Epoxy-amine adducts

Abstract

Disclosed in this invention is an epoxy-amine adduct comprising a heterocyclic amine comprising the reaction product of a polyethylene polyamine having 3 to 10 nitrogen atoms with an aldehyde having 1 to 8 carbon atoms, and at least one epoxide having one or more epoxy groups, wherein the heterocyclic amine has at least two nitrogen atoms in at least one ring, and the epoxide is substantially free of polyether modification. Also provided are a curing agent comprising the epoxy-amine adduct and a method for producing the epoxy-amine adduct.

Description

[Technical Field]

[0001] The present disclosure relates to epoxy-amine adducts, particularly epoxy-amine adducts of heterocyclic polyamines and epoxy resins.

[0002] background Epoxy-amine cure systems are often used in coatings. They utilize epoxy resins and curing agents with amine chemistry. For applications such as flooring coatings, there is a growing market demand for improved reactivity and performance at low application temperatures, typically below 15°C, and more frequently below 5°C. However, many of the amine curing agents in coatings suffer from deficiencies at these low temperatures, resulting in slow cure and poor surface quality. These surface defects are often referred to as surface whitening, carbamate formation, or water spot marks.

[0003] Primary amines react with atmospheric carbon dioxide and water to form carbamates, which can bleed and whiten to the surface. Whitening (sometimes called blooming or exudation) can have a detrimental effect on coating performance by causing gloss loss, increased yellowing, poor recoatability, and intercoat adhesion problems. Cold, humid conditions increase the likelihood of whitening.

[0004] In the related art industry, accelerators such as tertiary amines, phenols, phenolic derivatives including Mannich base compounds, or salicylic acid have traditionally been used to increase the rate of amine-epoxy reactions at low temperatures. However, these chemicals should be added at low levels because they can cause the epoxy resin to homopolymerize, weakening the resulting system. Furthermore, these chemicals have a significant impact on the tendency of the final epoxy system to yellow.

[0005] Diethylenetriamine (DETA) is well known for its use as a curing agent for epoxy resins in epoxy adhesives and other thermosetting resins (see WO 2013 / 003202). Recently, as disclosed in EP 3170849, DETA has been converted to a heterocyclic amine having two nitrogen atoms in the ring by reaction with formaldehyde. This cyclic amine can significantly improve the reactivity of epoxy systems at low temperatures. However, serious problems still exist at low application temperatures, such as whitening, slow film drying, and very poor water spot resistance. U.S. Patent Application Publication No. 2017 / 0247501 disclosed aqueous curable compositions obtained from the reaction of a polyalkylene polyether-modified polyepoxide resin with a polyamine component.

[0006] There is a need in the industry for curing agents that have fast curing properties, fast drying at low temperatures, and good early water resistance.

[0007] overview One of the objectives of the present disclosure is to provide an epoxy-amine adduct that can be used as a curing agent and that, when combined with an epoxy resin, can form a coating that has fast curing properties, fast drying properties at temperatures as low as 5°C, and excellent early water resistance.

[0008] This object of the present disclosure is achieved by providing an epoxy-amine adduct comprising: a) a heterocyclic amine comprising the reaction product of a polyethylene polyamine having 3 to 10 nitrogen atoms and an aldehyde having 1 to 8 carbon atoms; and b) at least one epoxide having one or more epoxy groups, wherein the heterocyclic amine has at least two nitrogen atoms in at least one ring, and the epoxide is substantially free of polyether modification.

[0009] Another object of the present disclosure is to provide a curable composition comprising the epoxy-amine adduct of the present disclosure and a plasticizer.

[0010] A further object of the present disclosure is a method for preparing the epoxy-amine adduct of the present disclosure, comprising the steps of: a) heterocyclic amines including the reaction product of a polyethylene polyamine having 3 to 10 nitrogen atoms with an aldehyde having 1 to 8 carbon atoms; and b) at least one epoxide having one or more epoxy groups, heating to a temperature of 120°C to 280°C for 0.5 to 10 hours; The heterocyclic amine has at least two nitrogen atoms in at least one ring, and the epoxide is substantially free of polyether modification; This is achieved by providing a method.

[0011] Detailed Description The following description is used for illustrative purposes only and is not used to limit the scope of the present disclosure.

[0012] The epoxy-amine adduct used in the present invention is a compound formed by combining a) one or more amines and b) one or more epoxides. This combination occurs through a chemical reaction, such as an addition reaction. When an excess amount of polyamine reacts with an insufficient epoxy resin, consuming nearly all of the epoxy groups, an epoxy-amine adduct is formed with the active hydrogen atoms of the remaining amino groups. This adduct typically has a high molecular weight, resulting in low volatility and low emission of amine odors. Furthermore, the reaction of this adduct with the epoxy resin is low in exothermicity.

[0013] wherein the two separate compounds that react to form the epoxy-amine adduct are a heterocyclic amine having at least two nitrogen atoms in at least one ring, and at least one epoxide that is substantially free of polyether modification.

[0014] Polyamines According to one embodiment of the present disclosure, the polyamine is a heterocyclic amine having at least two nitrogen atoms in the ring, as shown in formula (I), or a fused bicyclic heterocyclic amine having three nitrogen atoms, as shown in formula (II): [ka] [wherein X is independently selected from a hydrogen atom, a linear or branched C1-C4 alkyl group, and a substituted or unsubstituted phenyl group; Y1 is a direct bond, a divalent polyethylene polyamine group having 1 to 8 nitrogen atoms, or a divalent polyethylene polyamine derivative having 1 to 8 nitrogen atoms; R is independently a hydrogen atom or a group selected from a C1-C8 alkyl group, an alkenyl group, or an alkaryl group; and Y2 is a direct bond or a divalent polyethylene polyamine group having 1 to 7 nitrogen atoms.] The C1-C4 alkyl group, the polyethylene polyamine group having 1 to 8 nitrogen atoms, and the polyethylene polyamine group having 1 to 7 nitrogen atoms may be branched or unbranched. R may preferably be linear, branched, or cyclic.

[0015] Y1 and Y2 are preferably divalent polyethylene polyamine groups containing repeating units which may be linear or branched. Suitable divalent polyethylene polyamine group repeating units include those of the following formula (III): [ka] wherein R is independently a hydrogen atom or a group selected from a C1-C8 alkyl group, an alkenyl group, or an alkaryl group, and R from two consecutive repeat units can form a 5- or 6-membered ring with the backbone ethylene unit, and n=1-8 for Y1, or n=1-7 for Y2. R may preferably be linear, branched, or cyclic.

