting 1mol of dodecylphenol into a reaction kettle, heating to 55 ℃, adding 1mol of formaldehyde solution with the concentration of 38%, reacting for 4.5 hours to obtain a first mixture, dropwise adding 1.3mol of N-oil-based-1, 3-propylene diamine into the first mixture, reacting for 7 hours, then raising the temperature of a reaction system in the first mixture to 95 ℃, adding 0.75mol of glycidyl phenyl ether, and reacting for 9.5 hours to obtain the curing agent.
Example 4:
a method for preparing a novel epoxy resin curing agent, wherein: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the novel epoxy resin curing agent comprises the following steps:
putting 0.5mol of cardanol and 0.5mol of carvacrol into a reaction kettle, heating to 60 ℃, adding 1mol of formaldehyde solution with concentration of 37%, reacting for 5 hours to obtain a first mixture, dropwise adding 1mol of diethylenetriamine and 0.5mol of N-oil-based-1, 3-propanediamine into the first mixture, reacting for 8 hours, then raising the temperature of a reaction system of the first mixture to 100 ℃, adding 0.5mol of glycidyl butyl ether and 0.5mol of glycidyl allyl ether, and reacting for 10 hours to obtain the curing agent.
Example 5:
a method for preparing a novel epoxy resin curing agent, wherein: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the novel epoxy resin curing agent comprises the following steps:
putting 0.5mol of cardanol and 0.5mol of dodecylphenol into a reaction kettle, heating to 60 ℃, adding 1mol of formaldehyde solution with 37% concentration, reacting for 5 hours to obtain a first mixture, dropwise adding 1mol of diethylenetriamine and 0.5mol of dodecyldiethylenetriamine into the first mixture, reacting for 8 hours, then raising the temperature of a reaction system of the first mixture to 100 ℃, adding 0.5mol of glycidyl butyl ether and 0.5mol of glycidyl phenyl ether, and reacting for 10 hours to obtain the curing agent.
Example 6:
a method for preparing a novel epoxy resin curing agent, wherein: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the novel epoxy resin curing agent comprises the following steps:
putting 0.5mol of carvacrol and 0.5mol of dodecylphenol into a reaction kettle, heating to 60 ℃, adding 1mol of formaldehyde solution with 37% concentration, reacting for 5 hours to obtain a first mixture, dropwise adding 1mol of dodecyl dipropylene triamine and 0.5mol of N-oil-based-1, 3-propylene diamine into the first mixture, reacting for 8 hours, then raising the temperature of a reaction system of the first mixture to 100 ℃, adding 0.5mol of glycidyl allyl ether and 0.5mol of glycidyl phenyl ether, and reacting for 10 hours to obtain the curing agent.
Comparative example 1:
putting 1mol of cardanol into a reaction kettle, heating to 50 ℃, adding 0.9mol of formaldehyde solution with the concentration of 37%, reacting for 4 hours to obtain a first mixture, dropwise adding 0.7mol of diethylenetriamine into the first mixture, reacting for 6 hours, then raising the temperature of a reaction system to 90 ℃, adding 0.5mol of glycidyl butyl ether, and reacting for 9 hours to obtain the curing agent.
Comparative example 2:
putting 1mol of cardanol into a reaction kettle, heating to 50 ℃, adding 0.9mol of formaldehyde solution with the concentration of 37%, reacting for 4 hours to obtain a first mixture, dropwise adding 0.5mol of diethylenetriamine into the first mixture, reacting for 6 hours, then raising the temperature of a reaction system to 90 ℃, adding 1.5mol of glycidyl butyl ether, and reacting for 9 hours to obtain the curing agent.
