HARDENER FOR EPOXY RESINS

Description

Technical field

[0001] The invention relates to amines and their use as hardeners for epoxy resins, as well as epoxy resin compositions and applications thereof, in particular as molded parts or matrix resin for composite materials. State of the art

[0002] Primary diamines are most commonly used as hardeners for epoxy resins. However, the selection of inexpensive, commercially available primary diamines is very limited. In practice, 1,3-bis(aminomethyl)benzene (meta-xylylenediamine or MXDA) and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine or IPDA) are particularly frequently used. Both amines are characterized by low viscosity and good dilution properties with epoxy resins, crosslinking them to form mechanically high-quality, chemically resistant polymers. However, there are only a few manufacturers of these amines, as the production process is complex and requires significant investment in equipment and safety measures. This repeatedly leads to supply shortages and price fluctuations. Furthermore, both amines also have technical disadvantages.MXDA is highly reactive, and the exothermic energy released during curing with the epoxy resin is very high. In thick-film applications, this high heat input can lead to blistering, discoloration, or other inhomogeneities. Furthermore, MXDA achieves only moderate glass transition temperatures, which is a disadvantage, particularly for adhesives and matrix resins used in composites. IPDA is superior to MXDA in terms of heat generation during curing and glass transition temperature. However, even lower heat generation during curing and a wider selection of available primary diamines with advantageous curing and glass transition temperature properties would be desirable.

[0003] The use of N,N'-dialky-lated MXDA as a hardener for epoxy resins is known from US 2014 / 107313 and US 2015 / 344406, and the use of N-benzylated 1,2-ethanediamine as a hardener for epoxy resins is known from EP 3,344,677. With these amines, some functionality is lost due to the secondary amino groups, resulting in low glass transition temperatures after curing.

[0004] Polyamines derived from the reductive alkylation of dialdehydes such as terephthaldehyde with 1,2-propanediamine or 1,2-ethanediamine, containing two primary and two secondary amino groups, are known from US 2017 / 226278 and EP 3,344,678. They are comparatively highly viscous, dilute epoxy resins far less effectively than MXDA or IPDA, and also do not allow for high glass transition temperatures.

[0005] From WO 2019 / 230692, ethylated xylylenediamines with three or four ethyl groups are known at the α-positions of the amine groups. Due to high steric hindrance, these amines exhibit greatly reduced reactivity towards epoxy resins, resulting in very slow curing. Furthermore, they are highly viscous and very complex to produce, and the polymers cured with them are not very resistant to heat and UV light due to the tertiary carbon atom in the hardener. Description of the invention

[0006] The object of the present invention is therefore to provide a primary diamine for curing epoxy resins which is easy to produce and enables reliable curing with low exothermicity and a high glass transition temperature.

[0007] Surprisingly, an amine of formula (I) as described in claim 1 solves this problem. The amine of formula (I) can be prepared from readily available starting materials in a simple process. It is low-viscosity and effectively dilutes epoxy resins. With epoxy resins, it exhibits a long pot life and trouble-free curing with surprisingly low exothermicity. This allows its use in thick-film epoxy resin products such as molded parts, potting compounds, or matrix resins for composites, without the occurrence of bubbles, discoloration, or other inhomogeneities due to high heat generation. Surprisingly, very high glass transition temperatures are achieved with the amine of formula (I), especially with the amines in the 1,4-position and the amines with R = methyl.Furthermore, the amine of formula (I) is surprisingly low in odor, which is an advantage in handling and application and is highly valued by processors, and it enables cured epoxy resin compositions with particularly little yellowing, which is especially surprising in the case of A = phenylene.

[0008] The amine of formula (I) enables, in particular, the production of epoxy resin molded parts, potting compounds, and composites that are easy and error-free to manufacture, have attractive surfaces, and allow for high service temperatures. Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. Ways to implement the invention

[0009] The invention relates to the use of an amine of formula (I) for curing epoxy resins, where R stands for H or methyl, and A stands for a phenylene or cyclohexylene residue.

[0010] Substance names beginning with "Poly", such as polyamine or polyepoxide, denote substances that formally contain two or more of the functional groups appearing in their name per molecule.

[0011] A "primary amino group" is an amino group bonded to a single organic residue and bearing two hydrogen atoms; a "secondary amino group" is an amino group bonded to two organic residues, which may also be part of a ring together, and bearing one hydrogen atom; and a "tertiary amino group" is an amino group bonded to three organic residues, which may also be part of one or more rings in pairs or groups of three, and bearing no hydrogen atom.

[0012] The hydrogen atoms of primary and secondary amine groups are referred to as "amine hydrogen".

[0013] The "hydrogen amine equivalent weight" refers to the mass of an amine or an amine-containing composition that contains one mole equivalent of hydrogen amine. It is expressed in the unit "g / eq".

[0014] The term "epoxide equivalent weight" refers to the mass of a compound or composition containing epoxy groups that contains one mole equivalent of epoxy groups. It is expressed in the unit "g / eq".

[0015] A "thinner" is a substance that is soluble in an epoxy resin and reduces its viscosity, but which is not chemically incorporated into the epoxy resin polymer during curing.

[0016] The term "molecular weight" refers to the molar mass (in grams per mole) of a molecule. The term "mean molecular weight" refers to the number mean Mn of a polydisperse mixture of oligomeric or polymeric molecules, which is usually determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0017] The term "pot life" refers to the maximum time period from the mixing of the components and the application of an epoxy resin composition in which the mixed composition is in a sufficiently fluid state and can wet the substrate surfaces well.

[0018] The term "gelling time" refers to the period from the mixing of the components of an epoxy resin composition until it gels.

[0019] A temperature of 23 °C is referred to as "room temperature".

[0020] All industry standards and norms mentioned in this document refer to the versions valid at the time of initial filing, unless otherwise stated.

[0021] Weight percent (wt%) denotes the mass fraction of a component of a composition relative to the entire composition, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0022] Preferably, A is selected from the group consisting of 1,3-phenylene, 1,4-phenylene, 1,3-cyclohexylene and 1,4-cyclohexylene.

[0023] A is particularly preferred for 1,3-phenylene or 1,4-phenylene. Such an amine of formula (I) is particularly compatible with aromatic epoxy resins and enables particularly attractive surfaces after curing.

[0024] In particular, A stands for 1,4-phenylene. Such an amine of formula (I) enables a particularly high glass transition temperature.

[0025] Preferably the amine of formula (I) is selected from the group consisting of 1,4-bis(α-aminoethyl)benzene, 1,3-bis(α-aminoethyl)benzene, 1-α-aminoethyl-4-aminomethyl-benzene and 1-α-aminoethyl-3-aminomethyl-benzene.

[0026] Particularly preferred is 1,4-Bis(α-aminoethyl)benzene or 1,3-Bis(α-aminoethyl)benzene. These amines of formula (I) enable a particularly high glass transition temperature.

[0027] The most preferred option is 1,4-Bis(α-aminoethyl)benzene. It offers the highest glass transition temperatures and particularly low yellowing.

[0028] 1-α-Aminoethyl-4-aminomethyl-benzene and 1-α-Aminoethyl-3-aminomethyl-benzene enable particularly rapid curing.

[0029] The amine of formula (I) is preferably a component of a reaction product obtained from the reaction of at least one ketone of formula (II) with ammonia or hydroxylamine or an oxime of formula (III) and subsequent hydrogenation, where m stands for 0 or 1, n for 1 or 2 and (m+n) for 2, X stands for formyl or nitrile, A' stands for a phenylene or cyclohexylene residue, and R 1< stands for H or methyl and R 2< stands for H or an alkyl residue with 1 to 4 C atoms.

