CN116606218A - Modified aspartic acid ester resin containing imino, preparation method and application thereof - Google Patents

Modified aspartic acid ester resin containing imino, preparation method and application thereof Download PDF

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Publication number
CN116606218A
CN116606218A CN202310579042.4A CN202310579042A CN116606218A CN 116606218 A CN116606218 A CN 116606218A CN 202310579042 A CN202310579042 A CN 202310579042A CN 116606218 A CN116606218 A CN 116606218A
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acid ester
aspartic acid
imino
ester resin
modified aspartic
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Inventor
蔡水生
吕文章
何飞云
黄华冰
朱龙晖
赵粕利
谢夏陆
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Shenzhen Feiyang Junyan New Material Co ltd
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Shenzhen Feiyang Junyan New Material Co ltd
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • C08G18/3256—Reaction products of polyamines with aldehydes or ketones
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The application relates to the technical field of chemical coating, and in particular discloses an imino-containing modified aspartic acid ester resin, a preparation method and application thereof. An imino-containing modified aspartic acid ester resin is prepared from fatty amine, maleic acid ester, fumaric acid ester, ketone or aldehyde through reactionThe structural formula of the grease is as follows:

Description

Modified aspartic acid ester resin containing imino, preparation method and application thereof
Technical Field
The application relates to the technical field of chemical coating, in particular to modified aspartic acid ester resin containing imino, a preparation method and application thereof.
Background
The polyaspartic acid ester resin is prepared by Michael reaction of aliphatic or cycloaliphatic diamine or polyamine and maleate or fumarate. Because of steric hindrance and induction effect of maleate or fumarate, compared with common amino resin and isocyanate, the reaction speed of the aspartate resin is slow, and the construction time is longer, and the coating construction modes can be spraying, rolling coating, knife coating and the like, and no professional and expensive construction equipment is required. Compared with the general polyurethane resin, the reaction speed of hydroxyl of the secondary amine group of the aspartic acid ester is much faster, and the rapid curing can be realized without baking, heating and curing. In addition, the aspartic acid ester has small molecular weight and low viscosity, and can be constructed without adding solvent. Therefore, the aspartate coating belongs to high-solid environment-friendly coatings and is widely applied to the fields of waterproofing, terrace, corrosion prevention and the like.
The polyaspartic acid ester has small molecular weight and high ester bond content in the molecule, and the coating obtained after the polyaspartic acid ester resin reacts with isocyanate has poor hydrophobicity and water resistance and poor salt spray resistance. On the other hand, the reaction speed of the secondary amine group of the polyaspartic acid ester resin and isocyanate is faster, the actual drying time of the conventional asparaginic acid ester resin F420 and HDI trimer is only 20 minutes, the solvent is not released to be completely dried, the wetting of a paint film and a substrate is poor, the adhesive force performance of the paint film is poor, and finally the salt spray resistance of the paint is poor. The polyaspartic acid ester coating is limited to be not excellent enough in salt spray resistance, and is difficult to popularize in heavy-duty corrosion prevention fields such as engineering machinery corrosion prevention, ship corrosion prevention and the like.
The ketimine or aldimine is prepared by condensation dehydration reaction of ketone or aldehyde compounds and polyamine. The ketimine or aldimine absorbs water and then reacts reversely to generate polyamine, and the polyamine can react with epoxy or isocyanate groups to be cured. Thus, ketimine or aldimine compounds are used as moisture curing agents.
In the related art, ketimine is adopted to prolong the applicable period of curing of the asparaguse resin and isocyanate, and the scheme adopts aliphatic amine or ring amine and ketone compound to prepare ketimine through dehydration condensation reaction. Due to the extremely low viscosity of ketimine and the advantage of quick release of primary amine to react with isocyanate, adding appropriate amount of ketimine into the asparaguse resin system can effectively prolong the pot life of asparaguse resin. However, this solution has the following disadvantages when applied: 1. the storage stability is poor, ketimine is easy to hydrolyze in the storage process and release primary amine in advance, when the ketimine is mixed with isocyanate, the ketimine is instantly agglomerated to influence the use of the paint, and in the process of preparing the paint, the requirement on sealing and storage of the product is high, and dehydrating agents such as molecular sieves and the like are required to be added; 2. curing in a high humidity environment is required, and the defect of low hardness, performance deviation and the like of a paint film after curing is caused by incomplete hydrolysis of ketimine when the humidity is low.
