CN117362183A - Cardanol modified Schiff base epoxy curing agent and preparation method thereof - Google Patents

Cardanol modified Schiff base epoxy curing agent and preparation method thereof Download PDF

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Publication number
CN117362183A
CN117362183A CN202311304644.5A CN202311304644A CN117362183A CN 117362183 A CN117362183 A CN 117362183A CN 202311304644 A CN202311304644 A CN 202311304644A CN 117362183 A CN117362183 A CN 117362183A
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schiff base
cardanol
base epoxy
temperature
curing agent
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陈建
曾伟
蒋剑锋
周新领
左言刁
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Zhejiang Wansheng Co ltd
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Zhejiang Wansheng Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C211/39—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of an unsaturated carbon skeleton
    • C07C211/40—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of an unsaturated carbon skeleton containing only non-condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention belongs to the technical field of curing agents, and particularly relates to a cardanol modified Schiff base epoxy curing agent and a preparation method thereof. The invention provides a preparation method of a cardanol modified Schiff base epoxy curing agent, which comprises the following steps: mixing amine and formaldehyde, and performing aldol condensation reaction to obtain Schiff base; mixing the Schiff base and cardanol, and carrying out dehydration condensation reaction to obtain the cardanol modified Schiff base epoxy curing agent. The cardanol modified Schiff base epoxy hardener prepared by the preparation method provided by the invention has the characteristics of light color, low viscosity and better flexibility, and simultaneously has the performances of high drying speed, high hardness and the like. And the low viscosity is beneficial to reducing the use amount of organic solvents such as dimethylbenzene, n-butanol and the like in downstream application, and reducing carbon emission and VOC emission.

Description

Cardanol modified Schiff base epoxy curing agent and preparation method thereof
Technical Field
The invention belongs to the technical field of curing agents, and particularly relates to a cardanol modified Schiff base epoxy curing agent and a preparation method thereof.
Background
Cardanol is oily liquid obtained by refining natural cashew nut shell oil, contains benzene ring structure and has high temperature resistance; wherein polar hydroxyl groups provide wetting and activity of the system to the contact surface; the meta-position carbon 15 straight chain containing unsaturated double bonds can provide the system with good toughness, excellent hydrophobicity, low permeability and self-drying property. The biological source is a renewable resource with great utilization value, and is currently applied to the fields of surfactants, epoxy curing agents, rubber additives, friction materials and the like at home and abroad, and is used for replacing petroleum source products such as phenol, nonylphenol and the like.
However, the traditional cardanol curing agent has darker color and higher viscosity, and a large amount of organic solvent is needed in the use process.
Disclosure of Invention
The invention aims to provide a cardanol modified Schiff base epoxy curing agent and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a cardanol modified Schiff base epoxy curing agent, which comprises the following steps:
mixing amine and formaldehyde, and performing aldol condensation reaction to obtain Schiff base;
mixing the Schiff base and cardanol, and carrying out dehydration condensation reaction to obtain the cardanol modified Schiff base epoxy curing agent.
Preferably, the amine comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylene polyamine, hexamethylenediamine, pentylenediamine, m-xylylenediamine and isophoronediamine.
Preferably, the molar ratio of amine to formaldehyde is 1:0.5 to 2.0.
Preferably, the temperature of the aldol condensation reaction is 40-80 ℃ and the time is 0.5-1 h.
Preferably, the aldol condensation reaction is performed under a nitrogen atmosphere.
Preferably, the molar ratio of the amine to the cardanol is 1:0.5 to 2.0.
Preferably, the dehydration condensation reaction is carried out at a temperature of 30-60 ℃ for 0.5-1 h.
Preferably, the dehydration condensation reaction is followed by vacuum dehydration treatment of the resulting reaction system.
Preferably, the temperature of the vacuum dehydration treatment is 115-125 ℃, the vacuum degree is more than-0.095 MPa, and the time is 0.5-2 h;
the temperature rising rate of the vacuum dehydration treatment temperature is 1-3 ℃/min.
