Hardener for epoxy resin

Abstract

The present invention relates to the use of amines of formula (I) for curing epoxy resins, whereby synthetic resin articles having surprisingly high glass transition temperatures are formed with particularly low heat generation. According to the invention, the amines of formula (I) allow in particular epoxy resin moldings, potting compounds and composites that are simple and free of defects, have beautiful surfaces and allow high application temperatures.

Description

[Technical field]

[0001] The present invention relates to an amine and its use as a curing agent for epoxy resins and its use as a molding or matrix resin for epoxy resin compositions and especially composite materials. [Background technology]

[0002] The hardeners used for epoxy resins are usually primary diamines. However, the choice of cheap, 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 (isophoronediamine or IPDA) are particularly frequently used. Both amines are notable for their low viscosity and good dilution effect on epoxy resins, which they crosslink to obtain chemically stable polymers of high mechanical quality. However, only a few manufacturers exist for these amines. This is because the preparation process is demanding and requires high capital expenditures for plant and safety measures. This leads to frequent supply shortages and price fluctuations. In addition, both amines also have technical disadvantages. MXDA is very reactive and the exotherm released by the curing of epoxy resins is very high, which in the case of high build coatings can lead to blistering, discoloration or other inhomogeneities as a result of high heat input. Furthermore, only moderate glass transition temperatures are achieved with MXDA, which is disadvantageous, especially in the case of adhesives and matrix resins for composites. IPDA is superior to MXDA in terms of heat generation due to cure and glass transition temperature. However, a wider selection of available primary diamines with lower heat generation due to cure and advantageous properties in terms of cure and glass transition temperature is desirable.

[0003] US 2014 / 107313 and US 2015 / 344406 disclose the use of N,N'-dialkylated MXDA, and EP 3,344,677 discloses the use of N-benzylated ethane-1,2-diamine as a curing agent for epoxy resins. In the case of these amines, some of the functional groups are lost as a result of the secondary amino groups, which leads to a low glass transition temperature after curing.

[0004] US 2017 / 226278 and EP 3,344,678 disclose polyamines from the reductive alkylation of dialdehydes, such as terephthalaldehyde, with propane-1,2-diamine or ethane-1,2-diamine, which contain two primary and two secondary amino groups. These are of relatively high viscosity and are much less good than MXDA or IPDA as diluents for epoxy resins, and do not allow for similarly high glass transition temperatures.

[0005] WO 2019 / 230692 discloses xylylenediamines that are ethylated at the α-position of the amine group and have three or four ethyl groups. Due to high steric hindrance, these amines show very reduced reactivity with epoxy resins, which leads to very slow curing. In addition, they are highly viscous and very complicated to prepare, and the polymers thus cured are less stable to heat and ultraviolet light due to the tertiary carbon atoms in the curing agent. Summary of the Invention [Problem to be solved by the invention]

[0006] It is therefore an object of the present invention to provide a primary amine for the curing of epoxy resins that can be prepared in a simple manner and allows reliable curing with low exotherm and high glass transition temperature. [Means for solving the problem]

[0007] Surprisingly, this object is achieved by the amines of formula (I) as described in claim 1. The amines of formula (I) are adjustable in a simple process from readily available starting materials. They are of low viscosity and are good diluents for epoxy resins. They show problem-free curing with long pot life and surprisingly low exotherm with epoxy resins. This allows for use in high-build epoxy resin products, such as moldings, embedding compounds or matrix resins for composites, without blistering, discoloration or other inhomogeneities due to high heat generation. Surprisingly, the amines of formula (I) achieve very high glass transition temperatures, especially with 1,4 amines and amines with R=methyl. Furthermore, the amines of formula (I) have a surprisingly low odor, which is advantageous in handling and application and is highly appreciated by users, allowing cured epoxy resin compositions with particularly low yellowing, which is particularly surprising in the case of A=phenylene.

[0008] The amines of formula (I) enable epoxy resin mouldings, potting compounds and composites which can be easily produced in a particularly defect-free manner, have good surfaces and allow high use temperatures.

[0009] 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention relates to a process for curing epoxy resins, comprising the steps of: [ka] (In the formula, R is H or methyl, and A is a phenylene or cyclohexylene group. The present invention provides the use of an amine of the formula:

[0011] Substance names beginning with "poly", such as polyamine or polyepoxide, refer to substances that formally contain more than one of the functional groups present in the name per molecule.

[0012] A "primary amino group" refers to an amino group that is attached to a single organic group and carries two hydrogen atoms; a "secondary amino group" refers to an amino group that is attached to two organic groups that may together be part of a ring and carries one hydrogen atom; and a "tertiary amino group" refers to an amino group that is attached to three organic groups (two or three of which may be part of one or more rings) and carries no hydrogen atoms.

[0013] "Amine hydrogen" refers to the hydrogen atoms of primary and secondary amine groups.

[0014] "Amine hydrogen equivalent" refers to the mass of an amine or amine-containing composition that contains one molar equivalent of an amine hydrogen. It is expressed in units of "g / eq."

[0015] "Epoxide equivalent" refers to the mass of an epoxy-containing compound or composition that contains one molar equivalent of an epoxy group, and is expressed in units of "g / eq."

[0016] "Diluent" refers to a substance that is soluble in the epoxy resin, reduces its viscosity, and is not chemically incorporated into the epoxy resin polymer during the curing process.

[0017] "Molecular weight" refers to the molar mass of a molecule (grams per mole). "Average molecular weight" refers to the number average molecular weight M of a polydisperse mixture of oligomeric or polymeric molecules. n which is typically determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0018] "Pot life" refers to the maximum period from mixing of the components and application of the epoxy resin composition, in which the mixed composition is in a sufficiently free-flowing state and has good ability to wet the substrate surface.

[0019] "Gel time" refers to the time interval from mixing the components of an epoxy resin composition to its gelation.

[0020] "Room temperature" refers to a temperature of 23°C.

[0021] All industry standards and conventions mentioned herein refer to the editions in effect as of the original filing date unless otherwise noted.

[0022] Weight percent (wt%) values ​​refer to the proportion by mass of a component in a composition based on the entire composition, unless otherwise specified. The terms "mass" and "weight" are used interchangeably herein.

