CN114591492B - Water-based epoxy curing agent and preparation method and application thereof - Google Patents
Water-based epoxy curing agent and preparation method and application thereof Download PDFInfo
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
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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
- C08G59/5006—Amines aliphatic
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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
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Abstract
The invention discloses a water-based epoxy curing agent, a preparation method and application thereof. The aqueous epoxy curing agent is prepared by reacting the following raw materials in parts by mole: a) 1 part of a polyepoxide, b) 1.0 to 8 parts of a polyamine compound which can be blended with water in any ratio, c) 0 to 8 parts of a polyfunctional compound, d) 0.2 to 1.25 parts of a monoepoxide, e) 0.2 to 1.5 parts of an amine group-containing maleimide, preferably 0.5 to 1 part; wherein the polyfunctional compound has 4 or more active hydrogens. The curing agent obtained by the invention not only has good hydrophilic effect and good thinning property, so that a paint film prepared by mixing the curing agent with an epoxy dispersion has the advantages of excellent corrosion resistance, strong adhesive force, high hardness and the like; in addition, the waterborne epoxy curing agent introduces a furan structure and a maleimide structure, and utilizes the characteristic that the furan structure and the maleimide structure can carry out DA thermal reversible reaction, so that the waterborne epoxy coating has self-repairing capability after being mixed and cured with an epoxy dispersion, and the curing agent has simple preparation process and mild condition and can be cured at room temperature.
Description
Technical Field
The invention belongs to the technical field of waterborne epoxy coatings, and particularly relates to a waterborne epoxy curing agent applicable to a self-repairing coating, and a preparation method and application thereof.
Background
Conventional epoxy resin paint is generally solvent-based and contains a large amount of VOCs, which pollute the environment, so the development of paint to high solid and water-based paint has become a common knowledge in the paint industry. Among them, the water-based epoxy paint has a great number of advantages, such as low VOC content, small smell, safe use, capability of being cleaned by water, increasingly mature process technology, meeting the requirements of environmental protection and energy saving, etc., and rapidly becomes an important development direction of modern paint.
The aqueous epoxy coating alone cannot build sufficient strength by itself, requiring the introduction of an epoxy curing agent. Currently, there are many applications for waterborne two-component epoxy coatings on the market, such as high performance container primers, engineering and rail traffic primers and intermediate paints, architectural coatings, equipment primers, industrial plant floor paints, transportation vehicle primers, automotive repair primers, and industrial repair primers, among others. However, the water-based epoxy paint is influenced by external environment, and microstructure changes can occur in the use process of the water-based epoxy paint, microcracks with different sizes are generated, and the use of the coating is influenced, so that a researcher proposes a self-repairing technology.
The self-repairing mechanism is mainly divided into two major types of external-assistance type and intrinsic type, the external-assistance type self-repairing material is mainly realized by coating the microcapsule, however, the self-repairing property of the self-repairing material cannot be reused, the preparation process is complex, the cost is high, and the compatibility of the microcapsule and the matrix material can influence the self-repairing effect. The intrinsic self-repairing material comprises a light response type and a thermal response type, wherein the light response self-repairing material has long repairing time in a coating system, and is unfavorable for immediate repairing. Patent CN110373087a discloses a photo-responsive self-repairing coating, which uses two-dimensional material MXene as photo-thermal filler and MXene to improve photo-thermal efficiency, but the preparation process is relatively complex. And the thermal response self-repairing material is one of the important research directions at present.
Disclosure of Invention
The invention aims to provide a waterborne epoxy curing agent, a preparation method and application thereof, wherein the waterborne epoxy curing agent has good hydrophilic effect and good thinning property, and a paint film prepared by mixing the waterborne epoxy curing agent with an epoxy dispersion has excellent anti-corrosion performance, high adhesion and high hardness; the self-repairing capability of the existing water-based epoxy coating is realized by introducing the furan ring and the maleimide structure containing the amine group, the maleimide containing the amine group has the self-repairing performance and the curing crosslinking effect, but not a single self-repairing auxiliary agent, the synergistic effect of the two can exert better self-repairing effect, and the curing agent has the advantages of simple preparation process, mild condition and room temperature curing.
In order to achieve the above object, the technical scheme of the present invention is as follows:
in one aspect of the invention, a waterborne epoxy curing agent is provided, which is prepared by the reaction of the following raw materials in parts by mole:
a) 1 part of a polyepoxide compound;
b) 1.0 to 8 parts of a first polyamine compound, preferably 2 to 6 parts;
c) 0 to 8 parts of a polyfunctional compound, preferably 0 to 6 parts;
d) 0.2 to 1.25 parts of monoepoxide, preferably 0.4 to 0.9 parts;
e) 0.2 to 1.5 parts, preferably 0.5 to 1 part, of maleimide containing an amine group;
wherein the polyfunctional compound has 4 or more active hydrogens, and the maleimide having an amine group has 1 or more active hydrogens.
In the invention, the amount of each reaction raw material of the aqueous epoxy curing agent is based on 1 molar part of the amount of the polyepoxide compound.
