Water-based epoxy hardener

Abstract

To provide a water-based epoxy curing agent and a preparation method therefor.SOLUTION: Provided is a water-based epoxy curing agent, comprising a reaction product of a) at least one amine having at least one moiety -QNH- in the formula, where Q is a divalent hydrocarbon group, and the amine has at least one tertiary amino group and at least one primary amino group per molecule and b) at least one polyether polyol modified epoxide having one or more epoxide groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to epoxy curing agents, and in particular to aqueous epoxy curing agents containing epoxy-amine adducts, and methods for producing the same. [Background technology]

[0002] Epoxy-amine curing systems are frequently used in coatings. These curing systems utilize epoxy resins and curing agents that possess the chemical properties of amines. Due to pressing environmental concerns, water-based curing agents that avoid the use of volatile organic solvents are preferred.

[0003] U.S. Patent No. 8,143,331 (B2) teaches an aqueous curing agent based on an alkylated polyalkyleneamine (e.g., diethylenetriamine, triethylenetetramine) compound and a polyether polyol-modified polyepoxide resin. The alkylation is achieved by a reaction between the polyalkyleneamine and one or more aldehydes or ketones, followed by catalytic hydrogenation in the presence of a Pd / C catalyst.

[0004] Diethylenetriamine (DETA) is well known for its use as a curing agent for epoxy resins and other thermosetting plastics in epoxy adhesives, see International Publication 2013 / 003202 (WO 2013003202 A1). More recently, as disclosed in European Patent No. 3170849 (EP 3,170,849 B1), DETA is converted to a heterocyclic amine having two nitrogen atoms in the ring through reaction with formaldehyde. This cyclic amine can significantly improve the reactivity of epoxy systems at low temperatures. However, significant problems still remain at low application temperatures, such as blushing, slow thin-film drying, and extremely poor water spot resistance. U.S. Patent Application Publication 2017 / 0247501 (US 20170247501 A1) discloses an aqueous curing composition obtained from the reaction of a polyether-modified polyepoxide resin with a polyamine component.

[0005] The market still hopes for a water-based curing agent that can achieve a fast curing rate while maintaining a long pot life. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 8143331 [Patent Document 2] International Publication No. 2013 / 003202 [Patent Document 3] European Patent No. 3170849 [Patent Document 4] U.S. Patent Application Publication No. 2017 / 0247501 [Patent Document 5] U.S. Patent No. 4197389 [Patent Document 6] U.S. Patent No. 5280091 [Patent Document 7] International Publication No. 99 / 55772 [Non-patent literature]

[0007] [Non-Patent Document 1] ASTM C309-97 [Overview of the project] [Problems that the invention aims to solve]

[0008] One objective of this disclosure is to provide an epoxy curing agent that, when combined with epoxy resin, can achieve rapid curing and maintain a long pot life. [Means for solving the problem]

[0009] The purpose of this disclosure is, a) At least one amine having at least one -QNH- moiety in the formula, where Q is a divalent hydrocarbon group and the amine has at least one tertiary amino group and at least one primary amino group per molecule; and b) At least one polyether polyol-modified epoxide having one or more epoxy groups is achieved by an aqueous epoxy curing agent comprising the reaction product of

[0010] Preferably, Q is -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2CH2-, -CH2CH2CH(CH3)-, -CH2CH(CH3)CH2-, -CH(CH3)CH(CH3)-, or -CH2CH(CH2CH3)-.

[0011] Preferably, the amine comprises one or more compounds represented by formula (I):

Chemical formula

[0014] Preferably, the stoichiometric ratio is in the range of 1 to 100, preferably 1.2 to 30, and more preferably 1.5 to 10, where the stoichiometric ratio is the ratio of the number of equivalents of the active amine hydrogen atoms of the amine to the number of equivalents of the epoxy groups in the polyether polyol-modified epoxide.

[0015] Preferably, the at least one polyether polyol-modified polyepoxide resin comprises a reaction product of at least one polyepoxide compound and at least one polyether polyol.

[0016] Preferably, the polyether polyol is selected from polyethylene glycol, polypropylene glycol, or polybutylene glycol.

[0017] Preferably, the at least one polyepoxide compound is diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of 1,4-butanediol, diglycidyl ether of cyclohexanedimethylol, diglycidyl ether of resorcinol, triglycerol triglycidyl ether of glycerol, trimethylolpropane triglycidyl ether of trimethylolpropane, or novolac epoxy resin.

[0018] Preferably, the aqueous epoxy curing agent further contains water.

[0019] Preferably, Q is ethylene, propylene, or butylene.

[0020] Preferably, the aqueous epoxy curing agent further comprises one or more catalysts.

[0021] Preferably, the aqueous epoxy curing agent further comprises one or more additives selected from the group consisting of fillers, reinforcing agents, coupling agents, impact resistance modifiers, defoaming agents, dispersants, lubricants, colorants, marking materials, dyes, pigments, infrared absorbers, ultraviolet absorbers, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retardants, conductive additives, carbon black, graphite, carbon nanotubes, graphene, drying agents, release agents, leveling aids, flame retardants, separating agents, fluorescent whitening agents, rheological additives, photochromic additives, softeners, adhesion promoters, drip inhibitors, metallic pigments, stabilizers, metallic luminescence pigments, metallic coating particles, pore-forming agents, glass fibers, nanoparticles, or flow aids.

[0022] Another purpose of this disclosure is, The amine having at least one molar-QNH- and at least one polyether polyol-modified epoxide having one or more epoxy groups is heated at a temperature of 30°C to 150°C for 0.1 to 6 hours. Includes; Here, Q is a divalent hydrocarbon group, and the amine has at least one tertiary amino group and at least one primary amino group per molecule. The objective is to provide a method for producing an aqueous epoxy curing agent.

[0023] Preferably, the stoichiometric ratio of the amine to the epoxide is within the range of a molar ratio of 1 to 100, preferably 1.2 to 30, and more preferably 1.5 to 10.

[0024] Detailed explanation The following explanation is for illustrative purposes only and does not limit the scope of this disclosure.

[0025] The aqueous epoxy curing agent of this disclosure comprises an epoxy-amine adduct which is a reaction product of at least one amine and at least one polyether polyol-modified epoxide.

[0026] Epoxyamine adducts are compounds formed from a combination of a) one or more amines and b) one or more epoxides. These combinations can be achieved through chemical reactions, such as addition reactions. When an excess amount of amine reacts with a deficiency in epoxy resin and almost completely consumes the epoxy groups, an epoxyamine adduct with amine hydrogen atoms of the remaining amino groups is formed. Since these epoxyamine adducts typically have high molecular weights, they are less volatile and less likely to emit amine odors. Through addition with hydrophilic epoxides, the epoxy curing agent can have enhanced hydrophilicity. In formulations, the epoxy curing agent can be diluted with water to avoid the use of expensive and volatile organic solvents.

[0027] In this specification, two distinct compounds that react to form the epoxy-amine adduct are (a) at least one amine having at least one moiety-QNH- in its formula, where Q is a divalent hydrocarbon group having at least two carbon atoms, and the amine has at least one tertiary amino group and at least one primary amino group per molecule, and (b) at least one polyether polyol-modified epoxide.

[0028] [amine] According to one embodiment of the present disclosure, the amine has at least one moiety -QNH- in its formula, where Q is a divalent hydrocarbon group. The amine has both at least one tertiary amino group and at least one primary amino group per molecule.

[0029] Preferably, Q is selected from -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2CH2-, -CH2CH2CH(CH3)-, -CH2CH(CH3)CH2-, -CH(CH3)CH(CH3)-, or -CH2CH(CH2CH3)-.

