CN116178676A - Preparation method of cardanol modified amine curing agent - Google Patents

Preparation method of cardanol modified amine curing agent Download PDF

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Publication number
CN116178676A
CN116178676A CN202211270916.XA CN202211270916A CN116178676A CN 116178676 A CN116178676 A CN 116178676A CN 202211270916 A CN202211270916 A CN 202211270916A CN 116178676 A CN116178676 A CN 116178676A
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cardanol
paraformaldehyde
mannich base
base condensate
curing agent
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CN116178676B (en
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杨丽君
赵书英
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Tianjin Yinglin Pipe Equipment Co ltd
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Tianjin Yinglin Pipe Equipment Co ltd
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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
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a preparation method of a cardanol modified amine curing agent. Comprising the following steps: s11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle; s12, adding paraformaldehyde in batches after heating, and reacting after the paraformaldehyde is fully added; s13, after the reaction is finished, distilling at normal pressure and then distilling at reduced pressure to obtain a Mannich base condensate 1; s21, respectively adding cardanol and m-xylylenediamine into a reaction kettle; s22, adding paraformaldehyde in batches after heating, and reacting after the paraformaldehyde is fully added; s23, after the reaction is finished, distilling at normal pressure and then distilling at reduced pressure to obtain a Mannich base condensate 2; s31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the modified polyether amine into a reaction kettle; and S32, heating, stirring and uniformly mixing to obtain the product. The paint prepared by the curing agent has low acid absorption rate and good chloride ion permeation resistance.

Description

Preparation method of cardanol modified amine curing agent
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of a cardanol modified amine curing agent.
Background
Cardanol is a natural phenolic compound with an unsaturated C15 long side chain, which is structurally similar to urushiol. The unique structure of cardanol ensures that the cardanol has the characteristics of aromatic compounds and high temperature resistance; but also has the characteristics of aliphatic compounds, good flexibility, excellent hydrophobicity, low permeability and white dryness; in addition, the phenolic hydroxyl groups on the benzene ring in turn give it phenolic properties. The typical reaction is as follows: the double bond of cardanol can be subjected to addition polymerization, oxidation and hydrogenation reaction, phenolic aldehyde can be subjected to phenolic aldehyde polycondensation reaction, phenolic hydroxyl can be subjected to esterification and etherification reaction, and a plurality of novel compounds can be synthesized by utilizing the reactions.
Because the cardanol modified epoxy assimilating agent has the characteristics of reproducibility, low viscosity, low-temperature curing, good water resistance and the like, a plurality of products can be developed by using cardanol, the cardanol modified epoxy assimilating agent is mainly prepared in the application of cardanol, and the prepared curing agent is cured with epoxy resin to obtain a paint film with high stability, high temperature resistance and good operation at low temperature.
For example, chinese patent CN101333286B discloses a method for synthesizing cashew phenol aldehyde amine epoxy hardener. The curing agent synthesized by the method has the advantages that the polyamine and epoxy groups in the epoxy resin undergo a crosslinking reaction, and the phenolic hydroxyl groups have obvious catalytic action on the curing reaction, so that the curing agent can be cured at a low temperature (-5 ℃); the hydrocarbon group with good hydrophobicity and flexibility substitutes a long chain, so that the curing agent has excellent water resistance and flexibility. The synthesis is prepared from cardanol, formaldehyde and polyamine serving as raw materials in a molar ratio of cardanol to polyamine to formaldehyde=1.0: (0.7-1.0) to (0.7-1.0) through a Mannich reaction. The method comprises the following three steps: 1. uniformly mixing cardanol and polyamine according to a molar ratio, and then adding formaldehyde in batches, wherein the temperature is controlled below 60 ℃ and the adding time is 0.5-1.0 h. 2. Heating to 70-80 deg.c and maintaining for 3-5 hr. 3. Vacuum dehydration is carried out at the temperature of 70-80 ℃ and the vacuum degree of above 740mm until no liquid is distilled out. The curing agent is mainly a single-molecule compound, and the double bonds of the molecules on the chain are unstable, so that the anti-corrosion performance is poor.
