CN117362590A - Hyperbranched flexible waterborne epoxy resin curing agent and preparation method thereof - Google Patents

Hyperbranched flexible waterborne epoxy resin curing agent and preparation method thereof Download PDF

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Publication number
CN117362590A
CN117362590A CN202311440810.4A CN202311440810A CN117362590A CN 117362590 A CN117362590 A CN 117362590A CN 202311440810 A CN202311440810 A CN 202311440810A CN 117362590 A CN117362590 A CN 117362590A
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epoxy resin
hyperbranched
curing agent
flexible
diisocyanate
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CN117362590B (en
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张望清
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Hubei Borui Polymer Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4057—Carbamates
    • 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

Abstract

The invention provides a hyperbranched flexible waterborne epoxy resin curing agent and a preparation method thereof, belonging to the technical field of epoxy resin curing agents. The hyperbranched flexible waterborne epoxy resin curing agent has a branched structure, so that a compact crosslinked structure can be formed with epoxy resin, the micropore defect of a coating is reduced, and the service life of the coating is prolonged; in addition, the hyperbranched and flexible waterborne epoxy resin curing agent polyurethane chain segment has inherent flexibility, can toughen the epoxy resin and reduces the brittleness of the epoxy resin. Therefore, after the hyperbranched flexible aqueous epoxy resin curing agent provided by the invention cures aqueous epoxy resin, the formed paint film has good water resistance, high hardness, good flexibility and strong adhesive force, the adhesive force test reaches 0 level, and the hardness test reaches 2H or more.

Description

Hyperbranched flexible waterborne epoxy resin curing agent and preparation method thereof
Technical Field
The invention belongs to the technical field of epoxy resin curing agents, and particularly relates to a hyperbranched flexible water-based epoxy resin curing agent and a preparation method thereof.
Background
As an environment-friendly coating, the water-based epoxy coating has the outstanding advantages of low toxicity, small smell, good workability, strong coating adhesion and the like, and has an important role in the water-based coating. The general water-based epoxy paint comprises an epoxy main agent and a matched epoxy curing agent, wherein the epoxy main agent and the epoxy curing agent are mainly in three matching modes. First kind: conventional epoxy resin and an emulsified epoxy curing agent matched with the same, wherein the emulsified epoxy curing agent simultaneously plays roles of an emulsifying agent and a curing agent, and is the core of the system. Second kind: the aqueous epoxy resin and the conventional epoxy curing agent or aqueous epoxy curing agent matched with the aqueous epoxy resin are high in viscosity and are required to be matched with a diluent for use. Third kind: the aqueous epoxy resin emulsion and the aqueous epoxy curing agent matched with the aqueous epoxy resin emulsion have low viscosity and good construction performance. The waterborne epoxy curing agent has important influence on the performance of a paint film.
Currently, waterborne epoxy curatives are typically polyether and epoxy-modified polymeric polyamines. The modified polyamine curing agent and the aqueous epoxy resin react to form a three-dimensional polymer micro chain segment which is loose in accumulation and weak in water and gas blocking capability, so that the water resistance, hardness and flexibility of a paint film formed by curing the aqueous epoxy resin are poor, and the application of the paint film is limited.
Disclosure of Invention
In view of the above, the invention aims to provide a hyperbranched flexible waterborne epoxy resin curing agent and a preparation method thereof. After the hyperbranched flexible aqueous epoxy resin curing agent provided by the invention cures the aqueous epoxy resin, the formed paint film has good water resistance, high hardness, good flexibility and strong adhesive force.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a hyperbranched flexible waterborne epoxy resin curing agent, which is prepared from an acrylic ester end-capped polyurethane aqueous solution and a part of end-capped polyamine through Michael addition reaction; the partially blocked polyamine is partially blocked with a glycidyl ether.
Preferably, the solid content of the hyperbranched flexible aqueous epoxy resin curing agent is 50-75%.
Preferably, the mass concentration of the acrylic ester end-capped polyurethane aqueous solution is 30-60%; the molar ratio of acrylate groups in the acrylate-terminated polyurethane to primary amino groups in the partially-terminated polyamine was 1: (1-5).
The invention provides a preparation method of the hyperbranched flexible waterborne epoxy resin curing agent, which comprises the following steps:
and adding the acrylic ester end-capped polyurethane aqueous solution into the partially end-capped polyamine, and performing Michael addition reaction to obtain the hyperbranched flexible waterborne epoxy resin curing agent.