[0023] Preferably, A is selected from the group consisting of 1,3-phenylene, 1,4-phenylene, 1,3-cyclohexylene and 1,4-cyclohexylene.

[0024] More preferably, A is 1,3-phenylene or 1,4-phenylene.Such amines of formula (I) are particularly compatible with aromatic epoxy resins and allow a particularly good surface after curing.

[0025] In particular, A is 1,4-phenylene.Such amines of formula (I) enable particularly high glass transition temperatures.

[0026] The amine of formula (I) is preferably 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.

[0027] Particular preference is given to 1,4-bis(α-aminoethyl)benzene or 1,3-bis(α-aminoethyl)benzene. These amines of formula (I) allow particularly high glass transition temperatures.

[0028] Most preferred is 1,4-bis(α-aminoethyl)benzene, which allows for the highest glass transition temperature and particularly low yellowing.

[0029] 1-α-aminoethyl-4-aminomethylbenzene and 1-α-aminoethyl-3-aminomethylbenzene allow particularly rapid curing.

[0030] The amine of formula (I) is preferably at least one ketone of formula (II), ammonia or hydroxylamine or an oxime of formula (III) [ka] (In the formula, 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 group; R 1 is H or methyl, and R 2 is H or an alkyl group having 1 to 4 carbon atoms. and subsequent hydrogenation.

[0031] Preferably, A' is a phenylene group, especially 1,3-phenylene or 1,4-phenylene.

[0032] Preferably, R 1 is methyl.

[0033] Preferably, R 2 is an alkyl group having 1 to 4 carbon atoms, in particular methyl or ethyl or isobutyl.

[0034] Preferred ketones of formula (II) are 1,3-diacetylbenzene, 1,4-diacetylbenzene, 4-acetylbenzonitrile, 3-acetylbenzonitrile, 4-formylbenzonitrile or 3-formylbenzonitrile.

[0035] 1,3-diacetylbenzene or 1,4-diacetylbenzene are particularly preferred.

[0036] 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.

[0037] It is preferred to use ammonia or hydroxylamine or an oxime of formula (III) approximately stoichiometrically or in stoichiometric excess over the carbonyl group of the ketone of formula (II).

[0038] For ketones of formula (II) that do not contain a nitrile group, it is preferred to use ammonia or hydroxylamine for the reaction. The reaction proceeds with the release of water. The reaction is carried out, for example, in the presence of a catalyst, optionally a weak base, for example potassium carbonate.

[0039] For ketones of formula (II) containing a nitrile group, it is preferred to use oximes of formula (III) for the reaction.

[0040] Preferred oximes of formula (III) are 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.

[0041] With an oxime of formula (III), the reaction takes place in a transoximation reaction to give an oxime of formula [ka] This is preferably carried out in the presence of a strong acid, in particular perchloric acid.

[0042] The reaction may be represented by formula (IVa), (IVb), (IVc) or (IVd): [ka] (wherein A', m and n have the definitions already given). The reaction proceeds via an intermediate.

[0043] Prior to hydrogenation, the intermediate can be isolated and optionally purified by removal of volatile components, in particular by distillation or stripping, for example to remove potassium carbonate or perchloric acid, optionally followed by washing with water or an aqueous salt solution, or the reaction and hydrogenation are carried out in a one-pot process without isolation of the intermediate.

[0044] The hydrogenation can be carried out directly with molecular hydrogen or indirectly with hydrogen or hydride transfer from other reagents, such as formic acid or LiAlH4. The hydrogenation is preferably carried out with molecular hydrogen.

[0045] The hydrogenation is preferably carried out in the presence of a suitable catalyst. Preferred catalysts are palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams' catalyst or Raney nickel, in particular palladium on carbon or Raney nickel.

[0046] When molecular hydrogen is used, the hydrogenation is preferably carried out in a pressure apparatus at a hydrogen pressure of from 5 to 300 bar. It can be carried out in a batchwise process or, preferably, in a continuous process.

[0047] The hydrogenation is preferably carried out at a temperature in the range of 40-150° C. If A′ is phenylene, the hydrogenation conditions can be selected such that the phenylene groups are not hydrogenated or are hydrogenated as well. If the phenylene groups present are not hydrogenated in the hydrogenation, it is preferred to operate at a temperature in the range of 60-120° C. and a hydrogen pressure in the range of 10-120 bar. Otherwise, it is preferred to operate at a temperature in the range of 80-150° C. and a hydrogen pressure in the range of 150-250 bar.

[0048] Volatile constituents, in particular solvent and water present, are preferably removed from the reaction product after hydrogenation, in particular by distillation or stripping.

[0049] The reaction products can be further purified, in particular by distillation, which allows reaction products with a particularly high content of the amine of formula (I).

[0050] The present invention relates to at least one ketone of formula (II), ammonia or hydroxylamine or an oxime of formula (III) and subsequent hydrogenation as described above.

[0051] The ketone of formula (II) is preferably 1,3-diacetylbenzene or 1,4-diacetylbenzene, in which m is 0 and n is 2 in formula (II).

[0052] The reaction product preferably contains an amine of formula (I) in a content of at least 50% by weight, more preferably at least 80% by weight and in particular at least 90% by weight, based on the reaction product.

[0053] The amines of formula (I) may take the form of mixtures of amines of formula (I) in which A is a phenylene group and amines of formula (I) in which A is a cyclohexylene group, resulting in particular from partial hydrogenation of the phenylene group from the ketones of formula (I).

[0054] When the ketone of formula (II) used is 1,3-diacetylbenzene of technical grade quality containing a fraction of 1,3,5-triacetylbenzene, the reaction product contains in particular 1,3,5-tris(α-aminoethyl)benzene as a by-product.

[0055] In particular, the amines of formula (I) in the form of the reaction products described are used for curing epoxy resins.

[0056] Suitable epoxy resins are especially the commercially available glycidyl ethers of mono- or polyfunctional alcohols or phenols, in particular the epoxy resins specified herein.

[0057] It is preferred to mix the amine of formula (I), the epoxy resin and any further substances with one another, where the ratio of groups reactive towards epoxy groups, in particular the amine hydrogens of the amine of formula (I) and the epoxy groups, is preferably in the range from 0.5 to 1.5, in particular from 0.7 to 1.2.