Chinese patent CN107973899B discloses a method for preparing modified epoxy hardener based on cardanol, which comprises the following steps: weighing cardanol glycidyl ether and amine, adding the cardanol glycidyl ether and the amine into a reactor, heating to 60-160 ℃ under the protection of nitrogen, stirring and reacting for 1-10 hours, then adding cardanol and aldehyde at the temperature of not more than 75 ℃, reacting for 2-5 hours, vacuumizing at the temperature to remove water generated by the reaction, forming orange-yellow transparent oily substances, and discharging to obtain the cardanol modified amine epoxy resin curing agent. The method utilizes the reaction of cardanol glycidyl ether and amine to generate an intermediate with active amine which can be continuously modified. The cardanol epoxy curing agent is modified by introducing two cardanol fragments into the curing agent molecule, so that the toughness of a paint film after curing is increased, the defects of the traditional cardanol modified epoxy curing agent are improved to a certain extent, and the surface hardness of the paint film after curing for seven days under the condition of low temperature (-15 ℃) can reach H. The method changes the properties of the product, such as improving the color, hardness and the like of the product, but does not fundamentally solve the problems of chemical resistance and corrosion resistance, such as higher acid absorption rate and poorer chloride ion permeation resistance.
In conclusion, the corrosion resistance of the cardanol modified curing agent prepared by the existing method is not satisfactory, and the cardanol modified curing agent is mainly characterized by higher acid absorption rate and poorer chloride ion permeation resistance.
In view of this, the present invention has been made.
Disclosure of Invention
To overcome the above-mentioned drawbacks, a first object of the present invention is to provide a method for preparing a cardanol-modified amine curing agent. The cardanol modified amine curing agent prepared by the method can be quickly cured at room temperature, and the cured product has low acid absorption rate and excellent chloride ion permeation resistance.
In order to achieve the first object, the present invention adopts the following technical scheme:
the preparation method of the cardanol modified amine curing agent comprises the following steps:
s1, preparation of Mannich base condensate 1
S11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle;
s12, adding paraformaldehyde in batches after heating, and reacting after the paraformaldehyde is fully added;
s13, after the reaction is finished, distilling at normal pressure and then distilling at reduced pressure to obtain a Mannich base condensate 1;
s2, preparation of Mannich base condensate 2
S21, respectively adding cardanol and m-xylylenediamine into a reaction kettle;
s22, adding paraformaldehyde in batches after heating, and reacting after the paraformaldehyde is fully added;
s23, after the reaction is finished, distilling at normal pressure and then distilling at reduced pressure to obtain a Mannich base condensate 2;
s3, preparing a curing agent
S31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the modified polyether amine into a reaction kettle;
s32, heating, stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
In the invention, cardanol, ethylenediamine, diethylenetriamine and paraformaldehyde are respectively prepared into a Mannich base condensate 1, cardanol, m-xylylenediamine and paraformaldehyde are respectively prepared into a Mannich base condensate 2, and the cardanol, m-xylylenediamine and paraformaldehyde are mixed with modified polyetheramine to prepare the cardanol modified amine curing agent.
Further, step S12 is: heating to 70-90 ℃, adding paraformaldehyde in batches, and reacting for 1.5-2 h at 85-100 ℃ after the paraformaldehyde is added completely.
Further, step S13 is: after the reaction is finished, the mixture is distilled to 120 to 130 ℃ under normal pressure, and then distilled for 2 to 3 hours under reduced pressure, so as to obtain the Mannich base condensate 1.
Further, step S22 is: heating to 70-90 ℃, adding paraformaldehyde in batches, and reacting for 1.5-2 h at 85-100 ℃ after the paraformaldehyde is added completely.
Further, step S23 is: after the reaction is finished, the mixture is distilled to 120 to 130 ℃ under normal pressure, and then distilled for 2 to 3 hours under reduced pressure, so as to obtain the Mannich base condensate 2.
Further, in step S32, the temperature is raised to 60 to 85 ℃.