Preferably, the michael addition reaction comprises: reacting for 1-4 h at room temperature, heating to 40-60 ℃ and continuing to react for 1-3 h.
Preferably, the preparation method of the acrylic ester end-capped polyurethane aqueous solution comprises the following steps:
mixing diisocyanate, polyethylene glycol, polyether polyol and an organic metal catalyst, and performing a prepolymerization reaction to obtain a polyurethane prepolymer;
mixing the polyurethane prepolymer with hydroxyl-containing acrylic ester, a polymerization inhibitor and polyethylene glycol monomethyl ether, and carrying out polymerization reaction to obtain acrylic ester-terminated polyurethane;
and mixing the acrylic ester end-capped polyurethane with water to obtain an acrylic ester end-capped polyurethane aqueous solution.
Preferably, the diisocyanate comprises one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and trimethylhexane diisocyanate;
the molecular weight of the polyethylene glycol is 300-2000 Da;
the polyether polyol comprises polypropylene glycol, polytetrahydrofuran glycol or polyether triol; the molecular weight of the polyether polyol is 1000-3000 Da;
the organometallic catalyst comprises one or more of dibutyl tin dilaurate, stannous octoate and organic bismuth;
the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyethylene glycol is 1: (0.2 to 0.4); the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyether polyol is 1: (0.1 to 0.3); the mass of the organic metal catalyst is 0.001-0.1% of the mass of diisocyanate.
Preferably, the hydroxyl-containing acrylate comprises one or more of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy-1-methyl ethyl acrylate, 4-hydroxybutyl acrylate and monoglyceride acrylate; the polymerization inhibitor comprises one or more of hydroquinone, tert-butyl catechol and p-hydroxyanisole; the molecular weight of the polyethylene glycol monomethyl ether is 400-2000 Da;
the molar amount of the polyurethane prepolymer is calculated based on the molar amount of isocyanate groups in diisocyanate, and the molar ratio of the molar amount of the polyurethane prepolymer to the molar amount of hydroxyl groups in the hydroxyl group-containing acrylate is 1: (0.2 to 0.5); the molar ratio of the molar quantity of the polyurethane prepolymer to the molar quantity of the hydroxyl groups in the polyethylene glycol monomethyl ether is 1: (0.1 to 0.2); the mass of the polymerization inhibitor is 0.1-1.5% of the mass of the acrylic ester containing hydroxyl.
Preferably, the temperature of the polymerization reaction is 50-80 ℃ and the time is 2-6 h.
Preferably, the method for preparing the partially blocked polyamine comprises the following steps:
adding glycidyl ether into polyamine, and performing epoxy ring-opening addition reaction to obtain partially blocked polyamine;
the glycidyl ether comprises one or more of n-butyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether and cardanol glycidyl ether; the polyamine comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the molar ratio of primary amino groups in the polyamine to epoxy groups in the glycidyl ether is 1: (0.2 to 0.5);
the temperature of the epoxy ring-opening addition reaction is 40-60 ℃ and the time is 1-6 h.
The invention provides a hyperbranched flexible waterborne epoxy resin curing agent, which is prepared from an acrylic ester end-capped polyurethane aqueous solution and a part of end-capped polyamine through Michael addition reaction; the partially blocked polyamine is partially blocked with a glycidyl ether. The hyperbranched flexible waterborne epoxy resin curing agent disclosed by the invention has a branched structure which takes polyurethane as a main chain and takes an adduct of polyamine and glycidyl ether (namely, partially blocked polyamine) as a side chain, can form a compact crosslinked structure with epoxy resin, reduces micropore defects of a coating and prolongs the service life of the coating; in addition, the hyperbranched and flexible waterborne epoxy resin curing agent polyurethane chain segment has inherent flexibility, can toughen the epoxy resin and reduces the brittleness of the epoxy resin. Therefore, after the hyperbranched flexible aqueous epoxy resin curing agent provided by the invention cures aqueous epoxy resin, the formed paint film has good water resistance, high hardness, good flexibility and strong adhesive force, the adhesive force test reaches 0 level, and the hardness test reaches 2H or more.
In addition, the hyperbranched, flexible aqueous epoxy resin curing agent polyurethane chain segments of the invention are aqueous, provide emulsifying capability, and are applicable to both conventional epoxy resins and aqueous epoxy resin emulsions.
The hyperbranched flexible waterborne epoxy resin curing agent has emulsifying capacity, so that the storage stability is good, and the epoxy resin can be cured at room temperature or at 50-150 ℃.