[0016] Preferably, the heterocyclic polyamine simultaneously comprises a heterocyclic amine having at least two nitrogen atoms in the ring of formula (I) and a fused bicyclic heterocyclic amine having three nitrogen atoms of formula (II), as shown in the diagram above.

[0017] Preferred examples of X include a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a phenyl group, an isobutyl group, and an n-butyl group. More preferred examples of X include a hydrogen atom, a methyl group, and a phenyl group. The most preferred example of X is a hydrogen atom. Preferred examples of R include a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isobutyl group, an n-butyl group, a 3-methylbutyl group, and a cyclohexyl group. More preferred examples of R include a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a 3-methylbutyl group. The most preferred examples of R are a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group.

[0018] Heterocyclic amines or fused bicyclic heterocyclic amines can be prepared by reacting linear or branched polyethylene polyamines containing 3 to 10 nitrogen atoms with C1-C8 aldehydes. The synthesis protocol is detailed in EP 3170849.

[0019] Polyethylene Polyamine The linear or branched polyethylene polyamines are represented by the general formula (IV): [ka] wherein R is independently a hydrogen atom or a group selected from a C1-C8 alkyl group, an alkenyl group, or an alkaryl group, and n is an integer from 1 to 8. R may preferably be linear, branched, or cyclic.

[0020] Preferred polyethylene polyamines having 3 to 10 nitrogen atoms according to the present disclosure include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures thereof. More preferred polyethylene polyamines having 3 to 10 nitrogen atoms include DETA, TETA, TEPA, and PEHA. Even more preferred polyethylene polyamines are DETA and TETA. An even more preferred polyethylene polyamine is DETA. Preferred structures of linear and branched polyethylene polyamine compounds include those represented by the following formula: [ka] These include, but are not limited to:

[0021] Polyethylene polyamine compounds having 3 to 10 nitrogen atoms may be used individually or mixed together. It should be understood that commonly available polyethylene polyamine compounds having 3 to 10 nitrogen atoms, such as TETA, TEPA, and PEHA, are mixtures of linear and branched isomers and other homologs with cyclic structures. Some linear and branched isomers are listed above, and these commonly available polyethylene polyamine compounds are included in the definition of polyethylene polyamine compounds in the present disclosure.

[0022] According to some embodiments, the polyethylene polyamine compound having 3 to 10 nitrogen atoms is preferably substituted with an alkyl group. For example, the alkylated polyethylene polyamines disclosed in U.S. Patent No. 8,518,547 and the benzylated polyethylene polyamines disclosed in U.S. Patent Nos. 8,147,964 and 8,168,296 are included. The above-mentioned references are incorporated herein by reference.

[0023] aldehyde C1-C8 aldehyde compounds useful for producing heterocyclic polyamines include, but are not limited to, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde, isobutyraldehyde, trimethylacetaldehyde, 2-methylbutyraldehyde, isovaleraldehyde, valeraldehyde, hexanal, phenylacetaldehyde, benzaldehyde, vanillic aldehyde (also known as vanillin), o-tolualdehyde, o-anisaldehyde, salicylaldehyde, and 4-hydroxybenzaldehyde. Suitable examples of C1-C8 aldehyde compounds include formaldehyde, acetaldehyde, benzaldehyde, tolualdehyde, o-anisaldehyde, and salicylaldehyde. Other examples of C1-C8 aldehyde compounds include formaldehyde and benzaldehyde, with formaldehyde being a particularly suitable example. When formaldehyde is used as the C1-C8 aldehyde compound, it is typically used as an aqueous solution containing a certain amount of methanol as a stabilizer for ease of handling. For ease of handling, formaldehyde trimer, 1,3,5-trioxane, and paraformaldehyde in the oligomeric and polymeric forms are all solids and are therefore referred to as equivalents to aqueous formaldehyde solutions. In the present disclosure, paraformaldehyde is used as equivalents to formaldehyde.

[0024] In addition to the heterocyclic amine, the polyamine component may contain at least one polyfunctional amine. The polyfunctional amines used in the present invention are compounds that are amine functional and contain two or more active amine hydrogens.

[0025] Non-limiting examples of polyfunctional amines within the scope of the present disclosure include, but are not limited to, aliphatic amines, cycloaliphatic amines, aromatic amines, Mannich base derivatives of aliphatic amines, cycloaliphatic amines, or aromatic amines, polyamide derivatives of aliphatic amines, cycloaliphatic amines, or aromatic amines, amidoamine derivatives of aliphatic amines, cycloaliphatic amines, or aromatic amines, amine adduct derivatives of aliphatic amines, cycloaliphatic amines, or aromatic amines, and the like, or any combination thereof.

[0026] Preferably, the composition of the present disclosure uses two or more polyfunctional amines. For example, the at least one polyfunctional amine includes an aliphatic amine and a Mannich base derivative of an alicyclic amine. Also, the at least one polyfunctional amine includes one aliphatic amine and one different aliphatic amine.

[0027] Examples of aliphatic amines include polyethyleneamines (such as ethylenediamine or EDA, diethylenetriamine or DETA, triethylenetetraamine or TETA, tetraethylenepentamine or TEPA, pentaethylenehexamine or PEHA), 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 Dytec A), and the like, or combinations thereof. Additionally, poly(alkylene oxide) diamines and triamines commercially available under the Jeffamine name from Huntsman Corporation are useful in the present disclosure. Illustrative 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, and the like, or combinations thereof.

[0028] 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, meta-xylylenediamine, hydrogenated meta-xylylenediamine (commercially known as 1,3-BAC), isophoronediamine (IPDA), various isomers or norbornanediamines, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 2,4'-diaminodicyclohexylmethane, mixtures of methylene-bridged poly(cyclohexyl-aromatic)amines, etc., or combinations thereof. Mixtures of methylene-bridged poly(cyclohexyl-aromatic)amines, abbreviated as either MBPCAA or MPCA, are described in U.S. Pat. No. 5,280,091, the entire contents of which are incorporated herein by reference. In one embodiment of the present disclosure, the at least one multifunctional amine is a mixture of methylene-bridged poly(cyclohexyl-aromatic)amines (MPCA).