In view of the above-mentioned related art, the inventors believe that the addition of ketimine directly to an aspartic acid ester has the drawbacks of poor storage stability and poor hydrolysis resistance of the aspartic acid ester resin.
Disclosure of Invention
In order to overcome the defects of poor storage stability and poor hydrolysis resistance of the prior art, the application provides an imino-containing modified aspartic acid ester resin, a preparation method and application thereof. The ketone or aldimine modified aspartic acid ester resin is added to prepare the salt spray resistant paint, and the paint has the advantages of high coating hardness, good adhesive force, good salt spray resistant performance and the like. And the modified aspartic acid ester resin containing the imino has more excellent storage stability, hydrolysis resistance and adhesiveness.
In a first aspect, the application provides an imino-containing modified aspartic acid ester resin, which adopts the following technical scheme:
an imino-containing modified aspartic acid ester resin synthesized by reacting fatty amine with maleic acid ester or fumaric acid ester and ketone or aldehyde compounds, wherein the structural formula of the imino-containing modified aspartic acid ester resin is as follows:
wherein R1 is an alkyl group of 1 to 8 carbon atoms, R2 is a divalent hydrocarbon group, R3 and R4 are independently represented as monovalent aliphatic, cycloaliphatic or araliphatic residues, and R4 and R5 do not have tertiary amine nitrogen.
By adopting the technical scheme, the modified aspartic acid ester resin containing the imino group, which is prepared by the reaction of fatty amine and maleate or fumarate and ketone or aldehyde compounds, is applied to the coating and has the following advantages: 1. because the hydrolysis resistance of the ester bond is poor, the influence of the ester bond on the salt spray performance is large, the content of the ester bond is greatly reduced by introducing the imine group, the urea group content of a paint film is high, and the content of the ester bond is lower, so that the hydrolysis resistance of the aspartic acid ester is improved; 2. the introduction of ketimine or aldimine can reduce the reaction speed of aspartic acid ester and isocyanate, enhance the wetting effect of resin on a substrate, and further enhance the adhesive force of the coating; 3. compared with the imine-containing modified aspartic acid ester resin synthesized by directly adding ketimine or aldimine resin into aspartic acid ester and reacting fatty amine with maleic acid ester or fumaric acid ester and ketone or aldehyde compounds, the imine-containing modified aspartic acid ester resin has more excellent storage stability, can be solidified in an environment with lower relative humidity, and does not need to be supplemented with a metal catalyst; 4. the modified aspartate resin containing the imino groups, which is synthesized by the reaction of fatty amine, maleate or fumarate and ketone or aldehyde compounds, has higher primary amine conversion rate than the normal synthesized aspartate, and has higher purity.
Preferably, R3 and R4 are each 1 to 20 carbon atoms and are free of hydroxyl groups and optionally contain heteroatoms in the form of ether oxygen or tertiary amine nitrogen.
Preferably, R3 and R4 each have a divalent aliphatic residue of 3 to 20 carbon atoms and each have a portion of a heterocyclic ring of 5 to 8 ring atoms, wherein the ring is free of hydroxyl groups and optionally contains additional heteroatoms in the form of ether oxygen or tertiary amine nitrogen in addition to the nitrogen atom.
In a second aspect, the application provides a preparation method of modified aspartate resin containing imino, which adopts the following technical scheme:
a preparation method of modified aspartate resin containing imino comprises the following steps: firstly, maleic acid ester or fumaric acid ester is added into aliphatic amine in a dropwise manner, and the reaction is carried out for 12-48 hours at the temperature of 60-70 ℃ to obtain a reaction liquid; then adding ketone or aldehyde compounds into the reaction liquid, controlling the temperature to be 80-150 ℃ for reaction for 2-12 hours, and obtaining the modified aspartic acid ester resin containing imino after the reaction is completed.
By adopting the technical scheme, the preparation method of the modified aspartic acid ester resin containing the imino groups is simple, and the prepared modified aspartic acid ester resin containing the imino groups has more excellent storage stability and salt fog resistance.
Preferably, the ratio of the amount of the fatty amine to the amount of the substance of the maleate or fumarate and the ketone or aldehyde compound is 1: (0.1-1.9): (0.1-1.9).
Preferably, the aliphatic amine is one of 4,4 '-diaminodicyclohexylmethane, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, 2-methylpentanediamine, isophoronediamine, methylcyclohexanediamine, polyetheramine D230.