Further, in step S11, the molar ratio of cardanol, ethylenediamine and diethylenetriamine is 1: 1-2: 1 to 2;
in the step S12, the molar ratio of the total added paraformaldehyde to cardanol is 1-3: 1.
further, in step S21, the molar ratio of cardanol to m-xylylenediamine is 1:1 to 2;
in the step S22, the molar ratio of the total added paraformaldehyde to cardanol is 1-3: 1.
further, in step S31, the mass ratio of the mannich base condensate 1, the mannich base condensate 2, and the modified polyether amine is 1 to 2: 1-2: 1.
in the invention, the modified polyether amine is a ZY-1784 modified polyether amine curing agent.
As a preferable scheme, the invention further comprises adding nano carbon powder into the mixed material after heating, stirring and mixing uniformly in the step S32, wherein the adding amount of the nano carbon powder is 1-3% of the mass of the mixed material.
In the invention, nano carbon powder is added into the prepared curing agent, and a weak (corrosion-resistant) area of an epoxy ring opening which enters into crosslinking when the nano carbon powder is crosslinked with epoxy resin is formed on a molecular structure, so that the corrosion resistance is improved, and the chloride ion permeability is enhanced.
Compared with the prior art, the invention has the following advantages:
the cardanol modified amine curing agent prepared by the method can be quickly cured at room temperature, and can obtain a coating film with excellent adhesiveness to a wet surface, and the coating film has a glossy surface and high hardness; the cured product has low acid absorption rate and excellent resistance to permeation of chloride ions, water and chemicals. The curing agent is used for coating of environment-friendly adhesives for corrosion prevention, dust prevention, beautification and the like, coating of protective adhesives for surface treatment and protection of metals and the like, resin mortar, inner coatings of various medicine tanks and the like, and heavy anti-corrosion coatings of bridges, harbor buildings and the like, and is a curing agent with excellent performance.
Detailed Description
The following are specific embodiments of the present invention, which are described in order to further illustrate the invention, not to limit the invention.
Example 1
S1, preparation of Mannich base condensate 1
S11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle, wherein the molar ratio of cardanol to ethylenediamine to diethylenetriamine is 1:1:1, a step of;
s12, heating to 70 ℃, adding paraformaldehyde in batches, and reacting at 85 ℃ for 1.5 hours after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 1:1, a step of;
s13, after the reaction is finished, distilling to 120 ℃ under normal pressure, and then distilling under reduced pressure for 2 hours to obtain a Mannich base condensate 1;
s2, preparation of Mannich base condensate 2
S21, respectively adding cardanol and m-xylylenediamine into a reaction kettle, wherein the molar ratio of cardanol to m-xylylenediamine is 1:1, a step of;
s22, heating to 70 ℃, adding paraformaldehyde in batches, and reacting at 85 ℃ for 1.5 hours after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 1:1, a step of;
s23, after the reaction is finished, distilling to 120 ℃ under normal pressure, and then distilling under reduced pressure for 2 hours to obtain a Mannich base condensate 2;
s3, preparing a curing agent
S31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the ZY-1784 modified polyether amine curing agent into a reaction kettle, wherein the mass ratio of the Mannich base condensate 1 to the Mannich base condensate 2 to the ZY-1784 modified polyether amine curing agent is 1:1:1, a step of;
and S32, heating to 60 ℃, and stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
Example 2
S1, preparation of Mannich base condensate 1
S11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle, wherein the molar ratio of cardanol to ethylenediamine to diethylenetriamine is 1:2:2;
s12, heating to 90 ℃, adding paraformaldehyde in batches, and reacting for 2 hours at 100 ℃ after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 3:1, a step of;
s13, after the reaction is finished, distilling to 130 ℃ under normal pressure, and then distilling under reduced pressure for 3 hours to obtain a Mannich base condensate 1;
s2, preparation of Mannich base condensate 2
S21, respectively adding cardanol and m-xylylenediamine into a reaction kettle, wherein the molar ratio of cardanol to m-xylylenediamine is 1:2;
s22, heating to 90 ℃, adding paraformaldehyde in batches, and reacting for 2 hours at 100 ℃ after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 3:1, a step of;
s23, after the reaction is finished, distilling to 130 ℃ under normal pressure, and then distilling under reduced pressure for 3 hours to obtain a Mannich base condensate 2;
s3, preparing a curing agent
S31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the ZY-1784 modified polyether amine curing agent into a reaction kettle, wherein the mass ratio of the Mannich base condensate 1 to the Mannich base condensate 2 to the ZY-1784 modified polyether amine curing agent is 2:2:1, a step of;