[0029] Mannich base derivatives can be prepared by reacting the above-mentioned aliphatic amines, alicyclic amines, or aromatic amines with phenol or substituted phenols and formaldehyde. In this disclosure, an example of a substituted phenol that is practically used to prepare Mannich bases is cardanol obtained from cashew nut shell liquid. Alternatively, Mannich bases can be prepared by the exchange reaction of a polyfunctional amine with a tertiary amine containing a Mannich base, such as tris-dimethylaminomethylphenol (commercially available as Ancamine® K54 from Evonik Operation GmbH) or bis-dimethylaminomethylphenol.

[0030] Polyamide derivatives may be prepared by reacting an aliphatic, cycloaliphatic, or aromatic amine with a dimer fatty acid or a mixture of a dimer fatty acid and a fatty acid. Amidoamine derivatives may be prepared by reacting an aliphatic, cycloaliphatic, or aromatic amine with a fatty acid.

[0031] Amine adducts may be prepared by the reaction of aliphatic, cycloaliphatic, or aromatic amines with epoxy resins such as the diglycidyl ether of bisphenol A, the diglycidyl ether of bisphenol F, or epoxy novolac resins. The aliphatic, cycloaliphatic, and aromatic amines may be adducted with monofunctional epoxy resins such as phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, other alkyl glycidyl ethers, and the like.

[0032] In another aspect of the present disclosure, the curing agent includes a co-curing agent, which may be an amidoamine curing agent, an aliphatic curing agent, a polyamide curing agent, a cycloaliphatic curing agent, or a Mannich base curing agent that also includes a phenalkamine.

[0033] Epoxide According to the present disclosure, the epoxide is substantially free of polyether modifications. Preferably, the epoxide includes at least one mono- or multi-functional epoxide.

[0034] The at least one monofunctional epoxide includes one or more epoxides or epoxy resins having one epoxy group per molecule, and the at least one multifunctional epoxide includes, but is not limited to, epoxides having two, three, four, or at least five epoxy groups per molecule.

[0035] Useful compounds include numerous compounds known for this purpose that contain two or more epoxy groups per molecule, preferably two. These epoxy compounds are preferably either saturated or unsaturated. They are preferably aliphatic, alicyclic, aromatic, or heterocyclic and contain hydroxyl groups. They preferably contain substituents that do not undergo side reactions under the mixing or reaction conditions, such as alkyl or aryl substituents, ether moieties, etc. They are preferably glycidyl ethers derived from polyhydric phenols, especially bisphenols and novolaks, and have a molar mass based on the number of epoxy groups (EEW, "epoxy equivalent weight," "EV value") of 100 to 1500 g / eq, especially 150 to 250 g / eq.

[0036] Examples of polyhydric phenols include resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-glycidyloxyphenyl)methane (bisphenol E), an isomeric mixture of dihydroxydiphenylmethane (bisphenol F), 4,4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-dihydroxydiphenyl, and 4,4'-dihydroxybenzophenone. Bisphenol A and bisphenol F liquid diglycidyl ethers having an epoxy equivalent weight of 150 to 200 g / eq are particularly preferred.For example, polyglycidyl ethers of the following polyols may also be used: 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-polyoxy Ethylene-propylene glycol diglycidyl ether, polyoxytetramethylene glycol diglycidyl ether, polyglycidyl ethers of glycerol, hexane-1,2,6-triol, trimethylolpropane, trimethylolethane, pentaerythritol, or sorbitol, polyglycidyl ethers of oxyalkylated polyols (such as glycerol, trimethylolpropane, pentaerythritol, among others), diglycidyl ethers of cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane, and 2,2-bis(4-hydroxycyclohexyl)propane, polyglycidyl ethers of castor oil, triglycidyl tris(2-hydroxyethyl)isocyanurate.

[0037] Further useful components A) include poly(N-glycidyl) compounds obtained by dehydrohalogenation of the reaction products of epichlorohydrin with amines, such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine, or bis(4-methylaminophenyl)methane. Poly(N-glycidyl) compounds also include triglycidyl isocyanurate, triglycidyl urazole and its oligomers, N,N'-diglycidyl derivatives of cycloalkylene ureas, and especially diglycidyl derivatives of hydantoin.

[0038] Monofunctional epoxides include, but are 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; epoxy ethers of monohydric alcohols such as methyl, ethyl, butyl, 2-ethylhexyl, and dodecyl alcohol; epoxy ethers of monohydric phenols such as phenol, cresol, and other phenols substituted at the ortho- or para-positions; glycidyl esters of unsaturated carboxylic acids; epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids; acetals of glycidaldehyde; or combinations thereof. Monofunctional glycidyl ethers are preferably o-cresyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, or any alkyl C8-C 14 glycidyl ethers, or any combination thereof.

[0039] Polyfunctional epoxides include, but are not limited to, bisphenol A diglycidyl ether, bisphenol E diglycidyl ether, bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, novolac type epoxy resins, any other aliphatic diglycidyl ether or triglycidyl ether, any other alicyclic diglycidyl ether or triglycidyl ether, or any combination thereof. Preferably, the multifunctional epoxide is bisphenol A epoxy resin, bisphenol E diglycidyl ether, bisphenol F epoxy resin, 1,4-butanediol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, novolac type epoxy resin, or a combination thereof.

[0040] Preferably, the epoxide does not have any alkoxylate repeat units. The alkoxylate repeat units are of the formula: [ka] where n is an integer equal to or greater than 1 and R represents hydrogen, methyl, ethyl, or any other alkyl-containing monovalent group. Alkoxylate repeat units include, but are not limited to, ethoxylate, propoxylate, butoxylate, or any other alkoxylate.

[0041] Additionally, polyglycidyl esters of polycarboxylic acids obtained by reacting epichlorohydrin or similar epoxy compounds with aliphatic, cycloaliphatic, 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 dicarboxylic acids, such as dimerized or trimerized linoleic acid, can also be used, such as diglycidyl adipate, diglycidyl phthalate, and diglycidyl hexahydrophthalate.