Detailed Description
The invention provides a hyperbranched flexible waterborne epoxy resin curing agent, which is prepared from an acrylic ester end-capped polyurethane aqueous solution and a part of end-capped polyamine through Michael addition reaction; the partially blocked polyamine is partially blocked with a glycidyl ether.
In the present invention, the mass concentration of the acrylic ester-terminated polyurethane aqueous solution is preferably 30 to 60%, more preferably 40 to 55%, still more preferably 45 to 50%; the molar ratio of acrylate groups in the acrylate-terminated polyurethane to primary amino groups in the partially-terminated polyamine was 1: (1 to 5), more preferably 1: (1.5 to 4.5), more preferably 1: (2-4); the solid content of the hyperbranched, flexible, aqueous epoxy resin curing agent is preferably 50 to 75%, more preferably 52 to 65%, and even more preferably 55 to 60%.
The hyperbranched flexible waterborne epoxy resin curing agent has a branched structure, so that a compact crosslinked structure can be formed with epoxy resin, the micropore defect of a coating is reduced, and the service life of the coating is prolonged; in addition, the hyperbranched and flexible waterborne epoxy resin curing agent polyurethane chain segment has inherent flexibility, can toughen the epoxy resin and reduces the brittleness of the epoxy resin. Therefore, after the hyperbranched flexible aqueous epoxy resin curing agent provided by the invention cures aqueous epoxy resin, the formed paint film has good water resistance, high hardness, good flexibility and strong adhesive force, the adhesive force test reaches 0 level, and the hardness test reaches 2H or more.
In addition, the hyperbranched, flexible aqueous epoxy resin curing agent polyurethane chain segments of the invention are aqueous, provide emulsifying capability, and are applicable to both conventional epoxy resins and aqueous epoxy resin emulsions.
The hyperbranched flexible waterborne epoxy resin curing agent has emulsifying capacity, so that the storage stability is good, and the epoxy resin can be cured at room temperature or at 50-150 ℃.
The invention provides a preparation method of the hyperbranched flexible waterborne epoxy resin curing agent, which comprises the following steps:
and adding the acrylic ester end-capped polyurethane aqueous solution into the partially end-capped polyamine, and performing Michael addition reaction to obtain the hyperbranched flexible waterborne epoxy resin curing agent.
In the present invention, the preparation method of the acrylic ester-terminated polyurethane aqueous solution preferably comprises the steps of:
mixing diisocyanate, polyethylene glycol, polyether polyol and an organic metal catalyst, and performing a prepolymerization reaction to obtain a polyurethane prepolymer;
mixing the polyurethane prepolymer with hydroxyl-containing acrylic ester, a polymerization inhibitor and polyethylene glycol monomethyl ether, and carrying out polymerization reaction to obtain acrylic ester-terminated polyurethane;
and mixing the acrylic ester end-capped polyurethane with water to obtain an acrylic ester end-capped polyurethane aqueous solution.
The polyurethane prepolymer is prepared by mixing diisocyanate, polyethylene glycol, polyether polyol and an organic metal catalyst and performing a prepolymerization reaction.
In the present invention, the diisocyanate preferably includes one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and trimethylhexane diisocyanate; the molecular weight of the polyethylene glycol is preferably 300-2000 Da, more preferably 500-1800 Da, and even more preferably 800-1500 Da; the polyether polyol preferably comprises polypropylene glycol, polytetrahydrofuran glycol or polyether triol; the molecular weight of the polyether polyol is preferably 1000-3000 Da, more preferably 2000Da. In the present invention, the organometallic catalyst preferably includes one or more of dibutyltin dilaurate, stannous octoate, and organobismuth.
In the present invention, the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyethylene glycol is preferably 1: (0.2 to 0.4), more preferably 1: (0.25-0.35); the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyether polyol is preferably 1: (0.1 to 0.3), more preferably 1: (0.15 to 0.25); the mass of the organometallic catalyst is preferably 0.001 to 0.1% of the mass of the diisocyanate.
In the present invention, the temperature of the prepolymerization is preferably 50 to 80 ℃, more preferably 68 to 78 ℃, still more preferably 70 to 75 ℃; the time of the prepolymerization is preferably 2 to 6 hours, more preferably 3 to 5.5 hours, and still more preferably 4 to 5 hours. In the present invention, the prepolymerization is preferably carried out under stirring; the stirring speed is not particularly limited in the present invention, and a speed well known in the art may be used.
After the polyurethane prepolymer is obtained, the polyurethane prepolymer is preferably mixed with hydroxyl-containing acrylic ester, a polymerization inhibitor and polyethylene glycol monomethyl ether for polymerization reaction to obtain acrylic ester end-capped polyurethane.