[0030] Preferably, A' represents a phenylene residue, in particular 1,3-phenylene or 1,4-phenylene.

[0031] Preferably, R 1< stands for methyl.

[0032] Preferably, R 2< represents an alkyl group with 1 to 4 carbon atoms, in particular methyl or ethyl or isobutyl.

[0033] Preferably, the ketone of formula (II) is 1,3-diacetylbenzene, 1,4-diacetylbenzene, 4-acetylbenzonitrile, 3-acetylbenzonitrile, 4-formylbenzonitrile or 3-formylbenzonitrile. Particularly preferred is 1,3-diacetylbenzene or 1,4-diacetylbenzene.

[0034] For the reaction, the ketone of formula (II) is preferably dissolved in an organic solvent. Preferred organic solvents are alcohols, in particular methanol, ethanol or isopropanol.

[0035] Preferably, ammonia or hydroxylamine or an oxime of formula (III) is used approximately stoichiometrically or in stoichiometric excess relative to the carbonyl groups of the ketone of formula (II).

[0036] For ketones of formula (II) that are free of nitrile groups, ammonia or hydroxylamine is preferably used for the reaction. The reaction proceeds with the release of water. Optionally, the reaction is carried out in the presence of a catalyst, for example a weak base such as potassium carbonate.

[0037] For ketones of formula (II) containing a nitrile group, an oxime of formula (III) is preferably used for the reaction.

[0038] Preferably, the oxime of formula (III) is acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, methyl isopropyl ketoxime or methyl isobutyl ketoxime, in particular acetone oxime, methyl ethyl ketoxime or methyl isobutyl ketoxime.

[0039] With an oxime of formula (III), the reaction takes place in a transoximation with the release of the aldehyde or ketone of formula It is preferably carried out in the presence of a strong acid, in particular perchloric acid.

[0040] The implementation proceeds via an intermediate product of formula (IVa), (IVb), (IVc) or (IVd), where A', m and n have the meanings already mentioned.

[0041] Prior to hydrogenation, the intermediate product can be isolated and, if necessary, purified, in particular by removing the volatile components by distillation or stripping, possibly followed by washing with water or aqueous salt solutions to remove, for example, potassium carbonate or perchloric acid, or the reaction and hydrogenation can be carried out in a one-pot process without isolation of the intermediate product.

[0042] Hydrogenation can be carried out directly with molecular hydrogen or indirectly by hydrogen or hydride transfer from other reagents, such as formic acid or LiAlH₄. Hydrogenation with molecular hydrogen is preferred.

[0043] The hydrogenation is preferably carried out in the presence of a suitable catalyst. Preferred catalysts include palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams catalyst, or Raney nickel, in particular palladium on carbon or Raney nickel.

[0044] When using molecular hydrogen, the hydrogenation is preferably carried out in a pressure apparatus at a hydrogen pressure of 5 to 300 bar. This can be done in a batch process or, preferably, in a continuous process.

[0045] The hydrogenation is preferably carried out at a temperature in the range of 40 to 150 °C. If A' represents phenylene, the hydrogenation conditions can be selected such that the phenylene residue is either not hydrogenated or is also hydrogenated. If an existing phenylene residue is not to be hydrogenated during the hydrogenation, the process is preferably carried out at a temperature in the range of 60 to 120 °C and a hydrogen pressure in the range of 10 to 120 bar. Otherwise, the process is preferably carried out at a temperature in the range of 80 to 150 °C and a hydrogen pressure in the range of 150 to 250 bar.

[0046] Preferably, the volatile components, in particular any solvent and water that may be present, are removed from the reaction product after hydrogenation, especially by distillation or stripping.

[0047] The reaction product can be further purified, in particular by distillation. This yields a reaction product with a particularly high content of the amine of formula (I).

[0048] Another aspect of the invention is a reaction product containing at least one amine of formula (I), obtained from the reaction of at least one ketone of formula (II) with ammonia or hydroxylamine or an oxime of formula (III) and subsequent hydrogenation, as previously described.

[0049] The preferred ketone is 1,3-diacetylbenzene or 1,4-diacetylbenzene of formula (II). In formula (II), m represents 0 and n represents 2.

[0050] Preferably the reaction product contains an amine of formula (I) of at least 50 wt%, particularly preferably at least 80 wt%, and in particular at least 90 wt%, based on the reaction product.

[0051] The amine of formula (I) can exist as a mixture of an amine of formula (I) where A represents a phenylene residue and an amine of formula (I) where A represents a cyclohexylene residue, in particular resulting from a partial hydrogenation of a phenylene residue from the ketone of formula (II).

[0052] In the event that a technical grade 1,3-diacetylbenzene containing proportions of 1,3,5-triacetylbenzene was used as the ketone of formula (II), the reaction product contains in particular 1,3,5-tris(α-aminoethyl)benzene as a by-product.

[0053] The amine of formula (I), especially in the form of the described reaction product, is used for curing epoxy resins.

[0054] Suitable epoxy resins are in particular glycidyl ethers of commercially available mono- or polyfunctional alcohols or phenols, especially the epoxy resins mentioned in this document.

[0055] Preferably, the amine of formula (I), the epoxy resin and optionally other substances are mixed together, wherein the ratio of the groups reactive towards the epoxy groups, in particular the hydrogen amines of the amine of formula (I), and the epoxy groups is preferably in the range of 0.5 to 1.5, in particular 0.7 to 1.2.

[0056] Curing can take place at ambient temperature, particularly in the range of 5 to 40 °C, or it can take place at elevated temperatures. Preferably, it takes place at elevated temperatures, particularly in the range of 40 to 150 °C, more preferably 50 to 120 °C.

[0057] For curing at elevated temperature, the amine of formula (I) and / or the epoxy resin can be heated separately before mixing, and / or the mixed composition can be heated as such.

[0058] When curing occurs at elevated temperatures, the viscosity of the mixed composition is reduced, and curing proceeds particularly quickly. However, the released exothermic reaction is also particularly critical, as it can very quickly lead to a significant heating of the curing composition and cause blisters, discoloration, or other inhomogeneities.

[0059] The amine of formula (I) exhibits particularly low exothermicity with reliable, rapid curing. Furthermore, the cured material has a very high glass transition temperature, enabling high service temperatures.

[0060] Another object of the invention is an amine-functional adduct from the reaction of the amine of formula (I) and at least one epoxy resin or monoepoxide.

[0061] The epoxy resin or monoepoxide preferably has a mean epoxy equivalent weight in the range of 150 to 500 g / eq, preferably 156 to 250 g / eq.

[0062] Aromatic epoxy resins are particularly preferred, especially aromatic diepoxides such as bisphenol A, F, or A / F diglycidyl ethers or novolac epoxy resins, especially phenol-formaldehyde novolac glycidyl ethers. Such adducts enable particularly rapid curing and high glass transition temperatures.

[0063] Epoxy resins containing polyoxypropylene and / or polyoxyethylene units are also preferred. These are, in particular, diglycidyl ethers of polypropylene glycols or reaction products of bisphenol A, F, or A / F diglycidyl ethers with polypropylene glycols or polyethylene glycols. Such adducts are especially suitable as components of water-based hardeners for epoxy resins.

[0064] Aromatic monoepoxides, in particular cresyl glycidyl ethers, tert-butylphenyl glycidyl ethers or cardanol glycidyl ethers, are also preferred.