[0058] Curing can take place at ambient temperature, in particular in the range from 5 to 40° C., or at elevated temperature, which is preferably at elevated temperature, in particular in the range from 40 to 150° C., preferably from 50 to 120° C.

[0059] For curing at elevated temperatures, the amine of formula (I) and / or the epoxy resin can be heated individually before mixing and / or the mixed composition is heated in place.

[0060] Curing at elevated temperatures is of particular concern because the viscosity of the mixed composition is reduced and curing proceeds particularly rapidly, but the released exotherm also results in significant heating of the cured composition very rapidly, which can cause blistering, discoloration and other inhomogeneities.

[0061] The amines of formula (I) produce a particularly low exotherm coupled with a reliable and rapid cure. Furthermore, the cured materials have very high glass transition temperatures, which allows high use temperatures.

[0062] The present invention further provides an amine-functional adduct formed from the reaction of an amine of formula (I) with at least one epoxy resin or monoepoxide.

[0063] The epoxy resin or monoepoxide preferably has an average epoxy equivalent weight in the range of 150 to 500 g / eq, preferably 156 to 250 g / eq.

[0064] Particularly preferred are aromatic epoxy resins, especially aromatic diepoxides, such as especially bisphenol A, F or A / F diglycidyl ethers, or novolac epoxy resins, especially phenol-formaldehyde novolac glycidyl ethers. Such adducts allow particularly rapid cure and high glass transition temperatures.

[0065] Also preferred are epoxy resins containing polyoxypropylene and / or polyoxyethylene units. These are in particular the reaction products of diglycidyl ethers of polypropylene glycol or bisphenol A, F or A / F diglycidyl ethers with polypropylene glycol or polyethylene glycol. Such adducts are particularly suitable as components of water-based hardeners for epoxy resins.

[0066] Also preferred are aromatic monoepoxides, in particular cresyl glycidyl ether, tert-butylphenyl glycidyl ether or cardanol glycidyl ether.

[0067] Preference is given to adducts from the reaction of an amine of formula (I) with at least one diepoxide in a stoichiometric ratio ranging from 1 to 10 mol, preferably from 1.2 to 5 mol, in particular from 1.4 to 3 mol of amine of formula (I) per molar equivalent of epoxy groups.

[0068] The present invention further provides a curing agent for epoxy resins comprising at least one amine of formula (I) and / or at least one amine-functional adduct from the reaction of an amine of formula (I) with at least one epoxy resin or monoepoxide, and at least one further component selected from further amines A1, accelerators, diluents, stabilizers and surface-active additives.

[0069] The further amine A1 is preferably not an amine of formula (I).

[0070] The hardener preferably contains from 2% to 99% by weight, preferably from 5% to 90% by weight, in particular from 10% to 80% by weight of an amine of formula (I) and / or an amine-functional adduct from the reaction of an amine of formula (I) with at least one epoxy resin or monoepoxide.

[0071] The hardener is preferably not water-based. It preferably contains less than 15% by weight, especially less than 10% by weight, of water. Such hardeners are suitable for non-aqueous epoxy resin products.

[0072] Suitable further amines A1 are in particular amines not according to formula (I) which have at least two, preferably at least three, amine hydrogens.

[0073] Preferred further amines A1 are polyamines having at least three aliphatic amine hydrogens, in particular N-benzylethane-1,2-diamine, N-benzylpropane-1,2-diamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-phenylethyl)-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-1,3-bis(aminomethyl)benzene, 2,2-dimethylpropane-1,3-diamine, pentaerythritol, phenylmethylamine ... Tan-1,3-diamine (DAMP), pentane-1,5-diamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethylpentane-1,5-diamine (C11-neodiamine), hexane-1,6-diamine, 2,5-dimethylhexane-1,6-diamine, 2,2(4),4-trimethylhexane-1,6-diamine (TMD), heptane-1,7-diamine, octane-1,8-diamine, nonane-1,9 -diamine, decane-1,10-diamine, undecane-1,11-diamine, dodecane-1,12-diamine, 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]heptane (NBDA), 2.6]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), menthane-1,8-diamine, 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-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1,13-diamine or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofuran Dorofuran or other polytetrahydrofuran diamines, polyoxyalkylene diamines or triamines, in particular polyoxypropylene diamines or polyoxypropylene triamines, such as Jeffamine® D-230, Jeffamine® D-400 or Jeffamine® T-403 (all from Huntsman), polyalkylene amines, such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylene Hexamine (PEHA), dipropylenetriamine (DPTA), N-(2-aminoethyl)propane-1,3-diamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methylpentane-1,5-diamine, N3-(3-aminopentyl)pentane-1,3-diamine, N5-(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine, N,N'-bis(3-amino-1 1-ethylpropyl)-2-methylpentane-1,5-diamine, 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT), N-benzylated polyalkyleneamines having one or two benzyl groups, in particular benzylated DETA, TETA, N3 amines, N4 amines or DPTA, N-aminoethylpiperazine, 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), amine-functional adducts of the amines mentioned above with epoxides or mixtures of two or more of these amines.

[0074] The curing agent is preferably N-benzylethane-1,2-diamine, 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, an average molecular weight M in the range of 200 to 500 g / mol. n and polyoxypropylenediamine having an average molecular weight M in the range of 300 to 500 g / mol. n The compound also contains at least one further amine A1 selected from the group consisting of polyoxypropylene triamines having the formula:

[0075] Of these, N-benzylethane-1,2-diamine, MXDA, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane or bis(4-aminocyclohexyl)methane are preferred, as they enable particularly rapid curing.

[0076] Of these, IPDA is also preferred, as it allows for an inexpensive hardener with a high glass transition temperature.

[0077] The hardener may in particular also comprise a plurality of further amines A1.