[0042] Furthermore, mention should be made of glycidyl esters of unsaturated carboxylic acids, epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids. In addition to polyglycidyl ethers, 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 isomeric mixtures of higher alcohols, C 12 ~C 13 Glycidyl ethers of mixtures of alcohols, phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, p-octylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, glycidyl ethers of alkoxylated lauryl alcohol, and monoepoxides, such as epoxidized monounsaturated hydrocarbons (butylene oxide, cyclohexene oxide, styrene oxide), can also be used in proportions of up to 30% by weight, preferably 10 to 20% by weight, based on the mass of the polyglycidyl ether.

[0043] Preferred examples of useful epoxy compounds include glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A, bisphenol E, and / or bisphenol F, and glycidyl methacrylate. Other examples of such epoxides include triglycidyl isocyanurate (TGIC, trade name: ARALDIT 810, Huntsman), a mixture of diglycidyl terephthalate and triglycidyl trimellitate (trade names: ARALDIT PT 910 and 912, Huntsman), glycidyl ester of Versatic acid (trade name: CARDURA E10, Shell), 3,4-epoxycyclohexylmethyl 3,4'-epoxycyclohexanecarboxylate (ECC), ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythrityl tetraglycidyl ether (trade name: POLYPDX R 16, UPPC AG), and other Polypox products with free epoxy groups. Mixtures of the above epoxy compounds may also be used.

[0044] Particularly preferred epoxy components are 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-based polyepoxides.

[0045] According to the present disclosure, it is also possible to preferably use mixtures of these epoxy compounds in the epoxy resin.

[0046] Epoxy resins can be in various forms, such as crystalline, powder, semi-solid, or liquid. In liquid form, the epoxy resin may be dissolved in a solvent, such as water. It is preferred that the epoxy resin be in liquid form to facilitate the mixing process.

[0047] Epoxides are commercially available from various chemical manufacturers, such as DER™ 331, 332, 337, 351, or 731 from Olin Corporation, and Epodil® 742, 746, 747, 748, 750, 733, and 762 from Evonik Resource Efficiency GmbH. For example, European Patent Application Publication No. 675185 also describes several epoxy compounds.

[0048] Synthesis of adducts The addition reaction for synthesizing the epoxy-amine adducts according to the present disclosure involves contacting a heterocyclic amine with an epoxide, preferably in the presence of a plasticizer, the details of which are described below.

[0049] The reaction of the heterocyclic amine with the epoxide preferably 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 70°C to about 100°C. The elevated temperature ensures a rapid and complete addition reaction. The heating conditions are continued for 0.5 to 10 hours, preferably 1 to 5 hours. Preferably, the heating conditions are accompanied by vigorous stirring, such as stirring at 100 RPM, 150 RPM, or 200 RPM.

[0050] The reaction is preferably carried out under a protective atmosphere, more preferably under a nitrogen or argon atmosphere, in part to protect the amine from oxidation or other threats.

[0051] The synthesis is preferably carried out in the presence of a solvent or plasticizer. Preferred solvents or plasticizers for the reaction include, but are not limited to, water, acetonitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, Dowanol™ PM, t-butanol, isobutanol, and benzyl alcohol, and hydrocarbons such as toluene, xylene, hexane, and heptane. More preferred reaction solvents or plasticizers include water, methanol, ethanol, n-propanol, i-propanol, n-butanol, Dowanol™ PM, or benzyl alcohol. The solvent is preferably removed after the reaction is complete or remains mixed with the adduct. For example, after the reaction of an epoxide with an amine, benzyl alcohol remains as a plasticizer.

[0052] stoichiometric ratio In this disclosure, the stoichiometric ratio is calculated as the ratio of the number of equivalents of active amine hydrogens in the heterocyclic polyamine to the number of equivalents of epoxy groups in the epoxide. The chemical equivalent ratio is calculated using the following formula:

number

[0053] In producing the epoxy-amine adducts according to the present disclosure, the stoichiometric ratio is preferably in the range of 3-100, more preferably in the range of 4-40, and more preferably in the range of 5-15.

[0054] This stoichiometric ratio results in the epoxy-amine adduct having many unreacted hydrogen atoms bonded to the nitrogen atoms, reducing the reactivity of the adduct when mixed with an epoxy resin. If the stoichiometric ratio of epoxide to heterocyclic amine is too low, for example, less than 0.005, the resulting epoxy-amine adduct will have a low molecular weight and many primary amino groups will remain in the heterocyclic amine. The resulting adduct will have high reactivity with the epoxy resin, potentially reducing the surface quality of the final coating. If the stoichiometric ratio of epoxide to heterocyclic amine is too high, for example, greater than 0.40, the degree of crosslinking may be high, and the molecular weight of the adduct may become very high. The adduct may have a high viscosity due to the high level of crosslinking, making it unsuitable for use as a curing agent.

[0055] hardener The present disclosure further provides a curing agent comprising an epoxy-amine adduct. The curing agent is used to cure epoxy resins to form coatings, adhesives, sealants, etc. The curing agent includes one or more plasticizers in addition to the epoxy-amine adduct.

[0056] In some embodiments of the present disclosure, a plasticizer is added to the epoxy-amine adduct to form the curing agent. Preferably, the plasticizer is selected from the group consisting of aromatic compounds, aliphatic compounds, esters, ketones, ethers, alcohols, glycols, glycol ethers, and the like, and mixtures thereof. More preferably, ketones, such as acetone, methyl ethyl ketone, methyl isoamyl ketone, methyl propyl ketone, methyl amyl ketone, and diacetone alcohol, are used as plasticizers, often resulting in improved pot life with little or no sacrifice in drying speed. When ester plasticizers, such as esters of phthalic acid, are included in a composition or formulation, they typically need to be formulated in a package containing the epoxy resin to minimize reaction with the amine curing agent. Other preferred plasticizers include, but are not limited to, benzyl alcohol, n-butanol, isopropanol, toluene, xylene, nonylphenol, dodecylphenol, t-butylphenol, bisphenol A, cresol, cashew nut shell liquid, propylene glycol monomethyl ether (often abbreviated as PM), or aliphatic and / or aromatic hydrocarbon solvents, such as those commercially available under the trade name Shellsol. A mixture of two or more plasticizers or solvents may be used. Preferably, the at least one plasticizer used in the epoxy-amine adduct of the present disclosure includes benzyl alcohol, n-butanol, xylene, methyl ethyl ketone, nonylphenol, dodecylphenol, cardanol, esters of phthalic acid, or a combination thereof.