[0065] Preferably, adducts are formed from the reaction of the amine of formula (I) and at least one diepoxide in a stoichiometric ratio in the range of 1 to 10, preferably 1.2 to 5, in particular 1.4 to 3, mol of amine of formula (I) per molar equivalent of epoxide groups.

[0066] Although not the subject of the claimed invention, a hardener for epoxy resins is further disclosed here, comprising at least one amine of formula (I) and / or at least one amine-functional adduct from the reaction of the amine of formula (I) and at least one epoxy resin or monoepoxide, and at least one further component selected from further amines A1, accelerators, diluents, stabilizers and surfactant additives.

[0067] Preferably, the further amine A1 is not an amine of formula (I).

[0068] The hardener preferably contains 2 to 99 wt%, preferably 5 to 90 wt%, in particular 10 to 80 wt%, amine of formula (I) and / or amine-functional adduct from the reaction of the amine of formula (I) and at least one epoxy resin or monoepoxide.

[0069] The hardener is preferably non-water-based. It preferably contains less than 15% by weight, and in particular less than 10% by weight, water. Such a hardener is suitable for non-aqueous epoxy resin products.

[0070] Other suitable amines A1 are in particular amines with at least two, preferably at least three, hydrogen amines which do not correspond to formula (I).

[0071] Preferably as another amine A1are polyamines with at least three aliphatic amine hydrogens, in particular N-benzyl-1,2-ethanediamine, N-benzyl-1,2-propanediamine, N-benzyl-bis(aminomethyl)-1,3-benzene, N-(2-phenylethyl)-bis(aminomethyl)-1,3-benzene, N-(2-ethylhexyl)-bis(aminomethyl)-1,3-benzene, 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2(4),4-Trimethyl-1,6-hexanediamine (TMD), 1,7-Heptanediamine, 1,8-Octanediamine, 1,9-Nonanediamine, 1,10-Decanediamine, 1,11-Undecanediamine, 1,12-Dodecanediamine, 1,2-, 1,3- or 1,4-Diaminocyclohexane, 1,3-Bis(aminomethyl)cyclohexane, 1,4-Bis(aminomethyl)cyclohexane, Bis(4-aminocyclohexyl)methane, Bis(4-amino-3-methylcyclohexyl)methane, Bis(4-amino-3-ethylcyclohexyl)methane, Bis(4-amino-3,5-dimethylcyclohexyl)methane, Bis(4-amino-3-ethyl-5-methylcyclohexyl)methane 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6< ]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-menthanediamine, 3,9-Bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-bis(aminomethyl)benzene (MXDA), 1,4-bis(aminomethyl)benzene, bis(2-aminoethyl)ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-2,9-diamine, 4,9-Dioxadodecan-1,12-diamine, 5,8-Dioxadodecan-3,10-diamine, 4,7,10-Trioxatridecan-1,13-diamine or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofurans or other polytetrahydrofurandiamines, polyoxyalkylenediamines or triamines, in particular polyoxypropylenediamines or polyoxypropylenetriamines such as Jeffamine® < D-230, Jeffamine® < D-400 or Jeffamine® < T-403 (all from Huntsman), polyalkyleneamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA),N-(2-Aminoethyl)-1,3-propanediamine (N3-amine), N,N'-Bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-Bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-Aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-Aminopentyl)-1,3-pentanediamine, N5-(3-Amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, N,N'-Bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, 3-(2-Aminoethyl)aminopropylamine or bis(hexamethylene)triamine (BHMT), N-benzylated polyalkyleneamines with one or two benzyl groups, in particular benzylated DETA, TETA, N3-amine, N4-amine or DPTA, N-Aminoethylpiperazine, 3-(3-(Dimethylamino)propylamino)propylamine (DMAPAPA), amine-functional adducts of the aforementioned amines with epoxides, or mixtures of two or more of these amines.

[0072] Preferably, the hardener contains at least one other amine. A1selected from the group consisting of N-benzyl-1,2-ethanediamine, MPMD, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, MXDA, DETA, TETA, TEPA, N3-amine, N4-amine, DPTA, BHMT, polyoxypropylenediamines with a mean molecular weight M n in the range of 200 to 500 g / mol and polyoxypropylenetriamines with a mean molecular weight M n in the range of 300 to 500 g / mol.

[0073] Preferred compounds include N-benzyl-1,2-ethanediamine, MXDA, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, or bis(4-aminocyclohexyl)methane. This enables particularly rapid curing.

[0074] IPDA remains the preferred option. This enables the production of a cost-effective hardener with a high glass transition temperature.

[0075] The hardener can also contain more than one other amine. A1 contain.

[0076] Suitable accelerators are in particular acids or compounds hydrolyzable to acids, especially organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids such as phosphoric acid, or mixtures of the aforementioned acids and acid esters; nitrates such as calcium nitrate; tertiary amines such as in particular 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, salts of such tertiary amines, quaternary ammonium salts such as in particular benzyltrimethylammonium chloride, amidines such as in particular 1,8-diazabicyclo[5.4.0]-undec-7-ene, guanidines such as in particular 1,1,3,3-tetramethylguanidine, phenols, in particular bisphenols, phenol resins or Mannich bases such as in particular 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol or polymers of phenol, formaldehyde and N,N-dimethyl-1,3-propanediamine, phosphites such as in particular di- or triphenyl phosphites, or compounds containing mercapto groups.

[0077] Preferred accelerators are acids, nitrates, tertiary amines or Mannich bases, in particular salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol, or a combination of these accelerators.

[0078] Suitable thinners include in particular n-propanol, isopropanol, n-butanol, isobutanol, tert.Butanol, 1-Pentanol, 2-Pentanol, 3-Pentanol, 2-Methyl-1-butanol, 3-Methyl-1-butanol, 3-Methyl-2-butanol n-Hexanol, 2-Ethylhexanol, Xylol, 2-Methoxyethanol, Dimethoxyethanol, 2-Ethoxyethanol, 2-Propoxyethanol, 2-Isopropoxyethanol, 2-Butoxyethanol, 2-Phenoxyethanol, 2-Benzyloxyethanol, Benzylalkohol, Ethylenglykol, Ethylenglykoldimethylether, Ethylenglykoldiethylether, Ethylenglykoldibutylether, Ethylenglykoldiphenylether, Diethylenglykol, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Diethylenglykolmono-n-butylether, Diethylenglykoldimethylether, Diethylenglykoldiethylether, Diethylenglykoldi-n-butylylether, Propylenglykolbutylether, Propylenglykolphenylether, Dipropylenglykol, Dipropylenglykolmonomethylether, Dipropylenglykoldimethylether, Dipropylenglykoldi-n-butylether, 2,2,4-Trimethyl-1,3-pentandiolmonoisobutyrat, Diphenylmethan, Diisopropylnaphthalin, Erdölfraktionen wie zum Beispiel Solvesso ®< -Typen (von Exxon), Alkylphenole wie tert.Butylphenol, nonylphenol, dodecylphenol, cardanol, styrolated phenol, bisphenols, aromatic hydrocarbon resins, especially phenol-containing types, alkoxylated phenol, especially ethoxylated or propoxylated phenol, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphoric or sulfonic acid esters or sulfonamides.

[0079] Preferred thinners include those with a boiling point above 200 °C, in particular benzyl alcohol, styrolated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenol groups such as, in particular, the Novares® types LS 500, LX 200, LA 300 or LA 700 (from Rütgers), diisopropylnaphthalene or Cardanol, especially benzyl alcohol.