In the present invention, the polyepoxide compound is a compound having a furan ring structure and having 2 or more epoxy groups. Preferably, the polyepoxide compound is one or more of a glycidyl ether, a glycidyl ester or a glycidyl amine with a furan ring structure. In some examples, the polyepoxide compound is a glycidyl ether with a furan ring structure selected from 2, 5-furandimethanol diglycidyl ether having the following structural formula (i) or/and a 5,5' -alkyl difurfuryl alcohol diglycidyl ether having the following structural formula (ii):
wherein R in formula (II) 1 ,R 2 Each independently selected from hydrogen or methyl;
in some examples, the polyepoxide is a glycidyl ester with a furan ring structure selected from diglycidyl esters of 2, 5-furandicarboxylic acid having the following structural formula (iii):
the polyepoxide may also be a glycidyl amine with a furan ring structure selected from 2, 5-furandimethylamine glycidyl amine of the following formula (iv) and/or 5,5' -alkyl difurfuryl amine glycidyl amine of the following formula (v):
wherein R in formula (V) 3 ,R 4 Each independently selected from hydrogen or methyl;
in some embodiments, the polyepoxide compound may be selected from one or more of 2, 5-furandimethanol diglycidyl ether of formula (i), 5 '-alkyl difurfuryl alcohol diglycidyl ether of formula (ii), diglycidyl 2, 5-furandicarboxylate of formula (iii), 2, 5-furandimethylamine glycidyl amine of formula (iv), and 5,5' -alkyl difurfuryl amine glycidyl amine of formula (v).
In the present invention, the component b) the first polyamine compound is a polyamine compound which is miscible with water in any proportion. In some examples, the component b) the first polyamine compound is selected from one or more of diethylenetriamine, polyetheramine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine. In some preferred embodiments, the first polyamine compound is selected from one or more of diethylenetriamine, polyetheramine, and triethylenetetramine, wherein the polyetheramine is a diamido polyetheramine having a molar mass of 200-1000 g/mol.
In the present invention, the active hydrogen-containing functional group may be a hydroxyl group (phenolic hydroxyl group or alcoholic hydroxyl group), an amino group (-NH) 2 or-NH-), carboxyl groups, and the like.
Preferably, the polyfunctional compound is a compound having two or more amino groups.
According to the aqueous epoxy curing agent provided by the invention, the polyfunctional compound of the component b) can be selected from primary amines having 4 or more active hydrogens. In some examples, the polyfunctional compound is selected from one or more of aliphatic polyamines (e.g., aliphatic diamines, aliphatic triamines), cycloaliphatic polyamines (e.g., cycloaliphatic diamines, cycloaliphatic triamines), and aromatic polyamines (e.g., aromatic diamines, aromatic triamines) having a molar mass of no more than 1000g/mol. Preferably one or more selected from ethylenediamine, propylenediamine, butylenediamine, 2-methyl-1, 5-pentylene diamine, 1, 6-hexamethylenediamine, m-xylylenediamine, 1, 3-diaminomethylcyclohexane, 1-ethyl-1, 3-propylenediamine, p-aminodicyclohexylmethane, 2, 4-trimethyl-1, 6-hexamethylenediamine, p-xylylenediamine, isophoronediamine, 1, 3-cyclohexanedimethylamine and diethyltoluenediamine. In some preferred embodiments, the polyfunctional compound is selected from one or more of m-xylylenediamine, p-xylylenediamine, isophoronediamine, and 1, 3-cyclohexanedimethanamine.
In the present invention, the monoepoxide compound may be an aliphatic compound, a cycloaliphatic compound or an aromatic compound which is linked to an epoxy functional group. Moisture in the air is easy to react with primary amine to cause the coating to turn white, so that the primary amine on the mono-epoxy compound and the polyamine compound is utilized to react to obtain secondary amine, and the phenomenon of the coating turning white can be relieved. And meanwhile, the secondary amine obtained by the reaction can react with epoxy resin under mild conditions (without a catalyst at room temperature) to quickly establish a crosslinked structure. In some examples, the monoepoxide is selected from one or more of an epoxy ether of a phenol, an epoxy ester of an unsaturated alcohol, an epoxy ester of an unsaturated carboxylic acid, an aliphatic glycidyl ether, and an aromatic glycidyl ether, preferably selected from one or more of an epoxy ether of a phenol, an aliphatic glycidyl ether of Cl-C18, and an aromatic glycidyl ether of C10-C18. The epoxy ether of phenols is selected from the group consisting of epoxy ether of phenol, epoxy ether of cresol, epoxy ether of C1-C21 alkyl substituted phenol, epoxy ether of C7-C21 aralkyl substituted phenol, epoxy ether of C7-C21 alkylaryl substituted phenol, cardanol glycidyl ether or epoxy ether of alkoxy substituted phenol. The epoxy ester of unsaturated carboxylic acid is selected from glycidyl monocarboxylic acid (glycidyl octanoate, glycidyl decanoate, glycidyl laurate, glycidyl stearate, glycidyl eicosanoate), glycidyl neodecanoate, epoxidized methyl oleate, epoxidized n-butyl oleate, epoxidized methyl palmitoleate, and epoxidized ethyl linoleate. The aromatic glycidyl ether of C10-C18 is selected from phenyl glycidyl ether, o-tolyl glycidyl ether and benzyl glycidyl ether. The aliphatic glycidyl ether of Cl-C18 is selected from butyl glycidyl ether, C12-C14 alkyl glycidyl ether, tertiary butyl glycidyl ether, cyclohexyl glycidyl ether, allyl glycidyl ether, octyl glycidyl ether, isopropyl glycidyl ether, decyl glycidyl ether and p-tertiary butyl phenyl glycidyl ether.
In some examples, the monoepoxide is selected from one or more of cardanol glycidyl ether, butyl glycidyl ether, C12-C14 alkyl glycidyl ether, tolyl glycidyl ether, phenyl glycidyl ether, nonylphenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether. In some preferred embodiments, the monoepoxide compound is selected from one or more of butyl glycidyl ether, C12-C14 alkyl glycidyl ether, tolyl glycidyl ether, phenyl glycidyl ether, nonylphenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether.
In some examples, the reaction raw materials of the aqueous epoxy hardener further include: e) 0.1 to 0.6 parts by weight of water, preferably 0.2 to 0.4 parts by weight; f) 0 to 0.05 parts by weight (e.g., 0.005 parts, 0.009 parts, 0.01 parts, 0.015 parts, 0.02 parts, 0.03 parts) of unmodified polyetheramine, preferably 0 to 0.03 parts by weight. The parts of the reaction raw materials are based on the total mass of the aqueous epoxy curing agent.