The invention also provides the cardanol modified Schiff base epoxy hardener prepared by the preparation method, which has a structure shown in formula I or formula II:
the R1 is The R2 is
The invention provides a preparation method of a cardanol modified Schiff base epoxy curing agent, which comprises the following steps: mixing amine and formaldehyde, and performing aldol condensation reaction to obtain Schiff base; mixing the Schiff base and cardanol, and carrying out dehydration condensation reaction to obtain the cardanol modified Schiff base epoxy curing agent. The cardanol modified Schiff base epoxy hardener prepared by the preparation method provided by the invention has the characteristics of light color, low viscosity and better flexibility, and simultaneously has the performances of high drying speed, high hardness and the like. And the low viscosity is beneficial to reducing the use amount of organic solvents such as dimethylbenzene, n-butanol and the like in downstream application, and reducing carbon emission and VOC emission.
Drawings
FIG. 1 is a physical diagram of the cardanol-modified Schiff base epoxy hardener obtained in example 1;
FIG. 2 is a diagram of a commercial cardanol curing agent.
Detailed Description
The invention provides a preparation method of a cardanol modified Schiff base epoxy curing agent, which comprises the following steps:
mixing amine and formaldehyde, and performing aldol condensation reaction to obtain Schiff base;
mixing the Schiff base and cardanol, and carrying out dehydration condensation reaction to obtain the cardanol modified Schiff base epoxy curing agent.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes amine and formaldehyde to carry out aldol condensation reaction to obtain Schiff base.
In the present invention, the amine preferably includes one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylene polyamine, hexamethylenediamine, pentylene diamine, m-xylylenediamine and isophorone diamine; when the amine is preferably any two or more of the above-mentioned choices, the proportion of the amine in the present invention is not particularly limited, and those skilled in the art can be used.
In the present invention, the formaldehyde is preferably added in the form of paraformaldehyde or formaldehyde solution; the mass concentration of the formaldehyde solution is preferably 30%.
In the present invention, the molar ratio of amine to formaldehyde is preferably 1:0.5 to 2.0, more preferably 1:1.1 to 1.6, more preferably 1:1.3 to 1.4.
In the present invention, the temperature of the mixing is preferably 20 to 50 ℃; the mixing is preferably carried out under a nitrogen atmosphere; the oxygen content in the nitrogen atmosphere is preferably less than 0.1%. In the present invention, the mixing is preferably performed under stirring. The stirring time is not particularly limited, and the stirring time is based on the condition that formaldehyde is completely dissolved or the reaction system is not radiated any more. In a specific embodiment of the invention, the mixing is preferably: placing amine in a reactor, vacuumizing the reactor to-0.095 MPa, then injecting nitrogen until the pressure of the reactor reaches 0.2MPa, repeating for 3 times, then injecting nitrogen into the reactor to reach standard atmospheric pressure, and replacing air in the reactor with nitrogen; then adding formaldehyde under the stirring condition, and stirring at a controlled temperature until the formaldehyde is completely dissolved or the reaction system does not release heat.
In the present invention, the temperature of the aldol condensation reaction is preferably 40 to 80 ℃, more preferably 50 to 70 ℃, still more preferably 60 to 65 ℃; the time is preferably 0.5 to 1 hour, more preferably 0.6 to 0.9 hour, and still more preferably 0.7 to 0.8 hour.
After the aldol condensation reaction, the present invention preferably further comprises dehydrating the resulting reaction system under reduced pressure. The process of the present invention for the dehydration under reduced pressure is not particularly limited, and may be known to those skilled in the art.
After the Schiff base is obtained, the Schiff base and cardanol are mixed, and dehydration condensation reaction is carried out, so that the cardanol modified Schiff base epoxy curing agent is obtained.
In the present invention, the purity of the cardanol is preferably more than 90%.
In the present invention, the molar ratio of the amine to cardanol is preferably 1:0.5 to 2.0, more preferably 1:1.1 to 1.6, more preferably 1:1.3 to 1.4.
In the present invention, when the Schiff base and cardanol are mixed, the temperature of the reaction system is preferably not higher than 40 ℃, and more preferably 20 to 40 ℃.
In the present invention, the temperature of the dehydration condensation reaction is preferably 30 to 60 ℃, and more preferably 40 to 50 ℃; the time is preferably 0.5 to 1 hour, more preferably 0.6 to 0.9 hour, and still more preferably 0.7 to 0.8 hour.
After the dehydration condensation reaction, the present invention preferably further comprises subjecting the resulting reaction system to vacuum dehydration treatment. In the invention, the temperature of the vacuum dehydration treatment is preferably 115-125 ℃, the vacuum degree is preferably more than-0.095 MPa, and the time is preferably 0.5-2 h; the heating rate to the vacuum dehydration treatment temperature is preferably 1 to 3 ℃/min.