[0080] Thinners containing phenol groups also act as accelerators.

[0081] Suitable stabilizers are in particular stabilizers against oxidation, heat, light or UV radiation.

[0082] Suitable surface-active additives include, in particular, defoamers, deaerators, wetting agents, dispersants or leveling agents.

[0083] The hardener may contain other components, in particular: further adducts, in particular adducts of MPMD or 1,2-ethanediamine or 1,2-propanediamine with cresyl glycidyl ether or aromatic epoxy resins, in which unreacted MPMD, 1,2-ethanediamine or 1,2-propanediamine was removed by distillation after the reaction; monoamines such as, in particular, benzylamine or furfurylamine; polyamidoamines, in particular reaction products of a mono- or polyhydric carboxylic acid or its ester or anhydride, in particular a dimer fatty acid, with a polyamine used in stoichiometric excess, in particular DETA or TETA; Mannich bases, in particular phenalkamines, i.e., reaction products of phenols, in particular cardanol, with aldehydes, in particular formaldehyde, and polyamines; aromatic polyamines such as in particular 4,4'-, 2,4' and / or 2,2'-diaminodiphenylmethane, 2,4(6)-toluenediamine, 3,5-dimethylthio-2,4(6)-toluenediamine or 3,5-diethyl-2,4(6)-toluenediamine;or compounds containing mercapto groups, in particular liquid mercaptan-terminated polysulfide polymers, mercaptan-terminated polyoxyalkylene ethers, mercaptan-terminated polyoxyalkylene derivatives, polyesters of thiocarboxylic acids, 2,4,6-trimercapto-1,3,5-triazine, triethylene glycol dimercaptan or ethanedithiol.

[0084] Another aspect of the invention is an epoxy resin composition comprising a resin component containing at least one epoxy resin and a hardener component containing at least one amine of formula (I) and / or an amine-functional adduct resulting from the reaction of the amine of formula (I) and at least one epoxy resin or monoepoxide.

[0085] A suitable epoxy resin is obtained in a known manner, in particular from the reaction of epichlorohydrin with polyols, polyphenols or amines.

[0086] Suitable epoxy resins are in particular aromatic epoxy resins, especially the glycidyl ethers of: Bisphenol A, bisphenol F, or bisphenol A / F, where A stands for acetone and F for formaldehyde, which served as starting materials for the production of these bisphenols. In the case of bisphenol F, positional isomers may also be present, in particular derived from 2,4'- or 2,2'-hydroxyphenylmethane; dihydroxybenzene derivatives such as resorcinol, hydroquinone, or catechol; and other bisphenols or polyphenols such as bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxy-3-tert-dibromo-4-hydroxyphenyl)propane.butylphenyl) propane, 2,2-bis(4-hydroxyphenyl)butane (bisphenol-B), 3,3-bis(4-hydroxyphenyl)pentane, 3,4-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-Bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-Bis(4-hydroxyphenyl)cyclohexane (Bisphenol-Z), 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (Bisphenol-TMC), 1,1-Bis(4-hydroxyphenyl)-1-phenylethane, 1,4-Bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (Bisphenol-P), 1,3-Bis[2-(4-hydroxyphenyl)-2-propyl]benzene (Bisphenol-M), 4,4'-Dihydroxydiphenyl (DOD), 4,4'-Dihydroxybenzophenone, Bis(2-hydroxynaphth-1-yl)methane, Bis(4-hydroxynaphth-1-yl)methane, 1,5-Dihydroxynaphthalene, Tris(4-hydroxyphenyl)methane, 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethane, Bis(4-hydroxyphenyl)ether or Bis(4-hydroxyphenyl)sulfone; novolacs, which are in particular condensation products of phenol or cresols with formaldehyde or...Paraformaldehyde, acetaldehyde, crotonaldehyde, isobutyraldehyde, 2-ethylhexanal, benzaldehyde, or furfural; aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi-(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-P), or 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-M).

[0087] Other suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2 to C30 alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythrole, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane; a hydrogenated bisphenol A, F or A / F liquid resin, or the glycidylation products of hydrogenated bisphenol A, F or A / F; an N-glycidyl derivative of amides or heterocyclic nitrogenous bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin.

[0088] Preferably, the epoxy resin is a liquid resin or a mixture containing two or more liquid epoxy resins.

[0089] The term "epoxy liquid resin" refers to a technical polyepoxide with a glass transition temperature below 25°C.

[0090] The resin component may also contain additional amounts of epoxy solid resin.

[0091] The epoxy resin is in particular a liquid resin based on a bisphenol or novolac, especially with a mean epoxy equivalent weight in the range of 156 to 210 g / eq.

[0092] Particularly suitable are bisphenol-A diglycidyl ethers and / or bisphenol-F diglycidyl ethers, such as those commercially available from Olin, Huntsman, or Momentive. These liquid resins have a low viscosity for epoxy resins and allow for rapid curing and high hardness. They may contain proportions of bisphenol-A solid resin or novolac epoxy resins.

[0093] Phenol-formaldehyde novolac glycidyl ethers are also particularly suitable, especially those with a medium functionality in the range of 2.3 to 4, preferably 2.5 to 3. They may contain proportions of other epoxy resins, in particular bisphenol-A diglycidyl ether or bisphenol-F diglycidyl ether.

[0094] The resin component may contain a reactive diluent.

[0095] Preferred reactive diluents are epoxy group-containing reactive diluents, in particular butanediol diglycidyl ethers, hexanediol diglycidyl ethers, trimethylolpropane di- or triglycidyl ethers, phenyl glycidyl ethers, cresyl glycidyl ethers, guaiacol glycidyl ethers, 4-methoxyphenyl glycidyl ethers, pn-butylphenyl glycidyl ethers, p-tert-butylphenyl glycidyl ethers, 4-nonylphenyl glycidyl ethers, 4-dodecylphenyl glycidyl ethers, cardanol glycidyl ethers, benzyl glycidyl ethers, allyl glycidyl ethers, butyl glycidyl ethers, hexyl glycidyl ethers, 2-ethylhexyl glycidyl ethers, or glycidyl ethers of natural alcohols such as, in particular, C8 to C10, C12 to C14, or C13 to C15 alkyl glycidyl ethers.

[0096] Preferably, the epoxy resin composition contains at least one further component selected from the group consisting of thinners, accelerators, stabilizers, surfactant additives, fillers and pigments.

[0097] The substances already mentioned are particularly suitable as thinners, accelerators, stabilizers and surfactant additives.

[0098] Suitable fillers include, in particular, ground or precipitated calcium carbonate, optionally coated with fatty acids, especially stearates; barite (barytes); talc; quartz flour; quartz sand; silicon carbide; micaceous iron oxide; dolomite; wollastonite; kaolin; mica (potassium aluminum silicate); molecular sieves; aluminum oxide; zinc oxide; aluminum-doped zinc oxide; aluminum hydroxide; magnesium hydroxide; silica; cement; gypsum; fly ash; carbon black; graphite; wood flour; metal powders such as aluminum, copper, iron, zinc, silver, or steel; PVC powder; or hollow spheres. Calcium carbonate, barite, quartz flour, talc, or a combination thereof are preferred.

[0099] Suitable pigments include, in particular, titanium dioxides, iron oxides, chromium(III) oxides, corrosion protection pigments, organic pigments or carbon black, especially titanium dioxides.