[0078] Suitable accelerators are in particular acids or compounds hydrolysable by acids, in particular 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 in particular phosphoric acid or mixtures of the abovementioned acids and acid esters; nitrates, such as in particular 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-dimethyl imidazole, salts of such tertiary amines, quaternary ammonium salts, such as benzyltrimethylammonium chloride, in particular amidines, such as 1,8-diazabicyclo[5.4.0]undec-7-ene, in particular guanidines, such as 1,1,3,3-tetramethylguanidine, in particular phenols, in particular bisphenols, phenolic resins or Mannich bases, such as in particular 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol or polymers derived from phenol, formaldehyde and N,N-dimethylpropane-1,3-diamine, phosphites, such as in particular diphenyl phosphite or triphenyl phosphite or compounds which have a mercapto group.

[0079] Acids, nitrates, tertiary amines or Mannich bases, especially salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol or combinations of these accelerators are preferred.

[0080] Suitable diluents are 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, xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di ... diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, 2,2,4-trimethylpentane-1,3-diol monoisobutyrate, diphenylmethane, diisopropyl naphthalene, mineral oil fractions, for example the Solvesso® grades (from Exxon), alkylphenols, for example tert-butylphenol, nonylphenol, dodecylphenol, cardanol, styrenated phenols, bisphenols, aromatic hydrocarbon resins, especially the types containing phenolic groups, alkoxylated phenols, especially ethoxylated or propoxylated phenols, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphates or sulfonates or sulfonamides.

[0081] Of these, diluents with a boiling point above 200° C. are preferred, in particular benzyl alcohol, styrenated phenols, ethoxylated phenols, aromatic hydrocarbon resins containing phenolic groups, such as especially Novares® grades LS500, LX200, LA300 or LA700 (from Ruetgers), diisopropyl naphthalene or cardanol, in particular benzyl alcohol.

[0082] Diluents containing phenolic groups are also effective as accelerators.

[0083] Suitable stabilizers are especially those against oxidation, heat, light or UV radiation.

[0084] Suitable surface-active additives are especially antifoaming agents, degassing agents, wetting agents, dispersing agents or levelling agents.

[0085] The hardener may be further comprised of further components, in particular - further adducts, in particular adducts of MPMD or ethane-1,2-diamine or propane-1,2-diamine with cresyl glycidyl ether or aromatic epoxy resins (wherein unreacted MPMD, ethane-1,2-diamine or propane-1,2-diamine has been removed by distillation after the reaction); monoamines, such as in particular benzylamine or furfurylamine; - polyamidoamines, in particular the reaction products of mono- or polybasic carboxylic acids or their esters or anhydrides, in particular dimeric fatty acids, with polyamines, in particular DETA or TETA, used in stoichiometric excess; Mannich bases, in particular phenalkamines, ie 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)-tolylenediamine; 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 may include.

[0086] The present invention relates to - a resin component comprising at least one epoxy resin; - a hardener component comprising at least one amine of formula (I) and / or an amine-functional adduct formed from the reaction of an amine of formula (I) with at least one epoxy resin or monoepoxide; The epoxy resin composition further comprises:

[0087] Suitable epoxy resins are obtainable in known manner, in particular from the reaction of epichlorohydrin with polyols, polyphenols or amines.

[0088] Suitable epoxy resins are in particular aromatic epoxy resins, in particular bisphenol A, bisphenol F or bisphenol A / F, where A represents acetone and F represents formaldehyde used as reactant in the production of these bisphenols. In the case of bisphenol F, positional isomers may also be present, more particularly those derived from 2,4'- or 2,2'-hydroxyphenylmethane. dihydroxybenzene derivatives, such as resorcinol, hydroquinone or catechol; further 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, 2,2-bis(4-hydroxy-3-tert-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)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, (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; novolaks (which are in particular condensation products of phenols or cresols with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde or 2-ethylhexanal or 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); It is a glycidyl ether of the formula:

[0089] Further suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular - Saturated or unsaturated, branched or unbranched, cyclic or acyclic, difunctional, trifunctional or tetrafunctional C2-C 30 glycidyl ethers of alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol or alkoxylated glycerol or alkoxylated trimethylolpropane; - Hydrogenated bisphenol A, F or A / F liquid resins or glycidylation products of hydrogenated bisphenol A, F or A / F; - N-glycidyl derivatives of amide or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate or the reaction products of epichlorohydrin with hydantoin. It is.

[0090] The epoxy resin is preferably a liquid resin or a mixture comprising two or more liquid epoxy resins.

[0091] "Liquid epoxy resin" refers to commercial polyepoxides having a glass transition temperature below 25°C.

[0092] The resin component optionally further contains a proportion of a solid epoxy resin.

[0093] The epoxy resins are in particular liquid resins based on bisphenols on novolacs, in particular those having an average epoxy equivalent weight in the range of 156 to 210 g / eq.

[0094] Particularly suitable are bisphenol A diglycidyl ethers and / or bisphenol F diglycidyl ethers, such as those available from Olin, Huntsman, or Momentive. These liquid resins have low viscosity for epoxy resins, allowing for rapid cure and high hardness. They may contain a percentage of solid bisphenol A resins or novolac epoxy resins.

[0095] Also particularly suitable are phenol-formaldehyde novolac glycidyl ethers, especially those having an average functionality in the range from 2.3 to 4, preferably from 2.5 to 3. These may contain certain proportions of other epoxy resins, especially bisphenol A diglycidyl ether or bisphenol F diglycidyl ether.

[0096] The resin component may include a reactive excipient.

[0097] Preferred reactive excipients are reactive excipients containing epoxy groups, in particular butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane di- or triglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, guaiacol glycidyl ether, 4-methoxyphenyl glycidyl ether, p-n-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-dodecylphenyl glycidyl ether, cardanol glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether or glycidyl ethers of natural alcohols, such as, in particular, C8-C 10 Or C 12 ~C14 Or C 13 ~C 15 It is an alkyl glycidyl ether.

[0098] The epoxy resin composition preferably comprises at least one further component selected from the group consisting of diluents, accelerators, stabilizers, surface active additives, fillers and pigments.

[0099] Suitable fillers, accelerators, stabilizers and surface-active additives are in particular those already mentioned.

[0100] Suitable fillers are ground or precipitated calcium carbonate, in particular optionally coated with fatty acids, in particular stearic acid, barytes, talc, quartz flour, quartz sand, silicon carbide, biotite, 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, ground wood pulp, metal powders, such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow beads. Of these, calcium carbonate, barytes, quartz flour, talc or combinations thereof are preferred.