[0030] Preferably, the amine is of formula (I): [ka] [wherein n is an integer of 1 or more, and R1 and R2 are independently one or more compounds represented by: a substituted or unsubstituted C1-C16 alkyl group, a substituted or unsubstituted C1-C16 alkenyl group, a substituted or unsubstituted C1-C16 alkadienyl group, a substituted or unsubstituted C1-C16 cycloalkyl group, a substituted or unsubstituted C1-C16 cycloalkenyl group, a substituted or unsubstituted C1-C16 cycloalkadienyl group, a substituted or unsubstituted C1-C16 aryl group, or a substituted or unsubstituted C1-C16 aralkyl group].

[0031] More preferably, groups R1 and R2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.

[0032] More preferably, the amine is N,N-dimethylaminopropylamine (DMAPA), N,N-diethylaminopropylamine (DEAPA), N,N-dipropylaminopropylamine, N,N-dibutylaminopropylamine, N,N-dimethyldipropylenetriamine (DMAPAPA), N,N-diethyldipropylenetriamine, N 3 -[3-[(3-aminopropyl)amino]propyl]-N 1 ,N 1 -dimethyl-1,3-propanediamine, or a mixture thereof.

[0033] Preferably, the amine is of formula (II): [ka] [wherein i and j are independently integers of 1 or more, and R1 and R2 are independently substituted or unsubstituted C1-C16 alkyl groups, substituted or unsubstituted C1-C16 alkenyl groups, substituted or unsubstituted C1-C16 alkadienyl groups, substituted or unsubstituted C1-C16 cycloalkyl groups, substituted or unsubstituted C1-C16 cycloalkenyl groups, substituted or unsubstituted C1-C16 cycloalkadienyl groups, substituted or unsubstituted C1-C16 aryl groups, or substituted or unsubstituted C1-C16 aralkyl groups] comprising one or more compounds represented by these formulas.

[0034] The benefits of using such amines include a flexible main chain, tertiary amino (e.g., dimethylamino or diethylamino) groups that can be used as basic catalysts during crosslinking reactions, and active reactants in which the primary and secondary amino groups play a role.

[0035] Although the catalytic function of the tertiary amino group is important in that it accelerates the crosslinking reaction when the curing agent is mixed with the epoxy resin, it was surprisingly found that it does not significantly reduce the pot life of the mixture of the curing agent and the epoxy resin.

[0036] Epoxy-amine adducts According to this disclosure, the above-mentioned amine reacts with one or more epoxides to form an epoxide-amine adduct. In this reaction, the number of primary amino groups in the amine is reduced by its reaction with the epoxy groups in the epoxide. This reduction in the number of primary amino groups helps to increase the pot life.

[0037] The adduct can be formed in an addition reaction involving an amine and an epoxide. The amine is first heated, and then a liquid or solid epoxide is added dropwise. The reaction is completed in this system, and the reaction product is diluted with deionized water to form an aqueous solution of the curing agent. The epoxy addition reaction carried out to form the adduct according to this disclosure is carried out at 30 to 180°C, preferably 60 to 120°C, for several minutes to several hours. The reaction is carried out in the absence of water or in an aqueous solution. If water is not present in the reaction medium, water can be added to the reaction product after the reaction. The amount of water that can be added to the reaction product can depend on the desired solid content or viscosity of the final curing agent.

[0038] In order to obtain an epoxy-amine adduct having a fast curing rate and a long pot life when used as a curing agent for epoxy resins, the stoichiometric ratio between the amine hydrogen and the epoxy group is calculated as the ratio of the number of equivalent amine hydrogen atoms in the amine to the number of equivalent epoxy groups in the epoxide, and is preferably in the range of 1 to 100.

[0039] [Polyether polyol modified epoxide] According to this disclosure, the epoxy-amine adduct is formed by reacting the amine component with a polyether polyol-modified epoxide. The polyether polyol-modified epoxide preferably comprises at least one monofunctional or polyfunctional epoxide. The polyether polyol-modified epoxide can be synthesized by reacting one or more polyfunctional epoxides with one or more polyether polyols. The polyether polyol modification of the epoxide increases its hydrophilicity. Details of the polyether polyol are given below.

[0040] The aforementioned at least one monofunctional epoxide comprises one or more epoxides or epoxy resins having one epoxy group per molecule. The aforementioned at least one polyfunctional epoxide comprises, but is not limited to, epoxides having two, three, four, or at least five epoxy groups per molecule.

[0041] Useful compounds are numerous known compounds containing more than one epoxy group, preferably two, per molecule. These epoxide compounds are preferably either saturated or unsaturated. They are preferably aliphatic, alicyclic, aromatic, or heterocyclic and have a hydroxyl group. They preferably contain substituents that do not cause any side reactions under their mixing or reaction conditions, such as alkyl or aryl substituents, or ether moieties. These are preferably glycidyl ethers derived from polyhydric phenols, particularly bisphenols and novolacs, and having a molar mass (EEW, "epoxy equivalent weight," "EV value") based on the number of epoxy groups of 100 to 1500 g / eq, but particularly 150 to 250 g / eq.

[0042] Examples of polyhydric phenols include resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-glycidyloxyphenyl)methane (bisphenol E), a mixture of isomers of dihydroxydiphenylmethane (bisphenol F), 4,4′-dihydroxydiphenylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenylpropane, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, 2,2-bis(4-hydroxy-tert-butylphenyl)propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, etc., as well as chlorinated and brominated products of the above compounds, such as tetrabromobisphenol A. It is especially preferable to use liquid diglycidyl ethers based on bisphenol A and bisphenol F having an epoxy equivalent weight of 150-200 g / eq.Polyglycidyl ethers of polyols, such as ethane-1,2-diol diglycidyl ether, propane-1,2-diol diglycidyl ether, propane-1,3-diol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether (including neopentyl glycol diglycidyl ether), hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, higher polyoxyalkylene glycol diglycidyl ethers, such as higher polyoxyethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether, co-polyoxyethylene-propylene glycol It is also possible to use polyglycidyl ethers of glycerol, polyoxytetramethylene glycol, polyglycidyl ethers of glycerol, hexane-1,2,6-triol, trimethylolpropane, trimethylolethane, pentaerythritol, or sorbitol, polyglycidyl ethers of oxyalkylated polyols (e.g., glycerol, trimethylolpropane, pentaerythritol, etc.), diglycidyl ethers of cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane, and 2,2-bis(4-hydroxycyclohexyl)propane, polyglycidyl ethers of castor oil, and triglycidyl tris(2-hydroxyethyl) isocyanurate.

[0043] Further useful components include poly(N-glycidyl) compounds, which can be obtained by dehalogenating the reaction products of epichlorohydrin with amines, such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine, or bis(4-methylaminophenyl)methane. These poly(N-glycidyl) compounds also include triglycidyl isocyanurate, triglycidylurazole and their oligomers, N,N'-diglycidyl derivatives of cycloalkylene urea, and diglycidyl derivatives of hydantoin.

[0044] The monofunctional epoxide includes, but is not limited to, epoxidized unsaturated hydrocarbons such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide; halogen-containing epoxides such as epichlorohydrin; monohydric alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, 2-ethylhexyl alcohol, and dodecyl alcohol; epoxy ethers of monohydric phenols such as phenol, cresol, and other phenols substituted at the ortho or para position; glycidyl esters of saturated or unsaturated carboxylic acids; epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids; acetals of glycidaldehydes; or combinations thereof. Preferably, the monofunctional glycidyl ether is o-cresyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and any alkyl C8-C 14 This includes glycidyl ethers, or any combination thereof.