[0100] The epoxy resin composition may contain further auxiliary and additive substances, in particular the following: Reactive diluents, in particular those already mentioned, or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes, isocyanates or silicones containing reactive groups; polymers, in particular polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers with carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene copolymers, homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl(meth)acrylates, in particular chlorosulfonated polyethylenes or fluorine-containing polymers or sulfonamide-modified melamines; Fibers, in particular glass fibers, carbon fibers, cellulose fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers; other solids,especially wood granules or cellulose; nanofillers, especially carbon nanotubes; rheology modifiers, especially thickeners or anti-settling agents; adhesion promoters, especially organoalkoxysilanes; Flame-retardant substances, in particular the fillers already mentioned: aluminum hydroxide or magnesium hydroxide, antimony trioxide, antimony pentoxide, boric acid (B(OH) 3), zinc borate, zinc phosphate, melamine borate, melamine cyanurate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, polybrominated diphenyl oxides or diphenyl ethers, phosphates such as, in particular, diphenyl cresyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol diphosphate oligomer, tetraphenyl resorcinol diphosphite, ethylenediamine diphosphate, bisphenol A bis(diphenyl phosphate), tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloroisopropyl) phosphate, tris[3-bromo-2,2-bis(bromomethyl)-propyl] phosphate, tetrabromobisphenol A, bis(2,3-dibromopropyl ether) of bisphenol A, brominated epoxy resins,Ethylene bis(tetrabromophthalimide), ethylene bis(dibromonorbornane dicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadieno)cyclooctane or chlorinated paraffins; or other additives, in particular dispersed paraffin wax or biocides.

[0101] Preferably, the epoxy resin composition contains only a small amount of thinner. Preferably, it contains less than 20% by weight, more preferably less than 10% by weight, particularly less than 5% by weight, thinner, and most preferably less than 1% by weight of thinner, based on the total epoxy resin composition.

[0102] Preferably, the epoxy resin composition contains only a small amount of water, preferably less than 5 wt%, in particular less than 1 wt%, water, based on the total epoxy resin composition.

[0103] The resin and hardener components of the epoxy resin composition are stored in separate containers. Other components of the epoxy resin composition may be present as part of either the resin or the hardener component, with reactive components towards epoxy groups preferably being part of the hardener component. It is also possible that other components are present as separate, additional components.

[0104] Suitable containers for storing the resin or hardener components include, in particular, a drum, a pail, a bag, a bucket, a can, a cartridge, or a tube. The components are storable, meaning they can be stored for several months up to a year or longer before use without their respective properties changing to an extent relevant to their application.

[0105] The resin and hardener components are mixed shortly before or during application. The mixing ratio is preferably chosen such that the molar ratio of the epoxy-reactive groups to the epoxy groups is in the range of 0.5 to 1.5, particularly 0.7 to 1.2. In parts by weight, the mixing ratio between the resin and hardener components is typically in the range of 1:2 to 20:1.

[0106] The components are mixed continuously or batchwise using a suitable method, taking care to ensure that the time between mixing and application is short and that the application occurs within the pot life. Mixing and application can be carried out at ambient temperature, typically in the range of approximately 5 to 40°C, preferably approximately 10 to 35°C. Mixing and / or application are preferably carried out at elevated temperatures, particularly in the range of 40 to 150°C, preferably 50 to 120°C.

[0107] The curing of the epoxy resin composition begins with the mixing of the components through a chemical reaction. Primary and secondary amino groups, and any other groups reactive towards epoxy groups, react with the epoxy groups, opening their rings. As a result of these reactions, the composition polymerizes and thus hardens.

[0108] The curing process typically extends over several hours to several days. The duration depends on factors such as temperature, the reactivity of the components, their stoichiometry, and the presence or amount of accelerators.

[0109] In its freshly mixed state, the epoxy resin composition has a low viscosity. Preferably, the viscosity 5 minutes after mixing the resin and hardener components at 20 °C is in the range of 0.2 to 20 Pa·s, more preferably 0.3 to 10 Pa·s, and particularly 0.3 to 5 Pa·s, measured using a cone-plate viscometer at a shear rate of 10 s⁻¹.

[0110] The epoxy resin composition is applied to at least one substrate and / or into at least one mold.

[0111] Suitable substrates include in particular: Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, gypsum or natural stone such as granite or marble; repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy-modified cement mortar); metals or alloys such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-treated metals or alloys such as galvanized or chrome-plated metals; asphalt or bitumen; leather, textiles, paper, wood, with resins, for example phenolic, melamine or epoxy resins, bonded wood-based materials, resin-textile composites or other so-called polymer composites; Plastics such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, either untreated or surface-treated, for example by plasma, corona or flames;Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GFRP) and sheet molding compounds (SMC); insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (Foamglas); coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets; coatings, paints or varnishes, in particular coated floors which are covered with a further floor covering layer.

[0112] The substrates can be pretreated before application if necessary, in particular by physical and / or chemical cleaning processes or by applying an activator or a primer.

[0113] The substrates are coated and / or bonded.

[0114] A suitable mold is a device into which the mixed, liquid epoxy resin composition is poured and cured, and from which it can be demolded or removed after curing, with the cured composition forming a molded body.

[0115] The mold preferably consists, at least on the surface, of a material from which the hardened epoxy resin composition can be removed without damage, in particular metal, ceramic, plastic or silicone, which may optionally be provided with a non-stick coating, in particular Teflon, silicone or a wax.

[0116] Another object of the invention is a cured composition obtained from the described epoxy resin composition after mixing the resin and hardener components.

[0117] The epoxy resin composition is preferably used as a coating, primer, adhesive, sealant, potting compound, casting resin, impregnating resin, or as a molded body or matrix for composite materials such as, in particular, CFRP (containing carbon fibers) or GFRP (containing glass fibers) or wood composite material.

[0118] Another object of the invention is a method for producing a molded body, comprising the steps (i) Mixing the components of the epoxy resin composition, (ii) Pouring the mixed composition into a mold, followed by the hardening of the mixed composition, optionally under pressure and optionally by means of added heat.

[0119] The epoxy resin composition can be mixed with fibers, powders or granules before curing, especially with carbon fibers, glass fibers or wood powder and / or granules, to obtain a composite material.

[0120] The molded part can be produced in a single casting, or it can be built up in layers, for example to create a transparent molded part that can be used as a tabletop. Any other material can be cast between the layers, such as decorative objects like beads, pieces of wood, or shells.

[0121] After hardening, the molded part is preferably removed from the mold. It can then be further processed, in particular by cutting, drilling, drawing, grinding or polishing.

[0122] In the production of molded parts, low exothermicity during curing and a high glass transition temperature of the cured material are particularly advantageous.

[0123] Another object of the invention is an article containing the cured composition of the described epoxy resin composition.

[0124] The article is, in particular, a shaped body, especially a composite material, specifically a lamella, a panel, or a component of an industrial good. The article is also, in particular, a floor coating, wall coating, component coating, pipe coating, roof coating, or corrosion protection coating.

[0125] The article is, in particular, an article bonded with an epoxy resin composition.

[0126] Preferably, the article is a molded body.

[0127] Preferably, the molded body is made of a composite material. Examples

[0128] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described embodiments.

[0129] "AHEW" stands for amine hydrogen equivalent weight.

[0130] "EEW" stands for epoxy equivalent weight.

[0131] A temperature of 23±1°C and a relative humidity of 50±5% are referred to as "standard climate" ("NC").