Preferably, the ketone or aldehyde compound is a combination of one or more of butanone, methyl isopropyl ketone, methyl isobutyl ketone, formaldehyde, benzaldehyde and phenylacetaldehyde.
In a third aspect, the application provides an application of modified aspartate resin containing imino in a coating, which adopts the following technical scheme:
the application of the modified aspartate resin containing the imino in the coating comprises a component A and a component B;
the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
30-100 parts of HDI trimer;
the aspartate resin is modified aspartate resin containing imino.
Preferably, the dispersant is a high molecular weight block copolymer solution containing pigment affinic groups, preferably BYK163.
Preferably, the anti-settling agent is fumed silica.
Preferably, the defoamer is a defoamer that employs non-silicon, preferably BYK1790.
Preferably, the mesh number of the barium sulfate is 1000-3000 mesh, preferably 2000 mesh.
Preferably, the titanium dioxide is R606.
Preferably, the zinc phosphate is Nubirox 213.
Preferably, the solvent is a combination of one or more of ethyl acetate, butyl acetate, toluene and xylene.
In a fourth aspect, the application provides a preparation method of a coating, which adopts the following technical scheme:
a method of preparing a coating comprising the steps of:
and (3) preparation of the component A: firstly, adding an imino group-containing modified aspartic acid ester resin, a dispersing agent, an anti-settling agent, barium sulfate, zinc phosphate, titanium dioxide and a 3A molecular sieve into a reaction kettle, dispersing at a high speed for 15-30 minutes under the condition of a rotating speed of 3000 rpm, then adding a defoaming agent, a leveling agent and a solvent, and stirring for 10 minutes under the condition of a rotating speed of 1000 rpm to obtain a component A;
the A component and the B component are mixed according to the mol ratio of secondary amino groups to isocyanic acid groups of 1:1.05.
In summary, the application has the following beneficial effects:
1. the application adopts the imine group-containing modified aspartic acid ester resin prepared by the reaction of fatty amine and maleic acid ester or fumaric acid ester and ketone or aldehyde compounds to be applied to the coating, and the introduction of ketimine or aldimine can reduce the content of ester bonds in the aspartic acid ester and improve the hydrolysis resistance of the aspartic acid ester.
2. The introduction of ketimine or aldimine can reduce the reaction speed of aspartic acid ester and isocyanate, enhance the wetting effect of resin on a substrate, and further enhance the adhesive force of the coating.
3. Compared with the imine-containing modified aspartic acid ester resin synthesized by directly adding ketimine or aldimine resin into aspartic acid ester and reacting fatty amine with maleic acid ester or fumaric acid ester and ketone or aldehyde compounds, the imine-containing modified aspartic acid ester resin has more excellent storage stability, can be solidified in an environment with lower relative humidity, and does not need to be supplemented with a metal catalyst.
4. The modified aspartate resin containing the imino groups, which is synthesized by the reaction of fatty amine, maleate or fumarate and ketone or aldehyde compounds, has higher primary amine conversion rate than the normal synthesized aspartate, and has higher purity.
Detailed Description
Due to the extremely low viscosity of ketimine and the advantage of quick release of primary amine to react with isocyanate, adding appropriate amount of ketimine into the asparaguse resin system can effectively prolong the pot life of asparaguse resin. However, this solution has the following disadvantages when applied: 1. the storage stability is poor, ketimine is easy to hydrolyze in the storage process and release primary amine in advance, when the ketimine is mixed with isocyanate, the ketimine is instantly agglomerated to influence the use of the paint, and in the process of preparing the paint, the requirement on sealing and storage of the product is high, and dehydrating agents such as molecular sieves and the like are required to be added; 2. curing in a high humidity environment is required, and the defect of low hardness, performance deviation and the like of a paint film after curing is caused by incomplete hydrolysis of ketimine when the humidity is low.
The inventor of the application has found through a great deal of researches that the modified aspartate resin containing imino groups, which is prepared by reacting fatty amine with maleate or fumarate and ketone or aldehyde compounds, can effectively improve the hydrolysis resistance of the aspartate coating, enhance the adhesive force between the coating and a substrate, and have more excellent storage stability when applied to the aspartate coating.
The present application will be specifically described with reference to examples. The scope of the application is not limited to the following examples.
The following materials involved in the examples of the present application are all commercially available: 4,4 '-diaminodicyclohexylmethane, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, 2-methylpentanediamine, isophoronediamine, methylcyclohexanediamine, polyetheramine D230, butanone, methyl isopropyl ketone, methyl isobutyl ketone, formaldehyde, benzaldehyde and phenylacetaldehyde, BYK163, fumed silica, BYK1790, barium sulfate, R606, ethyl acetate, butyl acetate, toluene and xylene.