[0057] Epoxy Resin in Coating Composition The curing agents of the present disclosure are used with epoxy resins already known in the art to form coating compositions, preferably the epoxy resin is the same as or different from the epoxide used in the synthesis of the epoxy-amine adduct.

[0058] Many compounds known for this purpose are useful, including those containing two or more epoxy groups per molecule, preferably two. These epoxy compounds are preferably either saturated or unsaturated. They are preferably aliphatic, alicyclic, aromatic, or heterocyclic and contain hydroxyl groups. They preferably contain substituents that do not undergo side reactions under the mixing or reaction conditions, such as alkyl or aryl substituents, ether moieties, etc. They are preferably glycidyl ethers derived from polyhydric phenols, particularly bisphenols and novolaks, and have a molar mass based on the number of epoxy groups ME ("epoxy equivalent weight," "EV value") of 100 to 1500 g / eq, particularly 150 to 250 g / eq.

[0059] Examples of polyhydric phenols include resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-glycidyloxyphenyl)methane (bisphenol E), an isomeric mixture of dihydroxydiphenylmethane (bisphenol F), 4,4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzof Bisphenol A and bisphenol F liquid diglycidyl ethers having an epoxy equivalent weight of 150 to 200 g / eq are particularly preferred.For example, polyglycidyl ethers of the following polyols may also be used: 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-polyoxy Ethylene-propylene glycol diglycidyl ether, polyoxytetramethylene glycol diglycidyl ether, polyglycidyl ethers of glycerol, hexane-1,2,6-triol, trimethylolpropane, trimethylolethane, pentaerythritol, or sorbitol, polyglycidyl ethers of oxyalkylated polyols (such as glycerol, trimethylolpropane, pentaerythritol, among others), diglycidyl ethers of cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane, and 2,2-bis(4-hydroxycyclohexyl)propane, polyglycidyl ethers of castor oil, triglycidyl tris(2-hydroxyethyl)isocyanurate.

[0060] Further useful components A) include poly(N-glycidyl) compounds obtained by dehydrohalogenation of the reaction products of epichlorohydrin with amines, such as aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine, or bis(4-methylaminophenyl)methane. Poly(N-glycidyl) compounds also include triglycidyl isocyanurate, triglycidyl urazole and its oligomers, N,N'-diglycidyl derivatives of cycloalkylene ureas, and especially diglycidyl derivatives of hydantoin.

[0061] Additionally, polyglycidyl esters of polycarboxylic acids obtained by reacting epichlorohydrin or similar epoxy compounds with aliphatic, cycloaliphatic, 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 dicarboxylic acids, such as dimerized or trimerized linoleic acid, can also be used. Examples include diglycidyl adipate, diglycidyl phthalate, and diglycidyl hexahydrophthalate.

[0062] Furthermore, mention should be made of glycidyl esters of unsaturated carboxylic acids, epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids. In addition to polyglycidyl ethers, 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 isomeric mixtures of higher alcohols, C 12 ~C 13 Glycidyl ethers of mixtures of alcohols, phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, p-octylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, glycidyl ethers of alkoxylated lauryl alcohol, and monoepoxides, such as epoxidized monounsaturated hydrocarbons (butylene oxide, cyclohexene oxide, styrene oxide), can also be used in proportions of up to 30% by weight, preferably 10 to 20% by weight, based on the mass of the polyglycidyl ether.

[0063] Useful epoxy compounds preferably include glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A, bisphenol E, and / or bisphenol F, and glycidyl methacrylate. Other examples of such epoxides include triglycidyl isocyanurate (TGIC, trade name: ARALDIT 810, Huntsman), a mixture of diglycidyl terephthalate and triglycidyl trimellitate (trade names: ARALDIT PT 910 and 912, Huntsman), glycidyl ester of Versatic acid (trade name: CARDURA E10, Shell), 3,4-epoxycyclohexylmethyl 3,4′-epoxycyclohexanecarboxylate (ECC), ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythrityl tetraglycidyl ether (trade name: POLYPDX R 16, UPPC AG), and other Polypox products with free epoxy groups. Mixtures of the above epoxy compounds may also be used.

[0064] Particularly preferred epoxy components are 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-based polyepoxides.

[0065] According to the present disclosure, it is also possible to preferably use mixtures of these epoxy compounds in the epoxy resin.

[0066] Epoxy resins can be in various forms, such as crystalline, powder, semi-solid, or liquid. If in liquid form, the epoxy resin may be dissolved in a solvent, such as water. It is preferred that the epoxy resin be in liquid form to facilitate the mixing process.

[0067] Coating Composition The present disclosure further provides a coating composition comprising the epoxy-amine adduct and at least one epoxy resin.

[0068] In order to provide more functionality or features to meet industrial requirements, the coating composition preferably contains additives. Additives are understood to mean substances added to change the properties of the coating composition in a desired direction, such as viscosity, wetting properties, stability, reaction rate, blister formation, storage properties or adhesion, and use properties to suit the end use. Some additives are described, for example, in WO 99 / 55772, pages 15-25.

[0069] Preferred additives are selected from the group consisting of fillers, reinforcing agents, coupling agents, toughening agents, antifoaming agents, dispersants, lubricants, colorants, marking materials, dyes, pigments, IR absorbers, antistatic agents, antiblocking agents, nucleating agents, crystallization promoters, crystallization retarders, conductive additives, carbon black, graphite, carbon nanotubes, graphene, drying agents, mold release agents, leveling aids, flame retardants, separating agents, optical lighteners, rheology additives, photochromic additives, flexibilizers, adhesion promoters, anti-drip agents, metallic pigments, stabilizers, metallic luster pigments, metal coated particles, porosity inducers, glass fibers, nanoparticles, flow aids, or combinations thereof.

[0070] The additives preferably constitute no more than 90% by weight, preferably no more than 70% by weight, more preferably no more than 50% by weight, even more preferably no more than 30% by weight, relative to the total weight of the coating composition.

[0071] For example, it may be advantageous to add a total amount of 0.05% to 5% by weight of light stabilizers, such as sterically hindered amines, or other auxiliaries, such as those mentioned.

[0072] To prepare the curable composition of the present disclosure, it is further possible to add additives such as leveling agents, such as polysilicones, or adhesion promoters, such as acrylates. In addition, other components may also be present as needed. The auxiliary agents and additives used may also be chain transfer agents, plasticizers, stabilizers and / or inhibitors.

