CN117776933A - Aliphatic amine modified epoxy curing agent and preparation method thereof - Google Patents
Aliphatic amine modified epoxy curing agent and preparation method thereof Download PDFInfo
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- CN117776933A CN117776933A CN202311753391.XA CN202311753391A CN117776933A CN 117776933 A CN117776933 A CN 117776933A CN 202311753391 A CN202311753391 A CN 202311753391A CN 117776933 A CN117776933 A CN 117776933A
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- curing agent
- modified epoxy
- fatty amine
- epoxy curing
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 title description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000008098 formaldehyde solution Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 9
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 9
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 9
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 9
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004848 polyfunctional curative Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims 1
- 229920002866 paraformaldehyde Polymers 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention discloses an epoxy curing agent modified by epoxy and a preparation method thereof, which is prepared from 10-20% by mass of low molecular fatty amine, 15-30% by mass of formaldehyde, 35-55% by mass of monophenol and 15-20% by mass of organic alcohol. Through performance detection, the cured product has the characteristics of quick drying and high hardness, has toughness and impact resistance similar to those of polyamide curing agents, and has good curing performance under the condition of normal-temperature curing and also suitable for northern temperature below 0 ℃, and is mainly suitable for epoxy floor coatings, building structural adhesives and the like.
Description
Technical Field
The invention relates to an aliphatic amine modified epoxy curing agent which has good workability, moderate viscosity, low-temperature environment curing characteristic, good compatibility with most curing agents and epoxy products, low product toxicity, high glossiness of a cured film and wide proportioning range with epoxy resin, and can be adjusted by customers according to different requirements. The paint is mainly used for anticorrosive paint, epoxy glass fiber reinforced plastic, concrete mortar, construction performance improver, deep-color epoxy solvent floor surface coating, adhesive, epoxy dry coating glue and pouring sealant, and belongs to the technical field of high polymer materials.
Background
The double-component system composed of the epoxy resin and the epoxy resin curing agent is widely used in the fields of floor coatings, anticorrosive coatings, adhesives, composite materials and the like due to the characteristics of small curing shrinkage, good cohesiveness, heat resistance, chemical resistance, mechanical properties and electrical properties.
With the increasing importance of human society on environmental protection, primary polyethylene polyamine and aromatic amine curing agents have been replaced by non-toxic or low-toxic modified amines. During the use of the curing agent, extreme weather conditions, such as low air temperatures, are encountered. The common curing agent is difficult to realize, and only partial accelerator is needed to be added to achieve the effect. However, the addition of the accelerator in excess causes the cured epoxy resin to become brittle.
Disclosure of Invention
The invention aims to: the invention aims to provide the epoxy curing agent which has excellent performances such as appearance, flexibility, impact strength and the like, is cured at low temperature, has moderate curing time and good construction performance, is mainly used for bottom coating in floor coating and building structural adhesive, and can meet the use requirements of most customers; the invention also aims at providing a preparation method of the epoxy curing agent.
The technical scheme is as follows: in order to achieve the above purpose, the invention adopts the following technical scheme:
the fatty amine modified epoxy curing agent is prepared from the following raw materials in percentage by mass: 10% -20% of low molecular fatty amine, 15% -30% of formaldehyde, 35% -55% of monohydric phenol and 15% -20% of organic alcohols.
Preferably, the fatty amine modified epoxy curing agent is ethylene diamine.
Preferably, the fatty amine modified epoxy curing agent is the formaldehyde solution with the concentration of 37%.
Preferably, the aliphatic amine modified epoxy curing agent is phenol and cardanol.
The invention provides a preparation method of an epoxy resin modified epoxy curing agent, which comprises the following steps:
(1) Adding monohydric phenols and aliphatic amine into a reaction kettle according to mass percent, and stirring to uniformly mix the materials;
(2) Then introducing nitrogen or carbon dioxide protective gas, removing air in the kettle, and then starting to heat up to 50-60 ℃;
(3) Pouring the metered formaldehyde solution into an overhead tank;
(4) Dripping formaldehyde solution in the elevated tank into the reaction kettle in a specified time, and controlling the temperature to be 60-80 ℃;
(5) After the formaldehyde solution is dripped, the temperature is kept between 70 ℃ and 80 ℃ for 2 to 3 hours;
(6) And after the heat preservation is finished, vacuum dehydration is carried out until the mixture is clear and transparent.