After the vacuum dehydration treatment, the invention also preferably comprises the step of cooling and filtering the obtained reaction system. The cooling and filtering process is not particularly limited, and can be adopted by those skilled in the art.
The invention also provides the cardanol modified Schiff base epoxy hardener prepared by the preparation method, which has a structure shown in formula I or formula II:
the R1 is The R2 is
For further explanation of the present invention, the cardanol-modified schiff base epoxy hardener and the preparation method thereof provided by the present invention are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 1mol of diethylenetriamine into a reactor, vacuumizing the reactor to-0.095 MPa, then injecting nitrogen until the pressure of the reactor reaches 0.2MPa, repeating for 3 times, then injecting nitrogen into the reactor to reach standard atmospheric pressure, and replacing air in the reactor by using the nitrogen; then slowly adding 1.6mol of paraformaldehyde, and stirring at 40 ℃ under controlled temperature until the paraformaldehyde is completely dissolved; then adjusting the reaction temperature to 70 ℃, continuing to react for 0.9h, and then carrying out decompression dehydration to obtain Schiff base;
cooling the obtained Schiff base to 30 ℃, then slowly adding 1.3mol of cardanol (the purity is 93.5%), adjusting the temperature to 40 ℃ and reacting for 1h; heating, and simultaneously starting vacuum to dehydrate, wherein the heating speed is controlled to be 1 ℃/min, the vacuum degree is controlled to be-0.097 MPa, the temperature is increased to 115 ℃, and the vacuum dehydration is kept for 2 hours under the control of the temperature within the range; cooling, filtering and discharging to obtain the cardanol modified Schiff base epoxy curing agent.
Example 2
Adding 0.5mol of diethylenetriamine and 0.5mol of m-xylylenediamine into a reactor, vacuumizing the reactor to-0.095 MPa, then injecting nitrogen until the pressure of the reactor reaches 0.2MPa, repeating for 3 times, then injecting nitrogen into the reactor to reach standard atmospheric pressure, and replacing air in the reactor with nitrogen; then slowly adding 1mol of formaldehyde solution with the mass concentration of 30%, and stirring at 45 ℃ under controlled temperature until the reaction system does not release heat; then adjusting the reaction temperature to 75 ℃, continuing to react for 0.5h, and then carrying out decompression dehydration to obtain Schiff base;
cooling the obtained Schiff base to 35 ℃, then slowly adding 0.9mol of cardanol (the purity is 93.5%), adjusting the temperature to 55 ℃ and reacting for 0.5h; heating, and simultaneously starting vacuum to dehydrate, wherein the heating speed is controlled to be 2 ℃/min, the vacuum degree is controlled to be-0.096 MPa, the temperature is increased to 125 ℃, and the vacuum dehydration is maintained for 0.5h under the control of the temperature within the range; cooling, filtering and discharging to obtain the cardanol modified Schiff base epoxy curing agent.
Example 3
Adding 0.4mol of ethylenediamine, 0.3mol of polyethylene polyamine and 0.4mol of isophorone diamine into a reactor, vacuumizing the reactor to-0.095 MPa, then injecting nitrogen until the pressure of the reactor reaches 0.2MPa, repeating for 3 times, then injecting nitrogen into the reactor to reach standard atmospheric pressure, and replacing air in the reactor with nitrogen; then slowly adding 1.5mol of paraformaldehyde, and stirring at 30 ℃ under controlled temperature until the paraformaldehyde is completely dissolved; then adjusting the reaction temperature to 55 ℃, continuing to react for 1h, and then carrying out decompression dehydration to obtain Schiff base;
cooling the obtained Schiff base to 25 ℃, then slowly adding 1.3mol of cardanol (the purity is 93.5%), adjusting the temperature to 35 ℃ and reacting for 1h; heating, and simultaneously starting vacuum to dehydrate, wherein the heating speed is controlled to be 3 ℃/min, the vacuum degree is controlled to be-0.097 MPa, the temperature is increased to 120 ℃, and the vacuum dehydration is kept for 1h under the control of the temperature within the range; cooling, filtering and discharging to obtain the cardanol modified Schiff base epoxy curing agent.