In some examples, the unmodified polyetheramine is a polyetheramine having a molar mass of 200 to 5000g/mol, preferably having a functionality of 2 or 3. For example, the unmodified polyetheramine is polyetheramine D230, polyetheramine D400, polyetheramine T403, polyetheramine T5000. After polyether amine is added into the system, the curing agent can be adjusted to cure to obtain the shrinkage cavity phenomenon on the paint film.
The maleimide containing the amino group is prepared by reacting a second polyamine compound with maleic anhydride. In one embodiment, the reaction conditions of the maleic anhydride and the second polyamine compound are: the reaction is carried out at 100-140℃such as 100℃110℃120℃or 130℃preferably 120-140℃for 1-10 hours, preferably 3-8 hours.
In the present invention, the molar ratio of maleic anhydride to the second polyamine compound is 0.5 to 1.5, preferably 0.9 to 1.1. The second polyamine compound is a polyamine compound which can be mutually soluble with water in any proportion, and the second polyamine compound can be the same as or different from the first polyamine compound of the component b), is selected from one or more of diethylenetriamine, polyetheramine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine, and is preferably selected from one or more of diethylenetriamine, polyetheramine and triethylenetetramine, wherein the polyetheramine is diamine polyetheramine with the molar mass of 200-1000 g/mol.
In another aspect of the present invention, there is provided a method for preparing the aqueous epoxy hardener as described above, comprising the steps of: and (3) carrying out ring opening reaction on the polyepoxide compound, the first polyamine compound and the polyfunctional group compound to obtain an intermediate product i, and carrying out end capping reaction on the intermediate product i and the monoepoxide compound to obtain the waterborne epoxy curing agent applicable to the self-repairing coating.
According to the production method provided by the present invention, in some examples, the polyepoxide compound is added dropwise to the first polyamine compound and the polyfunctional compound in a ring-opening reaction for a reaction time of 0.5 to 4 hours (e.g., 1 hour, 2 hours, 3 hours), preferably 1 to 2.5 hours; the reaction temperature of the ring-opening reaction is 60 to 100 ℃ (e.g., 70 ℃, 75 ℃, 85 ℃, 90 ℃, preferably 80 to 100 ℃).
In some examples, water may also be added to the aqueous epoxy curing agent, and water may be added to the system prior to the addition of the mono-epoxy compound, primarily to reduce the viscosity of the system and adjust the solids content. The reaction time after the addition of the monoepoxy compound is 0.5 to 2 hours (e.g., 0.6 hours, 1.2 hours, 1.8 hours), preferably 1 to 2 hours, and the reaction temperature of the end-capping reaction is 60 to 100 ℃ (e.g., 70 ℃, 75 ℃, 85 ℃, 90 ℃), preferably 80 to 100 ℃.
In order to control the reaction speed and avoid excessively fast reaction heat release, the polyepoxide and the monoepoxy compound are required to be slowly added in the preparation method, and preferably the polyepoxide and the monoepoxy compound are added in a dropwise manner. In addition, the order of addition of water (e.g., deionized water) to disperse the viscosity reducing and monoepoxide to the reaction system can severely affect the performance (e.g., salt spray resistance) of the curing agent.
In some preferred embodiments of the present invention, the preparation method further comprises adding maleimide containing amine groups for reaction after the end capping reaction, wherein the reaction temperature is 60-100 ℃, the reaction time is 1-3 hours, DA thermal reversible reaction can be carried out by adding maleimide containing amine groups and epoxy compound containing furan, self-repairability is realized, and unmodified polyether amine can be added after the end capping reaction is finished to adjust the performance of the curing agent.
In some examples, the method of preparing further comprises: after the ring-opening reaction is finished, the reaction system is subjected to reduced pressure distillation to remove redundant first polyamine compounds and multifunctional group compounds in the reaction system.
In some embodiments, the method of preparation is: the preparation method comprises the steps of adding a first polyamine compound into a reaction bottle in advance, adding a polyepoxide compound into the reaction bottle in a dropwise manner, controlling the dropwise addition time to be 0.5-4h, preferably 1-2.5h, the reaction temperature to be 60-100 ℃, obtaining an intermediate product i after the dropwise addition, removing a system through reduced pressure distillation, further adding deionized water to disperse and reduce viscosity, adding a monoepoxide compound in a dropwise manner, controlling the dropwise addition time to be 0.5-2h, preferably 1-2h, the reaction temperature to be 60-100 ℃, then adding maleimide containing amino groups, so as to introduce a structure capable of carrying out DA thermal reversible reaction, realizing self-repairability, and finally but not necessarily adding unmodified polyether amine to adjust the performance of a curing agent.
According to the preparation method provided by the invention, other non-ideal structures can be generated in the obtained aqueous epoxy curing agent, but the preparation process does not involve separation of byproducts, and the aqueous epoxy curing agent is used as a whole, all evaluation effects are also based on the whole, and finally, the performance indexes of the obtained aqueous epoxy curing agent system applicable to self-repairing coatings comprise: amine number test, solids content, and pH.
In a further aspect of the invention there is provided the use of an aqueous epoxy hardener as described above or as obtained by a method of preparation as described above in the formulation of a coating, cured epoxy resin system.
The application of the epoxy resin curing agent disclosed by the invention is that an epoxy resin system comprises the epoxy resin curing agent disclosed by the invention, and the epoxy resin system can also contain an organic solvent or water. Any of the epoxy resins mentioned above in the preparation of the aqueous epoxy curing agent of the present invention can be cured by the aqueous epoxy curing agent. The epoxy resin curing agent can be applied to self-repairing coatings, can be used for coating room temperature coatings and baking coatings, and has a curing temperature which can be selected according to the change of a coating mode and is generally in the range of 5-200 ℃.
