CN117720423A - Bio-based phenolic amine epoxy curing agent and preparation method thereof - Google Patents
Bio-based phenolic amine epoxy curing agent and preparation method thereof Download PDFInfo
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- CN117720423A CN117720423A CN202311726728.8A CN202311726728A CN117720423A CN 117720423 A CN117720423 A CN 117720423A CN 202311726728 A CN202311726728 A CN 202311726728A CN 117720423 A CN117720423 A CN 117720423A
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- curing agent
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- epoxy curing
- paraformaldehyde
- eugenol
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 51
- -1 phenolic amine Chemical class 0.000 title claims abstract description 50
- 239000004593 Epoxy Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 11
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 37
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 37
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005770 Eugenol Substances 0.000 claims abstract description 34
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229960002217 eugenol Drugs 0.000 claims abstract description 34
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 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 description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- 235000020226 cashew nut Nutrition 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 241000628997 Flos Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
The invention discloses a bio-based phenolic amine epoxy curing agent and a preparation method thereof, wherein the bio-based phenolic amine epoxy curing agent is prepared from 39-65% of eugenol, 24-54% of aliphatic amine and 8-18% of paraformaldehyde by mass percent. Through performance detection, the phenolic amine prepared by the invention is used for curing epoxy resin, and various performance indexes of a cured product are excellent. Compared with the traditional phenolic amine curing agent T-31, the adhesive has the advantages of equivalent hardness and adhesive force, lower viscosity, better flexibility, higher curing speed and good technical effect.
Description
Technical Field
The invention relates to an epoxy curing agent, in particular to a bio-based phenolic amine epoxy curing agent and a preparation method thereof, and belongs to the technical field of high polymer materials.
Background
The double-component system composed of the epoxy resin and the epoxy 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. The selection of the curing agent plays a key role in the performance of the epoxy system, and the phenolic amine epoxy curing agent can endow the epoxy system with excellent heat resistance, chemical resistance and mechanical property, so that the epoxy curing agent is widely applied to the fields of base coat, heat-resistant adhesives, laminated materials and the like in floors.
Traditional phenolic amine epoxy curing agents (e.g., T-31) generally use petroleum-based phenol as a raw material. With the increasing reduction of traditional fossil fuels, it has been an important topic to find alternatives to fossil raw materials. The development and application of bio-based feedstocks is currently a popular research direction worldwide. Eugenol is a renewable raw material with environmental protection and abundant resources. Eugenol can be extracted from flos Caryophylli and cortex Cinnamomi, or can be obtained from hydrolysis and thermal degradation of lignin. Eugenol has a rigid benzene ring structure and phenolic hydroxyl, and can be used for replacing petroleum-based phenol to produce phenolic amine epoxy curing agents.
The invention develops the bio-based phenolic amine epoxy curing agent with mechanical property, heat resistance and chemical resistance reaching the level of the traditional phenolic amine epoxy curing agent, but with lower viscosity and better flexibility through a large number of experimental screening.
Disclosure of Invention
The invention aims to: the invention aims to develop a novel bio-based phenolic amine epoxy hardener by using eugenol to replace petroleum-based phenol; the invention also aims at providing a preparation method of the curing agent.
The technical scheme adopted by the invention for realizing the purposes is as follows:
a bio-based phenolic amine epoxy curing agent is prepared from the following raw materials:
eugenol, fatty amines and paraformaldehyde.
As a preferable scheme, the bio-based phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 39-65% of eugenol, 24-54% of fatty amine and 8-18% of paraformaldehyde.
As a preferable scheme, the bio-based phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 55% of eugenol, 35% of diethylenetriamine and 10% of paraformaldehyde.
As another preferable scheme, the bio-based phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 48% of eugenol, 43% of triethylene tetramine and 9% of paraformaldehyde.
As another preferable scheme, the bio-based phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 55% eugenol, 34% pentanediamine and 11% paraformaldehyde.
As a preferable scheme, the phenolic amine epoxy curing agent is one or a mixture of more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentylene diamine, hexamethylenediamine and polyether amine.
The invention relates to a preparation method of a bio-based phenolic amine epoxy curing agent, which comprises the following steps:
(1) Putting eugenol and fatty amine into a reaction kettle according to mass percent, and stirring to uniformly mix materials;
(2) Heating to 40-50 ℃;
(3) 5 times of metered paraformaldehyde are put into a reaction kettle, and each time is separated by 20 minutes;
(4) After the addition of all paraformaldehyde is completed, the temperature is raised to 70-80 ℃, and the temperature is kept for 2-3 hours;
(5) Opening vacuum to remove water generated by the reaction;
(6) Filtering and packaging to obtain the bio-based phenolic amine epoxy curing agent.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the invention uses the bio-based eugenol to replace petroleum-based phenol as the raw material, accords with the concept of slight environmental protection, has low toxicity of eugenol and is beneficial to the health of production personnel. In addition, phenol is solid at normal temperature, heating is needed during production and processing, eugenol is liquid at normal temperature, heating is not needed, and energy is saved.