[0045] The polyfunctional epoxide includes, but is not limited to, bisphenol A diglycidyl ether, bisphenol E diglycidyl ether, bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, novolac epoxy resin, any other aliphatic diglycidyl ether or triglycidyl ether, any other alicyclic diglycidyl ether or triglycidyl ether, or any combination thereof. Preferably, the polyfunctional epoxide is bisphenol A epoxy resin, bisphenol F epoxy resin, 1,4-butanediol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, or novolac epoxy resin, or any combination thereof.

[0046] Polyether polyol The polyether polyol according to this disclosure is given by formula (III): [ka] [In the formula, n is an integer greater than or equal to 1, and R a [The polyether polyol is represented by a monovalent group, including hydrogen, methyl, ethyl, or any other alkyl group. The polyether polyol includes, but is not limited to, polyethylene glycol, polypropylene glycol, polybutylene glycol, or any other polyether polyol.]

[0047] Suitable polyether polyols are described in U.S. Patent No. 4,197,389, starting from column 5, line 53, and continuing to column 6, line 20. Examples of polyether polyols useful in the present invention include polyethylene glycol, polypropylene glycol, or combinations thereof. Mixtures of polyether polyols of different molecular weights, as well as mixtures of different polyether polyols, can be used. The combinations of different polyether polyols can be first mixed and then reacted with at least one of the polyepoxide compounds, or reacted separately with at least one polyepoxide compound and then mixed or blended. Generally, polyether polyols having number-average molecular weights in the ranges of about 200 to 10,000 g / mol, about 400 to about 8,000 g / mol, about 600 to about 5,000 g / mol, or about 800 to about 2,500 g / mol are useful in this disclosure.

[0048] The modification can be achieved through a reaction between the polyether polyol and the epoxide under heated conditions. This reaction can optionally be accelerated with a suitable catalyst, such as a BF3-amine catalyst. The reaction conditions can follow the method described in U.S. Patent No. 4,197,389.

[0049] To produce polyether polyol-modified polyepoxide resins useful in the present invention, the reactant ratio of epoxy groups in the at least one polyepoxide compound to hydroxyl groups in the at least one polyether polyol is generally in the range of about 1.5:1 to about 8:1. The reactant ratio is, according to another aspect of the present disclosure, about 1.6:1, about 2:1, about 2.5:1, about 3:1, about 3.5:1, about 4:1, about 4.5:1, about 5:1, about 5.5:1, about 6:1, about 6.5:1, about 7:1, or about 7.5:1. In yet another aspect, the reactant ratio is in the range of about 1.8:1 to about 6:1. In yet another aspect, the reactant ratio of epoxy groups in the at least one polyepoxide compound to hydroxyl groups in the at least one polyether polyol is in the range of about 2:1 to about 4:1.

[0050] [Synthesis of epoxy-amine adducts] The addition reaction for synthesizing epoxy-amine adducts according to this disclosure involves contacting an amine with an epoxide, optionally in the presence of a plasticizer. Details of the plasticizer are discussed below.

[0051] Preferably, the reaction between the amine and the epoxide proceeds at a reaction temperature of about 50°C to about 150°C, more preferably about 60°C to about 140°C, and even more preferably about 60°C to about 90°C. The heating conditions are maintained for 0.1 to 10 hours, preferably 0.3 to 2 hours. Preferably, the heating conditions are accompanied by vigorous stirring, for example, at 100 revolutions per minute (RPM), 150 RPM, or 200 RPM.

[0052] The reaction is preferably carried out under a protective atmosphere, more preferably in a nitrogen or argon atmosphere, to partially protect the amine from oxidation or other threats.

[0053] The synthesis may optionally be carried out in the presence of a solvent or plasticizer. Preferred solvents or plasticizers for the reaction include water, acetonitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and Dowanol.(商標) It includes, but is not limited to, PM, t-butanol, isobutanol, and benzyl alcohol, and hydrocarbons such as toluene, xylene, hexane, and heptane. More preferred reaction solvents or plasticizers are water, methanol, ethanol, n-propanol, isopropanol, n-butanol, Dowanol (商標) It contains PM and benzyl alcohol. The solvent is preferably removed after the reaction is completed or remains mixed with the epoxy-amine adduct. For example, after the reaction of the above-mentioned epoxide and amine, benzyl alcohol remains as a plasticizer.

[0054] [Stoichiometric ratio] In this specification, the stoichiometric ratio is calculated as the ratio of the equivalent number of amine hydrogen atoms in the amine to the equivalent number of epoxy groups in the epoxide. This can be calculated according to formula (A): [Number]

[0055] Here, SR is the calculated stoichiometric ratio, and n a is the number of amine hydrogen atoms, and n e is the number of epoxy groups, M a is the mass weight of the amine, and M e is the mass weight of the epoxide. AHEW is the amine hydrogen equivalent weight in g / mol. The epoxy group content indicated by the epoxy equivalent weight or EEW is the ratio between the molecular weight of the monomer and the number of epoxy groups.

[0056] To produce the epoxy-amine adduct according to the present disclosure, the stoichiometric ratio is preferably within the range of 1 to 100, more preferably within the range of 1.2 to 30, and even more preferably within the range of 1.5 to 10.

[0057] This stoichiometric ratio results in an epoxy-amine adduct with numerous unreacted hydrogen atoms bonded to the nitrogen atom, which reduces the reactivity of the epoxy-amine adduct when mixed with the epoxy resin. If the stoichiometric ratio of the amine hydrogen to the epoxide is too high, for example, greater than 100, the resulting epoxy-amine adduct will have the disadvantage of a low molecular weight, and many primary amino groups in the amine will remain. The resulting epoxy-amine adduct may have high reactivity with the epoxy resin, which can degrade the surface quality of the final coating. If the stoichiometric ratio of the amine hydrogen to the epoxide is too low, for example, less than 1.2, the degree of crosslinking may be high, and the molecular weight of the epoxy-amine adduct may be extremely high. This epoxy-amine adduct will have the disadvantage of high viscosity due to the high level of crosslinking, and therefore will not be suitable for use as a curing agent.

[0058] hardening agent The epoxy-amine adduct can be used in aqueous curing agents for epoxy resins. In addition to the epoxy-amine adduct, the aqueous curing agent may contain one or more components. Details regarding these components are described below.

[0059] In addition to the epoxy-amine adduct, the aqueous curing agent may further contain at least one polyfunctional amine. Polyfunctional amines as used herein include compounds having an amine functional group and containing two or more amine hydrogen atoms.

[0060] Examples of polyfunctional amines within the scope of this disclosure, but not limited to, include, aliphatic amines, alicyclic amines, aromatic amines; Mannich base derivatives of aliphatic amines, alicyclic amines, or aromatic amines; polyamide derivatives of aliphatic amines, alicyclic amines, or aromatic amines; amide amine derivatives of aliphatic amines, alicyclic amines, or aromatic amines; amine adduct derivatives of aliphatic amines, alicyclic amines, or aromatic amines, etc., or any combination thereof.

[0061] Preferably, more than one polyfunctional amine is used in the composition of the present disclosure. For example, the at least one polyfunctional amine includes an aliphatic amine and a Mannich base derivative of an alicyclic amine. Alternatively, the at least one polyfunctional amine includes one aliphatic amine and one different aliphatic amine.