[0132] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH. Description of the measurement methods:

[0133] The viscosityThe viscosity was measured on a thermostatically controlled cone-plate viscometer Rheotec RC30 (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm). Low-viscosity samples with a viscosity of less than 100 mPa·s were measured with a shear rate of 100 s⁻¹, higher-viscosity samples with a shear rate of 10 s⁻¹.

[0134] The Amin number was determined by titration (with 0.1N HClO 4 in acetic acid against crystal violet).

[0135] Gas chromatograms (GC) measurements were performed in the temperature range of 60 to 320 °C with a heating rate of 15 °C / min and a residence time of 10 min at 320 °C. The injector temperature was 250 °C. A Zebron ZB-5 column (L = 30 m, ID = 0.25 mm, dj = 0.5 µm) was used at a gas flow rate of 1.5 ml / min. Detection was performed by flame ionization (FID).

[0136] Infrared spectra(FT-IR) measurements were taken as undiluted films on a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal ATR measuring unit with a diamond crystal. The absorption bands are given in wavenumbers (cm⁻¹).

[0137] 1< H-NMR spectra Measurements were taken on a Bruker Ascend 400 spectrometer at 400.14 MHz; chemical shifts δ are given in ppm relative to tetramethylsilane (TMS). True and pseudo-coupling patterns were not distinguished. Preparation of amines of formula (I): Amin A1: 1,4-Bis(α-aminoethyl)benzene

[0138] 50.0 g (0.31 mol) of 1,4-diacetylbenzene were dissolved in 800 ml of ethanol at 40 °C under a nitrogen atmosphere, mixed with 44.8 g of a hydroxylamine solution (50 wt% in water, 0.68 mol) and a solution of 52.2 g of potassium carbonate in 250 ml of water, resulting in a yellow coloration. The reaction mixture was then refluxed for 6 hours and left to stand overnight at room temperature, forming a white precipitate. The precipitate was subsequently collected by filtration, washed with water, and dried under vacuum for 1 hour. The resulting white powder was then dissolved in 800 ml of a mixture of isopropyl alcohol and 1,4-dioxane (1:1 by weight) and subsequently hydrogenated at 90°C, 90 bar hydrogen pressure, and a flow rate of 5 ml / min in a continuous hydrogenation apparatus with a Raney nickel fixed-bed catalyst. The hydrogenated solution was then concentrated on a rotary evaporator. 49 units were obtained.0 g of a yellowish oil, which was subsequently purified by distillation. At 68 to 75 °C (vapor temperature) and 0.04 mbar, 34.4 g of distillate were obtained as a clear, colorless oil with a viscosity at 20 °C of 15 mPa·s, an amine number of 680 mg KOH / g, a 1,4-bis(α-aminoethyl)benzene content of approximately 96% (retention time 9.7 min) determined by GC, and a calculated AHEW of 41.0 g / eq.

[0139] 1< H-NMR (CDCl 3 ): 7.31 (d, 4 H, Ar-H), 4.1 (q, 2 H, Ar-CH-N), 1.51 (br s, 4 H, NH 2 ), 1.39 (d, 6 H, CH 3 ).

[0140] FT-IR: 3359, 3279, 2957, 2920, 2856, 1594, 1508, 1448, 1367, 1328, 1188, 1097, 1015, 829, 699. Amin A2: 1,3-Bis(α-aminoethyl)benzene

[0141] The amine A2 was like for Amin A1The process was carried out as described, using 1,3-diacetylbenzene in the same quantity as 1,4-diacetylbenzene. 47.0 g of a yellowish oil were obtained, which was subsequently purified by distillation. At 55 to 60 °C (vapor temperature) and 0.06 mbar, 29.9 g of distillate were obtained as a clear, colorless oil with a viscosity of 25 mPa·s at 20 °C, an amine number of 661 mg KOH / g, and a 1,3-bis(α-aminoethyl)benzene content of approximately 95% (retention time 9.5 min) determined by GC, with a calculated AHEW of 41.0 g / eq.

[0142] 1< H-NMR (CDCl 3 ): 7.32 (t, 1 H, Ar-H), 7.27 (d, 2 H, Ar-H), 7.21 (s, 1 H, Ar-H), 4.1 (q, 2 H, Ar-CH-N), 1.51 (br s, 4 H, NH 2 ), 1.38 (d, 6 H, CH 3 ).

[0143] FT-IR: 3360, 3279, 2959, 2922, 2864, 1604, 1485, 1446, 1366, 1326, 1152, 1111, 1054, 857, 795, 706. Amin A3: 1-α-Aminoethyl-4-aminomethylbenzene

[0144] 50.0 g (0.34 mol) of 4-acetylbenzonitrile were dissolved in 800 ml of ethanol under a nitrogen atmosphere at 40 °C and treated with 2.4 g of aqueous perchloric acid (70 wt% HClO₄ in water). The reaction mixture was then slowly mixed with 45.0 g (0.52 mol) of methyl ethyl ketoxime with good stirring, refluxed for 16 h, and subsequently the volatile components (ethanol, methyl ethyl ketone, and excess methyl ethyl ketoxime) were removed by rotary evaporator. The resulting powder was washed with water, dried under vacuum for 1 hour, and then dissolved in 800 ml of a 1:1 mixture of isopropyl alcohol and 1,4-dioxane by weight. The mixture was hydrogenated at 80°C, 90 bar hydrogen pressure, and a flow rate of 5 ml / min in a continuous hydrogenation apparatus with a Raney nickel fixed-bed catalyst. The hydrogenated solution was then concentrated by rotary evaporation. 49.0 g of a yellowish oil were obtained, which was subsequently purified by distillation.At 75 to 80 °C (vapor temperature) and 0.06 mbar, 23.7 g of distillate were obtained as a clear, colorless oil with a viscosity of 56 mPa·s at 20 °C, an amine number of 710 mg KOH / g, and a 1-α-aminoethyl-4-aminomethylbenzene content of approximately 83% (retention time 9.5 min) and approximately 11.5% of a byproduct (retention time 11.5 min, presumably N-(1-(4-(Aminomethyl)phenyl)ethyl)-butan-2-amine) determined by GC. For further processing, an AHEW of 37.6 g / eq was used.

[0145] 1< H-NMR (CDCl 3 ): 7.27 (d, 4 H, Ar-H), 4.06 (q, 1 H, Ar-CH-N), 3.80 (s, 2 H, Ar-CH 2 -N), 2.90 (br s, 4 H, NH 2 ), 1.36 (d, 3 H, CH 3 ).

[0146] FT-IR: 3359, 3280, 2959, 2921, 2823, 1606, 1509, 1448, 1417, 1366, 1278, 1202, 1097, 1016, 832, 698. Amin A4: 1-α-Aminoethyl-3-aminomethylbenzene

[0147] The amine A4 was like for Amin A3The compound was prepared as described, using 3-acetylbenzonitrile in the same quantity instead of 4-acetylbenzonitrile. 48.0 g of a yellowish oil were obtained, which was subsequently purified by distillation. At 60 to 65 °C and 0.06 mbar, 19.6 g of distillate were obtained as a clear, colorless oil with a viscosity of 73 mPa·s at 20 °C, an amine number of 712 mg KOH / g, a 1-α-aminoethyl-3-aminomethylbenzene content of approximately 85% (retention time 9.4 min) determined by GC, and approximately 12% of a byproduct (retention time 11.3 min, presumably N-(1-(3-(Aminomethyl)phenyl)ethyl)-butan-2-amine). For further processing, an AHEW of 37.6 g / eq was used.