In the present invention, the hydroxyl group-containing acrylate preferably includes one or more of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate and monoglyceride acrylate; the polymerization inhibitor preferably comprises one or more of hydroquinone, tert-butyl catechol and p-hydroxyanisole; the molecular weight of the polyethylene glycol monomethyl ether is preferably 400 to 2000Da, more preferably 500 to 1500Da, and even more preferably 800 to 1000Da.
In the present invention, the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the hydroxyl group-containing acrylate is preferably 1: (0.2 to 0.5), more preferably 1: (0.25 to 0.45); the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyethylene glycol monomethyl ether is 1: (0.1 to 0.2), more preferably 1: (0.12-0.18). In the present invention, the mass of the polymerization inhibitor is preferably 0.1 to 1.5%, more preferably 0.4 to 1.2%, and still more preferably 0.8 to 1.0% of the mass of the hydroxyl group-containing acrylate.
In the present invention, mixing the polyurethane prepolymer with the hydroxyl group-containing acrylate, the polymerization inhibitor and the polyethylene glycol monomethyl ether preferably comprises: and adding hydroxyl-containing acrylic ester, a polymerization inhibitor and polyethylene glycol monomethyl ether into the polyurethane prepolymer.
In the present invention, the temperature of the polymerization reaction is preferably 50 to 80 ℃, more preferably 75 to 80 ℃; the polymerization time is preferably 2 to 6 hours, more preferably 2.5 to 5 hours, and still more preferably 3 to 4.5 hours. In the present invention, the polymerization is preferably carried out under stirring; the stirring speed is not particularly limited in the present invention, and a speed well known in the art may be used.
After the acrylic ester end-capped polyurethane is obtained, the acrylic ester end-capped polyurethane is mixed with water to obtain an acrylic ester end-capped polyurethane aqueous solution.
In the present invention, it is preferable to cool the acrylate-terminated polyurethane to 50℃and then add water thereto and cool it to room temperature. In the invention, the water is used in an amount such that the mass concentration of the acrylic ester-terminated polyurethane aqueous solution is 30 to 60%.
In the present invention, the method for preparing the partially blocked polyamine preferably comprises the steps of:
and adding glycidyl ether into polyamine to perform epoxy ring-opening addition reaction, so as to obtain partially-blocked polyamine.
In the present invention, the glycidyl ether preferably includes one or more of n-butyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether and cardanol glycidyl ether; the polyamine preferably comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. In the present invention, the molar ratio of primary amino groups to epoxy groups in the glycidyl ether in the polyamine is preferably 1: (0.2 to 0.5), more preferably 1: (0.25 to 0.45), more preferably 1: (0.3-0.4).
In the present invention, the temperature of the ring-opening addition reaction of epoxy is preferably 40 to 60 ℃, more preferably 45 to 55 ℃, and even more preferably 48 to 52 ℃. In the present invention, it is preferable to raise the temperature of the polyamine to the temperature of the epoxy ring-opening addition reaction, and then dropwise add glycidyl ether; the time for the dripping is preferably 2 to 3 hours. In the present invention, the time of the epoxy ring-opening addition reaction is preferably 1 to 6 hours, more preferably 1.5 to 5 hours, still more preferably 2 to 4.5 hours; the time of the epoxy ring-opening addition reaction is preferably calculated from the completion of the addition of the glycidyl ether. In the present invention, the epoxy ring-opening addition reaction is preferably carried out under stirring; the stirring speed is not particularly limited in the present invention, and a speed well known in the art may be used.
The acrylic ester end-capped polyurethane aqueous solution is added into the partially end-capped polyamine to perform Michael addition reaction, so that the hyperbranched flexible aqueous epoxy resin curing agent is obtained.
In the present invention, the aqueous solution of the acrylate-terminated polyurethane is preferably added dropwise, and the time for the dropwise addition is preferably 2 to 6 hours, more preferably 2.5 to 5 hours, and still more preferably 3 to 4.5 hours. In the present invention, the temperature of the dropping is preferably room temperature; the dropwise addition is preferably carried out under stirring.
In the present invention, the michael addition reaction preferably includes: reacting for 1-4 h at room temperature, more preferably for 2-3.5 h at room temperature; then the temperature is raised to 40-60 ℃, more preferably to 45-55 ℃, and the reaction is continued for 1-3 hours, more preferably for 1-2.5 hours. In the present invention, the Michael addition reaction is preferably carried out under stirring; the stirring speed is not particularly limited in the present invention, and a speed well known in the art may be used.