[0062] Exemplary aliphatic amines include polyethyleneamines (ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), etc.), polypropyleneamines, aminopropylated ethylenediamines, aminopropylated propylenediamines, 1,6-hexanediamine, 3,3,5-trimethyl-1,6-hexanediamine, 3,5,5-trimethyl-1,6-hexanediamine, 2-methyl-1,5-pentanediamine (commercially available as Dytek-A), etc., or combinations thereof. Additionally, poly(alkylene oxide)diamines and poly(alkylene oxide)triamines commercially available from Huntsman Corporation under the name Jeffamine are useful in this disclosure. Exemplary examples include, but are not limited to, Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® T-403, Jeffamine® EDR-148, Jeffamine® EDR-192, Jeffamine® C-346, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2001, etc., or combinations thereof.

[0063] Alicyclic and aromatic amines include, but are not limited to, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, hydrogenated ortho-toluenediamine, hydrogenated meta-toluenediamine, metaxylylenediamine, hydrogenated metaxylylenediamine (commercially known as 1,3-BAC), isophoronediamine (IPDA), various isomers or norbornanediamine, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, benzylated ethylenediamine, mixtures of methylene-crosslinked poly(cyclohexyl-aromatic)amines, or combinations thereof. The aforementioned mixtures of methylene-crosslinked poly(cyclohexyl-aromatic)amines are abbreviated as MBPCAA or MPCA and are described in U.S. Patent No. 5,280091, which is incorporated herein by reference in its entirety. According to certain embodiments of this disclosure, the at least one polyfunctional amine is a reaction product of 1,3-benzenedimethaneamine and epichlorohydrin (commercially available from Mitsubishi Gas Chemical Company as Gaskamine 328).

[0064] Mannich base derivatives can be produced by the reaction of the above-mentioned aliphatic amines, alicyclic amines, or aromatic amines with phenols or substituted phenols and formaldehyde. An exemplary substituted phenol used to produce Mannich bases useful in this disclosure is cardanol obtained from cashew nut shell liquid. Selectively, Mannich bases can be produced by the exchange reaction of a polyfunctional amine with a Mannich base containing a tertiary amine, such as tris(dimethylaminomethyl)phenol (commercially available from Evonik Operations GmbH as Ancamine® K54) or bis(dimethylaminomethyl)phenol.

[0065] Polyamide derivatives can be produced by reacting an aliphatic amine, an alicyclic amine, or an aromatic amine with a dimer fatty acid, or a mixture of a dimer fatty acid and a fatty acid. Amidoamine derivatives can be produced by reacting an aliphatic amine, an alicyclic amine, or an aromatic amine with a fatty acid.

[0066] Amine adducts can be produced by reacting an aliphatic amine, an alicyclic amine, or an aromatic amine with an epoxy resin, such as the diglycidyl ether of bisphenol A, the diglycidyl ether of bisphenol F, or an epoxy novolac resin. The aliphatic, alicyclic, and aromatic amines can also be added with a monofunctional epoxy resin, such as phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, or other alkyl glycidyl ethers.

[0067] In another embodiment of the present disclosure, the aqueous curing agent comprises a co-curing agent. The co-curing agent may be an amidoamine curing agent, an aliphatic curing agent, a polyamide curing agent, an alicyclic curing agent, or a Mannich base curing agent, including phenalkamine.

[0068] In some embodiments of this disclosure, a plasticizer is added to the aqueous curing agent. Preferably, the plasticizer is water. The addition of water to the adduct can help adjust the viscosity of the system and reduce the solids content.

[0069] Preferably, a curing accelerator can be added to the aqueous curing agent composition to speed up the curing process when the aqueous curing agent is mixed with the epoxy resin. The curing accelerator comprises one or more selected from tris(dimethylaminomethyl)phenol, benzyldimethylamine, various isomers of nonylphenol, triethanolamine, or N-(3-aminopropyl)iminodiethanol.

[0070] Other additives or components may be present in the system, depending on the end use or environment in which the system is used.

[0071] Epoxy resin in coating composition The epoxy-amine adducts of this disclosure can be used with epoxy resins already known in the art to form coating compositions. The epoxy resin is the same as or different from the epoxide used in the synthesis of the epoxy-amine adduct. Preferably, the epoxy resin is not essentially polyether polyol modified.

[0072] Useful compounds are numerous known compounds containing more than one epoxy group, preferably two, per molecule. These epoxide compounds are preferably either saturated or unsaturated. They are preferably aliphatic, alicyclic, aromatic, or heterocyclic and have a hydroxyl group. They preferably contain substituents that do not cause any side reactions under their mixing or reaction conditions, such as alkyl or aryl substituents, or ether moieties. These are preferably glycidyl ethers derived from polyhydric phenols, particularly bisphenols and novolacs, and having a molar mass ("epoxy equivalent weight", "EV value") based on the number of epoxy groups of 100 to 1500 g / eq, but especially 150 to 250 g / eq.

[0073] Examples of polyhydric phenols include resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-glycidyloxyphenyl)methane (bisphenol E), a mixture of isomers of dihydroxydiphenylmethane (bisphenol F), 4,4′-dihydroxydiphenylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenylpropane, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, 2,2-bis(4-hydroxy-tert-butylphenyl)propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, etc., as well as chlorinated and brominated products of the above compounds, such as tetrabromobisphenol A. It is especially preferable to use liquid diglycidyl ethers based on bisphenol A and bisphenol F having an epoxy equivalent weight of 150-200 g / eq.Polyglycidyl ethers of polyols, such as ethane-1,2-diol diglycidyl ether, propane-1,2-diol diglycidyl ether, propane-1,3-diol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether (including neopentyl glycol diglycidyl ether), hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, higher polyoxyalkylene glycol diglycidyl ethers, such as higher polyoxyethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether, co-polyoxyethylene-propylene glycol It is also possible to use polyglycidyl ethers of glycerol, polyoxytetramethylene glycol, polyglycidyl ethers of glycerol, hexane-1,2,6-triol, trimethylolpropane, trimethylolethane, pentaerythritol, or sorbitol, polyglycidyl ethers of oxyalkylated polyols (e.g., glycerol, trimethylolpropane, pentaerythritol, etc.), diglycidyl ethers of cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane, and 2,2-bis(4-hydroxycyclohexyl)propane, polyglycidyl ethers of castor oil, and triglycidyl tris(2-hydroxyethyl) isocyanurate.

[0074] Further useful components include poly(N-glycidyl) compounds, which can be obtained by dehalogenating the reaction products of epichlorohydrin with amines, such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine, or bis(4-methylaminophenyl)methane. These poly(N-glycidyl) compounds also include triglycidyl isocyanurate, triglycidylurazole and its oligomers, N,N'-diglycidyl derivatives of cycloalkylene urea, and diglycidyl derivatives of hydantoin.

[0075] Furthermore, polyglycidyl esters of polycarboxylic acids can also be used, obtained by the reaction of epichlorohydrin or a similar epoxide compound with aliphatic, alicyclic, or aromatic polycarboxylic acids, such as oxalic acid, succinic acid, adipic acid, glutaric acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, naphthalene-2,6-dicarboxylic acid, and higher diglycidyl dicarboxylates, such as dimerized or trimerized linolenic acid. Examples include diglycidyl adipate, diglycidyl phthalate, and diglycidyl hexahydrophthalate.