[0073] Optionally, the coating composition preferably contains an antioxidant additive. The antioxidant may comprise one or more structural units selected from sterically hindered phenols, sulfides, or benzoates. In the sterically hindered phenols, two ortho-hydrogens are replaced with compounds that are not hydrogen, preferably having at least 1 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and are preferably branched. The benzoates also preferably have a substituent at the ortho position relative to the OH group that is not hydrogen, and that is preferably branched, and has 1 to 20 carbon atoms, more preferably 3 to 15 carbon atoms.

[0074] In yet another embodiment, one or more catalysts are optionally incorporated into, and preferably as part of, the coating composition to promote the reaction between the epoxy groups of the epoxy resin and the amine groups of the coating composition. Useful catalysts that can be incorporated into the adhesive composition include Ancamide® products available from Evonik Resource Efficiency GmbH and products marketed as "Accelerators" available from Huntsman Corporation. One exemplary catalyst is piperazine-based Accelerator 399 available from Huntsman Corporation. If used, such catalysts preferably comprise from 0% to about 10% by weight of the total adhesive composition.

[0075] Preferably, a coating composition according to the present disclosure consists of the components identified above.

[0076] The present disclosure also relates to articles of manufacture comprising the compositions disclosed herein. For example, the article may include a coating composition comprising the reaction product of an epoxy-amine adduct and an epoxy composition. Articles of manufacture 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 also be applied to metal or cementitious substrates. Coatings based on these coating compositions may be solvent-free or contain diluents, such as water or organic solvents, as needed for specific applications. Coatings may contain various types and levels of pigments for use in paint and primer applications. For use in protective coatings applied to metal substrates, the coating composition may comprise a layer having a thickness ranging from 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 may comprise a layer having a thickness ranging from 50 to 10,000 μm, depending on the type of product and the desired final properties. Coating products that offer limited mechanical and chemical resistance have layers with thicknesses in the range of 50 to 500 μm, preferably 100 to 300 μm; on the other hand, coating products such as self-leveling floors that offer high mechanical and chemical resistance have layers with thicknesses in the range of 1,000 to 10,000 μm, preferably 1,500 to 5,000 μm.

[0077] Those skilled in the art will recognize that the coatings of the present disclosure, with appropriate surface preparation, are suitable for use on many substrates, including, but not limited to, concrete and various types of metals and alloys, such as steel and aluminum. The coatings of the present disclosure are suitable for painting or coating large metal objects or cementitious substrates, such as ships, bridges, industrial plants and equipment, and floors.

[0078] The coatings of the present disclosure may be applied by any number of techniques, including spray, brush, roller, paint mitt, etc. To apply the very high solids or 100% solids coatings of the present disclosure, a multi-component spray application device can be used, where the amine and epoxy components are mixed in the line leading to the spray gun, within the spray gun itself, or the two components are combined as they exit the spray gun. The use of this technique can alleviate limitations associated with the formulation's pot life, which typically decreases as both the amine reactivity and solids content increase. Heated multi-component devices can be employed to reduce the viscosity of the components, thereby further facilitating application.

[0079] Construction and flooring applications include compositions comprising the coating compositions of the present disclosure in combination with concrete or other materials commonly used in the construction industry. Applications of the compositions of the present disclosure include, but are not limited to, using the compositions as primers, deep-penetration primers, coatings, curing compounds, and / or sealants for new or old concrete, as referenced in ASTM C309-97, which is incorporated herein by reference. The coating compositions of the present disclosure can be applied to surfaces as primers or sealants prior to the application of a coating to improve adhesive bonds. With respect to concrete and cement applications, a coating is an agent applied to a surface to create a protective or decorative layer or covering. Crack injection and crack filling products can also be prepared from the compositions disclosed herein. The coating compositions of the present disclosure may be mixed with cementitious materials, such as concrete mix, to form polymer or modified cements, tile grouts, and the like. Non-limiting examples of composite products or articles comprising the coating compositions disclosed herein include tennis rackets, skis, bike frames, airplane wings, fiberglass-reinforced composites, and other molded articles.

[0080] In a specific application in the present disclosure, these curing agent compositions can be applied to the manufacture of epoxy filament-wound tanks, injection composites such as wind turbine blades, aerospace adhesives, industrial adhesives, and other related applications. Composites are materials made from various substances. In resin technology, composites refer to resin-impregnated systems in which the resin is reinforced by adding reinforcing materials such as fillers and fibers, improving the general properties of the resulting product. These materials work together but do not dissolve in each other. In this application, the binder component includes an epoxy resin and an epoxy curing agent. There are many types of composite applications, such as prepreg, laminate, filament winding, braiding, pultrusion, wet laying, and injection composites. Resin infusion or resin transfer molding is a method in which resin is introduced into a composite mold, and the reinforcing material is already placed in the mold and closed before the resin is introduced. Variations of this method exist, such as vacuum-assisted or (high) pressure resin transfer.

[0081] The use of epoxy resins cured and / or crosslinked with amine-based curing agents is well known. These coating materials are used in a wide variety of applications, including coatings, primers, tie coats, and finishes. They can be applied to many substrates. They can be used in laminates, adhesives, flooring, dust-free finishes, secondary containment, linings, reinforcements, repair compounds, tooling, potting, and casting. They can be used in a variety of industries, such as construction (food production, bridges, sewage treatment plants), automotive, marine applications (ship painting, buoy painting, shipping containers), aviation (part bonding, honeycomb reinforcement for cabin structures, satellite re-entry shields), electronics (printed circuit boards, potting for electronic components, wire insulation), sports (tennis rackets, golf clubs, canoes, skis), and many more applications, such as filament winding for containers and tanks, laminates for wind energy, aircraft propellers, syntactic foams, and many others known to those skilled in the art.

[0082] The present disclosure also includes articles of manufacture containing the above-described coating compositions. Such articles include, but are not limited to, adhesives, coatings, primers, sealants, curing compounds, building products, flooring products, composite products, laminates, potting compounds, grouts, fillers, cement-based grouts, or self-leveling flooring. Additional components or additives may be used together with the compositions of the present disclosure to produce articles of manufacture. Furthermore, such coatings, primers, sealants, curing compounds, or grouts may be applied to metal or cement substrates.