Example 4
Adding 0.3mol of pentaethylenehexamine, 0.4mol of hexamethylenediamine and 0.4mol of m-xylylenediamine into a reactor, vacuumizing the reactor to-0.095 MPa, then injecting nitrogen into the reactor until the pressure reaches 0.2MPa, repeating for 3 times, then injecting nitrogen into the reactor until the standard atmospheric pressure is reached, and replacing the air in the reactor with the nitrogen; then slowly adding 1.8mol of paraformaldehyde, and stirring at 50 ℃ under controlled temperature until the paraformaldehyde is completely dissolved; then adjusting the reaction temperature to 80 ℃, continuing to react for 1h, and then carrying out decompression dehydration to obtain Schiff base;
cooling the obtained Schiff base to 38 ℃, then slowly adding 1.7mol of cardanol (the purity is 94.3%), adjusting the temperature to 60 ℃ and reacting for 1h; heating, and simultaneously starting vacuum to dehydrate, wherein the heating speed is controlled to be 1.5 ℃/min, the vacuum degree is controlled to be-0.098 MPa, the temperature is increased to 125 ℃, and the vacuum dehydration is kept for 2 hours under the control of the temperature within the range; cooling, filtering and discharging to obtain the cardanol modified Schiff base epoxy curing agent.
Example 5
Adding 0.45mol of diethylenetriamine, 0.05mol of polyethylenepolyamine, 0.1mol of m-xylylenediamine and 0.4mol of isophorone diamine into a reactor, vacuumizing the reactor to-0.095 MPa, then injecting nitrogen to the pressure of the reactor to reach 0.2MPa, repeating for 3 times, then injecting nitrogen into the reactor to reach standard atmospheric pressure, and replacing air in the reactor with nitrogen; then slowly adding 1.4mol of formaldehyde solution with the mass concentration of 30%, and stirring at 45 ℃ under controlled temperature until the reaction system does not release heat any more; then adjusting the reaction temperature to 60 ℃, continuing to react for 0.5h, and then carrying out decompression dehydration to obtain Schiff base;
cooling the obtained Schiff base to 20 ℃, then slowly adding 0.8mol of cardanol (the purity is 94.3%), adjusting the temperature to 40 ℃ and reacting for 0.8h; heating, and simultaneously starting vacuum to dehydrate, wherein the heating speed is controlled to be 2 ℃/min, the vacuum degree is controlled to be-0.096 MPa, the temperature is increased to 115 ℃, and the vacuum dehydration is kept for 1.5h under the control of the temperature within the range; cooling, filtering and discharging to obtain the cardanol modified Schiff base epoxy curing agent.
Example 6
Adding 0.4mol of ethylenediamine, 0.2mol of tetraethylenepentamine and 0.4mol of m-xylylenediamine into a reactor, vacuumizing the reactor to-0.095 MPa, then injecting nitrogen into the reactor until the pressure of the reactor reaches 0.2MPa, repeating for 3 times, then injecting nitrogen into the reactor to reach standard atmospheric pressure, replacing air in the reactor by using the nitrogen, then slowly adding 1.3mol of formaldehyde solution with the mass concentration of 30%, and stirring at the temperature of 30 ℃ until the reaction system does not release heat any more; then adjusting the reaction temperature to 50 ℃, continuing to react for 1h, and then carrying out decompression dehydration to obtain Schiff base;
cooling the obtained Schiff base to 30 ℃, then slowly adding 1.1mol of cardanol (the purity is 94.3%), adjusting the temperature to 45 ℃ and reacting for 0.5h; heating, and simultaneously starting vacuum to dehydrate, wherein the heating speed is controlled to be 1 ℃/min, the vacuum degree is controlled to be-0.098 MPa, the temperature is increased to 115 ℃, and the vacuum dehydration is kept for 1h under the control of the temperature within the range; cooling, filtering and discharging to obtain the cardanol modified Schiff base epoxy curing agent.
Performance testing
Test example 1
A physical diagram of the cardanol-modified schiff base epoxy hardener obtained in example 1 is shown in fig. 1, and a physical diagram of a conventional commercially available cardanol hardener is shown in fig. 2; as can be seen from fig. 1 to 2, the cardanol modified schiff base epoxy hardener provided by the invention has the characteristic of light color compared with the traditional cardanol hardener.