[0101] Suitable pigments are especially titanium dioxide, iron oxide, chromium(III) oxide, anticorrosion pigments, organic pigments or carbon black, especially titanium dioxide.

[0102] The epoxy resin composition may contain further auxiliaries and additives, in particular reactive excipients, in particular those already mentioned or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, in particular acetoacetylated polyols, butyrolactones, carbonates, aldehydes, isocyanates or silicones with reactive groups; - polymers, in particular polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers containing 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 polyethylene or fluorine-containing polymers or sulfonamide-modified melamine; - fibres, in particular glass, carbon, cellulose, metal, ceramic or polymer fibres, such as polyamide or polyethylene fibres; - further solids, in particular wood pellets or cellulose; - nanofillers, especially carbon nanotubes; - rheology modifiers, in particular thickeners or anti-settling agents; - adhesion improvers, in particular organoalkoxysilanes; - flame retardant substances, in particular the aluminium hydroxide or magnesium hydroxide fillers already mentioned, 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 oligomers, tetraphenylresorcinol 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(dibromonorbornanedicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadieno)cyclooctane, or chloroparaffins; or - further additives, in particular dispersed paraffin wax or biocides may optionally include.

[0103] The epoxy resin composition preferably has a slightly low content of diluent, preferably less than 20% by weight, more preferably less than 10% by weight, especially less than 5% by weight, most preferably less than 1% by weight of diluent based on the total epoxy resin composition.

[0104] The epoxy resin composition preferably has a slightly low content of water, preferably less than 5% by weight, in particular less than 1% by weight, based on the entire epoxy resin composition.

[0105] The resin component and the hardener component of the epoxy resin composition are stored in separate containers. The further components of the epoxy resin composition can be present as components of the resin component or the hardener component; the further components that are reactive towards epoxy groups are preferably components of the hardener component. It is also possible for the further components to be present as separate further components.

[0106] Suitable containers for storage of the resin component or the hardener component are especially vats, hobs, bags, buckets, cans, cartridges or tubes. The components are storable, meaning that they can be stored for several months to a year or more before use, to the extent appropriate for their use, without change in their respective properties.

[0107] The resin component and the hardener component are mixed immediately before or during application. The mixing ratio is preferably selected so that the molar ratio of groups reactive towards epoxy groups to epoxy groups is in the range of 0.5 to 1.5, in particular 0.7 to 1.2. In parts by weight, the mixing ratio between the resin component and the hardener component is typically in the range of 1:2 to 20:1.

[0108] The components are mixed continuously or batchwise using a suitable method, taking care to ensure that not too much time passes during mixing and application of the components and that application occurs within the pot life. Mixing and application can typically be carried out at ambient temperatures in the range of about 5-40° C., preferably about 10-35° C. Mixing and / or application can preferably be carried out at elevated temperatures, particularly in the range of 40-150° C., preferably 50-120° C.

[0109] The mixing of the components initiates the curing of the epoxy resin composition by chemical reaction. The primary and secondary amino groups, as well as any additional groups present that are reactive towards epoxy groups, react with the epoxy group, resulting in its ring opening. Primarily as a result of these reactions, the composition polymerizes and thereby cures.

[0110] Curing typically lasts from a few hours to a few days, the duration of which depends on factors including temperature, the reactivity of the components, their stoichiometry and the presence / amount of accelerators.

[0111] When freshly mixed, the epoxy resin composition has a low viscosity. The viscosity at 20° C. 5 minutes after mixing the resin and hardener components is preferably less than 10 s -1 The viscosity of the polymer is in the range of 0.2 to 20 mP·s, preferably 0.3 to 10 mP·s, and particularly preferably 0.3 to 5 mP·s, as measured using a cone-plate viscometer at a shear rate of 0.2 to 20 mP·s, preferably 0.3 to 10 mP·s, and particularly preferably 0.3 to 5 mP·s.

[0112] The epoxy resin composition is applied to at least one substrate and / or at least one mold.

[0113] Suitable substrates are in particular - glass, glass ceramics, concrete, mortar, cement screed, fibre cement, brick, tile, plaster or natural rock, e.g. granite or marble; - repair or levelling compounds based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar); - Surface-finished metals or alloys, including metals or alloys, such as zinc-plated or chromium-plated metals, e.g. aluminium, iron, steel, copper and other non-ferrous metals; - Asphalt or bitumen; - leather, textiles, paper, wood, wood-based materials, resin-textile composites or further polymer composites which are bound with resins, such as phenolic resins, melamine resins or epoxy resins; - 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 (in each case untreated or surface-treated, for example by means of plasma, corona or flame); - fibre reinforced plastics, such as carbon fibre reinforced plastics (CFP), glass fibre reinforced plastics (GFP) and sheet moulding compounds (SMC); - Thermal insulation foams, especially made of EPS, XPS, PUR, PIR, rock wool, mineral wool or foam glass; - Coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metals or alloys or painted metal sheets; - coated floors which have been overcoated with a coating, paint or varnish, in particular a further layer of floor finish It is.

[0114] The substrate may optionally be pre-treated prior to application, especially by physical and / or chemical cleaning methods or by application of activators or primers.

[0115] The substrates are in particular bonded together by coating and / or gluing.

[0116] A suitable mould is an apparatus into which the mixed liquid epoxy resin composition is poured, in which it is cured, and from which it can be demoulded / removed after curing, where the cured composition forms a moulded body.

[0117] The mold preferably consists at least of a material on the surface (from which the cured epoxy resin composition can be detached again without damage), in particular made of metal, ceramic, plastic or silicone, optionally provided with a non-stick coating, in particular of Teflon, silicone or wax.

[0118] The present invention further provides a cured composition obtainable from the described epoxy resin composition after the resin component and the hardener component are mixed.

[0119] The epoxy resin compositions are preferably used as coatings, primers, adhesives, sealants, embedding compounds, casting resins, impregnating resins or as mouldings or matrices for composite materials, such as in particular CFRP (containing carbon fibres) or GFRP (containing glass fibres) or composite wood.