For further explanation of the present invention, the hyperbranched, flexible aqueous epoxy resin curing agent and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
3000 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) and 2000 g of dried polypropylene glycol (DL 2000, molecular weight 2000Da, lanxing Dong Da) are added into a reaction kettle, and stirred uniformly, and heated to 75 ℃ for reaction for 4 hours to obtain a polyurethane prepolymer;
adding 464 g of acrylic acid-2-hydroxyethyl ester, 3.0 g of para-hydroxyanisole and 550 g of polyethylene glycol monomethyl ether (MPEG, molecular weight 550Da, jiangsu sea Andrographing) into the polyurethane prepolymer, and continuously reacting for 3 hours to obtain acrylic ester end-capped polyurethane;
cooling the acrylic ester end-capped polyurethane to 50 ℃, adding 7130 g of pure water, and cooling to room temperature to obtain an acrylic ester end-capped polyurethane aqueous solution A1;
824 g of diethylenetriamine is added into a reaction kettle, stirring is carried out, the temperature is raised to 40 ℃, 1040 g of n-butyl glycidyl ether is added into a high-level tank, the n-butyl glycidyl ether is dropwise added into the reaction kettle at a constant speed within 3 hours, and the temperature is controlled to be not more than 60 ℃; after the dripping is finished, continuing to react for 2 hours to obtain partially blocked polyamine B1;
at room temperature, 1864 g of partially blocked polyamine B1 is added into a reaction kettle, 14260 g of acrylic ester blocked polyurethane aqueous solution A1 is dropwise added into the reaction kettle in 3 hours under stirring, and the reaction is continued for 3 hours after the dropwise addition; then, the temperature is raised to 60 ℃ to react for 1 hour, and the temperature is reduced to room temperature, thus obtaining the hyperbranched flexible waterborne epoxy resin curing agent C1 with the solid content of 55 percent.
Example 2
1000 g of polyethylene glycol (PEG 1000, molecular weight 1000Da, shanghai Dong Da) and 2000 g of dried polypropylene glycol (DL 2000, molecular weight 2000Da, lanxing Dong Da) are added into a reaction kettle, and stirred uniformly, and heated to 75 ℃ for reaction for 4 hours to obtain polyurethane prepolymer;
adding 580 g of acrylic acid-2-hydroxyethyl ester, 7.0 g of para-hydroxyanisole and 550 g of polyethylene glycol monomethyl ether (MPEG, molecular weight 550Da, jiangsu sea Andrographing) into the polyurethane prepolymer, and continuously reacting for 3 hours to obtain acrylic ester end-capped polyurethane;
cooling the acrylic ester end-capped polyurethane to 50 ℃, adding 5250 g of pure water, and cooling to room temperature to obtain an acrylic ester end-capped polyurethane aqueous solution A2;
partially blocked polyamine B1, 1864 g, was prepared in the same manner as in example 1;
at room temperature, 1864 g of partially blocked polyamine B1 is added into a reaction kettle, 10500 g of acrylic ester blocked polyurethane aqueous solution A2 is dropwise added into the reaction kettle in 3 hours under stirring, and the reaction is continued for 3 hours after the dropwise addition; then, the temperature is raised to 60 ℃ to react for 1 hour, and the temperature is reduced to room temperature, so as to obtain the hyperbranched flexible water-based epoxy resin curing agent C2 with 57 percent of solid content.
Example 3
600 g of polyethylene glycol (PEG 600, molecular weight 600Da, shanghai Dong) and 1000 g of dried polypropylene glycol (DL 1000, molecular weight 1000Da, lanxing Dong) are added into a reaction kettle, and stirred uniformly, and heated to 75 ℃ for reaction for 4 hours to obtain polyurethane prepolymer;
adding 580 g of acrylic acid-2-hydroxyethyl ester, 7.0 g of para-hydroxyanisole and 550 g of polyethylene glycol monomethyl ether (MPEG, molecular weight 550Da, jiangsu sea Andrographing) into the polyurethane prepolymer, and continuously reacting for 3 hours to obtain acrylic ester end-capped polyurethane;
cooling the acrylic ester end-capped polyurethane to 50 ℃, adding 3850 g of pure water, and cooling to room temperature to obtain an acrylic ester end-capped polyurethane aqueous solution A3;
partially blocked polyamine B1, 1864 g, was prepared in the same manner as in example 1;
at room temperature, 1864 g of partially blocked polyamine B1 is added into a reaction kettle, 7700 g of acrylic ester blocked polyurethane aqueous solution A3 is dripped into the reaction kettle in 3 hours under stirring, and the reaction is continued for 3 hours after the dripping is finished; then, the temperature is raised to 60 ℃, the reaction is carried out for 1 hour, the temperature is reduced to the room temperature, and the hyperbranched flexible aqueous epoxy resin curing agent C3 with the solid content of 59 percent is obtained.