In addition, the aqueous epoxy curing agent applicable to self-healing coating obtained by the present invention may be dispersed or dissolved in water, and the composition may be obtained by mixing water into the aqueous epoxy curing agent applicable to self-healing coating in the presence or absence of a surfactant.
The aqueous epoxy curing agent obtained by the invention can be used for effectively curing an aqueous epoxy resin system. Preferred examples of aqueous epoxy resins are aqueous bisphenol A type epoxy resins having a molecular weight of 350 to 5000, dispersed in nonionic form or nonionic and ionic complex form with or without glycol ether co-solvents. Commercial products of aqueous epoxy resins include, for example, epicz resins 3520, 3522, 3540 available from shell chemicals. These curable systems contain water, one or more epoxy resins, and one or more aqueous epoxy curing agents of the present invention that are useful in self-healing coatings. These aqueous curable epoxy resin systems can be cured at room temperature or elevated temperature conditions or further catalyzed with commercial tertiary amine accelerators such as 2,4, 6-tris (dimethylaminomethyl phenol) (DMP-30) or phenols for curing at lower curing temperatures. These lower curing temperatures are typically in the range of 5-20 ℃. The aqueous epoxy curing agents obtained in accordance with the present invention are also typically used to formulate thermosetting coatings having good corrosion protection of the coated substrate.
The aqueous epoxy curing agent can be applied to curing in the fields of epoxy paint, adhesives and the like, and can also be used as a component of adhesives and fiber sizing agents.
The auxiliaries may be, but are not required to be, added to the system in which the curing agent of the invention is prepared, or may be, but are not required to be, added to the curing system in which the curing agent is used; the adjuvants include, but are not limited to, defoamers, dispersants, thickeners, leveling agents, adhesion promoters, and the like.
A coating comprising the curing agent of the present invention.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention introduces maleimide group and furan group into the curing agent at the same time, can carry out reversible Diels-Alder (DA) reaction, introduces the structure into the main chain, the branched chain and the side chain of the polymer, and prepares the self-repairing material with linear, star-shaped and trapezoid network structure, which is used for preparing the thermally responsive self-repairing polymer material.
The aqueous epoxy curing agent has good hydrophilic effect and good thinning property, so that the paint film prepared by applying the curing agent to an epoxy dispersion has excellent anti-corrosion performance, and the curing agent can be cured at room temperature in the use process. Meanwhile, the preparation process of the waterborne epoxy curing agent applicable to the self-repairing coating is simple, the condition is mild, the VOC content of a paint film is greatly reduced in the use process, and the requirements of green and environment protection and sustainable development are met. According to the invention, the furan ring and maleimide structure are introduced into the waterborne epoxy curing agent, and the structure capable of carrying out DA thermal reversible reaction is introduced, so that the waterborne epoxy coating has good self-repairing capability, and meanwhile, the maleimide structure contains amino groups, so that curing crosslinking and self-repairing characteristics are considered, and a better self-repairing effect can be exerted by the cooperation of the two structures.
Detailed Description
So that the technical features and content of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
The sources of materials used in the following examples/comparative examples are as follows:
synthesis of glycidyl furandicarboxylate: 312g of furandicarboxylic acid and 388g of epichlorohydrin are added, 2.5g of tetrabutylammonium bromide is added for reaction for 3 hours at 80 ℃, and 160g of solid sodium hydroxide is added for reaction for 3 hours at 50 ℃ to stop the reaction. Filtering the mixed liquid, removing generated salt and redundant sodium hydroxide, performing extraction water washing treatment, adding quantitative dichloromethane into the filtrate, mixing uniformly, pouring into a separating funnel, performing water washing with deionized water for multiple times until the pH value of the water phase reaches neutrality, and separating out an organic phase. Then adding a certain amount of anhydrous sodium sulfate for drying, filtering to obtain a liquid phase, and removing epichlorohydrin and methylene dichloride by using a rotary evaporator to obtain a yellow liquid.
5,5' -alkyl difurfuryl amine glycidol amine: 412g of furandicarboxylic acid and 776g of epichlorohydrin are added, 5g of tetrabutylammonium bromide is added for reaction for 3 hours at 80 ℃, and 320g of solid sodium hydroxide is added for reaction for 3 hours at 50 ℃ to stop the reaction. Filtering the mixed liquid, removing generated salt and redundant sodium hydroxide, performing extraction water washing treatment, adding quantitative dichloromethane into the filtrate, mixing uniformly, pouring into a separating funnel, performing water washing with deionized water for multiple times until the pH value of the water phase reaches neutrality, and separating out an organic phase. Then adding a certain amount of anhydrous sodium sulfate for drying, filtering to obtain a liquid phase, and removing epichlorohydrin and methylene dichloride by using a rotary evaporator to obtain a yellow liquid.
Test method
Pencil hardness reference GB/T6739 pencil test method for paint film hardness;
adhesion is referred to GB/T9286 cross-hatch test of paint films of color paint and varnish;
water resistance reference GB/T1733 "paint film Water resistance assay";
salt spray resistance refers to GB/T1765 for preparation of paint film for measuring resistance to damp and heat, salt spray and weather (artificially accelerated).
Self-repair rate test: after the coating is solidified, the sharp object is used for cross damage to the surface of the coating, the coating is put into a 100-DEG oven for 2 hours to self-repair, and the change of the coating before and after repair is observed through an optical microscope.
Amine number test of curing agent: the method comprises the steps of firstly dissolving a sample to be tested in methanol by a titration method, then adding di-n-butylamine-chlorobenzene solution into the solution, carrying out potential titration by using hydrochloric acid standard solution until mutation occurs, carrying out blank titration by using the same method, and finally calculating the obtained result according to the equivalent KOH mass of the sample, wherein the unit is mg KOH/g.