Performance test:
comparing the application effects of the curing agents of the examples 1-6 and the comparative examples 1-2 and the commercial curing agent in the curing of bisphenol A epoxy resin, respectively weighing the curing agent and the epoxy resin according to the mass ratio (curing agent: epoxy resin=1:3), uniformly mixing, taking tin plate as a base material, uniformly coating to prepare a paint film with the thickness of about 0.2mm, and respectively examining the surface drying time of the epoxy resin paint film in the water at 25 ℃, the water at 0 ℃, the pure water at 25 ℃ and the seawater at 25 ℃, wherein the test results are shown in table 1.
TABLE 1 surface drying time of epoxy resin paint films under the action of different curing Agents
| Examples | Anhydrous condition at 25 DEG C | Anhydrous condition at 0 DEG C | Pure water at 25 DEG C | Sea water at 25 DEG C |
| Example 1 | 35min | 45min | 35min | 37min |
| Example 2 | 33min | 39min | 38min | 41min |
| Example 3 | 37min | 41min | 42min | 39min |
| Example 4 | 39min | 45min | 41min | 47min |
| Example 5 | 36min | 43min | 36min | 40min |
| Example 6 | 36min | 40min | 43min | 45min |
| Comparative example 1 | 75min | 123min | 144min | 145min |
| Comparative example 2 | 69min | 155min | 143min | 141min |
| Commercially available | 96min | 3h or more | 3h or more | 3h or more |
As can be seen from Table 1, the epoxy resin curing agent and the epoxy resin of examples 1-6 are uniformly mixed, the tack-free time of the coating film at 25 ℃ under anhydrous conditions is 33-39min, the tack-free time of comparative examples 1-2 is 69-75min, the tack-free time of the commercially available curing agent is 96min, which indicates that the tack-free time of the curing agent of examples 1-6 is superior to that of the curing agent of comparative examples 1-2 and the commercially available curing agent, and the curing agent of comparative examples 1-2 is superior to that of the commercially available curing agent; the epoxy resin curing agent and the epoxy resin of the examples 1-6 are uniformly mixed, the surface drying time of a coating film under the anhydrous condition of 0 ℃ is 39-45min, the surface drying time of the comparative examples 1-2 is 123-155min, the surface drying time of the commercially available curing agent is more than 3h, and the fact that the surface drying time of the curing agent of the examples 1-6 is superior to that of the curing agent of the comparative examples 1-2 and the commercially available curing agent and the curing agent of the comparative examples 1-2 is superior to that of the commercially available curing agent is shown; the epoxy resin curing agent and the epoxy resin of the examples 1-6 are uniformly mixed, the surface drying time of a coating film at 25 ℃ of pure water is 35-43min, the surface drying time of the comparative examples 1-2 is 143-144min, the surface drying time of a commercially available curing agent is more than 3h, and the fact that the surface drying time of the curing agent of the examples 1-6 is superior to that of the curing agent of the comparative examples 1-2 and the commercially available curing agent and the curing agent of the comparative examples 1-2 is superior to that of the commercially available curing agent is shown; the epoxy resin curing agent and the epoxy resin of the examples 1-6 are uniformly mixed, the surface drying time of a coating film at 25 ℃ is 37-47min, the surface drying time of the comparative examples 1-2 is 141-145min, the surface drying time of the commercially available curing agent is more than 3h, the surface drying time of the curing agent of the examples 1-6 is better than that of the curing agent of the comparative examples 1-2 and the commercially available curing agent, the curing agent of the comparative examples 1-2 is better than the commercially available curing agent, and the result shows that the novel water-type epoxy resin curing agent can rapidly cure the epoxy resin at a lower temperature and is suitable for curing reaction under a water-containing condition.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (4)
1. A preparation method of an epoxy resin curing agent is characterized by comprising the following steps: the curing agent is prepared by condensing alkylphenol and formaldehyde, then carrying out addition reaction with polyamine, and finally carrying out end capping modification by an end capping agent;
the preparation method of the epoxy resin curing agent comprises the following steps:
(1) Heating alkylphenol to 50-60 ℃, then adding formaldehyde solution with the mass concentration of 37-40%, and reacting for 4-5 hours to obtain a first mixture;
(2) Adding polyamine into the first mixture, reacting for 6-8 hours, then heating the first mixture to 100 ℃, adding a blocking agent into the first mixture, and reacting for 9-10 hours to obtain the epoxy resin curing agent;
the end-capping agent in the step (2) is any one or a mixture of two of glycidyl butyl ether, glycidyl allyl ether and glycidyl phenyl ether;
the mol ratio of the alkylphenol to the polyamine is 1:1-1.5, and the mol ratio of the alkylphenol to the end capping agent is 1:0.5-1.