Example 4
600 g of polyethylene glycol (PEG 600, molecular weight 600Da, shanghai Dong Da) and 1000 g of dried polypropylene glycol (DL 1000, molecular weight 1000Da, lanxing Dong Da) are added into a reaction kettle, and stirred uniformly, and heated to 75 ℃ for reaction for 4 hours to obtain polyurethane prepolymer;
adding 580 g of acrylic acid-2-hydroxyethyl ester, 5.0 g of para-hydroxyanisole and 550 g of polyethylene glycol monomethyl ether (MPEG, molecular weight 550Da, jiangsu sea Andrographing) into the polyurethane prepolymer, and continuously reacting for 3 hours to obtain acrylic ester end-capped polyurethane;
cooling the acrylic ester end-capped polyurethane to 50 ℃, adding 3606 g of pure water, and cooling to room temperature to obtain an acrylic ester end-capped polyurethane aqueous solution A4;
partially blocked polyamine B1, 1864 g, was prepared in the same manner as in example 1;
at room temperature, 1864 g of partially blocked polyamine B1 is added into a reaction kettle, 7212 g of acrylic ester blocked polyurethane aqueous solution A4 is dropwise added into the reaction kettle under stirring within 3 hours, and the reaction is continued for 3 hours after the dropwise addition is finished; and then heating to 60 ℃, reacting for 1 hour, and cooling to room temperature to obtain the hyperbranched flexible water-based epoxy resin curing agent C4 with the solid content of 60%.
Example 5
Acrylic ester end-capped aqueous polyurethane solution A4, 7212 g, prepared in the same manner as in example 4;
partially blocked polyamine B1, 2330 g, prepared as in example 1;
at room temperature, 2330 g of partially blocked polyamine B1 is added into a reaction kettle, 7212 g of acrylic ester blocked polyurethane aqueous solution A4 is dropwise added into the reaction kettle under stirring within 3 hours, and the reaction is continued for 3 hours after the dropwise addition is completed; then, the temperature is raised to 60 ℃, the reaction is carried out for 1 hour, the temperature is reduced to the room temperature, and the hyperbranched flexible aqueous epoxy resin curing agent C5 with the solid content of 62 percent is obtained.
Example 6
Acrylic ester end-capped aqueous polyurethane solution A4, 7212 g, prepared in the same manner as in example 4;
824 g of diethylenetriamine and 120 g of ethylenediamine are added into a reaction kettle, the temperature is raised to 40 ℃ by stirring, 1040 g of n-butyl glycidyl ether and 328 g of benzyl glycidyl ether are added into a high-level tank, the mixture of n-butyl glycidyl ether and benzyl glycidyl ether in the high-level tank is dropwise added into the reaction kettle at a constant speed within 3 hours, and the temperature is controlled to be not more than 60 ℃; after the dripping is finished, continuing to react for 2 hours to obtain partially blocked polyamine B2;
2312 g of partially blocked polyamine B2 is added into a reaction kettle at room temperature, 7212 g of acrylic ester blocked polyurethane aqueous solution A4 is dropwise added into the reaction kettle in 3 hours under stirring, and the reaction is continued for 3 hours after the dropwise addition; then, the temperature is raised to 60 ℃, the reaction is carried out for 1 hour, the temperature is reduced to the room temperature, and the hyperbranched flexible aqueous epoxy resin curing agent C6 with the solid content of 62 percent is obtained.
Comparative example 1
200 g of diethylenetriamine and 112 g of dimer acid are reacted for 2.5 hours at 170 ℃, nitrogen is continuously introduced in the reaction process to remove water as a by-product of production, and the reaction is naturally cooled to room temperature after the reaction is finished. 50g of epoxy resin E44, 200 g of polyethylene glycol diglycidyl ether, 150 g of polypropylene glycol diglycidyl ether and 100 g of n-butyl glycidyl ether are stirred and dissolved uniformly, then transferred into a reaction system of the previous step, stirred and reacted for 2 hours at room temperature, and then heated to 50 ℃ for reaction for 3 hours; after the reaction is finished, 300g of distilled water is added into the system, and the mixture is stirred uniformly and discharged to prepare the aqueous epoxy resin curing agent: the solid content was 66%, the viscosity at 25℃was 5200mPas, the pH was 9.3 and the active hydrogen equivalent was 210g/mol.