[0076] Additionally, glycidyl esters of saturated or unsaturated carboxylic acids and epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids should be mentioned. In addition to the polyglycidyl ether, small amounts of monoepoxides, such as methyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, ethylhexyl glycidyl ether, long-chain aliphatic glycidyl ethers, such as cetyl glycidyl ether and stearyl glycidyl ether, monoglycidyl ethers of higher isomer alcohol mixtures, glycidyl ethers of C12-C13 alcohol mixtures, phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, p-octylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, glycidyl ether of alkoxylated lauryl alcohol, and monoepoxides, such as epoxidized monounsaturated hydrocarbons (butylene oxide, cyclohexene oxide, styrene oxide), can be used in amounts up to 30% by weight, preferably 10% to 20% by weight, based on the mass of the polyglycidyl ether.

[0077] Useful epoxide compounds preferably include glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A, bisphenol E and / or bisphenol F, and glycidyl methacrylates. Other examples of such epoxides include triglycidyl isocyanurate (TGIC, trade name: ARALDITE 810, Huntsman), a mixture of diglycidyl terephthalate and triglycidyl trimellitate (trade names: ARALDITE PT 910 and 912, Huntsman), glycidyl esters of versatic acid (trade name: CARDURA E10, Shell), 3,4-epoxycyclohexylmethyl 3,4′-epoxycyclohexanecarboxylate (ECC), ethylhexyl glycidyl ether, butyl glycidyl ether, and pentaerythrityl tetraglycidyl ether. Mixtures of the listed epoxide compounds can also be used.

[0078] Particularly preferred epoxide components are polyepoxides based on bisphenol A diglycidyl ether, bisphenol E diglycidyl ether, bisphenol F diglycidyl ether, 4,4′-methylenebis[N,N-bis(2,3-epoxypropyl)aniline], hexanediol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, propane-1,2,3-triol triglycidyl ether, pentaerythritol tetraglycidyl ether, and diglycidyl hexahydrophthalate.

[0079] According to this disclosure, preferably, a mixture of the above-mentioned epoxide compounds can also be used in the epoxy resin.

[0080] The epoxy resin may be in various forms, such as crystalline, powder, semi-solid, or liquid. For the liquid form, the epoxy resin may be dissolved or dispersed in a solvent, such as water. The epoxy resin may be in aqueous emulsions or dispersions of various concentrations. Preferably, the epoxy resin is in liquid form to facilitate the mixing process.

[0081] Components in the coating composition This disclosure further provides a coating composition comprising the epoxy-amine adduct and at least one epoxy resin.

[0082] To introduce more functionality or features to satisfy industrial requirements, the coating composition preferably includes additives. Additives are understood to mean substances added to modify the properties of the coating composition in a desired direction, such as viscosity, wetting properties, stability, reaction rate, blistering, storability or adhesion, and use properties, to suit the end application. Some additives are described, for example, in International Publication No. 99 / 55772 (WO 99 / 55772), pp. 15-25.

[0083] Preferred additives are selected from the group consisting of fillers, reinforcing agents, coupling agents, impact modifiers, defoaming agents, dispersants, lubricants, colorants, marking materials, dyes, pigments, infrared absorbers, ultraviolet absorbers, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retarders, conductive additives, carbon black, graphite, carbon nanotubes, graphene, drying agents, release agents, leveling aids, flame retardants, separating agents, fluorescent whitening agents, rheological additives, photochromic additives, softeners, adhesion promoters, drip inhibitors, metallic pigments, stabilizers, metallic luminescence pigments, metallic coating particles, pore-forming agents, glass fibers, nanoparticles, flow aids, or combinations thereof.

[0084] The additive preferably constitutes 90% by weight or less, more preferably 70% by weight or less, more preferably 50% by weight or less, and even more preferably 30% by weight or less, based on the total weight of the coating composition.

[0085] For example, it is advantageous to add a light stabilizer, such as a sterically hindered amine, or other auxiliary agents as described, in an amount of, for example, 0.05% to 5% by weight of the total.

[0086] In order to produce the curable compositions of this disclosure, additional additives such as leveling agents, e.g., silicones, or adhesion promoters, e.g., acrylate-based ones, may be added. Furthermore, other components may be optionally present. The auxiliary agents and additives used may also be chain transfer agents, plasticizers, stabilizers, and / or inhibitors.

[0087] In some cases, the coating composition preferably includes an antioxidant additive. The antioxidant may include one or more sterically hindered structural units selected from phenols, sulfides, or benzoates. Here, in the sterically hindered phenol, two ortho-hydrogen atoms are substituted with a non-hydrogen compound having at least 1 to 20 carbon atoms, more preferably 3 to 15, and preferably branched. The benzoate also preferably has a non-hydrogen substituent at the ortho position relative to its OH group, having 1 to 20 carbon atoms, more preferably 3 to 15, and preferably branched.

[0088] In yet another embodiment, one or more catalysts may be introduced into the coating composition, preferably as part of the coating composition, to facilitate the reaction between the epoxy groups of the epoxy resin and the amine groups of the coating composition, as needed. Useful catalysts that may be introduced into the coating composition include Ancamine® products available from Evonik Operations GmbH and products marketed as “Accelerators” available from Huntsman Corporation. Exemplary catalysts are Ancamine® K54 available from Evonik Operations GmbH and piperazine-based Accelerator® 399 available from Huntsman Corporation. When used, such catalysts may be present in an amount of 0 to about 10% by weight of the total adhesive composition.

[0089] Preferably, the coating composition according to this disclosure comprises the components specified above.

[0090] This disclosure is also directed toward articles containing the compositions disclosed herein. For example, an article may include a coating composition comprising a reaction product of an epoxy-amine adduct and an epoxy resin. Articles produced from the coating compositions disclosed herein include, but are not limited to, adhesives, coatings, primers, sealants, curable compounds, construction products, flooring products, and composite products. Furthermore, such coatings, primers, sealants, or curable compounds can be applied to metal or cementitious substrates. Coatings based on these coating compositions may be solvent-free or may contain diluents, such as water or organic solvents, as required for a particular application. Coatings may contain a variety of types and levels of pigments for use in paint and primer applications. For use in protective coatings applied to metal substrates, the coating compositions may include a layer having a thickness in the range of 40 to 400 μm (micrometers), preferably 80 to 300 μm, and more preferably 100 to 250 μm. Furthermore, for use in flooring or construction products, the coating composition includes a layer having a thickness in the range of 50 to 10,000 μm, depending on the type of product and the required final properties. A coating product that provides limited mechanical resistance and chemical resistance includes a layer having a thickness in the range of 50 to 500 μm, preferably 100 to 300 μm; in contrast, a coating product, such as a self-leveling floor that provides high mechanical resistance and chemical resistance, includes a layer having a thickness in the range of 1,000 to 10,000 μm, preferably 1,500 to 5,000 μm.

[0091] Numerous substrates are suitable for applications of the coatings of this disclosure, with appropriate surface preparation as is well known to those skilled in the art. Such substrates include, but are not limited to, concrete and various types of metals and alloys, such as steel and aluminum. The coatings of this disclosure are suitable for painting or coating large metal objects or cementitious substrates, including ships, bridges, industrial plants and equipment, and floors.

[0092] The coatings of this disclosure can be applied by a number of techniques, including sprays, brushes, rollers, paint mitts, etc. To apply the extremely high solids content or 100% solids content coatings of this disclosure, a multi-component spray application apparatus can be used, in which the amine and epoxide components are mixed in the line leading to the spray gun, in the spray gun itself, or by mixing the two components together as they leave the spray gun. The use of this technique can mitigate the limitations on the pot life of the formulation, which typically decrease as both the amine reactivity and the solids content increase. A heated multi-component apparatus can be used to reduce the viscosity of the components, thereby improving ease of application.