The invention obtains the optimal raw material proportioning composition through a large number of experimental screening, uses eugenol as an initial raw material, provides a basic phenolic aldehyde amine structure, and meets the hardness requirement of a curing system; and the eugenol molecule contains two side chain groups, so that the viscosity of the phenolic amine curing agent prepared from the eugenol is lower under the condition of the same raw material molar ratio.
In the experimental process, the invention finds that the dosage of the paraformaldehyde is very critical, the dosage of the paraformaldehyde is less than that of the invention, and the curing agent shows lack of hardness in performance test; above the amount of the present invention, the product has increased viscosity and is inconvenient to use. Therefore, the invention obtains the optimal composition and dosage ratio of each raw material through a large number of experimental screening.
The result of performance detection shows that the phenolic amine curing agent prepared by the invention has hardness, chemical resistance and similar to that of the traditional product T-31, but has lower viscosity, better heat resistance and flexibility, and good technical effect is obtained.
Drawings
FIG. 1 is a reaction equation of example 1 of the present invention.
Detailed Description
Example 1
1. A bio-based phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 55% of eugenol, 35% of diethylenetriamine and 10% of paraformaldehyde.
2. The preparation method of the bio-based phenolic amine epoxy curing agent comprises the following steps:
(1) Putting eugenol and diethylenetriamine into a reaction kettle according to mass percent, and stirring to uniformly mix materials;
(2) Heating to 50-60 ℃;
(3) 5 times of metered paraformaldehyde are put into a reaction kettle, and each time is separated by 20 minutes;
(4) After the addition of all paraformaldehyde is completed, the temperature is raised to 70-80 ℃, and the heat is preserved for 3 hours;
(5) Opening vacuum to remove water generated by the reaction;
(6) Filtering and packaging to obtain the bio-based phenolic amine epoxy curing agent.
Example 2
1. A bio-based phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 42% of eugenol, 46% of triethylene tetramine and 12% of paraformaldehyde.
2. The preparation method of the bio-based phenolic amine epoxy curing agent comprises the following steps:
(1) Putting eugenol and triethylene tetramine into a reaction kettle according to the mass percentage, and stirring to uniformly mix the materials;
(2) Heating to 50-60 ℃;
(3) 5 times of adding the metered paraformaldehyde into a reaction kettle, wherein each time is separated by 20 minutes;
(4) After the addition of all paraformaldehyde is completed, the temperature is raised to 70-80 ℃, and the heat is preserved for 3 hours;
(5) Opening vacuum to remove water generated by the reaction;
(6) Filtering and packaging to obtain the bio-based phenolic amine epoxy curing agent.
Example 3
1. A bio-based phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 55% eugenol, 34% pentanediamine and 11% paraformaldehyde.
2. The preparation method of the bio-based phenolic amine epoxy curing agent comprises the following steps:
(1) Putting eugenol and pentanediamine into a reaction kettle according to the mass percentage, and stirring to uniformly mix the materials;
(2) Heating to 50-60 ℃;
(3) 5 times of adding the metered paraformaldehyde into a reaction kettle, wherein each time is separated by 20 minutes;
(4) After the addition of all paraformaldehyde is completed, the temperature is raised to 70-80 ℃, and the heat is preserved for 3 hours;
(5) Opening vacuum to remove water generated by the reaction;
(6) Filtering and packaging to obtain the bio-based phenolic amine epoxy curing agent.
Comparative example 1
The product was evaluated using the same raw materials as in example 3, namely eugenol, hexamethylenediamine and paraformaldehyde, but with reduced amounts of paraformaldehyde. The material is prepared from the following raw materials in percentage by mass: 58% eugenol, 36% hexamethylenediamine and 6% paraformaldehyde. The preparation method comprises the following steps:
(1) Putting eugenol and hexamethylenediamine into a reaction kettle according to mass percent, and stirring to uniformly mix the materials;
(2) Heating to 50-60 ℃;
(3) 5 times of metered paraformaldehyde are put into a reaction kettle, and each time is separated by 20 minutes;
(4) After the addition of all paraformaldehyde is completed, the temperature is raised to 70-80 ℃, and the heat is preserved for 3 hours;
(5) Opening vacuum to remove water generated by the reaction;
(6) Filtering and packaging to obtain the product.
Comparative example 2
1. The cashew phenolic amine epoxy curing agent is prepared from the following raw materials in percentage by mass: 65% of cardanol, 22% of diethylenetriamine and 13% of paraformaldehyde.