[0148] 1< H-NMR (CDCl 3 ): 7.27 (t, 1 H, Ar-H), 7.26 (m, 3 H, Ar-H), 4.06 (q, 1 H, Ar-CH-N), 3.78 (s, 2 H, Ar-CH 2 -N), 2.93 (br s, 4 H, NH 2 ), 1.34 (d, 3 H, CH 3).

[0149] FT-IR: 3360, 3280, 2960, 2921, 2863, 1605, 1589, 1485, 1444, 1368, 1327, 1286, 1155, 1109, 1049, 999, 828, 788, 704. Production of amine-functional adducts: Adduct-1:

[0150] A mixture of 24.64 g Amin A1 (0.15 mol) and 18.57 g of benzyl alcohol were heated to 80 °C. With thorough stirring, 18.70 g of Araldite® < GY 250 (0.1 mol EP groups) were slowly stirred in, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20 °C of 44.2 Pa·s, an amine number of 260 mg KOH / g, and a calculated AHEW of 123.8 g / eq. Adduct-2:

[0151] A mixture of 22.53 g Amin A3(0.15 mol) and 17.67 g of benzyl alcohol were heated to 80 °C. To this, 18.70 g of Araldite® < GY 250 (0.1 mol EP groups) were slowly added with good stirring, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20 °C of 22.8 Pa·s, an amine number of 268 mg KOH / g, and a calculated AHEW of 117.8 g / eq. Adduct-3:

[0152] A mixture of 22.53 g Amin A4(0.15 mol) and 17.67 g of benzyl alcohol were heated to 80 °C. To this, 18.70 g of Araldite® < GY 250 (0.1 mol EP groups) were slowly added with good stirring, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20 °C of 31.5 Pa·s, an amine number of 255 mg KOH / g, and a calculated AHEW of 117.8 g / eq. Other substances and abbreviations used:

[0153] Araldite® < GY 250: Bisphenol A diglycidyl ether, EEW 187 g / Eq (from Huntsman) Araldite® < DY-E: Monoglycidyl ethers of C12 to C14 alcohols, EEW approx. 290 g / Eq (from Huntsman) MXDA: 1,3-Bis(aminomethyl)benzene, AHEW 34 g / Eq (from Mitsubishi Gas Chemical) IPDA: 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, AHEW 42.6 g / Eq (Vestamin® < IPD, from Evonik) 1,3-BAC 1,3-Bis(aminomethyl)cyclohexane, AHEW 35.5 g / Eq (from Mitsubishi Gas Chemical) B-EDAN Benzyl-1,2-ethanediamine, prepared as described below, 150.2 g / mol, AHEW 50.1 g / eq Ancamine ®< K542,4,6-Tris(dimethylaminomethyl)phenol (from Evonik) N-Benzyl-1,2-ethanediamine (B-EDA):

[0154] 180.3 g (3 mol) of 1,2-ethanediamine were placed at room temperature, mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol, and stirred for 2 hours. The mixture was then hydrogenated at 80°C, 80 bar hydrogen pressure, and a flow rate of 5 ml / min in a continuous hydrogenation apparatus with a Pd / C fixed-bed catalyst. The hydrogenated solution was concentrated at 65°C using a rotary evaporator, removing unreacted 1,2-ethanediamine, water, and isopropanol. The resulting reaction mixture was purified by distillation at 80°C under vacuum. A colorless liquid was obtained with an N-benzyl-1,2-ethanediamine content of > 97%, determined by GC. Production of hardeners and epoxy resin compositions: Examples 1 to 8:

[0155] For each example, the resin and hardener components listed in Table 1 were separately heated to a temperature of 60 °C. A total of 20 g of epoxy resin composition was then prepared using these preheated components by mixing them in the weight ratios specified in Table 1 for 15 seconds using a centrifugal mixer (SpeedMixer™ < DAC 150, FlackTek Inc.) and then immediately testing as follows:

[0156] The mixed composition was placed in a test tube thermostatically controlled at 60 °C using a water bath, and a thermocouple was positioned in the center of the mixture. This allowed the time until the maximum temperature (given in the table as ) was reached to be measured. time to peak exotherm) and the maximum temperature (peak exothermic temperature) Determined in the mixed material. The values ​​given in the table are averages of three measurements.

[0157] The TgThe glass transition temperature (GST) was measured using DSC on solidified samples taken from the center of the test tube from the assay described above. These samples had been stored under standard climate conditions for 14 days prior to measurement. The measurement was performed using a Mettler Toledo DSC 3+ 700 instrument and the following measurement programs: (1) -10 °C for 2 min, (2) -10 to 200 °C with a heating rate of 10 K / min (= 1st run), (3) 200 to -10 °C with a cooling rate of -50 K / min, (4) -10 °C for 2 min, (5) -10 to 180 °C with a heating rate of 10 K / min (= 2nd run). 1 8. Table 1: Composition (in parts by weight) and properties of the examples up to Example 1 2 3 4 5 (Ref.) 6 (Ref.) 7 (Ref.) 8 (Ref.) Harz-Komp: Araldite® < GY 250 187.0 187.0 187.0 187.0 187.0 187.0 187.0 187.0 Hardener compound: Amin A1 41.0 - - - - - - - Amin A2 - 41.0 - - - - - - Amin A3 - - 37.6 - - - - - Amin A4 - - - 37.6 - - - - MXDA - - - - 34.0 - - - IPDA - - - - - 42.6 - - 1,3-BAC - - - - - - 35.5 - B-EDA - - - - - - - 50.1 time to peak exotherm [min] 21 20 23 20 12 21 8 12 peak exothermic temperature 66°C 65°C 75°C 74°C 150°C 74°C 213°C 201°C Tg 1st / 2nd run [°C] 52 / 141 65 / 128 72 / 120 68 / 100 93 / 100 76 / 155 133 / 140 53 / 88 Examples 9 to 24:

[0158] For each example, the ingredients of the resin component listed in Tables 2 to 4 were mixed in the specified quantities (in parts by weight) using a centrifugal mixer (SpeedMixer™< DAC 150, FlackTek Inc.) and stored in the absence of moisture.

[0159] The ingredients of the hardener component listed in Tables 2 to 4 were also processed and stored.

[0160] Subsequently, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer and immediately tested as follows: viscosity The measurement was taken 5 minutes after mixing the resin and hardener components as described, at a temperature of 20 °C.

[0161] The Gelling time was determined by moving a freshly mixed quantity of approximately 3 g under standard climate conditions with a spatula at regular intervals until the mass gelled.

[0162] The Shore D Hardness was determined according to DIN 53505 on cylindrical test specimens (diameter 20 mm, thickness 5 mm) which were stored in standard climate conditions and the hardness was measured 1 day (24h) and 2 days after production.

[0163] Furthermore, a film with a thickness of 500 µm was applied to a glass plate and stored and cured under standard climate conditions. The following was then examined on this film: King's hardness (Pendulum hardness according to König according to DIN EN ISO 1522) was determined after 1 day, 2 days, 7 days and after 14 days. After 14 days the aspect The film was judged on its quality. A film with a glossy, non-sticky surface and no texture was described as "beautiful." "Texture" referred to any kind of drawing or pattern on the surface. A film with reduced gloss was described as "matte."