[0093] Construction and flooring applications include compositions comprising the coating compositions of this disclosure in combination with concrete or other materials commonly used in the construction industry. Applications of the compositions of this disclosure include, but are not limited to, the use of the compositions as primers, deep-penetration primers, coatings, curing compounds, and / or sealants for new or old concrete, e.g., as referenced herein by reference to ASTM C309-97. As a primer or sealant, the coating compositions of this disclosure can be applied to a surface to improve adhesive bonding before coating application. In concrete and cement-based applications, the coatings are agents used for application to a surface to produce a protective or decorative layer or a coat. Crack injection and crack filling products can also be manufactured from the compositions disclosed herein. The coating compositions of this disclosure can be mixed with cementitious materials, e.g., concrete mix, to form polymer cement or modified cement, tile grout, etc.

[0094] This disclosure is illustrated below by examples and comparative examples. [Examples]

[0095] In the following examples, the materials or definitions used are listed below.

[0096] DER (商標) 331 is a diglycidyl ether of bisphenol A from Olin Corporation, and is a liquid reaction product of epichlorohydrin and bisphenol A. DER (商標) 331 has an EEW of 182-192 g / mol.

[0097] Epon® 828 epoxy resin is commercially available from Hexion Specialty Chemicals, Inc. and has a number-average molecular weight of approximately 400 and an epoxy equivalent weight of approximately 185–192.

[0098] Dimethylaminopropylamine and N,N-dimethyldipropylenetriamine are commercially purchased from Solvay SA.

[0099] The Ancamine® 2655 curing agent obtained from Evonik Operations GmbH is an aliphatic amine (N,N′-bis(3-aminopropyl)ethylenediamine) with an AHEW of approximately 29 g / eq.

[0100] The benzylated amine here is the benzylated product of a mixture of diethylenetriamine (DETA) and triethylenetetramine (TETA). It has an AHEW of approximately 58 g / eq.

[0101] Gaskamine® 328 from Mitsubishi Gas Chemical Co., Inc. is a modified polyamine curing agent with excellent chemical resistance, wet surface adhesion, and rapid curing properties. It is a reaction product of 1,3-benzenedimethaneamine and epichlorohydrin. It has an AHEW of approximately 55 g / eq.

[0102] Polyalkylene polyamines, such as diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA), may be commercially available from a variety of manufacturers.

[0103] m-xylylenediamine (MXDA) has an AHEW of 34 g / eq.

[0104] The curing agent OH-802 (benzylated EDA), manufactured from EDA and benzyl chloride, is from PTI Japan Co., Ltd. It has an AHEW of 61 g / eq.

[0105] Ancamine® K54 (hereinafter abbreviated as K54) is tris-(dimethylaminomethyl)phenol from Evonik Operations GmbH. It is a Lewis base catalyst for curing liquid epoxy resins.

[0106] Cresyl glycidyl ether (hereinafter abbreviated as CGE), sold by Evonik Operations GmbH as Epodil® 742, is a reactive diluent used to reduce the viscosity of epoxy resin systems. CGE has an EEW of approximately 181 g / eq.

[0107] Grilonit V34-4 / 5 is an epoxy-functional emulsifier with an average molecular weight of approximately 1000 g / mol and an EEW of approximately 365 g / eq. It is a propoxylated epoxy resin blended with DGEBA.

[0108] Sebacic acid from Sigma Aldrich is used as a co-curing agent for epoxy systems.

[0109] The amine hydrogen equivalent weight (AHEW) in g / mol is calculated as the molecular weight of the amine divided by the number of amine hydrogen atoms per molecule.

[0110] The epoxy group content, indicated by epoxy equivalent weight (EEW), is the ratio between the molecular weight of the epoxide and the number of epoxy groups.

[0111] The stoichiometric ratio is calculated as the ratio of the number of equivalents of active amine hydrogen atoms in the amine to the number of equivalents of epoxy groups in the epoxide. This can be calculated according to formula (A) when there is simply one amine and one epoxide:

number

[0112] If it is two or more amines and / or epoxides, n a n is the sum of the number of amine hydrogen atoms for each type of amine, and e This is the sum of the number of epoxy groups for each type of epoxide.

[0113] The curing agent usage level is expressed as the amount of curing agent per 100 units of resin (phr). In the synthesis example, this is calculated as the amount of epoxy-amine adduct per diluted epoxy resin having an EEW of 195 g / mol.

[0114] The following protocol was used to test the physical performance or properties of the sample: Viscosity was measured at 25°C using a Brookfield DV-II+Pro viscometer. Tensile strength and elongation were measured according to ISO 527-2. Glass transition temperature was tested using DSC according to ASTM E1356-08. Film curing time (TFST) was measured using a Beck-Koller Drying Recorder according to ASTM D5895.

[0115] Pot life was measured using an evaluation based on gloss. Since aqueous curing agents typically have low viscosity and changes in viscosity over time are usually difficult to observe, a better evaluation of pot life is provided by evaluating the gloss of aqueous curing agents in the form of thin-film coatings. After mixing the epoxy resin and curing agent, the resulting mixture was maintained for a specific time (0, 10, 20, 30, or 60 minutes) and then applied to a thickness of 150 μm. The film appearance was visually graded after 1 day.

[0116] Glossiness was evaluated using a reference scale in which a poor surface was assigned a score of "1" and a mirror-like surface was assigned a score of "5".

[0117] The curing rate was measured by scratching a thin film coating, prepared from the aqueous curing agent and epoxy resin in a predetermined mixing ratio, with a sharp needle using a specially designed apparatus at various time points after the coating was prepared. When measuring the curing rate, the coating film was processed above the carrier, below the apparatus, and its surface was in contact with the tip of the needle. A scratch was then formed on the uncured coating. By observing the appearance of the scratch, a curing phase, or so-called "stage," was determined.

[0118] Surface hardness was tested in relation to the softness of the coating surface being tested, using both a pencil hardness test with a pencil hardness tester and a pendulum hardness test based on the damping of pendulum vibrations. Pencils with hardness grades from 6B to 9H (6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H) were used. The pencils were scratched across the entire surface at a constant pressure at an angle of 45°. Optical evaluation was performed by observing at what hardness level the pencil damaged the surface. The coating films were stored in an environment with a constant temperature of 25°C and a relative humidity of 50%. These samples were tested for their surface hardness 1, 3, and 7 days after their manufacture.

[0119] Synthesis of polyether polyol-modified polyepoxides Polyether polyol modified polyepoxide (Epoxy A) 379 g of polyethylene glycol 1000 (0.758 equivalents of OH) and 490 g of bisphenol A diglycidyl ether having an epoxy equivalent weight of 190 g / eq (2.58 equivalents of epoxy) were charged into a stirred reactor equipped with a thermocouple and a reflux condenser. The ratio of epoxy groups or epoxy equivalents in the polyepoxide compound to hydroxyl groups in the polyol was 3.4:1. 3 g of BF-amine catalyst, commercially available from Evonik Operations GmbH as Anchor® 1040, was then added to the reactor. While the reactor contents were stirred, the reactor temperature rose to 170°C. This temperature was maintained until the epoxy equivalent weight increased to approximately 475-500 g / eq. The reactor contents were then cooled to produce a reaction product named Epoxide A. The epoxy equivalent weight was 498 g / eq, and the viscosity at 40°C was 33 poise (3.3 Pa·s).