Example 1:
51.5g of diethylenetriamine and 49g of maleic anhydride are added into a reaction bottle, and the mixture is reacted for 5 hours at 140 ℃ to obtain maleimide containing amino groups.
206g of diethylenetriamine is added into a reaction bottle, and the temperature is preheated to 100 ℃; gradually dripping 240g of furan dimethanol glycidyl ether into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, carrying out reduced pressure distillation on the materials in the reaction bottle by utilizing a vacuum pump, adding 210g of deionized water into the reaction system for dispersion after removing redundant diethylenetriamine, gradually dripping 90g of phenyl glycidyl ether into the reaction bottle by utilizing a peristaltic pump for reaction at 60 ℃, keeping the dripping time for 1 hour, preserving heat for half an hour, adding 15g of polyether amine D400 and the maleimide containing amino, and stirring uniformly to obtain the curing agent. The resulting curing agent had a solids content of 75.6% by weight, an amine number of 458mg KOH/g and a pH of 9.7.
Example 2:
103g of diethylenetriamine and 49g of maleic anhydride are added into a reaction bottle and reacted for 5 hours at 100 ℃ to obtain maleimide containing amino.
412g of diethylenetriamine are added into a reaction bottle, and the temperature is preheated to 80 ℃; gradually dripping 240g of furan dimethanol glycidyl ether into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, carrying out reduced pressure distillation on the materials in the reaction bottle by utilizing a vacuum pump, removing redundant diethylenetriamine in a reaction system, adding 210g of deionized water into the system for dispersion, gradually dripping 60g of phenyl glycidyl ether into the reaction bottle at 100 ℃ by utilizing a peristaltic pump for reaction, keeping the dripping time for 1 hour, preserving heat for half an hour, adding 15g of polyether amine D400 and the maleimide containing amino, and stirring uniformly to obtain the curing agent. The resulting curing agent had a solids content of 76.2 wt.%, an amine number of 545mg KOH/g and a pH of 10.1.
Example 3:
34.3g of diethylenetriamine and 49g of maleic anhydride are added into a reaction bottle and reacted for 5 hours at 120 ℃ to obtain maleimide containing amino.
618g of diethylenetriamine is added into a reaction bottle, and the temperature is preheated to 60 ℃; gradually dripping 240g of furan dimethanol glycidyl ether into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, carrying out reduced pressure distillation on the materials in the reaction bottle by utilizing a vacuum pump, removing redundant diethylenetriamine in a reaction system, adding 210g of deionized water into the system for dispersion, gradually dripping 135g of phenyl glycidyl ether into the reaction bottle by utilizing a peristaltic pump for reaction at 80 ℃, keeping the dripping time for 1 hour, preserving heat for half an hour, adding 15g of polyether amine D400 and the maleimide containing amino, and stirring uniformly to obtain the curing agent. The resulting curing agent had a solids content of 76.4% by weight, an amine number of 415mg KOH/g and a pH of 9.0.
Example 4:
51.5g of diethylenetriamine and 49g of maleic anhydride are added into a reaction bottle, and the mixture is reacted for 5 hours at 140 ℃ to obtain maleimide containing amino groups.
206g of diethylenetriamine is added into a reaction bottle, and the temperature is preheated to 100 ℃; gradually dripping 240g of furan dimethanol glycidyl ether into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, carrying out reduced pressure distillation on the materials in the reaction bottle by utilizing a vacuum pump, removing redundant diethylenetriamine in a reaction system, adding 210g of deionized water into the system for dispersion, gradually dripping 90g of phenyl glycidyl ether into the reaction bottle by utilizing a peristaltic pump for reaction at 60 ℃, keeping the dripping time for 1 hour, preserving heat for half an hour, adding the maleimide containing the amino, and stirring uniformly to obtain the curing agent. The resulting curing agent had a solids content of 75.2% by weight, an amine number of 464mg KOH/g and a pH of 9.9.
Example 5:
103g of diethylenetriamine and 49g of maleic anhydride are added into a reaction bottle and reacted for 5 hours at 100 ℃ to obtain maleimide containing amino.
412g of diethylenetriamine and 60g of ethylenediamine are added into a reaction flask, and the temperature is preheated to 80 ℃; gradually dripping 268g of glycidyl furandicarboxylate into a reaction bottle through a peristaltic pump to perform ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, carrying out reduced pressure distillation on the materials in the reaction bottle by utilizing a vacuum pump, removing redundant diethylenetriamine in a reaction system, adding 210g of deionized water into the system for dispersion, gradually dripping 60g of phenyl glycidyl ether into the reaction bottle by utilizing a peristaltic pump for reaction at 100 ℃, keeping the dripping time for 1 hour, preserving heat for half an hour, adding the maleimide containing the amino, and stirring uniformly to obtain the curing agent. The resulting curing agent had a solids content of 75.4 wt.%, an amine number of 493mg KOH/g and a pH of 10.0.
Example 6:
80g of polyether amine D230 and 49g of maleic anhydride are added into a reaction bottle, and the mixture is reacted for 5 hours at 120 ℃ to obtain maleimide containing amino.
920g of polyetheramine D230 was added to the reaction flask and the temperature was preheated to 60 ℃; gradually dripping 430g of 5,5' -alkyl difurfuryl amine glycidol amine into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, 410g of deionized water is added into the system for dispersion, then 135g of phenyl glycidyl ether is gradually dripped into a reaction bottle by a peristaltic pump for reaction at 80 ℃, the dripping time is 1 hour, the heat preservation is carried out for half an hour, and then the maleimide containing amino is added, and the curing agent is obtained after uniform stirring. The resulting curing agent had a solids content of 79.7% by weight, an amine number of 283mg KOH/g and a pH of 8.1.