[0120] The present invention relates to a process for producing a molded body, comprising the steps of: (i) mixing the components of the epoxy resin composition; (ii) adding the mixed composition to a mold; Thereafter, the process further comprises the step of curing the mixed composition, optionally under pressure and optionally with supplied heat.

[0121] The epoxy resin composition, before being cured, may be mixed with fibres, powders or pellets, in particular carbon fibres, glass fibres or wood flour and / or pellets, to obtain a composite material.

[0122] The molding can be produced in one go in a mold, for example to produce a transparent molding that can be used as a tabletop, or it can be layered, where it is possible to cast any desired further material between the layers, for example decorative objects such as pearls, pieces of wood or shells.

[0123] After hardening, the shaped body is preferably removed from the mold. It can be further processed, in particular by cutting, punching, stretching, grinding or polishing.

[0124] In the production of moulded bodies, the low heat build-up on curing and the high glass transition temperature of the curable material are particularly advantageous.

[0125] The present invention further provides articles comprising cured compositions formed from the described epoxy resin compositions.

[0126] The article is in particular a moulding, in particular a composite material, in particular a lamella, a panel or a component of an industrial article.

[0127] The article may in particular also be a floor coating, a wall coating, a component coating, a pipe coating, a roof coating or a corrosion resistant coating.

[0128] The article is especially also an article bonded by means of an epoxy resin composition.

[0129] The article is preferably a molded body.

[0130] The molding is preferably a composite material. EXAMPLES

[0131] In the following, examples are presented that are intended to further clarify the invention described, but the invention is of course not limited to these described examples.

[0132] "AHEW" means amine hydrogen equivalent weight.

[0133] "EEW" means epoxy equivalent weight.

[0134] "Standard Climatic Conditions" ("SCC") refers to a temperature of 23±1°C and a relative air humidity of 50±5%.

[0135] Chemicals used were from Sigma-Aldrich Chemie GmbH unless otherwise stated.

[0136] Measurement method description: Viscosity was measured with a thermostatically controlled Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm). Low-viscosity samples with viscosities below 100 mPa s were measured at 100 s -1 At a shear rate of 10 s, the higher viscosity sample -1 The measurement was performed at a speed of .

[0137] The amine value was determined by titration (0.1 N HClO4 in acetic acid against crystal violet).

[0138] Gas chromatograms (GC) were measured in the temperature range of 60-320°C with a heating rate of 15°C / min and a run time of 10 min at 320°C. The injection temperature was 250°C. A Zebron ZB-5 column was used (L=30m, ID=0.25mm, dj=0.5μm) with a gas flow rate of 1.5ml / min. Detection was by flame ionization (FID).

[0139] Infrared spectra (FT-IR) were measured as undiluted films on a Nicolet iS5 FT-IR instrument from Thermo Scientific equipped with a horizontal ATR measurement unit with a diamond crystal. Absorption bands are expressed in wavenumbers (cm -1 ) to report.

[0140] 1 H NMR spectra were measured on a Bruker Ascend400 type spectrometer at 400.14 MHz; chemical shifts δ are reported in ppm relative to tetramethylsilane (TMS). No distinction was made between true and pseudo-coupling patterns.

[0141] Preparation of amines of formula (I): Amine A1: 1,4-bis(α-aminoethyl)benzene 50.0 g (0.31 mol) of 1,4-diacetylbenzene was dissolved in 800 ml of ethanol at 40° C. under nitrogen atmosphere, and 44.8 g of hydroxylamine solution (50% by weight in water, 0.68 mol) and a solution of potassium carbonate (52.2 g) in water (250 ml) were added, which resulted in a yellow color. The reaction mixture was then boiled under reflux for 6 hours and then left to stand overnight at room temperature, during which a white precipitate was formed. The precipitate was then collected by filtration, washed with water and dried under reduced pressure 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 then hydrogenated in a continuous hydrogenation apparatus with a fixed-bed Raney nickel catalyst at 90° C., a hydrogen pressure of 90 bar and a flow rate of 5 ml / min, and the hydrogenation solution was concentrated on a rotary evaporator. 49.0 g of a yellowish oil was obtained, which was then purified by distillation. At 68-75 °C (vapor temperature) and 0.04 mbar, 34.4 g of distillate was obtained as a clear, colorless oil with a viscosity of 15 mPa·s at 20 °C, an amine value of 680 mg KOH / g, a 1,4-bis(α-aminoethyl)benzene content of approximately 96% determined by GC (retention time 9.7 min) and a calculated AHEW of 41.0 g / eq. 1 H NMR(CDCl3):7.31(d,4H,Ar-H),4.1(q,2H,Ar-CH-N),1.51(br s,4H,NH2),1.39(d,6H,CH3). FT-IR:3359,3279,2957,2920,2856,1594,1508,1448,1367,1328,1188,1097,1015,829,699.

[0142] Amine A2: 1,3-bis(α-aminoethyl)benzene Amine A2 was prepared as described for amine A1, except using the same amount of 1,3-diacetylbenzene rather than 1,4-diacetylbenzene. 47.0 g of yellowish oil was obtained, which was then purified by distillation. 29.9 g of distillate at 55-60 °C (vapor temperature) and 0.06 mbar was obtained as a clear, colorless oil at 20 °C with a viscosity of 25 mPa s, an amine value of 661 mg KOH / g and a 1,3-bis(α-aminoethyl)benzene content of about 95% determined by GC (retention time 9.5 min) and a calculated AHEW of 41.0 g / eq. 1 H NMR(CDCl3):7.32(t,1H,Ar-H),7.27(d,2H,Ar-H),7.21(s,1H,Ar-H),4.1(q,2H,Ar-CH-N),1.51(br s,4H,NH2),1.38(d,6H,CH3). FT-IR:3360,3279,2959,2922,2864,1604,1485,1446,1366,1326,1152,1111,1054,857,795,706.