[0120] Polyether polyol modified polyepoxide (Epoxy B) Polyether polyol-modified polyepoxide B was synthesized according to the same method described for the synthesis of polyether polyol-modified polyepoxide A. The reactants were 2000 polyethylene glycol 3043.8 g (3.04 equivalents of OH) and 1144.6 g of bisphenol A diglycidyl ether with an epoxy equivalent weight of 190 g / eq (6.09 equivalents of epoxy). The ratio of epoxy groups or epoxy equivalents in the polyepoxide compound to hydroxyl groups in the polyol was 2:1. After the process of synthesizing the polyether polyol-modified epoxide, the final product was named Epoxide B. Its epoxy equivalent weight was 1392 g / eq and its viscosity at 70°C was 668 mPa·s. Viscosity was determined using a Brookfield DV-II+ cone and plate viscometer, CP52 spindle, 100 RPM. Gel chromatography (GPC), THF solvent, and polystyrene calibration standard were used to determine the viscosity.n The (number-average molecular weight) is 4017 g / mol, and M w The weight-average molecular weight was 7866 g / mol. The low molecular weight unreacted epoxy resin was analyzed for its molecular weight distribution and M n and M w It was excluded from the decision.

[0121] 1. Synthesis of benzylated amines in a molar ratio of 1.1:1 210 g (2.0 mol) of DETA, 90 g (0.62 mol) of TETA, and 4.5 g of Pd / C catalyst were placed in a 1-liter autoclave batch reactor. The reactor was sealed and then purged with nitrogen, and then hydrogen, to remove all air from the reactor. 338 g (3.2 mol) of benzaldehyde was added to the reactor over a period of approximately 15-20 minutes. After the addition of benzaldehyde was complete, the reactor contents were stirred for a further 15 minutes or until the reaction was complete, at which point the exothermic reaction began to subside. At this point, the reactor was pressurized with hydrogen to 120 psi and heated to 80°C. When the rate of hydrogen absorption slowed, the pressure was increased to 800 psi and the temperature was raised to 120°C. This hydrogenation process was continued until the hydrogen absorption rate decreased to less than 0.0034 MPa / min (0.5 psi / min). The total hydrogenation time was approximately 5 hours. The catalyst was removed by cooling the reactor to 60°C, releasing the pressure, and filtering the reaction product. Water was removed using a rotary evaporator operated under a 20 mmHg vacuum and a temperature up to 120°C. The resulting reaction product was a benzylated amine with a viscosity of 40 mPa·s, an AHEW of approximately 54 g / eq, a theoretical amine value of 830, and an actual (measured) amine value of 794.

[0122] Synthesis of epoxy-amine adducts Synthesis example (SE) 1 DMAPA (22.15 g, 0.2168 mol, AHEW = 51 g / eq) and DMAPAPA (29.53 g, 0.1854 mol, AHEW = 53 g / eq) were loaded into a 500 mL flask. The mixture was stirred and heated to 80-95°C, and 23.74 g of epoxide B (EEW ​​= 1392 g / eq) was added dropwise. After this addition, 97.98 g of epoxide A (EEW ​​= 498 g / eq) was added dropwise. This reaction was allowed to proceed for 1 hour. Benzylated ethylenediamine (22.09 g) and 2,4,6-tris(dimethylaminomethyl)phenol (3.75 g, as a curing accelerator) were added, and the mixture was cooled. As a final step, the mixture was diluted with deionized water (200.75 g) to obtain an aqueous solution suitable as an aqueous curing agent. The solid content of the epoxy-amine adduct is 50% by weight.

[0123] The product was obtained as a clear liquid with a quantitative yield, having an amine value of 150 meqKOH / g and a viscosity of 599 mPa·s at 25°C. The calculated amine hydrogen equivalent weight was 350.7 g / Eq.

[0124] SE 2 SE 2 utilized the same method as described in SE 1. Its stoichiometric ratios, AHEW, and solids content are shown in Table 1.

[0125] Table 1 shows the quantities of raw materials required to produce the synthetic and comparative (CSE) examples. The measured amine hydrogen equivalent weights, stoichiometric ratios, viscosity, and solids content are also listed at the end.

[0126] CSE 1 had a viscosity of approximately 25,000–45,000 mPa·s at 25°C. CSE 3 exhibited a gel-like appearance, making viscosity testing difficult. Both SE 1 and SE 2 showed significantly lower viscosities than either of the aforementioned CSEs.

[0127] Table 1 [Table 1-1] Table 1 - Continued [Table 1-2]

[0128] Table 2 shows the viscosity values ​​of aqueous mixtures of additives for synthetic and comparative examples with different solid content by weight. Since the CSE 2 sample showed significant gelation, CSE 2 was not tested for viscosity at various solid content levels. A small amount of precipitate was observed in the CSE 4 sample with 30% solid content by weight. More precipitate was observed in the CSE 4 sample with 20% solid content by weight. The viscosity results for CSE 7 were tested after one week of aging.

[0129] Table 2 [Table 2]

[0130] SE 1 and 2 exhibited significantly lower viscosities than the comparative examples under a wide range of solid content (at least within the range of 20% to 50% by weight). This low viscosity makes the epoxy-amine adducts of this disclosure suitable for a variety of applications where low viscosity is desirable.

[0131] Manufacturing and performance of test samples The samples in Test Example (TE) and Comparative Test Example (CTE) were prepared for performance testing by compounding the products (epoxyamine adducts or mixtures) obtained in the corresponding Synthesis Examples (SE 1-SE 2 and CSE 1-CSE 7) with 185-192 g / eq of EEW Epon® 828. The level of epoxyamine adduct used in the diluted resin follows the curing agent usage level, indicated as the curing agent usage level (phr). The epoxyamine adduct was mixed with the epoxy resin using a speed mixer. The coating mixture was then applied to the test substrate and cured in an artificial climate chamber at 25°C and 50% relative humidity. For the TFST test, two samples of the coating mixture were stored in artificial climate chambers at 10°C and 50% relative humidity, and 25°C and 50% relative humidity, respectively.

[0132] The drying time, gloss level, and hardness development were measured accordingly.

[0133] Table 3 [Table 3-1] Table 3 - Continued [Table 3-2]

[0134] The surface hardness of the test sample and the comparative test sample was tested one, three, and seven days after the manufacture of the aforementioned test sample and comparative test sample.

[0135] Table 4: Development of surface hardness [Table 4]

[0136] Based on the measured TFST values, an indicator of the curing process, test examples TE1 and TE2 exhibited significantly faster curing than any of the comparative test examples CTE1-CTE5. The thin film curing time of test example TE1 was similar to that of comparative test examples CTE6 and CTE7.

[0137] Regarding the onset of surface hardness, another indicator of the curing process, test example TE 1 showed faster curing than comparative test example CTE 1. The onset of surface hardness for TE 1 was similar to that of comparative test examples CTE 2 and CTE 6.

[0138] Regarding the development of surface gloss, test example TE 1 showed a longer time to lose coalescence (an indicator of pot life) than CTE 1.

[0139] A variety of embodiments and forms are possible. Some of these embodiments and forms are described herein. After reading this specification, those skilled in the art will understand that these embodiments and forms are for illustrative purposes only and do not limit the scope of this disclosure. Embodiments may follow one or more of the embodiments listed below.

[0140] The above description is provided to enable those skilled in the art to manufacture and use the disclosure and is provided in connection with the application and its requirements. Various modifications to preferred embodiments will be apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Accordingly, the disclosure is not intended to be limited to the embodiments shown, and the broadest scope that does not contradict the principles and features disclosed herein should be accepted. In this regard, certain embodiments within the disclosure may, broadly speaking, not demonstrate all the benefits of the disclosure.