and S32, heating to 85 ℃, and stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
Example 3
S1, preparation of Mannich base condensate 1
S11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle, wherein the molar ratio of cardanol to ethylenediamine to diethylenetriamine is 1:1.5:1.5;
s12, heating to 80 ℃, adding paraformaldehyde in batches, and reacting at 90 ℃ for 1.8 hours after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 2:1, a step of;
s13, after the reaction is finished, distilling to 125 ℃ under normal pressure, and then distilling under reduced pressure for 2.5 hours to obtain a Mannich base condensate 1;
s2, preparation of Mannich base condensate 2
S21, respectively adding cardanol and m-xylylenediamine into a reaction kettle, wherein the molar ratio of cardanol to m-xylylenediamine is 1:1.5;
s22, heating to 80 ℃, adding paraformaldehyde in batches, and reacting at 90 ℃ for 1.8 hours after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 2:1, a step of;
s23, after the reaction is finished, distilling to 125 ℃ under normal pressure, and then distilling under reduced pressure for 2.5 hours to obtain a Mannich base condensate 2;
s3, preparing a curing agent
S31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the ZY-1784 modified polyether amine curing agent into a reaction kettle, wherein the mass ratio of the Mannich base condensate 1 to the Mannich base condensate 2 to the ZY-1784 modified polyether amine curing agent is 1.5:1.5:1, a step of;
and S32, heating to 70 ℃, and stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
Example 4
S1, preparation of Mannich base condensate 1
S11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle, wherein the molar ratio of cardanol to ethylenediamine to diethylenetriamine is 1:1.2:1.2;
s12, heating to 85 ℃, adding paraformaldehyde in batches, and reacting at 95 ℃ for 1.6 hours after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 1.5:1, a step of;
s13, after the reaction is finished, distilling to 128 ℃ under normal pressure, and then distilling under reduced pressure for 2.2 hours to obtain a Mannich base condensate 1;
s2, preparation of Mannich base condensate 2
S21, respectively adding cardanol and m-xylylenediamine into a reaction kettle, wherein the molar ratio of cardanol to m-xylylenediamine is 1:1.2;
s22, heating to 85 ℃, adding paraformaldehyde in batches, and reacting at 95 ℃ for 1.6 hours after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 1.5:1, a step of;
s23, after the reaction is finished, distilling to 128 ℃ under normal pressure, and then distilling under reduced pressure for 2.2 hours to obtain a Mannich base condensate 2;
s3, preparing a curing agent
S31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the ZY-1784 modified polyether amine curing agent into a reaction kettle, wherein the mass ratio of the Mannich base condensate 1 to the Mannich base condensate 2 to the ZY-1784 modified polyether amine curing agent is 1.8:1.8:1, a step of;
and S32, heating to 75 ℃, and stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
Example 5
S1, preparation of Mannich base condensate 1
S11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle, wherein the molar ratio of cardanol to ethylenediamine to diethylenetriamine is 1:1.8:1.8;
s12, heating to 75 ℃, adding paraformaldehyde in batches, and reacting for 1.4 hours at 88 ℃ after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 1.4:1, a step of;
s13, after the reaction is finished, distilling to 122 ℃ under normal pressure, and then distilling under reduced pressure for 2.4 hours to obtain a Mannich base condensate 1;
s2, preparation of Mannich base condensate 2
S21, respectively adding cardanol and m-xylylenediamine into a reaction kettle, wherein the molar ratio of cardanol to m-xylylenediamine is 1:1.8;
s22, heating to 75 ℃, adding paraformaldehyde in batches, and reacting for 1.4 hours at 88 ℃ after the paraformaldehyde is added completely, wherein the molar ratio of the added paraformaldehyde to cardanol is 1.4:1, a step of;
s23, after the reaction is finished, distilling to 122 ℃ under normal pressure, and then distilling under reduced pressure for 2.4 hours to obtain a Mannich base condensate 2;
s3, preparing a curing agent
S31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the ZY-1784 modified polyether amine curing agent into a reaction kettle, wherein the mass ratio of the Mannich base condensate 1 to the Mannich base condensate 2 to the ZY-1784 modified polyether amine curing agent is 1.4:1.4:1, a step of;
and S32, heating to 65 ℃, and stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
Example 6
The embodiment is different from embodiment 1 in that the step S32 of heating, stirring and mixing uniformly further comprises adding nano carbon powder into the mixed material, wherein the adding amount of the nano carbon powder is 1% of the mass of the mixed material.