Example 7:
51.5g of diethylenetriamine and 49g of maleic anhydride are added into a reaction bottle, and the mixture is reacted for 5 hours at 140 ℃ to obtain maleimide containing amino groups.
103g of diethylenetriamine and 170g of isophoronediamine are added into a reaction bottle, and the temperature is preheated to 100 ℃; gradually dripping 240g of furan dimethanol glycidyl ether into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, 210g of deionized water is added into the system for dispersion, then 90g of phenyl glycidyl ether is gradually dripped into a reaction bottle by a peristaltic pump for reaction at 60 ℃, the dripping time is 1 hour, the heat preservation is carried out for half an hour, then 15g of polyetheramine D400 and the maleimide containing amine groups are added, and the curing agent is obtained after uniform stirring. The resulting curing agent had a solids content of 77.4% by weight, an amine number of 365mg KOH/g and a pH of 8.7.
Comparative example 1:
103g of diethylenetriamine and 49g of maleic anhydride are added into a reaction bottle and reacted for 5 hours at 100 ℃ to obtain maleimide containing amino.
412g of diethylenetriamine are added into a reaction bottle, and the temperature is preheated to 80 ℃; gradually dripping 3992 g of E51 into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and keeping the temperature for half an hour; after the ring-opening reaction is finished, carrying out reduced pressure distillation on the materials in the reaction bottle by utilizing a vacuum pump, removing redundant diethylenetriamine in a reaction system, adding 210g of deionized water into the system for dispersion, gradually dripping 60g of phenyl glycidyl ether into the reaction bottle at 100 ℃ by utilizing a peristaltic pump for reaction, keeping the dripping time for 1 hour, preserving heat for half an hour, adding 15g of polyether amine D400 and the maleimide containing amino, and stirring uniformly to obtain the curing agent. The resulting curing agent had a solids content of 79.5% by weight, an amine number of 466mg KOH/g and a pH of 9.7.
Comparative example 2
412g of diethylenetriamine are added into a reaction bottle, and the temperature is preheated to 80 ℃; gradually dripping 240g of furan dimethanol glycidyl ether into a reaction bottle through a peristaltic pump to carry out ring-opening reaction, wherein the dripping time lasts for 1 hour, and the heat preservation is continued for half an hour; after the ring-opening reaction is finished, carrying out reduced pressure distillation on the materials in the reaction bottle by utilizing a vacuum pump, removing redundant diethylenetriamine in the reaction system, adding 210g of deionized water into the system for dispersion, gradually dripping 60g of phenyl glycidyl ether into the reaction bottle by utilizing a peristaltic pump for reaction at 80 ℃, keeping the dripping time for 1 hour, preserving heat for half an hour, adding 15g of polyether amine D400, and stirring uniformly to obtain the curing agent. The resulting curing agent had a solids content of 71.3% by weight, an amine number of 460mg KOH/g and a pH of 9.7.
Paint films were prepared by mixing the aqueous epoxy curatives obtained in each of examples and comparative examples with aqueous epoxy emulsions, wherein the formulations of the A and B components used to prepare the paint films were as shown in tables 1 and 2 below:
formulation of A Components of Table 1
Table 2 formulation of B Components
The main paint (A component) obtained in the table 1 and the curing agent (B component) obtained in the table 2 are mixed according to the mass ratio of 10:1, mixing, stirring for 15min, and adding a small amount of deionized water to adjust the construction viscosity to obtain a mixed paint liquid: and then the mixed paint liquid is subjected to plate making according to industry operation standards (flash leveling for 10min and baking at 80 ℃ for 30 min), so as to obtain a paint film. After the paint film is kept stand and maintained for 7 days under the standard conditions of 23+/-2 ℃ and 50+/-5% of humidity, various tests can be carried out according to the test method.
The resulting paint films were tested according to the test methods described above, and the results of the performance tests are shown in Table 3 below:
TABLE 3 thermal stability of curing Agents and paint film Performance test results
| Curing agent | Self-repair rate | Adhesion force | Waterproof | Salt spray resistance | Activation period (h) | Hardness of pencil |
| Example 1 | 70％ | 0 | 5 | 5 | 4.5 | 3H |
| Example 2 | 65％ | 0 | 5 | 5- | 4 | 3H |
| Example 3 | 73％ | 0 | 5 | 5- | 4 | 2H |
| Example 4 | 74％ | 0 | 5 | 5- | 4 | 3H |
| Example 5 | 69％ | 0 | 5 | 5 | 4.5 | 2H |
| Example 6 | 78％ | 0 | 5 | 5 | 5 | 2H |
| Example 7 | 68％ | 0 | 5 | 5 | 5 | 2H |
| Comparative example 1 | No restoration effect | 0 | 5 | 5- | 4.5 | 3H |
| Comparative example 2 | No restoration effect | 0 | 5 | 5- | 4.5 | 3H |
Each test is executed according to national standard, and the test method is described in detail; tolerance data are test results after 20 days of tracking.
Wherein, the grade of the adhesion test result is 0-5 grade, the 0 grade adhesion is optimal, and the 5 grade is worst:
the level of the water resistance test result is 0-5 level, the 5 level is optimal, and the 0 level is worst;
the salt spray resistance test results are rated from 0 to 5, the 5 th most excellent and the 0 th worst.
Having described embodiments of the present invention, the foregoing description is illustrative, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (35)
1. The waterborne epoxy curing agent is characterized by being prepared by reacting the following raw materials in parts by mole:
a) 1 part of a polyepoxide compound;
b) 1.0 to 8 parts of a first polyamine compound;
c) 0-8 parts of a polyfunctional compound;
d) 0.2-1.25 parts of a monoepoxide compound;
e) 0.2-1.5 parts of maleimide containing amino;
wherein the polyfunctional compound has 4 or more active hydrogens.