[0141] Preferred embodiments of the present invention are as follows: 1. A water-based epoxy curing agent, a) at least one amine having at least one moiety -QNH- in the formula, where Q is a divalent hydrocarbon group, and the amine has at least one tertiary amino group and at least one primary amino group per molecule; and b) At least one polyether polyol-modified epoxide having one or more epoxy groups A water-based epoxy curing agent containing the reaction products of [the specified substance].

[0142] 2. The aqueous epoxy curing agent described in 1, wherein Q is -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2CH2-, -CH2CH2CH(CH3)-, -CH2CH(CH3)CH2-, -CH(CH3)CH(CH3)-, or -CH2CH(CH2CH3)-.

[0143] 3. The amine is of formula (I): [ka] The aqueous epoxy curing agent according to 1., comprising one or more compounds represented by [wherein n is an integer of 1 or more, and R1 and R2 are independently substituted or unsubstituted C1-C16 alkyl, alkenyl, alkadienyl, cycloalkyl, cycloalkenyl, cycloalkadienyl, aryl, or aralkyl group].

[0144] 4. The amine is N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dipropylaminopropylamine, N,N-dibutylaminopropylamine, N,N-dimethyldipropylenetriamine, N,N-diethyldipropylenetriamine, N 3 -[3-[(3-aminopropyl)amino]propyl]-N 1 ,N 1 The aqueous epoxy curing agent described in 3. is -dimethyl-1,3-propanediamine or a mixture thereof.

[0145] 5. The amine is of formula (II): [ka] The aqueous epoxy curing agent according to 1., comprising one or more compounds represented by the formula [wherein i and j are independently integers of 1 or more, and R1 and R2 are independently substituted or unsubstituted C1-C16 alkyl, alkenyl, alkadienyl, cycloalkyl, cycloalkenyl, cycloalkadienyl, aryl, or aralkyl group].

[0146] 6. The aqueous epoxy curing agent according to 1, wherein the stoichiometric ratio is in the range of 1 to 100, where the stoichiometric ratio is the ratio of the number of equivalents of active amine hydrogen atoms in the amine to the number of equivalents of epoxy groups in the polyether polyol modified epoxide.

[0147] 7. The aqueous epoxy curing agent according to 1, wherein the at least one polyether polyol-modified polyepoxide resin comprises a reaction product of at least one polyepoxide compound and at least one polyether polyol.

[0148] 8. The aqueous epoxy curing agent according to 7, wherein the polyether polyol is selected from polyethylene glycol, polypropylene glycol, or polybutylene glycol.

[0149] 9. The aqueous epoxy curing agent according to 7, wherein the at least one polyepoxide compound is diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, 1,4-butanediol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, or novolac epoxy resin.

[0150] 10. An aqueous epoxy curing agent according to any of the above, further comprising water.

[0151] 11. The aqueous epoxy curing agent according to any one of the above, wherein Q is ethylene, propylene, or butylene.

[0152] 12. The aqueous epoxy curing agent described in 1., further comprising one or more catalysts.

[0153] 13. An aqueous epoxy curing agent according to any one of the above, further comprising one or more additives selected from the group consisting of fillers, reinforcing agents, coupling agents, impact resistance modifiers, defoaming agents, dispersants, lubricants, colorants, marking materials, dyes, pigments, infrared absorbers, ultraviolet absorbers, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retardants, conductive additives, carbon black, graphite, carbon nanotubes, graphene, drying agents, release agents, leveling aids, flame retardants, separating agents, fluorescent whitening agents, rheological additives, photochromic additives, softeners, adhesion accelerators, drip inhibitors, metallic pigments, stabilizers, metallic luminescence pigments, metallic coating particles, pore-forming agents, glass fibers, nanoparticles, or flow aids.

[0154] 14. A method for producing an aqueous epoxy curing agent as described in any of 1 to 13, The amine having at least one molar-QNH- and at least one polyether polyol-modified epoxide having one or more epoxy groups is heated at a temperature of 30°C to 150°C for 0.1 to 6 hours. Includes; The method wherein Q is a divalent hydrocarbon group, and the amine has at least one tertiary amino group and at least one primary amino group per molecule.

[0155] 15. The method according to 14, wherein the stoichiometric ratio of the amine to the epoxide is in the range of a molar ratio of 1 to 100.

Claims

1. A water-based epoxy hardener, a) At least one amine having at least one moiety -QNH- in the formula, where Q is -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)-, -CH2CH2CH2CH2CH2-, -CH2CH2CH(CH3)-, -CH2CH(CH3)CH2-, -CH(CH3)CH(CH3)-, or -CH2CH(CH2CH3)-, and the amine has at least one tertiary amino group and at least one primary amino group per molecule, and the amine is of formula (I): 【Chemistry 1】 [wherein n is an integer of 1 or more, and R1 and R2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl] comprising one or more compounds represented by: and b) At least one polyether polyol-modified epoxide having one or more epoxy groups A water-based epoxy curing agent containing the reaction products of [the specified substance].

2. The amines are N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dipropylaminopropylamine, N,N-dibutylaminopropylamine, N,N-dimethyldipropylenetriamine, N,N-diethyldipropylenetriamine, N ３ -[3-[(3-aminopropyl)amino]propyl]-N １ , N １ The aqueous epoxy curing agent according to claim 1, which is -dimethyl-1,3-propanediamine or a mixture thereof.

3. The aqueous epoxy curing agent according to claim 1, wherein the stoichiometric ratio is in the range of 1 to 100, where the stoichiometric ratio is the ratio of the number of equivalents of active amine hydrogen atoms in the amine to the number of equivalents of epoxy groups in the polyether polyol modified epoxide.

4. The aqueous epoxy curing agent according to claim 1, wherein the at least one polyether polyol-modified polyepoxide comprises a reaction product of at least one polyepoxide compound and at least one polyether polyol.

5. The aqueous epoxy curing agent according to claim 4, wherein the polyether polyol is selected from polyethylene glycol, polypropylene glycol, or polybutylene glycol.

6. The aqueous epoxy curing agent according to claim 4, wherein the at least one polyepoxide compound is diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, 1,4-butanediol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, or novolac epoxy resin.

7. The aqueous epoxy curing agent according to claim 1, further comprising water.

8. The aqueous epoxy curing agent according to claim 1, wherein Q is ethylene, propylene, or butylene.

9. The aqueous epoxy curing agent according to claim 1, further comprising one or more catalysts.

10. The aqueous epoxy curing agent according to claim 1, further comprising one or more additives selected from the group consisting of fillers, reinforcing agents, coupling agents, impact resistance modifiers, defoaming agents, dispersants, lubricants, colorants, marking materials, dyes, pigments, infrared absorbers, ultraviolet absorbers, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retardants, conductive additives, carbon black, graphite, carbon nanotubes, graphene, drying agents, release agents, leveling aids, flame retardants, separating agents, fluorescent whitening agents, rheological additives, photochromic additives, softeners, adhesion accelerators, drip inhibitors, metallic pigments, stabilizers, metallic luminescence pigments, metallic coating particles, pore-forming agents, glass fibers, nanoparticles, or flow aids.

11. A method for producing an aqueous epoxy curing agent according to any one of claims 1 to 10, Heating an amine having at least one moiety-QNH- and at least one polyether polyol-modified epoxide having one or more epoxy groups at a temperature of 30°C to 150°C for 0.1 to 6 hours. Including; The method wherein Q is a divalent hydrocarbon group, and the amine has at least one tertiary amino group and at least one primary amino group per molecule.

12. The method according to claim 11, wherein the stoichiometric ratio of the amine to the epoxide is in the range of a molar ratio of 1 to 100.

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