Example 7
The embodiment is different from embodiment 2 in that the step S32 of heating, stirring and mixing uniformly further comprises adding nano carbon powder to the mixed material, wherein the adding amount of the nano carbon powder is 3% of the mass of the mixed material.
Example 8
The embodiment is different from embodiment 3 in that the step S32 of heating, stirring and mixing uniformly further comprises adding nano carbon powder to the mixed material, wherein the adding amount of the nano carbon powder is 2% of the mass of the mixed material.
Example 9
The embodiment is different from embodiment 4 in that the step S32 of heating, stirring and mixing uniformly further comprises adding nano carbon powder into the mixed material, wherein the adding amount of the nano carbon powder is 1.5% of the mass of the mixed material.
Example 10
The embodiment is different from embodiment 5 in that the step S32 of heating, stirring and mixing uniformly further comprises adding nano carbon powder to the mixed material, wherein the adding amount of the nano carbon powder is 2.5% of the mass of the mixed material.
Comparative example 1
S1, preparing Mannich base condensate
S11, respectively adding cardanol, ethylenediamine, diethylenetriamine and m-xylylenediamine into a vacuum reaction kettle, wherein the molar ratio of cardanol, ethylenediamine, diethylenetriamine to m-xylylenediamine is 2:1:1:1, a step of;
s12, heating to 70 ℃, adding paraformaldehyde in batches, and reacting at 85 ℃ for 1.5 hours after the paraformaldehyde is added completely, wherein the molar ratio of the added total paraformaldehyde to cardanol is 1:1, a step of;
s13, after the reaction is finished, distilling to 120 ℃ under normal pressure, and then distilling under reduced pressure for 2 hours to obtain a Mannich base condensate;
s2, preparing a curing agent
S21, respectively adding the Mannich base condensate and the ZY-1784 modified polyether amine curing agent into a reaction kettle, wherein the mass ratio of the Mannich base condensate to the ZY-1784 modified polyether amine curing agent is 1:1, a step of;
and S22, heating to 60 ℃, and stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
Comparative example 2
The cardanol-modified amine-based epoxy hardener prepared according to the method of example 1 of CN101333286B is specifically as follows:
on a 500ml reaction barrel, a stirrer, a condenser, a water separator, a thermometer and a charging port are arranged, 150g of cardanol and 30g of ethylenediamine are added, the mixture is stirred uniformly, 15g of paraformaldehyde is added in batches, the temperature is controlled below 60 ℃, the addition time is 0.5h, the temperature is increased to 70-80 ℃, the temperature is kept for 4h, then vacuum dehydration is carried out, the dehydration temperature is 70-80 ℃ and is not more than 90 ℃ at maximum, and no liquid is distilled out.
Test example 1
The test example examined the effect of different curing agents on the acid resistance of the resulting coating under the same primer.
The test method comprises the following steps: the epoxy primer SL-18 is used as main adhesive, and the curing agents prepared in the examples and the comparative examples are respectively adopted, wherein the mass ratio of the curing agents is 5:1, uniformly mixing to prepare the coating, so as to examine the influence of different curing agents on the acid resistance of the prepared coating.
The method for testing the acid absorption rate comprises the following steps: the resulting coating was applied to a 2X 2cm carbon steel to a thickness of about 2mm. The test sample is immersed in different acid solutions after weighing, after soaking for 30 days at normal temperature, the test sample is washed with clean water, dried to constant weight, weighed and the mass increase rate is calculated.
The method for detecting the chlorine ion permeability comprises the following steps: the experimental conditions were carried out according to JTJ275-2000 appendix C.2: the coated sheet was 321 μm thick in 3% NaCl solution and left to stand at 23℃for 30d.