The performance characterization of the cardanol-modified schiff base epoxy curing agents obtained in examples 1 to 6 is shown in table 1;
table 1 characterization of the properties of the cardanol-modified schiff base epoxy curatives obtained in examples 1 to 6
Solid content (%) Viscosity (mPa.s, 25 ℃ C.) Amine number (mgKOH/g)
Example 1 ≥95％ 1030 284
Example 2 ≥95％ 1140 290
Example 3 ≥95％ 980 302
Example 4 ≥95％ 1200 294
Example 5 ≥95％ 860 310
Example 6 ≥95％ 1100 311
Commercial cardanol curing agent ≥95％ 11200 298
Test standard ASDMD2369 ASDMD2196 ASDMD2074
As can be seen from Table 1, the cardanol modified Schiff base epoxy curing agents prepared in examples 1 to 6 have a solid content which is not much different from the amine value and a viscosity which is significantly reduced, compared with the commercial cardanol curing agents.
Test example 2
The cardanol modified Schiff base epoxy curing agent obtained in examples 1-6 is used as a curing agent to prepare a paint film, and the preparation process is as follows: controlling the room temperature to be 25+/-2 ℃, mixing the curing agent and the epoxy resin in proportion, uniformly stirring, uniformly coating on a substrate, and drying under the conditions of temperature and humidity specified by corresponding test standards to obtain a test sample;
the dryness at 25℃was measured according to test standard ASTM-D5895, and the test results obtained are shown in Table 2;
table 2 drying Properties of the cured paint films of the cardanol-modified Schiff base epoxy curing Agents obtained in examples 1 to 6
As can be seen from table 2: the cardanol modified schiff base epoxy hardener prepared in examples 1, 2, 3, 5 and 6 has a slightly faster drying speed than the commercially available cardanol hardener, and the cardanol modified schiff base epoxy hardener prepared in example 4 has a slightly slower drying speed, has little influence on application and can meet the requirements;
testing the properties of the cured paint film, wherein the adhesion is tested according to GB/T1720-79 (89); flexibility was tested according to GB/T1731-1993; impact resistance was tested according to GB/T1732-1993; pencil hardness was tested according to GB/T6739-2006; the test results obtained are shown in Table 3;
TABLE 3 paint film Performance test results
From table 3, it can be seen that the epoxy hardener based on the bio-based cardanol modified schiff base has excellent drying property and mechanical property, and also has the characteristics of low viscosity and light color, can be widely used in the fields of coatings such as terraces, industries, engineering, containers, ships and the like, can effectively reduce the viscosity of components, reduces the use amount of organic solvents in downstream application, and has long-term value space for future carbon emission requirements.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.

Claims (10)

1. The preparation method of the cardanol modified Schiff base epoxy curing agent is characterized by comprising the following steps of:
mixing amine and formaldehyde, and performing aldol condensation reaction to obtain Schiff base;
mixing the Schiff base and cardanol, and carrying out dehydration condensation reaction to obtain the cardanol modified Schiff base epoxy curing agent.
2. The method according to claim 1, wherein the amine comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylene polyamine, hexamethylenediamine, pentylenediamine, m-xylylenediamine and isophoronediamine.
3. The method of claim 1, wherein the molar ratio of amine to formaldehyde is 1:0.5 to 2.0.
4. The method according to claim 1, wherein the aldol condensation reaction is carried out at a temperature of 40 to 80 ℃ for a time of 0.5 to 1 hour.
5. The process according to claim 1 or 4, wherein the aldol condensation reaction is carried out in a nitrogen atmosphere.
6. The method of claim 1, wherein the molar ratio of amine to cardanol is 1:0.5 to 2.0.
7. The method according to claim 1, wherein the dehydration condensation reaction is carried out at a temperature of 30 to 60 ℃ for a time of 0.5 to 1 hour.
8. The method according to claim 1 or 7, wherein the dehydration condensation reaction is followed by subjecting the resulting reaction system to vacuum dehydration treatment.
9. The method according to claim 8, wherein the vacuum dehydration treatment is carried out at a temperature of 115 to 125 ℃, a vacuum degree of-0.095 MPa or more, and a time of 0.5 to 2 hours;
the temperature rising rate of the vacuum dehydration treatment temperature is 1-3 ℃/min.
10. The cardanol modified schiff base epoxy hardener prepared by the preparation method of any one of claims 1 to 9, which is characterized in that the cardanol modified schiff base epoxy hardener has a structure shown in formula i or formula ii:
the R1 is The R2 is->
CN202311304644.5A 2023-10-10 2023-10-10 Cardanol modified Schiff base epoxy curing agent and preparation method thereof Pending CN117362183A (en)

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