CN110437658B - Anticorrosion auxiliary agent, preparation method and electrophoretic coating with high corrosion resistance - Google Patents
Anticorrosion auxiliary agent, preparation method and electrophoretic coating with high corrosion resistance Download PDFInfo
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- CN110437658B CN110437658B CN201910767568.9A CN201910767568A CN110437658B CN 110437658 B CN110437658 B CN 110437658B CN 201910767568 A CN201910767568 A CN 201910767568A CN 110437658 B CN110437658 B CN 110437658B
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- epoxy resin
- polyurea
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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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- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
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- 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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
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Abstract
The invention discloses an anticorrosive additive, which comprises the following main components of a compound with a structure shown in a formula I:
wherein R is1The structural formula of (A) is:
R2is cycloalkyl or alkyl. The anti-corrosion additive introduces a polyurea structure on the chain segment, so that the anti-corrosion property of the electrophoretic coating can be effectively improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an anticorrosive additive, a preparation method thereof and an electrophoretic coating with high corrosion resistance.
Background
The electrophoretic paint is one of water-based paints, and has been widely applied to the coating of the automobile industry and other industries due to the advantages of environmental protection, high utilization rate, high automation degree, excellent performance and the like. With the continuous prevalence of the electrophoretic coating, the customer base is growing, and the salt spray performance required by the electrophoretic coating is higher and higher, so that the research of improving the corrosion resistance is a constant development direction of the electrophoretic coating.
Disclosure of Invention
The invention aims to provide a functional resin capable of improving the corrosion prevention covering power of a cationic water-based paint and a preparation method thereof, and solves one or more of the problems in the prior art.
The invention provides an anticorrosive additive, which mainly comprises a compound with a structure shown in a formula I:
wherein R is1The structural formula of (A) is:
R2is cycloalkyl or alkyl.
A preparation method of a corrosion prevention auxiliary agent comprises the following steps:
s1, carrying out chain extension reaction on urea, polyether amine and diethylenetriamine to obtain polyurea amine with a polyurea structure with amino groups at two ends;
the chemical equation of step S1 is as follows:
s2, reacting the polyureaurethane containing the polyurea structure with epoxy resin with the molecular weight of 850-900 to obtain modified epoxy resin with the polyurea structure;
the chemical equation of step S2 is as follows:
s3, adding the modified epoxy resin with the polyurea structure into a neutralizer for neutralization to obtain the anticorrosion auxiliary agent.
The neutralizing agent may be lactic acid.
In some embodiments, the polyetheramine is an amine compound with a polyether segment in the middle and primary monoamines at both ends, and has a molecular weight of 230-2000.
In some embodiments, the chain extension reaction of urea, polyetheramine, and diethylenetriamine comprises the steps of: and (3) continuously stirring urea, polyether amine and diethylenetriamine in a nitrogen atmosphere, and reacting at the temperature of 120-150 ℃ until the amine value reaches a specified range to obtain the polyurea amine containing the polyurea structure.
In some embodiments, reacting a polyureauramine containing a polyurea structure with an epoxy resin comprises the steps of: adding epoxy resin with the molecular weight of 850-900 into the polyureaurethane with the polyurea structure, heating to 110-120 ℃, and then preserving the heat for 2-3h to obtain the modified epoxy resin with the polyurea structure.
In some embodiments, the temperature for adding the neutralizing agent to the modified epoxy resin of the polyurea structure for neutralization is 50 to 60 ℃.
An electrophoretic coating with high corrosion resistance comprises a main emulsion and the corrosion-resistant auxiliary agent.
In some embodiments, the preservative comprises 80-95% of the main emulsion and 5-20% of the preservative auxiliary by weight percentage.
An electrophoretic coating with high corrosion resistance comprises a main emulsion and the anti-corrosion additive prepared by the method.
In some embodiments, the preservative comprises 80-95% of the main emulsion and 5-20% of the preservative auxiliary by weight percentage.
Wherein, the main body emulsion is prepared by the following method:
s1, adding micromolecule basic epoxy resin, a chain extender, a catalyst and an organic solvent into a reaction vessel, carrying out chain extension reaction at the temperature of 120-3000 ℃ to obtain macromolecular epoxy resin with the epoxy equivalent of 1000-3000,
s2, heating to 90-95 ℃ in macromolecular epoxy resin with the epoxy equivalent of 1000-3000 under continuous stirring, adding amine compound containing active hydrogen, heating to 115-125 ℃, then preserving heat for 3 hours to obtain chain-extended amine modified main epoxy resin,
s3, adding chain-extended amine modified main epoxy resin and a closed isocyanate curing agent into a reaction container, adding a neutralizing agent for neutralization, and adding deionized water for dilution until the solid content is 33% -35%.