[0164] As a measure of yellowing, the color change after exposure to a weathering tester was determined for several examples. For this purpose, another film with a thickness of 500 µm was applied to a glass plate and stored / cured under standard climate conditions for two weeks. It was then exposed to the elements in a Q-Sun Xenon Xe-1 weathering tester with a Q-SUN Daylight-Q optical filter and a xenon lamp with a luminous intensity of 0.51 W / m² at 340 nm at a temperature of 65°C for 72 hours. Q-Sun (72h)). Subsequently, the color difference ΔE of the film exposed to this color was determined in comparison to the corresponding unexposed film using a colorimeter NH310 from Shenzhen 3NH Technology Co. LTD, equipped with Silicon Photoelectric Diode Detector, Light Source A, Color Space Measurement Interface CIE L*a*b*C*H*.

[0165] The TgThe glass transition temperature (GD) value was measured on samples cured for 14 days under standard climate conditions (from the test specimen for Shore D hardness) as described for Example 1. 9 14. Table 2: Composition and properties of the examples up to 1 < not measurable (too brittle) Example 9 10 11 12 13 (Ref.) 14 (Ref.) Resin component: Araldite® < GY 250 167.2 167.2 167.2 167.2 167.2 167.2 Araldite® < DY-E 31.8 31.8 31.8 31.8 31.8 31.8 Hardener component: Amin A1 41.0 - - - - - Amin A2 - 41.0 - - - - Amin A3 - - 37.6 - - - Amin A4 - - - 37.6 - - MXDA - - - - 34.0 - IPDA - - - - - 42.6 Viscosity (10') [Pa·s] 0.41 0.43 0.37 0.41 0.38 0.60 Gelling time (h:min) > 8:00 > 8:00 > 4:30 4:20 4:10 3:00 Shore D (1d NK) 36 40 75 75 82 nm 1< (2d NK) 63 62 77 79 82 nm 1< King's hardness [s] (1d NK) 18 13 21 18 21 87 (2d NK) 118 64 56 53 29 155 (7d NK) 168 164 101 109 32 196 (14d NK) 178 174 105 133 42 205 aspect beautiful, uneven lightweight structure nice frosted structure frosted Q-Sun (72h) ΔE 1.5 4.8 6.2 8.8 10.4 1.4 Tg 1st / 2nd run [°C] 69 / 106 65 / 90 53 / 88 50 / 80 54 / 77 57 / 104 15 21. Table 3: Composition and properties of the examples up to Example 15 16 17 18 19 (Ref.) 20 (Ref.) 21 (Ref.) Resin component: Araldite® < GY 250 167.2 167.2 167.2 167.2 167.2 167.2 167.2 Araldite® < DY-E 31.8 31.8 31.8 31.8 31.8 31.8 31.8 Hardener component: Amin A1 20.5 - - - - - - Amin A2 - 20.5 - - - - - Amin A3 - - 18.8 - - - - Amin A4 - - - 18.8 - - - MXDA - - - - 17.0 34.0 - IPDA 21.3 21.3 21.3 21.3 21.3 - 42.6 Benzyl alcohol 25.0 25.0 25.0 25.0 25.0 25.0 25.0 Salicylic acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ancamine ®< K54 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Viscosity (10') [Pa·s] 0.62 0.61 0.58 0.58 0.39 0.37 0.62 Gelling time (h:min) 4:15 4:35 4:15 4:15 2:40 3:00 3:00 Shore D (1d NK) 66 52 71 62 77 78 77 (2d NK) 78 72 78 75 78 79 79 King's hardness [s] (1d NK) 42 18 52 39 59 36 91 (2d NK) 118 85 111 95 106 42 143 (7d NK) 160 143 158 155 145 60 155 (14d NK) 164 158 161 157 150 74 158 aspect nice nice nice nice nice structure nice Tg 1st / 2nd run [°C] 47 / 97 47 / 92 46 / 88 48 / 84 44 / 59 46 / 76 57 / 99 22 24. Table 4: Composition and properties of the examples up to Example 22 23 24 Resin component: Araldite® < GY 250 167.2 167.2 167.2 Araldite® < DY-E 31.8 31.8 31.8 Hardener component: Adduct-1 24.8 - - Adduct-2 - 23.6 - Adduct-3 - - 23.6 B-EDA 20.0 20.0 20.0 IPDA 17.0 17.0 17.0 Benzyl alcohol 17.6 17.9 17.9 Ancamine ®< K54 2.0 2.0 2.0 Viscosity (10') [Pa·s] 0.56 0.55 0.58 Gelling time (h:min) > 3:30 > 3:30 > 3:30 Shore D (1d NK) 62 62 65 (2d NK) 77 76 77 King's hardness [s] (1d NK) 36 32 38 (2d NK) 84 70 71 (7d NK) 153 145 144 (14d NK) 164 168 167 aspect nice nice nice Tg 1st / 2nd run [°C] 50 / 79 51 / 79 49 / 77

Claims

1. Use of an amine of the formula (I) for curing of epoxy resins: where R is H or methyl, and A is a phenylene or cyclohexylene radical.

2. Use according to Claim 1, characterized in that A is selected from the group consisting of 1,3-phenylene, 1,4-phenylene, 1,3-cyclohexylene and 1,4-cyclohexylene.

3. Use according to either of Claims 1 and 2, characterized in that the amine of the formula (I) is selected from the group consisting of 1,4-bis(α-aminoethyl)benzene, 1,3-bis(α-aminoethyl)benzene, 1-α-aminoethyl-4-aminomethylbenzene and 1-α-aminoethyl-3-aminomethylbenzene.

4. Use according to any of Claims 1 to 3, characterized in that the amine of the formula (I) is 1,4-bis(α-aminoethyl)benzene or 1,3-bis(α-aminoethyl)benzene.

5. Use according to any of Claims 1 to 4, characterized in that the amine of the formula (I) is a constituent of a reaction product obtained from the reaction of - at least one ketone of the formula (II) with - ammonia or hydroxylamine or an oxime of the formula (III) and subsequent hydrogenation, where m is 0 or 1, n is 1 or 2 and (m+n) is 2, X is formyl or nitrile, A' is a phenylene or cyclohexylene radical, R1 is H or methyl, and R2 is H or an alkyl radical having 1 to 4 carbon atoms.

6. Amine-functional adduct from the reaction of the amine of the formula (I) as described in any of Claims 1 to 5 with at least one epoxy resin or monoepoxide.

7. Epoxy resin composition comprising - a resin component comprising at least one epoxy resin and - a hardener component containing at least one amine of the formula (I) as described any of Claims 1 to 5 and / or an amine-functional adduct according to Claim 6.

8. Cured composition obtained from the epoxy resin composition according to Claim 7 after the resin component and the curing agent component have been mixed.

9. Process for producing a shaped body, comprising the steps of (i) mixing the components of the epoxy resin composition according to Claim 7, (ii) adding the mixed composition to a casting mold, followed by the curing of the mixed composition, optionally under pressure and optionally by means of supplied heat.

10. Article comprising the cured composition according to Claim 8.

11. Article according to Claim 10, characterized in that it is a shaped body.

12. Article according to Claim 11, characterized in that the shaped body is a composite material.

13. Reaction product containing at least one amine of the formula (I) obtained from the reaction of - at least one ketone of the formula (II) with - ammonia or hydroxylamine or an oxime of the formula (III) and subsequent hydrogenation, where R is H or methyl, A is a phenylene or cyclohexylene radical, m is 0 or 1, n is 1 or 2 and (m+n) is 2, X is formyl or nitrile, A' is a phenylene or cyclohexylene radical, R1 is H or methyl, and R2 is H or an alkyl radical having 1 to 4 carbon atoms.

14. Reaction product according to Claim 13, characterized in that the ketone of the formula (II) is 1,3-diacetylbenzene or 1,4-diacetylbenzene.