[0083] The present disclosure is illustrated by the following examples and comparative examples.

[0084] Example In the following examples, the materials or definitions used are as follows:

[0085] DER™ 331 is a diglycidyl ether of bisphenol A manufactured by Olin Corporation and is a liquid reaction product of epichlorohydrin and bisphenol A. DER™ 331 has an EEW of 182-192 g / mol.

[0086] Epodil® 742, an o-cresyl glycidyl ether manufactured by Evonik Specialty Chemicals, is a monofunctional reactive diluent used to reduce the viscosity of epoxy resin systems. Epodil® 742 has an EEW of 167-195 g / mol.

[0087] Epodil® 748 is a 12 ~C 14 A glycidyl ether of a mixture of aliphatic alcohols, Epodil® 748 is a monofunctional reactive diluent used to reduce the viscosity of epoxy resin systems, providing excellent viscosity reduction. Epodil® 748 has an EEW of 275-300 g / mol.

[0088] Benzyl alcohol, commercially available from Fisher Scientific UK Ltd., is an aryl alcohol and is used as a plasticizer.

[0089] The amine hydrogen equivalent weight (g / mol) or AHEW is calculated as the molecular weight of the amine as a curing agent divided by the number of active hydrogen atoms per molecule.

[0090] The epoxy group content, denoted as epoxide equivalent weight or EEW, is the ratio of the molecular weight of the epoxide to the number of epoxy groups.

[0091] The stoichiometric ratio is calculated as the ratio of the number of equivalents of active amine hydrogens in the heterocyclic polyamine to the number of equivalents of epoxy groups in the epoxide.

number

[0092] The hardener use level is the dosage of hardener relative to the resin, taken as 100. In the synthesis examples, the hardener use level is calculated as the amount of epoxy-amine adduct per diluted epoxy resin having an EEW of 195 g / mole.

[0093] To test the physical performance or properties of the samples, the following protocol is used: Viscosity was measured with a Brookfield DV-II+Pro viscometer at 25° C. Tensile strength and elongation were measured according to ISO 527-2. Glass transition temperature was tested using DSC according to ASTM E1356-08.

[0094] Drying times were tested on a BY drying recorder according to ASTM D5895. Stage 1 is also known as "tack-free time". Stage 2 represents "tack-free time". Stage 3 represents "cure dry time". Stage 4 is "cure dry time".

[0095] The hardness was tested using a Shore D tester according to Chinese national standard GB / T2411.

[0096] Water spot resistance, also known as "carbamation resistance" or "whitening resistance," was measured according to the test method described below. After curing for a certain period of time, such as one or two days, a cotton ball soaked in water was placed on the coating surface and then covered with water glass. The next day, the cotton ball was removed and the appearance of the coating surface was visually evaluated and rated using a number from 1 to 5 as shown in Table 1.

[0097] [Table 1]

[0098] For flooring applications, a Stage 3 duration of less than 16 hours is preferred, and a Stage 4 duration of less than 24 hours is more preferred. Coatings with a Shore D hardness greater than 50 are typically suitable for light traffic and foot traffic. A final Shore D hardness greater than 75 is preferred. A water spot resistance rating of 3 is the minimum requirement for flooring coating surfaces. A 1d water spot resistance rating of 4 is highly preferred.

[0099] Synthesis of heterocyclic polyamines Diethylenetriamine (DETA, 650 g) was charged to a reactor equipped with a nitrogen inlet, condenser, addition funnel, and overhead stirrer. Aqueous formaldehyde (818.1 g) was added to the DETA via the addition funnel to maintain the temperature below 60 °C. After the addition, the reaction was maintained at 60 °C for 30 minutes. The water was then removed under reduced pressure. The product was obtained as a clear liquid in quantitative yield with an amine value of 873 mEq KOH / g and a viscosity of 8,900 mPa·s at 25 °C. The amine hydrogen equivalent weight was calculated to be 68 g / eq. NMR analysis indicated that 39 mol% of the DETA had formed 1-(2-aminoethyl)imidazolidine, representing 37 wt% of the calculated total product weight.

[0100] For convenience, the synthesized heterocyclic polyamine will be referred to hereinafter as "PA1."

[0101] Synthesis of epoxy-amine adducts A comparative synthetic example (CSE) sample was prepared by mixing benzyl alcohol with PA1 at room temperature without the addition of epoxide.

[0102] The samples of Synthesis Examples SE1-SE13 were synthesized according to the protocols described below. The reactant weights, total weights, amine hydrogen equivalents, and stoichiometric ratios for CSE and SE1-SE13 are shown in Tables 2 and 3.

[0103] First, PA1 was dissolved in benzyl alcohol and heated to 80°C under a N2 atmosphere. Then, epoxy resin DER™ 331 or Epodil® 742 was slowly added to this solution. The resulting mixture was stirred at 80°C to 85°C for 1 hour. The resulting product was cooled to 50°C and discharged.

[0104] [Table 2]

[0105] [Table 3]

[0106] Test sample preparation and performance For performance testing, test examples (TE1-TE13) and comparative test examples (CTE) were prepared by compounding the products (adducts or mixtures) obtained in the corresponding synthesis examples (SE1-SE13 and CSE) with an EEW of 195 g / mol. The diluted resin was a 90:10 resin blend of DER™ 331 and Epodil® 748 by weight. The epoxy-amine adduct use level relative to the diluted resin was determined according to the curing agent use level (phr). All samples were conditioned at 5°C for 24 hours before testing. The epoxy-amine adduct was mixed with the diluted resin using a speed mixer at 1,500 rpm for 2 minutes. The resulting coating mixture was then applied to the test substrate and cured in a climate chamber at 5°C and 85% relative humidity.

[0107] Details of CTE and TE1 to TE13 are listed in Tables 4 and 5.

[0108] Drying time, hardness development, and water spot resistance were measured accordingly.

[0109] [Table 4]

[0110] [Table 5]

[0111] Synthetic Examples TE3, 4, 10, and 11 showed excellent results with respect to fast dry time, hardness development, and water spot resistance at 5° C., which are desirable properties for winter floor coating applications.