Test results and analysis
Table 1 summarizes the basic parameters of the aqueous epoxy resin curing agents prepared in examples 1 to 6 and comparative example 1.
TABLE 1 waterborne epoxy curing agent parameters
The results in Table 1 show that aqueous epoxy resin curing agents of suitable viscosity can be prepared with different active hydrogen equivalents according to the corresponding implementation method.
Application example 1
The aqueous epoxy resin curing agents prepared in examples 1 to 6 and comparative example 1 were uniformly mixed with commercially available winning AR555 aqueous epoxy resin (55% solid content, 1300g/mol of epoxy equivalent) in a certain proportion, sprayed on the surface of a steel plate, dried at 70 ℃ for 45 minutes, and then cured at room temperature for 7 days, and then subjected to paint film performance test (paint film thickness: 55 to 60 μm). The mixing ratio of the aqueous epoxy resin curing agent to the aqueous epoxy emulsion is calculated according to theory, namely the ratio of the number of active hydrogen moles in the aqueous epoxy resin curing agent to the number of epoxy groups in the epoxy emulsion is 1:1.
Test methods and criteria: pencil hardness of paint film, GB/T6739-2006; paint film flexibility, GB/T1731-2020; the adhesive force is measured by a cross-hatch method, GB/T9286-2021; wet film adhesion: soaking the test board in distilled water at 25 ℃ for 144 hours, wiping, and then testing the adhesive force by a cross-hatch method; salt spray resistance, GB/T1771-2007. The test results are shown in Table 2.
TABLE 2 paint film Performance test results
Curing agent Hardness of Flexibility of the product Adhesion force Wet film adhesion Salt spray resistance
Example 1 2H <1mm Level 1 Level 2 600 hours
Example 2 2H <1mm Level 0 Level 1 700 hours
Example 3 3H <1mm Level 0 Level 1 800 hours
Example 4 3H <1mm Level 0 Level 1 800 hours
Example 5 3H <1mm Level 0 Level 1 800 hours
Example 6 3H <1mm Level 0 Level 1 800 hours
Comparative example 1 3H <2mm Level 1 Level 2 400 hours
The results in Table 2 show that the hyperbranched, flexible aqueous epoxy resin curing agent prepared according to the corresponding implementation method can be used together with commercial aqueous epoxy resin to prepare a paint film with proper hardness, good flexibility, good adhesive force and excellent salt spray resistance, and compared with the aqueous epoxy resin curing agent in comparative example 1, the flexibility, adhesive force and salt spray resistance of the paint film formed by room temperature curing are obviously improved.
Application example 2
The aqueous epoxy resin curing agents prepared in examples 1 to 6 and comparative example 1 were uniformly mixed with epoxy resin E44 (98% solid content, epoxy equivalent weight 250 g/mol) in a certain proportion, stirred uniformly, sprayed on the surface of a steel plate, dried at 70 ℃ for 60 minutes, and then cured at room temperature for 7 days, and then subjected to paint film performance test (paint film thickness 55-60 μm). The mixing ratio of the aqueous epoxy resin curing agent to the epoxy resin E44 is calculated according to theory, namely, the ratio of the number of active hydrogen moles in the aqueous epoxy resin curing agent to the number of epoxy groups in the epoxy emulsion is 1:1. The test methods and standards are as in table 2. The test results are shown in Table 3.
TABLE 3 paint film Performance test results
Curing agent Hardness of Flexibility of the product Adhesion force Wet film adhesion Salt spray resistance
Example 1 2H <1mm Level 1 Level 2 600 hours
Example 2 2H <1mm Level 0 Level 1 700 hours
Example 3 3H <1mm Level 0 Level 1 800 hours
Example 4 3H <1mm Level 0 Level 1 800 hours
Example 5 >3H <1mm Level 1 Level 1 800 hours
Example 6 >3H <1mm Level 1 Level 1 800 hours
Comparative example 1 3H <2mm Level 1 Level 2 500 hours
The results in Table 3 show that the hyperbranched, flexible aqueous epoxy resin curing agent prepared according to the corresponding implementation method can be used together with conventional epoxy resin E44 to prepare a paint film with proper hardness, good flexibility, good adhesive force and excellent salt spray resistance, and compared with the aqueous epoxy resin curing agent in comparative example 1, the flexibility, adhesive force and salt spray resistance of the paint film formed by curing at 70 ℃ are obviously improved.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.