2. The method for preparing the epoxy resin curing agent according to claim 1, characterized in that: the alkylphenol in the step (1) is any one or a mixture of two of cardanol, carvacrol and dodecylphenol.
3. The method for preparing the epoxy resin curing agent according to claim 1, characterized in that: the molar ratio of the alkylphenol to formaldehyde in the step (1) is 1:0.9-1.1.
4. The method for preparing the epoxy resin curing agent according to claim 1, characterized in that: the polyamine in the step (2) is any one or a mixture of two of dodecyl dipropylene triamine, diethylenetriamine and N-oil-based-1, 3-propylene diamine.
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| EP0114875A1 (en) * | 1982-07-26 | 1984-08-08 | Lowell O Cummings | Method for making phenol-formaldehyde-polyamine curing agents for epoxy resins. |
| CN101585906A (en) * | 2008-05-21 | 2009-11-25 | 考格尼斯知识产权管理有限责任公司 | Curing agents for epoxy resins |
| CN102633991A (en) * | 2012-04-10 | 2012-08-15 | 卡德莱化工(珠海)有限公司 | Alkylphenol modified phenolic amide curing agent and preparation method thereof |
| CN110204690A (en) * | 2019-06-06 | 2019-09-06 | 广州百云宝能源科技有限公司 | A kind of epoxy dry-hang glue curing agent and preparation method thereof |
| CN110615881A (en) * | 2019-08-20 | 2019-12-27 | 浙江万盛股份有限公司 | Preparation method of water-based epoxy curing agent |
| CN110938209A (en) * | 2019-12-17 | 2020-03-31 | 岳阳中展科技有限公司 | Preparation method and application of cardanol-based waterborne epoxy resin curing agent |
| CN111763151A (en) * | 2020-06-29 | 2020-10-13 | 浙江万盛股份有限公司 | Preparation method of cardanol modified polyamine curing agent with high corrosion resistance |
-
2020
- 2020-12-29 CN CN202011587258.8A patent/CN112724370B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0114875A1 (en) * | 1982-07-26 | 1984-08-08 | Lowell O Cummings | Method for making phenol-formaldehyde-polyamine curing agents for epoxy resins. |
| CN101585906A (en) * | 2008-05-21 | 2009-11-25 | 考格尼斯知识产权管理有限责任公司 | Curing agents for epoxy resins |
| CN102633991A (en) * | 2012-04-10 | 2012-08-15 | 卡德莱化工(珠海)有限公司 | Alkylphenol modified phenolic amide curing agent and preparation method thereof |
| CN110204690A (en) * | 2019-06-06 | 2019-09-06 | 广州百云宝能源科技有限公司 | A kind of epoxy dry-hang glue curing agent and preparation method thereof |
| CN110615881A (en) * | 2019-08-20 | 2019-12-27 | 浙江万盛股份有限公司 | Preparation method of water-based epoxy curing agent |
| CN110938209A (en) * | 2019-12-17 | 2020-03-31 | 岳阳中展科技有限公司 | Preparation method and application of cardanol-based waterborne epoxy resin curing agent |
| CN111763151A (en) * | 2020-06-29 | 2020-10-13 | 浙江万盛股份有限公司 | Preparation method of cardanol modified polyamine curing agent with high corrosion resistance |
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