The types and manufacturers of the raw materials are only used for fully disclosing the raw materials of the application, and the raw materials are not limited to the manufacturers, so that the raw materials used in practical application are not limited to the manufacturers, and the raw materials of other manufacturers with the same efficacy are also applicable.
Examples
Example 1
A preparation method of modified aspartate resin containing imino comprises the following steps:
a 1L four-necked glass flask was taken, 210g (1 mol) of 4,4' -diaminodicyclohexylmethane was added thereto, 309.6g (1.8 mol) of diethyl maleate was added dropwise thereto, and the temperature was raised to 60℃for reaction for 24 hours to obtain a reaction solution;
then 30g (0.3 mol) of methyl isobutyl ketone is weighed and added into the reaction solution, the temperature is raised to 120 ℃ for reaction for 6 hours, after the reaction is finished, the temperature is reduced to 100 ℃ for reduced pressure distillation, and the excessive methyl isobutyl ketone is extracted, thus obtaining the modified aspartic acid ester resin 1 containing imino groups.
Example 2
A preparation method of modified aspartate resin containing imino comprises the following steps:
a 1L four-necked glass flask was taken, 210g (1 mol) of 4,4' -diaminodicyclohexylmethane was added thereto, 240.8g (1.4 mol) of diethyl maleate was added dropwise thereto, and the temperature was raised to 60℃for reaction for 12 hours to obtain a reaction solution;
70g (0.7 mol) of methyl isobutyl ketone is weighed and added into the reaction solution, the temperature is raised to 120 ℃ for reaction for 12 hours, after the reaction is finished, the temperature is reduced to 100 ℃ for reduced pressure distillation, and the excessive methyl isobutyl ketone is extracted, so that the modified aspartic acid ester resin 2 containing the imino groups is obtained.
Example 3
A preparation method of modified aspartate resin containing imino comprises the following steps:
a 1L four-necked glass flask was taken, 210g (1 mol) of 4,4' -diaminodicyclohexylmethane was added thereto, 172g (1.0 mol) of diethyl maleate was added dropwise thereto, and the mixture was heated to 60℃to react for 24 hours to obtain a reaction solution;
then 110g (1.1 mol) of methyl isobutyl ketone is weighed and added into the reaction solution, the temperature is raised to 120 ℃ for reaction for 2 hours, after the reaction is finished, the temperature is reduced to 100 ℃ for reduced pressure distillation, and the excessive methyl isobutyl ketone is extracted, thus obtaining the modified aspartic acid ester resin 3 containing imino groups.
Example 4
A preparation method of modified aspartate resin containing imino comprises the following steps:
a 1L four-necked glass flask was taken, 210g (1 mol) of 4,4' -diaminodicyclohexylmethane was added thereto, 240.8g (1.4 mol) of diethyl maleate was added dropwise thereto, and the temperature was raised to 60℃for 24 hours to obtain a reaction solution;
then 148.4g (0.7 mol) of benzaldehyde is weighed and added into the reaction solution, the temperature is raised to 130 ℃ for reaction for 6 hours, after the reaction is finished, the temperature is reduced to 100 ℃ for reduced pressure distillation, and the excessive benzaldehyde is extracted, thus obtaining the modified aspartic acid ester resin 4 containing imino groups.
Example 5
A preparation method of modified aspartate resin containing imino comprises the following steps:
a 1L four-necked glass flask was taken, 238g (1 mol) of 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane was added thereto, 240.8g (1.4 mol) of diethyl maleate was added dropwise thereto, and the temperature was raised to 60℃for 24 hours to obtain a reaction solution;
70g (0.7 mol) of methyl isobutyl ketone is weighed and added into the reaction solution, the temperature is raised to 130 ℃ for reaction for 6 hours, after the reaction is finished, the temperature is reduced to 100 ℃ and reduced pressure distillation is carried out, and the excessive methyl isobutyl ketone is extracted, thus obtaining the modified aspartic acid ester resin 5 containing imino groups.
In other embodiments, the aliphatic amine may be selected from one of 2-methylpentanediamine, isophorone diamine, methylcyclohexane diamine, polyetheramine D230; the ketone or aldehyde compound may also be selected from one or more of butanone, methyl isopropyl ketone, formaldehyde and phenylacetaldehyde.