Has the advantages that: the anti-corrosion additive introduces a polyurea structure on the chain segment, so that the anti-corrosion property of the electrophoretic coating can be effectively improved.
Detailed Description
The following examples further illustrate the present invention in detail.
Example (b):
the first step is as follows: preparing a main resin:
to a reaction flask equipped with a thermometer, a stirrer and a reflux condenser were added the formulated amounts of 201 epoxy resin, bisphenol a and a first portion of methyl isobutyl ketone in that order. After the addition is finished, starting stirring, heating the reaction system to 120 ℃, preserving the heat, adding triphenylphosphine, heating the reaction system to 150 ℃, continuing to react for 1h at the temperature, and cooling when the epoxy equivalent of the reaction system reaches a theoretical value (EEW-1140.5); when the temperature of the system is reduced to be below 100 ℃, adding N-methylethanolamine, ketimine and a second part of methyl isobutyl ketone into the reaction system, heating to 120 ℃ again, and continuing to react for 2 hours at the temperature; after the reaction is finished, the temperature of the reaction system is reduced to 70 ℃, and the main body resin with the solid content of 85.0% is obtained.
The specific formula is as follows:
| components | Dosage (g) |
| 201 epoxy resin (EEW 185) | 1480 |
| Bisphenol A | 684 |
| Triphenylphosphine | 3 |
| Methyl isobutyl ketone | 114 |
| N-methylethanolamine | 86 |
| Ketimine | 174 |
| Methyl isobutyl ketone | 390 |
| Total weight of | 2931 |
Prepared from diethylenetriamine and methyl isobutyl ketone according to a molar ratio of 1: 2, preparing the final product with solid content as follows: 73 percent
The second step is that: preparing a curing agent:
adding 4, 4' -diphenylmethane diisocyanate and dibutyltin dilaurate in formula amount into a reaction bottle provided with a thermometer, a stirrer and a reflux condenser tube, stirring and heating to 60 ℃, then beginning to dropwise add ethylene glycol monobutyl ether, cooling by using a water bath in the dropwise adding process, controlling the temperature not to exceed 65 ℃, continuing to react for 2 hours at 80 ℃ after the dropwise adding is finished, analyzing the content of residual isocyanate groups in the reaction system by using a standard di-n-butylamine back titration method, and adding methyl isobutyl ketone for dilution when the content of the residual isocyanate groups is less than 0.2% to obtain the totally-closed isocyanate crosslinking agent with the final solid content of 80%.
The specific formula is as follows:
| components | Dosage (g) |
| 4, 4' -diphenylmethane diisocyanate | 1000 |
| Ethylene glycol monobutyl ether | 944 |
| Dibutyl tin dilaurate | 1.5 |
| Methyl isobutyl ketone | 486.5 |
| Total weight of | 2432 |
The third step: preparing a main emulsion:
adding the main resin of the first step, the curing agent of the second step and ethylene glycol monobutyl ether in the formula amount into a reaction bottle with a stirrer, starting stirring, uniformly mixing a reaction system, adding acetic acid for neutralization to ionize the resin, finally adding deionized water, emulsifying for 30min, and then carrying out reduced pressure distillation to remove the organic solvent in the emulsion, thus obtaining the main emulsion with the solid content of 35%.
The specific formula is as follows:
| components | Dosage (g) |
| The main resin of the first step | 500 |
| Curing agent of the second step | 200 |
| Ethylene glycolMonobutyl ether | 8 |
| Acetic acid | 20 |
| Deionized water | 1001 |
| Total amount of | 1729 |
The fourth step: preparing an auxiliary resin:
in a reaction flask equipped with a thermometer and a stirrer, urea, polyureaurethane (D230) and diethylenetriamine were added in the amounts as formulated in order. And after the feeding is finished, introducing nitrogen to start stirring, heating the reaction system to 120 ℃, keeping the temperature, reacting for 3 hours, and cooling when the amine value of the reaction system reaches a theoretical value to obtain the polyureaurethane containing a polyurea structure.
The specific formula is as follows:
the fifth step: preparing the polyurea amine modified epoxy resin:
adding the polyurea amine obtained in the fourth step into a reaction bottle with a stirrer, starting stirring, adding the polyether amine, maintaining the temperature at 120 ℃, and keeping the temperature for 2 hours to obtain the polyurea amine modified epoxy resin with the solid content of 85%.