2. The preparation method of the bio-based phenolic amine epoxy curing agent comprises the following steps:
(1) Adding cardanol and diethylenetriamine into a reaction kettle according to mass percent, and stirring to uniformly mix materials;
(2) Heating to 50-60 ℃;
(3) 5 times of metered paraformaldehyde are put into a reaction kettle, and each time is separated by 20 minutes;
(4) After the addition of all paraformaldehyde is completed, the temperature is raised to 70-80 ℃, and the heat is preserved for 3 hours;
(5) Opening vacuum to remove water generated by the reaction;
(6) And filtering and packaging to obtain the cashew phenolic aldehyde amine type epoxy curing agent.
Example 4 Performance test
Epoxy resin (828 of Jiangsu Sanmu chemical Co., ltd.) and the epoxy curing agent prepared above were mixed in a mass ratio of 2:1, and uniformly coated on a tin plate to form a film with a film thickness of 40. Mu.m. The basic properties after curing are measured as follows in table 1.
TABLE 1
Note that: the hardness is tested according to the method specified by national standard GB/T6739-1996; flexibility is tested according to the method specified by national standard GB/T6742-86; the adhesive force is tested according to the method specified by national standard GB/T9286-88.
The performance test results show that the bio-based phenolic amine epoxy curing agent prepared by adopting the optimized raw materials and the specific mass ratio through a large number of experimental screening has the hardness and the adhesive force equivalent to those of T-31, but has better chemical resistance, heat resistance and flexibility, and is better than that of comparative example 1 with less dosage of paraformaldehyde, and comparative example 2 is another bio-based phenolic amine epoxy curing agent prepared by using another bio-based phenol-cardanol at present, and has quite superior performances. The phenolic amine intermediate performance prepared from eugenol is quite similar to that of comparative example 2, 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 (8)
1. A bio-based phenolic amine epoxy curing agent is characterized by being prepared from the following raw materials: eugenol, fatty amine, paraformaldehyde.
2. The bio-based phenolic amine epoxy curing agent according to claim 1, which is characterized by being prepared from the following raw materials in percentage by mass: 39-65% of eugenol, 24-54% of fatty amine and 8-18% of paraformaldehyde.
3. The bio-based phenolic amine epoxy curing agent according to claim 1, which is characterized by being prepared from the following raw materials in percentage by mass: 55% of eugenol, 35% of diethylenetriamine and 10% of paraformaldehyde.
4. The bio-based phenolic amine epoxy curing agent according to claim 1, which is characterized by being prepared from the following raw materials in percentage by mass: 48% of eugenol, 43% of triethylene tetramine and 9% of paraformaldehyde.
5. The bio-based phenolic amine epoxy curing agent according to claim 1, which is characterized by being prepared from the following raw materials in percentage by mass: 55% eugenol, 34% pentanediamine and 11% paraformaldehyde.
6. The bio-based phenolic amine epoxy curing agent according to claim 1, wherein the aliphatic amine is one or a mixture of several of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentylene diamine, hexamethylenediamine and polyetheramine.
7. The method for preparing the bio-based phenolic amine epoxy curing agent according to any one of claims 1 to 6, comprising the following steps:
(1) Putting eugenol and fatty amine into a reaction kettle according to mass percent, and stirring to uniformly mix materials;
(2) Heating;
(3) Adding the metered paraformaldehyde into a reaction kettle for multiple times;
(4) Continuing the temperature and preserving the heat after the addition of all paraformaldehyde is finished;
(5) Opening vacuum to remove water generated by the reaction;
(6) Filtering and packaging to obtain the bio-based phenolic amine epoxy curing agent.
8. The method for preparing the bio-based phenolic amine epoxy hardener of claim 7, comprising the steps of:
(1) Putting eugenol and fatty amine into a reaction kettle according to mass percent, and stirring to uniformly mix materials;
(2) Heating to 50+/-5 ℃;
(3) 5 times of metered paraformaldehyde are put into a reaction kettle, and each time is separated by 20 minutes;
(4) After the addition of all paraformaldehyde is completed, the temperature is raised to 70-80 ℃, and the temperature is kept for 2-3 hours;
(5) Opening vacuum to remove water generated by the reaction;
(6) Filtering and packaging to obtain the bio-based phenolic amine epoxy curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311726728.8A CN117720423A (en) | 2023-12-15 | 2023-12-15 | Bio-based phenolic amine epoxy curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311726728.8A CN117720423A (en) | 2023-12-15 | 2023-12-15 | Bio-based phenolic amine epoxy curing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117720423A true CN117720423A (en) | 2024-03-19 |
Family
ID=90201004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311726728.8A Pending CN117720423A (en) | 2023-12-15 | 2023-12-15 | Bio-based phenolic amine epoxy curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117720423A (en) |
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2023
- 2023-12-15 CN CN202311726728.8A patent/CN117720423A/en active Pending
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