Claims (10)

1. The hyperbranched flexible waterborne epoxy resin curing agent is characterized by being prepared from an acrylic ester end-capped polyurethane aqueous solution and a part of end-capped polyamine through Michael addition reaction; the partially blocked polyamine is partially blocked with a glycidyl ether.
2. The hyperbranched, flexible, aqueous epoxy resin curative according to claim 1, wherein the solids content of the hyperbranched, flexible, aqueous epoxy resin curative is 50-75%.
3. The hyperbranched, flexible, aqueous epoxy resin curing agent according to claim 1, characterized in that the mass concentration of the acrylate-terminated polyurethane aqueous solution is 30-60%; the molar ratio of acrylate groups in the acrylate-terminated polyurethane to primary amino groups in the partially-terminated polyamine was 1: (1-5).
4. A process for preparing the hyperbranched, flexible, aqueous epoxy resin curing agent according to any one of claims 1 to 3, comprising the steps of:
and adding the acrylic ester end-capped polyurethane aqueous solution into the partially end-capped polyamine, and performing Michael addition reaction to obtain the hyperbranched flexible waterborne epoxy resin curing agent.
5. The method of claim 4, wherein the michael addition reaction comprises: reacting for 1-4 h at room temperature, heating to 40-60 ℃ and continuing to react for 1-3 h.
6. The method of preparing the aqueous solution of acrylate-terminated polyurethane according to claim 4, comprising the steps of:
mixing diisocyanate, polyethylene glycol, polyether polyol and an organic metal catalyst, and performing a prepolymerization reaction to obtain a polyurethane prepolymer;
mixing the polyurethane prepolymer with hydroxyl-containing acrylic ester, a polymerization inhibitor and polyethylene glycol monomethyl ether, and carrying out polymerization reaction to obtain acrylic ester-terminated polyurethane;
and mixing the acrylic ester end-capped polyurethane with water to obtain an acrylic ester end-capped polyurethane aqueous solution.
7. The process of claim 6 wherein the diisocyanate comprises one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and trimethylhexane diisocyanate;
the molecular weight of the polyethylene glycol is 300-2000 Da;
the polyether polyol comprises polypropylene glycol, polytetrahydrofuran glycol or polyether triol; the molecular weight of the polyether polyol is 1000-3000 Da;
the organometallic catalyst comprises one or more of dibutyl tin dilaurate, stannous octoate and organic bismuth;
the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyethylene glycol is 1: (0.2 to 0.4); the molar ratio of isocyanate groups in the diisocyanate to hydroxyl groups in the polyether polyol is 1: (0.1 to 0.3); the mass of the organic metal catalyst is 0.001-0.1% of the mass of diisocyanate.
8. The preparation method according to claim 6, wherein the hydroxyl-containing acrylate comprises one or more of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate and monoglyceride acrylate; the polymerization inhibitor comprises one or more of hydroquinone, tert-butyl catechol and p-hydroxyanisole; the molecular weight of the polyethylene glycol monomethyl ether is 400-2000 Da;
the molar amount of the polyurethane prepolymer is calculated based on the molar amount of isocyanate groups in diisocyanate, and the molar ratio of the molar amount of the polyurethane prepolymer to the molar amount of hydroxyl groups in the hydroxyl group-containing acrylate is 1: (0.2 to 0.5); the molar ratio of the molar quantity of the polyurethane prepolymer to the molar quantity of the hydroxyl groups in the polyethylene glycol monomethyl ether is 1: (0.1 to 0.2); the mass of the polymerization inhibitor is 0.1-1.5% of the mass of the acrylic ester containing hydroxyl.
9. The method according to claim 6 or 8, wherein the polymerization reaction is carried out at a temperature of 50 to 80 ℃ for a time of 2 to 6 hours.
10. The method of claim 4, wherein the method of preparing the partially end-capped polyamine comprises the steps of:
adding glycidyl ether into polyamine, and performing epoxy ring-opening addition reaction to obtain partially blocked polyamine;
the glycidyl ether comprises one or more of n-butyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether and cardanol glycidyl ether; the polyamine comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the molar ratio of primary amino groups in the polyamine to epoxy groups in the glycidyl ether is 1: (0.2 to 0.5);
the temperature of the epoxy ring-opening addition reaction is 40-60 ℃ and the time is 1-6 h.
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