(7) After complete dehydration, cooling to below 65 ℃, adding metered methanol, and fully stirring for 30 minutes to obtain the fatty amine modified epoxy hardener.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the invention is synthesized by Mannich reaction according to the performance requirement of application occasions, and has low-temperature solidification performance because of containing phenolic hydroxyl.
The invention discovers that the dosage of each raw material is very critical in the experimental process. When the amount of the aliphatic amine is less than the amount of the present invention, the curing speed becomes slow. When the amount of the long-chain cardanol is smaller than the amount of the present invention, the flexibility of the cured product is deteriorated. Therefore, the invention obtains the optimal composition and dosage ratio of each raw material through a large number of experimental screening. The performance test shows that the epoxy curing agent prepared by the invention has excellent performance indexes such as hardness, flexibility and the like, and is also suitable for curing at about 0 ℃ in the north under the condition of normal-temperature curing, and has good curing performance. Can meet the application requirements of floor coating and building structural adhesive in the terrace, and achieves very good technical effects.
Drawings
FIG. 1 is a flow chart of the reaction equation of the present invention.
Detailed Description
Example 1
1. The fatty amine modified epoxy curing agent is prepared from the following raw materials in percentage by mass:
10% ethylenediamine (99.8% from Nanjing Le Xuan), 30% phenol, 25% cardanol, 15% formaldehyde (37%), 20% methanol.
2. A method for preparing an aliphatic amine modified epoxy hardener, comprising the steps of:
(1) Adding phenol, cardanol and ethylenediamine into a reaction kettle according to the mass percentages, and stirring to uniformly mix the materials;
(2) Then introducing nitrogen protection gas, discharging air in the kettle, and starting to heat up to 50-60 ℃;
(3) Pouring the metered formaldehyde solution with the volume concentration of 37% into an overhead tank;
(4) Dripping formaldehyde solution in the elevated tank into the reaction kettle in a specified time, and controlling the temperature to be 60-80 ℃;
(5) After the formaldehyde solution is dripped, the temperature is kept between 70 and 80 ℃ for 3 hours;
(6) And after the heat preservation is finished, vacuum dehydration is carried out until the mixture is clear and transparent.
(7) After complete dehydration, cooling to below 65 ℃, adding metered methanol, and fully stirring for 30 minutes to obtain the fatty amine modified epoxy hardener.
Example 2
1. The fatty amine modified epoxy curing agent is prepared from the following raw materials in percentage by mass:
15% ethylenediamine (99.8% content available from Nanjing Le Xuan Co.), 25% phenol, 20% cardanol, 20% formaldehyde (37% concentration by volume) and 20% methanol.
2. A method for preparing an aliphatic amine modified epoxy hardener, comprising the steps of:
(1) Adding phenol, cardanol and ethylenediamine into a reaction kettle according to the mass percentages, and stirring to uniformly mix the materials;
(2) Then introducing nitrogen protection gas, discharging air in the kettle, and starting to heat up to 50-60 ℃;
(3) Pouring the metered formaldehyde solution with the volume concentration of 37 percent into an overhead tank;
(4) Dripping formaldehyde solution in the elevated tank into the reaction kettle in a specified time, and controlling the temperature to be 60-80 ℃;
(5) After the formaldehyde solution is dripped, the temperature is kept between 70 and 80 ℃ for 3 hours;
(6) And after the heat preservation is finished, vacuum dehydration is carried out until the mixture is clear and transparent.
(7) After complete dehydration, cooling to below 65 ℃, adding metered methanol, and fully stirring for 30 minutes to obtain the fatty amine modified epoxy hardener.
Example 3
1. The fatty amine modified epoxy curing agent is prepared from the following raw materials in percentage by mass:
20% ethylenediamine (99.8% content available from Nanjing Le Xuan Co., ltd.), 15% phenol, 20% cardanol, 30% formaldehyde (37% concentration by volume) and 15% methanol.
2. A method for preparing an aliphatic amine modified epoxy hardener, comprising the steps of:
(1) Adding phenol, cardanol and ethylenediamine into a reaction kettle according to the mass percentages, and stirring to uniformly mix the materials;
(2) Then introducing nitrogen protection gas, discharging air in the kettle, and starting to heat up to 50-60 ℃;
(3) Pouring the metered formaldehyde solution (37% volume concentration) into an overhead tank;
(4) Dripping formaldehyde solution in the elevated tank into the reaction kettle in a specified time, and controlling the temperature to be 60-80 ℃;
(5) After the formaldehyde solution is dripped, the temperature is kept between 70 and 80 ℃ for 3 hours;
(6) And after the heat preservation is finished, vacuum dehydration is carried out until the mixture is clear and transparent.