[0143] Amine A3: 1-α-aminoethyl-4-aminomethylbenzene 50.0 g (0.34 mol) of 4-acetylbenzonitrile was dissolved in 800 ml of ethanol at 40° C. under nitrogen atmosphere, and 2.4 g of aqueous perchloric acid (70% by weight HClO4 in water) was added. Then, 45.0 g (0.52 mol) of methyl ethyl ketoxime was gradually added to the reaction mixture with thorough stirring, which was boiled under reflux for 16 hours, and then the volatile components (ethanol, methyl ethyl ketone and excess methyl ether ketoxime) were removed on a rotary evaporator. The resulting powder was washed with water, dried under reduced pressure for 1 hour, then dissolved in 800 ml of a mixture of isopropyl alcohol and 1,4-dioxane (1:1 by weight) and hydrogenated at 80° C., 90 bar hydrogen pressure and a flow rate of 5 ml / min in a continuous hydrogenation apparatus with a fixed bed Raney nickel catalyst, and the hydrogenation solution was finally concentrated under reduced pressure. 49.0 g of a yellowish oil was obtained, which was then purified by distillation. At 75-80 °C (vapor temperature) and 0.06 mbar, 23.7 g of distillate was obtained as a clear colorless oil with a viscosity of 56 mP·s at 20 °C, an amine value of 710 mg KOH / g and a 1-α-aminoethyl-4-aminomethylbenzene content of about 83% determined by GC (retention time 9.5 min) and about 11.5% by-product (retention time 11.5 min, probably N-(1-(4-(aminomethyl)phenyl)ethyl)butan-2-amine). 37.6 g / eq of AHEW was used for further use. 1 H NMR(CDCl3):7.27(d,4H,Ar-H),4.06(q,1H,Ar-CH-N),3.80(s,2H,Ar-CH2-N),2.90(br s,4H,NH2),1.36(d,3H,CH3). FT-IR:3359,3280,2959,2921,2823,1606,1509,1448,1417,1366,1278,1202,1097,1016,832,698.

[0144] Amine A4: 1-α-aminoethyl-3-aminomethylbenzene Amine A4 was prepared as described for amine A3, except that the same amount of 3-acetylbenzonitrile was used rather than 4-acetylbenzonitrile. 48.0 g of yellowish oil was obtained, which was then purified by distillation. 19.6 g of distillate at 60-65 °C and 0.06 mbar was obtained as a clear colorless oil with a viscosity of 73 mPa·s at 20 °C, an amine value of 712 mg KOH / g and a 1-α-aminoethyl-3-aminomethylbenzene content of about 85% (retention time 9.4 min) and about 12% by-product (retention time 11.3 min, probably N-(1-(3-(aminomethyl)phenyl)ethyl)butan-2-amine) determined by GC. 37.6 g / eq of AHEW was used for further use. 1 H NMR(CDCl3):7.27(t,1H,Ar-H),7.26(m,3H,Ar-H),4.06(q,1H,Ar-CH-N),3.78(s,2H,Ar-CH2-N),2.93(br s,4H,NH2),1.34(d,3H,CH3). FT-IR:3360,3280,2960,2921,2863,1605,1589,1485,1444,1368,1327,1286,1155,1109,1049,999,828,788,704.

[0145] Preparation of amine-functional adducts: Addendum-1: A mixture of 24.64 g of amine A1 (0.15 mol) and 18.57 g of benzyl alcohol was heated to 80°C. To this was gradually added 18.70 g of Araldite® GY250 (0.1 mol of EP groups) with good stirring while the temperature of the reaction mixture was maintained at 70-90°C. The reaction mixture was held within this temperature range for 1 hour and then cooled. A clear slightly yellowish liquid was obtained with a viscosity of 44.2 Pa s at 20°C, an amine value of 260 mg KOH / g and a calculated AHEW of 123.8 g / eq.

[0146] Addendum-2: A mixture of 22.53 g of amine A3 (0.15 mol) and 17.67 g of benzyl alcohol was heated to 80°C. To this was added slowly, with good stirring, 18.70 g of Araldite® GY250 (0.1 mol of EP groups) while maintaining the temperature of the reaction mixture at 70-90°C. The reaction mixture was held within this temperature range for 1 hour and then cooled. A clear slightly yellowish liquid was obtained with a viscosity of 22.8 Pa s at 20°C, an amine value of 268 mg KOH / g and a calculated AHEW of 117.8 g / eq.

[0147] Addendum-3: A mixture of 22.53 g of amine A4 (0.15 mol) and 17.67 g of benzyl alcohol was heated to 80°C. To this was added slowly, with good stirring, 18.70 g of Araldite® GY250 (0.1 mol of EP groups) while maintaining the temperature of the reaction mixture at 70-90°C. The reaction mixture was held within this temperature range for 1 hour and then cooled. A clear slightly yellowish liquid was obtained with a viscosity of 31.5 Pa s at 20°C, an amine value of 255 mg KOH / g and a calculated AHEW of 117.8 g / eq.

[0148] Further substances and abbreviations used: Araldite® GY 250: Bisphenol A diglycidyl ether, EEW 187 g / eq (from Huntsman) Araldite® DY-E:C 12 ~C 14 Monoglycidyl ether of alcohol, EEW approx. 290g / eq (from Huntsman) MXDA: 1,3-bis(aminomethyl)benzene, AHEW34g / 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 35.5g / eq (from Mitsubishi Gas Chemical) B-EDA N-benzylethane-1,2-diamine prepared as follows, 150.2 g / mol, AHEW 50.1 g / eq Ancamine® K54 2,4,6-tris(dimethylaminomethyl)phenol (from Evonik)

[0149] N-Benzylethane-1,2-diamine (B-EDA): An initial charge of 180.3 g (3 mol) of ethane-1,2-diamine was mixed with a solution of benzaldehyde (106.0 g (1 mol)) in isopropanol (1200 ml) at room temperature, stirred for 2 hours, then hydrogenated in a continuous hydrogenator with a fixed bed Pd / C catalyst at 80° C., 80 bar hydrogen pressure and a flow rate of 5 ml / min, the hydrogenated solution was concentrated on a rotary evaporator at 65° C., resulting in the removal of unreacted ethane-1,2-diamine, water and isopropanol. The reaction mixture thus obtained was purified by distillation under reduced pressure at 80° C. This gave a colorless liquid with a content of N-benzylethane-1,2-diamine of >97% as determined by GC.