2. The aqueous epoxy hardener of claim 1 prepared by reacting raw materials comprising the following mole fractions
a) 1 part of a polyepoxide compound;
b) 2-6 parts of a first polyamine compound;
c) 0-6 parts of a polyfunctional compound;
d) 0.4-0.9 parts of monoepoxide;
e) 0.5-1 part of maleimide containing amino;
wherein the polyfunctional compound has 4 or more active hydrogens.
3. The aqueous epoxy curing agent according to claim 1, wherein the polyepoxide compound is a compound having a furan ring structure and having 2 or more epoxy groups.
4. The aqueous epoxy curing agent according to claim 3, wherein the polyepoxide compound is one or more of glycidyl ether, glycidyl ester or glycidyl amine having a furan ring structure;
wherein the glycidyl ether with furan ring structure is selected from 2, 5-furan dimethanol diglycidyl ether with the following structural formula (I) or/and 5,5' -alkyl difurfuryl alcohol diglycidyl ether with the following structural formula (II):
wherein R in formula (II) 1 ,R 2 Each independently selected from hydrogen or methyl;
wherein the glycidyl ester with furan ring structure is selected from diglycidyl 2, 5-furandicarboxylate with the following structural formula (III):
wherein the glycidylamine with furan ring structure is selected from 2, 5-furan dimethylamine glycidylamine with the following structural formula (IV) or/and 5,5' -alkyl difurfuryl amine glycidylamine with the following structural formula (V):
wherein R in formula (V) 3 ,R 4 Each independently selected from hydrogen or methyl.
5. The aqueous epoxy curing agent according to claim 1, wherein the component b) the first polyamine compound is a polyamine compound which is miscible with water in any proportion; the first polyamine compound is selected from one or more of diethylenetriamine, polyetheramine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine, wherein the polyetheramine is diamido polyetheramine with the molar mass of 200-1000 g/mol.
6. The aqueous epoxy curing agent of claim 5, wherein the component b) the first polyamine compound is selected from one or more of diethylenetriamine, polyetheramine and triethylenetetramine.
7. The aqueous epoxy curing agent according to claim 1, wherein the polyfunctional compound is a compound containing two or more amino groups, and the polyfunctional compound is one or more selected from the group consisting of aliphatic polyamines, alicyclic polyamines and aromatic polyamines, and has a molar mass of not more than 1000g/mol.
8. The aqueous epoxy curing agent of claim 7, wherein the polyfunctional compound is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methyl-1, 5-pentylene diamine, 1, 6-hexamethylenediamine, m-xylylenediamine, 1, 3-diaminomethylcyclohexane, 1-ethyl-1, 3-propylenediamine, p-aminodicyclohexylmethane, 2, 4-trimethyl-1, 6-hexamethylenediamine, p-xylylenediamine, isophoronediamine, 1, 3-cyclohexanedimethylamine, and diethyltoluenediamine.
9. The aqueous epoxy curing agent of claim 8, wherein the polyfunctional compound is selected from one or more of m-xylylenediamine, p-xylylenediamine, isophoronediamine, and 1, 3-cyclohexanediamine.
10. The aqueous epoxy curing agent of claim 1, wherein the monoepoxy compound is an aliphatic, cycloaliphatic, or aromatic compound attached to an epoxy functional group.
11. The aqueous epoxy curing agent of claim 10, wherein the monoepoxy compound is selected from one or more of epoxy ethers of phenols, epoxy esters of unsaturated alcohols, epoxy esters of unsaturated carboxylic acids, aliphatic glycidyl ethers, and aromatic glycidyl ethers.
12. The aqueous epoxy curing agent of claim 11, wherein the monoepoxy compound is selected from one or more of the group consisting of phenolic epoxy ethers, cl-C18 aliphatic glycidyl ethers, and C10-C18 aromatic glycidyl ethers.
13. The aqueous epoxy hardener of claim 12 wherein the monoepoxy compound is selected from one or more of cardanol glycidyl ether, butyl glycidyl ether, C12-C14 alkyl glycidyl ether, tolyl glycidyl ether, phenyl glycidyl ether, nonylphenyl glycidyl ether and p-tert-butylphenyl glycidyl ether.
14. The aqueous epoxy curing agent according to claim 1, wherein the amine group-containing maleimide is obtained by reacting maleic anhydride with a polyamine compound which can be blended with water in an arbitrary ratio.
15. The aqueous epoxy hardener of claim 14 wherein the reaction conditions of the maleic anhydride and the polyamine compound that can be blended with water in any ratio are: reacting for 1-10h at 100-140 ℃;
the molar ratio of maleic anhydride to polyamine compound which can be blended with water in any ratio is 0.5 to 1.5;
the polyamine compound which can be blended with water in any ratio is selected from one or more of diethylenetriamine, polyether amine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine, wherein the polyether amine is diamido polyether amine with the molar mass of 200-1000 g/mol.
16. The aqueous epoxy hardener of claim 15 wherein the reaction conditions of the maleic anhydride and the polyamine compound that can be blended with water in any ratio are: reacting for 3-8h at 120-140 ℃;
the molar ratio of maleic anhydride to polyamine compound which can be blended with water in any ratio is 0.9 to 1.1;
the polyamine compound which can be blended with water in any ratio is selected from one or more of diethylenetriamine, polyether amine and triethylenetetramine, wherein the polyether amine is diamido polyether amine with the molar mass of 200-1000 g/mol.