[0112] Various aspects and embodiments are possible. Some of these aspects and embodiments are described herein. After reading this specification, those skilled in the art will understand that these aspects and embodiments are merely exemplary and do not limit the scope of the present disclosure. The embodiment may be according to any one or more of the following embodiments:

[0113] The above description is presented to enable any person skilled in the art to make and use the present disclosure, and is provided in the context of an application and its requirements. Various modifications to the preferred embodiment 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 present disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. In this regard, certain embodiments within the present disclosure may not represent all of the benefits of the present disclosure when considered broadly.

Claims

1. An epoxy-amine adduct for forming a coating, comprising: a) heterocyclic amines comprising the reaction product of a polyethylene polyamine having 3 to 10 nitrogen atoms with an aldehyde having 1 to 8 carbon atoms; and b) at least one epoxide having one or more epoxy groups; and the heterocyclic amine has at least two nitrogen atoms in at least one ring, and the epoxide is substantially free of polyether modification; a stoichiometric ratio in the range of 3 to 100, said stoichiometric ratio being the ratio of the number of equivalents of active amine hydrogens of said heterocyclic amine to the number of equivalents of epoxy groups in said epoxide; the polyethylene polyamine is selected from diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures thereof; and The aldehyde is selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, trimethylacetaldehyde, 2-methylbutyraldehyde, isovaleraldehyde, valeraldehyde, and hexanal; Epoxy-amine adducts.

2. 2. The epoxy-amine adduct of claim 1, wherein the stoichiometric ratio is in the range of 4 to 40.

3. 3. The epoxy-amine adduct of claim 1 or 2, wherein the epoxide comprises one or more monofunctional or polyfunctional epoxides.

4. The epoxide may be o-cresyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, or any alkyl C ８ ~C １４ 4. The epoxy-amine adduct of claim 1, further comprising one or more monofunctional epoxides selected from the group of glycidyl ethers.

5. 5. The epoxy-amine adduct of claim 1, wherein the epoxide comprises one or more multifunctional epoxides selected from the group consisting of bisphenol A diglycidyl ether, bisphenol E diglycidyl ether, bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, or Novalac epoxy resin.

6. The heterocyclic amine is represented by formula (I): 【Chemistry 1】 [wherein X independently represents a hydrogen atom, a linear or branched C １ ~C ４ is selected from an alkyl group, or a substituted or unsubstituted phenyl group; Y １ is a direct bond or a divalent polyethylenepolyamine group having 1 to 8 nitrogen atoms, and R is independently a hydrogen atom or C １ ~C ８ is a group selected from an alkyl group, an alkenyl group, or an alkaryl group.

6. The epoxy-amine adduct of claim 1, comprising at least one amine represented by

7. The heterocyclic amine is represented by formula (II): 【Chemistry 2】 [wherein X independently represents a hydrogen atom, a linear or branched C １ ~C ４ is selected from an alkyl group, or a substituted or unsubstituted phenyl group; Y ２ is a direct bond or a divalent polyethylenepolyamine group having 1 to 7 nitrogen atoms, and R is independently a hydrogen atom or C １ ~C ８ is a group selected from an alkyl group, an alkenyl group, or an alkaryl group.

7. The epoxy-amine adduct of claim 1, comprising at least one amine represented by

8. The heterocyclic amine is: a) Formula (I): 【Transformation 3】 [wherein X independently represents a hydrogen atom, a linear or branched C １ ~C ４ is selected from an alkyl group, or a substituted or unsubstituted phenyl group; Y １ is a direct bond or a divalent polyethylenepolyamine group having 1 to 8 nitrogen atoms, and R is independently a hydrogen atom or C １ ~C ８ is a group selected from an alkyl group, an alkenyl group, or an alkaryl group. and at least one amine represented by b) Formula (II) 【Chemistry 4】 [wherein X independently represents a hydrogen atom, a linear or branched C １ ~C ４ is selected from an alkyl group, or a substituted or unsubstituted phenyl group; Y ２ is a direct bond or a divalent polyethylenepolyamine group having 1 to 7 nitrogen atoms, and R is independently a hydrogen atom or C １ ~C ８ is a group selected from an alkyl group, an alkenyl group, or an alkaryl group.

8. The epoxy-amine adduct of claim 1, comprising at least one amine represented by the formula:

9. A curing agent comprising the epoxy-amine adduct of any one of claims 1 to 8 and a plasticizer.

10. 10. The curing agent of claim 9, further comprising one or more additives, said one or more additives comprising up to 90% by weight of the total weight of said curing agent.

11. 11. The curing agent of claim 9 or 10, further comprising one or more catalysts.

12. 12. The curing agent of any one of claims 9 to 11, wherein the plasticizer comprises one or more selected from benzyl alcohol, n-butanol, xylene, methyl ethyl ketone, nonylphenol, dodecylphenol, cardanol, or esters of phthalic acid.

13. 13. The curing agent of any one of claims 9 to 12, wherein the one or more additives are selected from the group consisting of fillers, reinforcing agents, coupling agents, toughening agents, antifoaming agents, dispersing agents, lubricants, colorants, marking materials, dyes, pigments, IR absorbers, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retarders, conductive additives, carbon black, graphite, carbon nanotubes, graphene, drying agents, mold release agents, leveling aids, flame retardants, separating agents, optical lighteners, rheology additives, photochromic additives, flexibilizers, adhesion promoters, anti-drip agents, metallic pigments, stabilizers, metal luster pigments, metal coated particles, porosity inducers, glass fibers, nanoparticles, or flow aids.

14. A method for producing the epoxy-amine adduct according to any one of claims 1 to 8, comprising the steps of: a) heterocyclic amines comprising the reaction product of a polyethylene polyamine having 3 to 10 nitrogen atoms with an aldehyde having 1 to 8 carbon atoms; and b) at least one epoxide having one or more epoxy groups; to a temperature of 120°C to 280°C for 0.5 to 10 hours; the heterocyclic amine has at least two nitrogen atoms in at least one ring, and the epoxide is substantially free of polyether modification; a stoichiometric ratio in the range of 3 to 100, said stoichiometric ratio being the ratio of the number of equivalents of active amine hydrogens of said heterocyclic amine to the number of equivalents of epoxy groups in said epoxide; the polyethylene polyamine is selected from diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and mixtures thereof; and The aldehyde is selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, trimethylacetaldehyde, 2-methylbutyraldehyde, isovaleraldehyde, valeraldehyde, and hexanal; method.

15. 15. The method of claim 14, wherein the stoichiometric ratio is in the range of 4 to 40.

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