[0150] Preparation of hardener and epoxy resin composition: Examples 1 to 8: For each example, the resin and hardener components identified in Table 1 were separately heated to a temperature of 60° C. These preheated components were then used to produce epoxy resin compositions in total 20 g portions by mixing the components in the weight ratios shown in Table 1 using a centrifugal mixer (SpeedMixer™ DAC150, FlackTek Inc.) for 15 seconds, which were then immediately tested as described below.

[0151] The mixed composition was introduced into a test tube maintained at 60°C using a thermostatically controlled water bath, and a temperature sensor was placed in the center of the mixed material, which was used to determine the time to attainment of maximum temperature in the mixed material (reported in the table as time to peak exotherm) and the maximum temperature level (peak exotherm temperature). Values ​​reported in the table are the average from three measurements.

[0152] The Tg values ​​(glass transition temperature) were measured by DSC on hardened samples from the center of the test tubes from the above determination, which were further stored under standard climatic conditions and then measured for 14 days. The measurements were carried out with a Mettler Toledo DSC3+700 instrument and the measurement program (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).

[0153] [Table 1]

[0154] Examples 9 to 24: For each example, the components of the resin components identified in Tables 2-4 were mixed in the amounts (parts by weight) identified using a centrifugal mixer (SpeedMixer™ DAC150, FlackTek Inc.) and stored with exclusion of moisture.

[0155] The hardener component ingredients identified in Tables 2-4 were similarly processed and stored.

[0156] The two components of each composition were then processed using a centrifugal mixer into a homogenous liquid which was immediately tested as described below.

[0157] Viscosity was measured in the manner described 5 minutes after mixing the resin and hardener components, at a temperature of 20°C.

[0158] Gelling time was determined by moving about 3 g of freshly mixed mass with a spatula at regular intervals under standard climatic conditions until the mass started to gel.

[0159] The Shore D hardness was determined according to DI 53505 on cylindrical specimens (diameter 20 mm, thickness 5 mm) stored under standard climatic conditions, involving measurements of the hardness 1 day (24 hours) and 2 days after formation.

[0160] Furthermore, the film was applied to a glass plate with a layer thickness of 500 μm, which was stored / cured under standard climatic conditions. The König hardness (König pendulum hardness according to DIN EN ISO 1522) was determined on this film after 1, 2, 7 and 14 days. After 14 days, the appearance of the film was evaluated. If the film had a glossy, tack-free surface without structure, it was described as "good". "Structure" refers to any kind of marking or pattern on the surface. Films with reduced gloss were called "dull".

[0161] As a measure of yellowing, the change in color of some examples was determined after stress in a weathering tester. For this, further films were applied to glass plates in a layer thickness of 500 μm, which were stored / cured for 2 weeks under standard climatic conditions and then exposed to a Q-SUN Daylight-Q optical filter and 0.51 W / m at 340 nm. 2 The test was then stressed at a temperature of 65°C in a model Q-Sun Xenon Xe-1 weathering tester with a xenon lamp having a light output of 10 ... * a * b * C * H * The difference in color ΔE of the stressed films relative to the corresponding unstressed films was determined using an NH310 colorimeter from Shenzen 3NH Technology Co.LTD equipped with a 3-phase IR spectrophotometer.

[0162] Tg values ​​(glass transition temperature) were measured as described for Example 1 on samples (from specimens for Shore D hardness) cured for 14 days under standard climatic conditions.

[0163] [Table 2]

[0164] [Table 3]

[0165] [Table 4]

Claims

1. Use of an amine of formula (I): 【Chemical 1】 (wherein R is H or methyl, and A is a phenylene or cyclohexylene group) for curing an epoxy resin.

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 claim 1 or 2, characterized in that 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-aminomethylbenzene and 1-α-aminoethyl-3-aminomethylbenzene.

4. Use according to claim 1 or 2, characterized in that the amine of formula (I) is 1,4-bis(α-aminoethyl)benzene or 1,3-bis(α-aminoethyl)benzene.

5. The amine of formula (I) is - at least one ketone of formula (II), and - ammonia or hydroxylamine or an oxime of formula (III) 【Chemical 2】 (wherein 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 group, R １ is H or methyl, and R ２ is H or an alkyl group having 1 to 4 carbon atoms) The use according to claim 1 or 2, characterized in that it is a component of the reaction product obtained from the reaction with and subsequent hydrogenation.

6. An amine-functionalized adduct from the reaction of an amine of formula (I) according to claim 1 with at least one epoxy resin or monoepoxide.

7. A curing agent for an epoxy resin, comprising at least one amine of formula (I) according to claim 1 and / or at least one adduct according to claim 6, and at least one further component selected from a further amine A1, an accelerator, a diluent, a stabilizer and a surface-active additive.

8. - A resin component comprising at least one epoxy resin, - A curing agent component containing at least one amine of formula (I) according to claim 1 and / or the amine-functionalized adduct according to claim 6 An epoxy resin composition comprising.

9. - A resin component comprising at least one epoxy resin, A curing agent component containing the curing agent according to claim 7 An epoxy resin composition comprising.

10. A cured composition obtained from the epoxy resin composition according to claim 8 after the resin component and the curing agent component are mixed.

11. A process for manufacturing a shaped body, (i) Mixing the components of the epoxy resin composition according to claim 8, (ii) Adding the mixed composition to a mold, Subsequently, optionally under pressure and optionally by heat supplied, curing the mixed composition. A process comprising the step of.

12. An article comprising the cured composition according to claim 10.

13. The article according to claim 12, characterized in that it is a shaped body.

14. The article according to claim 13, characterized in that the shaped body is a composite material.

15. A reaction product containing at least one amine of formula (I), - with at least one ketone of formula (II), - ammonia or hydroxylamine or an oxime of formula (III) 【Chemical formula 3】 (wherein, R is H or methyl, A is a phenylene or cyclohexylene group, 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 group, R １ is H or methyl, and R ２ is H or an alkyl group having 1 to 4 carbon atoms) A reaction product containing at least one amine of formula (I), obtained from the reaction with and subsequent hydrogenation of the above.

16. The reaction product according to claim 15, characterized in that the ketone of formula (II) is 1,3-diacetylbenzene or 1,4-diacetylbenzene.

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