Application example
The modified aspartate resin containing the imino group prepared in the embodiment is applied to the components of the coating to obtain the polyaspartic acid ester coating.
Application example 1
A method for preparing a coating comprising an imino-modified aspartic acid ester resin comprising the steps of: and (3) preparation of the component A: according to parts by weight, adding 30 parts of modified aspartic acid ester resin containing imino groups 1, 1 part of dispersant BYK163, 0.4 part of anti-settling agent H15 gas silicon, 13 parts of R606 titanium white powder, 27 parts of barium sulfate, 15 parts of zinc phosphate and 3 parts of 3A molecular sieve into a reaction kettle, dispersing at a high speed for 15-30 minutes at a rotating speed of 3000 rpm, then adding 0.2 part of BYK1790 defoamer, 0.1 part of EFKA3600 flatting agent, 0.1 part of BYK410 rheological agent, 1.5 parts of KH560 silane coupling agent and 8.7 parts of solvent, and stirring for 10 minutes at the rotating speed of 1000 rpm to obtain a component A;
the A component and the B component HDI trimer are sprayed on a board according to the mol ratio of secondary amine groups to isocyanic acid groups of 1:1.05, and the wet film thickness is 100um.
Application examples 2 to 5
The difference from application example 1 is that the imino-group containing modified aspartic acid ester resins employed in application examples 2 to 5 are respectively an imino-group containing modified aspartic acid ester resin 2, an imino-group containing modified aspartic acid ester resin 3, an imino-group containing modified aspartic acid ester resin 4 and an imino-group containing modified aspartic acid ester resin 5.
Comparative examples of application
Comparative examples 1 to 2 were used
The difference from application example 1 is that the aspartic acid ester resins used in application comparative examples 1-2 are F420 and F520, respectively.
Comparative example 3 was used
The difference from comparative example 1 was that ketimine was also used in comparative example 3.
Comparative example 4 was used
The difference from comparative example 2 was that ketimine was also used in comparative example 4.
Table 1: composition ratio Table of the coatings in application examples 1 to 5 and application comparative examples 1 to 4
Performance test
1. The aspartic acid ester resin coatings of application examples 1 to 5 and comparative application examples 1 to 4 were sprayed on a board at room temperature under a relative humidity of 60%, the wet film thickness was 100 μm, and the paint film properties were tested, and the test results are shown in Table 2.
Pot life: pot life time of the coating was measured according to GB/T31416-2015;
real drying time: the dry time of the coating was measured according to GB/T1728-1989;
adhesion force: the adhesion of the coating film of the coating after curing was measured according to GB/T9286-1998;
pencil hardness: the hardness of the coating film of the coating after curing is measured according to GB/T2739-2006;
salt spray resistance: salt spray resistance of the cured coating film was measured according to GB/T1771-2007.
TABLE 2 test data for application examples 1-5 and for the coatings prepared in comparative examples 1-4
As can be seen from the combination of application examples 1-5 and application comparative examples 1-2 and the combination of Table 2, the modified aspartate resin containing imino groups prepared by the application is applied to a coating, has more excellent adhesive force and salt spray resistance than the traditional aspartate coating without imino groups, and can maintain better hardness.
As can be seen from the combination of application examples 1 to 5 and application comparative examples 3 to 4 and table 2, application comparative examples 3 to 4 directly adopt a mode of adding small molecular ketimine, and have large change in thermal storage viscosity and poor storage stability of resin; and, since ketimine was added to comparative examples 3 to 4, it had better hardness and salt spray resistance than comparative examples 1 to 2.
As can be seen from the combination of application examples 1 to 5 and comparative examples application examples 1 to 2 and Table 2, when the proportion of the imine in the imine-group-containing modified aspartic acid ester resin is higher, the corresponding ester group content is lower, and the hot-water boiling time at 100℃is longer; although ketimine was added to comparative examples 3 to 4, it had good resistance to boiling time at 100℃but had poor storage stability and low hardness.
2. The aspartic acid ester resin coatings of application examples 1 to 5 and comparative application examples 1 to 2 were sprayed on a board at room temperature under a relative humidity of 30%, the wet film thickness was 100 μm, and the paint film properties were tested, and the test results are shown in Table 3.