(7) After complete dehydration, cooling to below 65 ℃, adding metered methanol, and fully stirring for 30 minutes to obtain the fatty amine modified epoxy hardener.
Example 4 Performance test
According to the following table 1, an epoxy resin (828 from Jiangsu Sanmu chemical Co., ltd.), a diluent, a filler, an auxiliary agent and an aliphatic amine modified epoxy curing agent were mixed in proportion to prepare an epoxy floor middle-coating mortar layer, and uniformly coated on the epoxy seal primer. The basic properties measured after curing are shown in table 2 below.
Table 1: experimental formulation
Table 2: results of test of Performance of examples of fatty amine modified curing agents with different formulation ratios
The performance of example 2 was optimized by comprehensive analysis of the three examples.
Table 3: example 2 Low temperature Cure Performance comparison
| Curing at 0 ℃ for 72h | Curing at 10 ℃ for 72h | Curing at 25 ℃ for 72h | |
| Adhesion force | 1-2 grade | 1-2 grade | 1-2 grade |
| Flexibility of the product | 1 | 1 | 1 |
| Hardness (Shore) | 76 | 79 | 81 |
| Impact | 50 positive and negative directions | 50 positive and negative directions | 50 positive and negative directions |
。
The performance detection results show that the modified epoxy curing agent prepared from different raw materials through a large number of experimental screening has excellent performance indexes such as appearance, hardness, flexibility and the like, the curing time is moderate, the application requirements of most customers are met, and a very good technical effect is achieved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The fatty amine modified epoxy curing agent is characterized by being prepared from the following raw materials in percentage by mass:
10% -20% of low molecular fatty amine, 15% -30% of formaldehyde, 35% -55% of monohydric phenol and 15% -20% of organic alcohols.
2. The fatty amine-modified epoxy curing agent according to claim 1, characterized in that: the low molecular weight fatty amines used include ethylenediamine.
3. The fatty amine modified epoxy curing agent of claim 1, wherein the formaldehyde is 37% formaldehyde solution or paraformaldehyde.
4. The fatty amine-modified epoxy curing agent according to claim 1, characterized in that: the monophenols used are phenol and cardanol.
5. The fatty amine-modified epoxy curing agent according to claim 1, characterized in that: the organic alcohol is methanol or ethanol.
6. The method for preparing the fatty amine modified epoxy curing agent according to any one of claims 1 to 5, comprising the steps of:
(1) According to the mass percentage, the monophenols and the low molecular fatty amine are put into a reaction kettle and stirred, so that the materials are uniformly mixed;
(2) Then introducing nitrogen or carbon dioxide protective gas, removing air in the kettle, and then starting to heat up to 50-60 ℃;
(3) Pouring the metered formaldehyde solution into an overhead tank;
(4) Dripping formaldehyde solution in the elevated tank into the reaction kettle in a specified time, and controlling the temperature to be 60-80 ℃;
(5) After the formaldehyde solution is dripped, the temperature is kept between 70 and 80 ℃ for 2 to 3 hours;
(6) After the heat preservation is finished, vacuum dehydration is carried out until the mixture is clear and transparent;
(7) After complete dehydration, cooling to below 65 ℃, adding metered organic alcohols, and fully stirring for 30 minutes to obtain the fatty amine modified epoxy curing agent.
7. Use of the fatty amine modified epoxy hardener of any one of claims 1 to 5 as an epoxy resin hardener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311753391.XA CN117776933A (en) | 2023-12-19 | 2023-12-19 | Aliphatic amine modified epoxy curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311753391.XA CN117776933A (en) | 2023-12-19 | 2023-12-19 | Aliphatic amine modified epoxy curing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117776933A true CN117776933A (en) | 2024-03-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311753391.XA Pending CN117776933A (en) | 2023-12-19 | 2023-12-19 | Aliphatic amine modified epoxy curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117776933A (en) |
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2023
- 2023-12-19 CN CN202311753391.XA patent/CN117776933A/en active Pending
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