AMINE HARDENER WITH HIGH RENEWABLE CARBON CONTENT

Description

Technical area

[0001] The invention relates to alkylated amines with a high renewable carbon content and their use as hardeners for epoxy resins. State of the art

[0002] Amines are used in industry and construction, among other things, as hardeners in epoxy resin compositions. Depending on the application, properties such as high reactivity with low exothermicity and / or rapid, trouble-free curing at ambient temperatures to produce coatings or bodies with a uniform surface without blushing-related clouding, spots, or craters are required. The cured bodies or coatings should exhibit high hardness with low brittleness to withstand mechanical stress as well as possible, and for visually demanding applications, they should have a high degree of gloss and a low tendency to yellow. For many applications, it is crucial that the epoxy resin composition has a low viscosity to ensure quick and easy application, good flow and deaeration, and, where appropriate, good penetration into the substrate.Since many epoxy resins have a rather high viscosity, efficient dilution of these resins using amine hardeners is particularly advantageous because less thinner or solvent needs to be used to achieve a suitable viscosity and / or a higher filler content is possible.

[0003] Today, there is increasing demand for sustainable epoxy resin compositions. In particular, they should contain a high proportion of raw materials from renewable biological sources, i.e., be largely bio-based. Therefore, there is a need for sustainable amine hardeners. A common measure of the sustainability of chemical raw materials is the Renewable Carbon Index (RCI), which indicates the carbon content from renewable biological sources. It is calculated by dividing the number of carbon atoms derived from renewable sources by the total number of carbon atoms in the raw material.

[0004] Hardeners containing amines with a high Renewable Carbon Index are known, for example, from US Pat. No. 9,676,898 or WO 2015 / 124792, which describe bis(aminomethyl)furans or bisfurfurylamines and their use as hardeners for epoxy resins. However, these amines are complex to produce, prone to blushing, and their diluting effect on the epoxy resin could be improved.

[0005] Sustainable hardeners containing alkylated amines with a tetrahydrofuran ring are known from EP 3 350 245. These hardeners exhibit incomplete curing with reduced final hardness, especially when applied to large areas and under cold conditions such as 8 °C. The production of amine-functional hardeners from renewable sources for epoxy resins is also known from A.-S. Mora et al., Molecules 2019, 24, 3285 (doi:10.3390 / molecules24183285).

[0006] Benzylated amines are also known, for example from EP 2 731 927, EP 3 180 383, or EP 3 344 677. As hardeners for epoxy resins, these amines have a good diluting effect and enable rapid, trouble-free curing, even with large-area application and at low ambient temperatures. However, they cannot be produced using biobased methods. Description of the invention

[0007] The object of the present invention is therefore to provide a hardener for epoxy resins which has a high Renewable Carbon Index (RCI), is easy to produce, dilutes the epoxy resin well and enables trouble-free curing.

[0008] Surprisingly, this object is achieved with a curing agent comprising an amine of formula (I) as described in claim 1. The amine of formula (I) is obtained in a simple process from the reductive alkylation of a primary aliphatic amine with furfural based on renewable raw materials. The amine of formula (I) has a high RCI, preferably at least 0.45, in particular at least 0.7.

[0009] The hardener containing the amine of formula (I) is surprisingly effective at diluting epoxy resins. N-furfuryl-1,2-ethanediamine in particular dilutes the epoxy resin particularly efficiently, even more so than the well-known N-benzyl-1,2-ethanediamine. This is surprising, since the amount of N-furfuryl-1,2-ethanediamine required to cure the epoxy resin is lower than with N-benzyl-1,2-ethanediamine due to the lower amine equivalent weight. Due to the oxygen in the furan ring and thus the potential for hydrogen bond formation, one would expect a lower diluting effect than with N-benzyl-1,2-ethanediamine. The hardener according to the invention is very low-odor, which is another major advantage for many applications. It enables rapid and trouble-free curing to a high final hardness.Particularly surprising is the low exothermicity during curing, which is significantly lower than when using N-benzyl-1,2-ethanediamine, although the processing times and curing rates with N-furfuryl-1,2-ethanediamine are only slightly longer or slower compared to N-benzyl-1,2-ethanediamine. The low exothermicity enables use in thick-layer epoxy resin products such as molded articles, casting compounds, or matrix resins for composites, without the occurrence of bubbles, discoloration, or other inhomogeneities due to high heat development. When applied over large areas, the hardener enables ambient-temperature-curing epoxy resin coatings with attractive, glossy surfaces and very little tendency toward blushing.What is particularly surprising is that N-furfuryl-1,2-ethanediamine can also be used in the form of a reaction product with low purity and which can be produced particularly cost-effectively, without any significant loss in the curing of the epoxy resins.