TABLE 3 data for the test under low humidity conditions of the coatings prepared in application examples 1 to 5 and application comparative examples 1 to 4
In combination with application examples 1-5 and application comparative examples 3-4 and Table 3, it is known that in an environment with low humidity, application comparative examples 3-4 can not be deblocked into primary amine to participate in film formation under the low humidity condition by adding small molecular ketimine, so that the paint film performance is low; in application examples 1-5, the ketimine structure is introduced into the polyaspartic acid ester, and the prepared imine modified polyaspartic acid ester still contains an-NH group and can still participate in film formation with an HDI trimer under the condition of low humidity, so that the polyimide resin can be cured under the condition of low humidity, and the influence on hardness is smaller than that of adding micromolecular ketimine.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (9)

1. The imino-containing modified aspartic acid ester resin is characterized in that the imino-containing modified aspartic acid ester resin is synthesized by reacting fatty amine with maleate or fumarate and ketone or aldehyde compounds, and the structural formula of the imino-containing modified aspartic acid ester resin is as follows:
wherein R1 is an alkyl group of 1 to 8 carbon atoms, R2 is a divalent hydrocarbon group, R3 and R4 are independently represented as monovalent aliphatic, cycloaliphatic or araliphatic residues, and R4 and R5 do not have tertiary amine nitrogen.
2. The modified aspartic acid ester resin containing an imino group according to claim 1, wherein: r3 and R4 are each a heteroatom having from 1 to 20 carbon atoms and containing no hydroxyl groups and optionally in the form of ether oxygen or tertiary amine nitrogen.
3. The modified aspartic acid ester resin containing an imino group according to claim 1, wherein: r3 and R4 each have a divalent aliphatic residue of 3 to 20 carbon atoms and each have a portion of a heterocyclic ring of 5 to 8 ring atoms, wherein the ring is free of hydroxyl groups and optionally contains additional heteroatoms in the form of ether oxygen or tertiary amine nitrogen in addition to the nitrogen atom.
4. A method for producing the modified aspartic acid ester resin containing an imino group according to any one of claims 1 to 3, characterized by comprising the steps of: firstly, maleic acid ester or fumaric acid ester is added into aliphatic amine in a dropwise manner, and the reaction is carried out for 12-48 hours at the temperature of 60-70 ℃ to obtain a reaction liquid; then adding ketone or aldehyde compounds into the reaction liquid, controlling the temperature to be 80-150 ℃ for reaction for 2-12 hours, and obtaining the modified aspartic acid ester resin containing imino after the reaction is completed.
5. The method for producing an imino-group containing modified aspartic acid ester resin as defined in claim 4, wherein: the ratio of the amount of the substances of the fatty amine to the substances of the maleate or fumarate and the ketone or aldehyde compounds is 1: (0.1-1.9): (0.1-1.9).
6. The method for producing an imino-group containing modified aspartic acid ester resin as defined in claim 4, wherein: the aliphatic amine is one of 4,4 '-diamino dicyclohexylmethane, 3' -dimethyl-4, 4-diamino dicyclohexylmethane, 2-methyl pentamethylene diamine, isophorone diamine, methyl cyclohexane diamine and polyether amine D230.
7. The method for producing an imino-group containing modified aspartic acid ester resin as defined in claim 4, wherein: the ketone or aldehyde compound is one or a plurality of compositions of butanone, methyl isopropyl ketone, methyl isobutyl ketone, formaldehyde, benzaldehyde and phenylacetaldehyde.
8. Use of the modified aspartate resin with imino groups according to any of the claims 1-3 in a coating, characterized in that the coating comprises a component a and a component B;
the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
30-100 parts of HDI trimer;
the aspartic acid ester resin is the modified aspartic acid ester resin containing imino groups in the claims 1-3.
9. A method of preparing the coating of claim 8, comprising the steps of:
and (3) preparation of the component A: firstly, adding an imino group-containing modified aspartic acid ester resin, a dispersing agent, an anti-settling agent, barium sulfate, zinc phosphate, titanium dioxide and a 3A molecular sieve into a reaction kettle, dispersing at a high speed for 15-30 minutes under the condition of a rotating speed of 3000 rpm, then adding a defoaming agent, a leveling agent and a solvent, and stirring for 10 minutes under the condition of a rotating speed of 1000 rpm to obtain a component A;
the A component and the B component are mixed according to the mol ratio of secondary amino groups to isocyanic acid groups of 1:1.05.
CN202310579042.4A 2023-05-22 2023-05-22 Modified aspartic acid ester resin containing imino, preparation method and application thereof Pending CN116606218A (en)

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