The test results are shown in Table 1:
Figure DEST_PATH_IMAGE001
from the test results, when the cardanol modified amine curing agent prepared by the invention is selected as the curing agent, the acid absorption rate of the paint prepared by taking the epoxy primer SL-18 as the primer is lower, which shows that the paint has better corrosion resistance and better chloride ion permeability under an acidic environment.

Claims (10)

1. The preparation method of the cardanol modified amine curing agent is characterized by comprising the following steps of:
s1, preparation of Mannich base condensate 1
S11, respectively adding cardanol, ethylenediamine and diethylenetriamine into a vacuum reaction kettle;
s12, adding paraformaldehyde in batches after heating, and reacting after the paraformaldehyde is fully added;
s13, after the reaction is finished, distilling at normal pressure and then distilling at reduced pressure to obtain a Mannich base condensate 1;
s2, preparation of Mannich base condensate 2
S21, respectively adding cardanol and m-xylylenediamine into a reaction kettle;
s22, adding paraformaldehyde in batches after heating, and reacting after the paraformaldehyde is fully added;
s23, after the reaction is finished, distilling at normal pressure and then distilling at reduced pressure to obtain a Mannich base condensate 2;
s3, preparing a curing agent
S31, respectively adding the Mannich base condensate 1, the Mannich base condensate 2 and the modified polyether amine into a reaction kettle;
s32, heating, stirring and mixing uniformly to obtain the cardanol modified amine curing agent.
2. The method according to claim 1, wherein,
step S12 is: heating to 70-90 ℃, adding paraformaldehyde in batches, and reacting for 1.5-2 h at 85-100 ℃ after the paraformaldehyde is added completely.
3. The method according to claim 1, wherein,
step S13 is: after the reaction is finished, the mixture is distilled to 120 to 130 ℃ under normal pressure, and then distilled for 2 to 3 hours under reduced pressure, so as to obtain the Mannich base condensate 1.
4. The method according to claim 1, wherein,
step S22 is: heating to 70-90 ℃, adding paraformaldehyde in batches, and reacting for 1.5-2 h at 85-100 ℃ after the paraformaldehyde is added completely.
5. The method according to claim 1, wherein,
step S23 is: after the reaction is finished, the mixture is distilled to 120 to 130 ℃ under normal pressure, and then distilled for 2 to 3 hours under reduced pressure, so as to obtain the Mannich base condensate 2.
6. The method according to any one of claims 1 to 5, wherein in step S32, the temperature is raised to 60 to 85 ℃.
7. The method according to claim 6, wherein,
in step S11, the molar ratio of cardanol, ethylenediamine and diethylenetriamine is 1: 1-2: 1 to 2;
in the step S12, the molar ratio of the total added paraformaldehyde to cardanol is 1-3: 1.
8. the method according to claim 6, wherein,
in step S21, the molar ratio of cardanol to m-xylylenediamine is 1:1 to 2;
in the step S22, the molar ratio of the total added paraformaldehyde to cardanol is 1-3: 1.
9. the method according to claim 7 or 8, wherein,
in the step S31, the mass ratio of the Mannich base condensate 1, the Mannich base condensate 2 and the modified polyether amine is 1-2: 1-2: 1.
10. the preparation method according to claim 9, further comprising adding nano carbon powder to the mixed material after the heating and stirring and mixing in the step S32, wherein the adding amount is 1-3% of the mass of the mixed material.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333286A (en) * 2007-06-26 2008-12-31 上海经天新材料科技有限公司 Amine epoxy curing agent modified by cardanol
CN104271691A (en) * 2012-04-24 2015-01-07 陶氏环球技术有限公司 Epoxy resin composition for marine maintenance and repair coatings with improved overcoat ability

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333286A (en) * 2007-06-26 2008-12-31 上海经天新材料科技有限公司 Amine epoxy curing agent modified by cardanol
CN104271691A (en) * 2012-04-24 2015-01-07 陶氏环球技术有限公司 Epoxy resin composition for marine maintenance and repair coatings with improved overcoat ability

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