The specific formula is as follows:
and a sixth step: preparing an anticorrosive additive:
and (3) sequentially adding the polyureaurethane modified epoxy resin and the lactic acid in the fifth step into a reaction bottle provided with a thermometer and a stirrer, starting stirring after the addition is finished, keeping the temperature at 50 ℃, keeping the temperature for 30 minutes, adding a specified amount of pure water, and stirring for 1 hour to obtain the anticorrosive additive with the final solid content of 35.0%.
The specific formula is as follows:
| components | Dosage (g) |
| The epoxy resin modified by the polyureaurethane of the fifth step | 1500 |
| Lactic acid | 200 |
| Pure water | 4146 |
| Total weight of | 5846 |
The seventh step: preparing an electrophoretic coating:
the electrophoretic paint is prepared according to the formula, and then the electrophoretic paint is placed in an electrophoresis tank for curing for 24 hours. The temperature of the bath solution is controlled at 30 ℃, the voltage is controlled at 200V, and electrophoresis is carried out for 1 minute. Then baking the film for 20 minutes at 180 ℃ to obtain a paint film with better paint film appearance.
The specific formula is as follows:
| components | Dosage (g) |
| The third step of the main emulsion | 300 |
| The corrosion preventing additive of the sixth step | 50 |
| HLS-5008 Black pulp (HLS product) | 50 |
| Deionized water | 550 |
| Total weight of | 950 |
Wherein HLS-5008 black pulp (HLS product) is purchased from Jiangsu, Inc. of Laolison chemical technology.
The phosphated panels after electrophoresis of the examples and the coatings without the addition of auxiliaries were tested for salt spray performance under NSS conditions, with the relevant parameters shown in Table 1.
TABLE 1 comparison of the NSS salt spray Performance without adjuvant
As can be seen from the data in table 1, the salt spray resistance in the examples is significantly improved relative to the conventional electrodeposition coating due to the addition of the polyurea structure, which is significantly narrower than the non-added cross-hatch width, and is free from foaming and rusting.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these should be considered as within the scope of the present invention.
Claims (11)
1. The anticorrosion auxiliary agent is characterized in that the main component of the anticorrosion auxiliary agent is a compound with a structure shown in a formula I:
wherein R is1The structural formula of (A) is:
R2is an alkyl group.
2. The corrosion protection additive of claim 1, wherein R is2Is a cycloalkane group.
3. The preparation method of the anticorrosion auxiliary agent is characterized by comprising the following steps:
s1, carrying out chain extension reaction on urea, polyether amine and diethylenetriamine to obtain polyurea amine with a polyurea structure with amino groups at two ends;
s2, reacting the polyureaurethane containing the polyurea structure with epoxy resin with the molecular weight of 850-900 to obtain modified epoxy resin with the polyurea structure;
s3, adding the modified epoxy resin with the polyurea structure into a neutralizer for neutralization to obtain the anticorrosion auxiliary agent.
4. The method for preparing corrosion protection assistant according to claim 3, wherein the polyether amine is an amine compound having a polyether segment in the middle and primary monoamine at both ends, and has a molecular weight of 230-2000.
5. The preparation method of the corrosion protection additive according to claim 3, wherein the chain extension reaction of the urea, the polyether amine and the diethylenetriamine comprises the following steps: and (3) continuously stirring urea, polyether amine and diethylenetriamine in a nitrogen atmosphere, and reacting at the temperature of 120-150 ℃ until the amine value reaches a specified range to obtain the polyurea amine containing the polyurea structure.
6. The method for preparing the corrosion protection additive according to claim 3, wherein the reaction of the polyureauramine containing polyurea structure and the epoxy resin comprises the following steps: adding epoxy resin with the molecular weight of 850-900 into the polyureaurethane with the polyurea structure, heating to 110-120 ℃, and then preserving the heat for 2-3h to obtain the modified epoxy resin with the polyurea structure.
7. The method for preparing an anticorrosion aid according to claim 3, wherein the temperature of the modified epoxy resin of the polyurea structure added with the neutralizer for neutralization is 50-60 ℃.
8. An electrodeposition paint having high corrosion resistance, comprising a main emulsion and the corrosion-preventing assistant according to claim 1.
9. The electrodeposition paint with high corrosion resistance according to claim 8, comprising 80 to 95% by weight of the main emulsion and 5 to 20% by weight of the corrosion prevention aid.
10. An electrodeposition paint having high corrosion resistance, comprising a main emulsion and the corrosion prevention aid prepared by the method of any one of claims 3 to 7.
11. The electrodeposition paint with high corrosion resistance according to claim 10, comprising 80 to 95% by weight of the main emulsion and 5 to 20% by weight of the corrosion prevention aid.
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