17. The aqueous epoxy hardener of claim 1 wherein the reaction materials of the aqueous epoxy hardener further comprise 0.1 to 0.6 parts by weight of water, f) 0 to 0.05 parts by weight of unmodified polyetheramine, the parts of each reaction material used being based on the total mass of the aqueous epoxy hardener; the unmodified polyetheramine is polyetheramine with the molar mass of 200-5000g/mol and the functionality of 2 or 3.
18. The aqueous epoxy hardener of claim 17 wherein the reaction materials of the aqueous epoxy hardener further comprise 0.2 to 0.4 parts by weight water; f) 0-0.03 weight part of unmodified polyetheramine, and the parts of each reaction raw material are based on the total mass of the aqueous epoxy curing agent.
19. The aqueous epoxy curing agent of claim 1, wherein the amine group-containing maleimide is formed by reacting a second polyamine compound with maleic anhydride.
20. The aqueous epoxy curative of claim 19 wherein the reaction conditions of the maleic anhydride and the second polyamine compound are: reacting at 100-140 deg.C for 1-10h.
21. The aqueous epoxy curative of claim 20 wherein the reaction conditions of the maleic anhydride and the second polyamine compound are: reacting for 3-8h at 120-140 ℃.
22. The aqueous epoxy curative of claim 19 wherein the molar ratio of maleic anhydride to the second polyamine compound is from 0.5 to 1.5.
23. The aqueous epoxy curative of claim 22 wherein the molar ratio of maleic anhydride to the second polyamine compound is from 0.9 to 1.1.
24. The aqueous epoxy curing agent of claim 19, wherein the second polyamine compound is a polyamine compound that is miscible with water in any proportion, the second polyamine compound being the same or different from the first polyamine compound of component b) and being one or more selected from the group consisting of diethylenetriamine, polyetheramine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine.
25. The aqueous epoxy curative of claim 24 wherein the second polyamine compound is selected from one or more of diethylenetriamine, polyetheramine and triethylenetetramine.
26. The aqueous epoxy curing agent of claim 25, wherein the polyetheramine is a bis-amine polyetheramine having a molar mass of 200-1000 g/mol.
27. The method for preparing the aqueous epoxy curing agent according to claim 1, comprising the steps of: and (3) carrying out ring opening reaction on the polyepoxide compound, the first polyamine compound and the polyfunctional group compound to obtain an intermediate product i, and carrying out end capping reaction on the intermediate product i and the monoepoxide compound to obtain the waterborne epoxy curing agent.
28. The production method according to claim 27, wherein the polyepoxide compound is added dropwise to the first polyamine compound and the polyfunctional compound in a ring-opening reaction, the reaction time of the ring-opening reaction is 0.5 to 4 hours, and the reaction temperature of the ring-opening reaction is 60 to 100 ℃.
29. The method according to claim 28, wherein the polyepoxide compound is added dropwise to the first polyamine compound and the polyfunctional compound in a ring-opening reaction, the reaction time of the ring-opening reaction is 1 to 2.5 hours, and the reaction temperature of the ring-opening reaction is 80 to 100 ℃.
30. The process of claim 27, wherein the reaction time after addition of the monoepoxide is 0.5 to 2 hours and the reaction temperature of the capping reaction is 60 to 100 ℃.
31. The process of claim 30 wherein the reaction time after addition of the monoepoxide is 1 to 2 hours and the reaction temperature of the capping reaction is 80 to 100 ℃.
32. The method of manufacturing according to claim 27, further comprising: after the end capping reaction, adding maleimide containing amino group for reaction at 60-100 deg.c for 1-3 hr.
33. The process of claim 32 wherein the end capping reaction is completed with an unmodified polyetheramine.
34. Use of an aqueous epoxy hardener as claimed in any of the claims 1-26 or obtainable by a method of preparation as claimed in any of the claims 27-33 for the preparation of a coating, cured epoxy resin system.
35. A coating comprising the aqueous epoxy curative of any one of claims 1-26.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010121397A1 (en) * | 2009-04-23 | 2010-10-28 | 广州秀珀化工股份有限公司 | Water-soluble epoxy curing agent and method for preparing the same |
| WO2013124251A2 (en) * | 2012-02-22 | 2013-08-29 | Basf Se | Blends for composites |
| CN105315437A (en) * | 2015-11-03 | 2016-02-10 | 广州秀珀化工涂料有限公司 | Nonionic self-emulsifying waterborne epoxy curing agent and preparation method thereof |
| CN106554482A (en) * | 2016-11-25 | 2017-04-05 | 中国建材检验认证集团厦门宏业有限公司 | A kind of preparation method of the star-like aqueous epoxy curing agent of high-performance |
| CN110066383A (en) * | 2019-04-18 | 2019-07-30 | 万华化学集团股份有限公司 | A kind of aqueous epoxy curing agent of ionic and its preparation method and application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010121397A1 (en) * | 2009-04-23 | 2010-10-28 | 广州秀珀化工股份有限公司 | Water-soluble epoxy curing agent and method for preparing the same |
| WO2013124251A2 (en) * | 2012-02-22 | 2013-08-29 | Basf Se | Blends for composites |
| CN105315437A (en) * | 2015-11-03 | 2016-02-10 | 广州秀珀化工涂料有限公司 | Nonionic self-emulsifying waterborne epoxy curing agent and preparation method thereof |
| CN106554482A (en) * | 2016-11-25 | 2017-04-05 | 中国建材检验认证集团厦门宏业有限公司 | A kind of preparation method of the star-like aqueous epoxy curing agent of high-performance |
| CN110066383A (en) * | 2019-04-18 | 2019-07-30 | 万华化学集团股份有限公司 | A kind of aqueous epoxy curing agent of ionic and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 水性环氧树脂固化剂的制备与改性;周子鹄;贾元峰;惠海军;朱婧;刘刚;孙再武;刘娅莉;;广州化工(第11期);第114-116页 * |
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