[0010] 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

[0011] The invention relates to the use of a hardener containing at least one amine of formula (I) for curing epoxy resins, where A is a linear alkylene radical having 2 to 10 C atoms and X is H or furfuryl.

[0012] The "RCI" refers to the "Renewable Carbon Index" of a substance or mixture of substances, where the RCI stands for the ratio of the number of C atoms from bio-based sources to the total number of C atoms of the substance or mixture of substances.

[0013] A "primary amino group" is an amino group that is bonded to a single organic residue and carries two hydrogen atoms; a "secondary amino group" is an amino group that is bonded to two organic residues, which may also be part of a ring, and carries one hydrogen atom; and a "tertiary amino group" is an amino group that is bonded to three organic residues, which may also be part of one or more rings in twos or threes, and does not carry a hydrogen atom.

[0014] The hydrogen atoms of primary and secondary amine groups are called "amine hydrogen".

[0015] The "amine hydrogen equivalent weight" is the mass of an amine or amine-containing compound containing one molar equivalent of amine hydrogen. It is expressed in the unit "g / eq."

[0016] The "epoxide equivalent weight" is the mass of an epoxy-containing compound or composition that contains one molar equivalent of epoxy groups. It is expressed in the unit "g / eq."

[0017] Substance names beginning with "poly," such as polyamine or polyepoxide, refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0018] A "thinner" is a substance that is soluble in an epoxy resin and reduces its viscosity, but which is not chemically bound into the epoxy resin polymer during curing.

[0019] "Molecular weight" refers to the molar mass (in grams per mole) of a molecule. "Mean molecular weight" refers to the number average M n of a polydisperse mixture of oligomeric or polymeric molecules, which is usually determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0020] Pot life is the maximum period of time from the mixing of the components and the application of an epoxy resin composition during which the mixed composition is in a sufficiently flowable state and can wet the substrate surfaces well.

[0021] The term "gel time" refers to the time from the mixing of the components of an epoxy resin composition until they gel.

[0022] “Room temperature” is defined as 23 °C.

[0023] All industry standards and norms mentioned in this document refer to the versions valid at the time of filing the initial application, unless otherwise stated.

[0024] Percentages by weight (% by weight) refer to the mass fraction of a component of a composition relative to the total composition, unless otherwise stated. The terms "mass" and "weight" are used synonymously in this document.

[0025] Preferably, A represents 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene or 1,10-decylene.

[0026] Particularly preferably, A is selected from the group consisting of 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, and 1,6-hexylene. These amines are particularly readily available and have a high RCI, and are particularly compatible with epoxy resins.

[0027] Most preferably, A represents 1,2-ethylene. Such an amine of formula (I) enables epoxy resin compositions with particularly rapid and trouble-free curing and a particularly high RCI, even if the C atoms of residue A do not originate from a bio-based source.

[0028] Preferably, X is H. Such an amine of formula (I) dilutes the epoxy resin particularly well and enables particularly rapid curing and particularly high final hardness.

[0029] Preferably, the amine of formula (I) is selected from the group consisting of N-furfuryl-1,2-ethanediamine, N,N'-difurfuryl-1,2-ethanediamine, N-furfuryl-1,3-propanediamine, N,N'-difurfuryl-1,3-propanediamine, N-furfuryl-1,4-butanediamine, N,N'-difurfuryl-1,4-butanediamine, N-furfuryl-1,5-pentanediamine, N,N'-difurfuryl-1,5-pentanediamine, N-furfuryl-1,6-hexanediamine and N,N'-difurfuryl-1,6-hexanediamine.

[0030] Of these, N-furfuryl-1,2-ethanediamine or N,N'-difurfuryl-1,2-ethanediamine is preferred. N-furfuryl-1,2-ethanediamine is particularly preferred.

[0031] In a preferred embodiment of the invention, the amine of formula (I) is used as a mixture of amine of formula (I) where X = H and amine of formula (I) where X = furfuryl in a weight ratio ranging from 50 / 50 to 98 / 2, in particular 60 / 40 to 95 / 5. Such a mixture can be produced particularly cost-effectively and enables rapid and trouble-free curing of the epoxy resin.

[0032] The amine of formula (I) is preferably prepared by reductive alkylation of at least one amine of formula H 2 NA-NH 2 with furfural and hydrogen.

[0033] Furfural is preferably based on renewable raw materials and has an RCI of 1. This enables amines of formula (I) with a high RCI.

[0034] Commercially available furfural typically comes from a bio-based source. For example, on an industrial scale, furfural is extracted from hemicellulose from plant materials, particularly by the action of sulfuric acid on the C5 sugars contained therein during dehydration, or during pulp production using the magnesium bisulfite process, where released furfural can be extracted from the cooking liquor.

[0035] Preferred amines of the formula H 2 NA-NH 2 are 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine or 1,6-hexanediamine, in particular 1,2-ethanediamine.

[0036] In a preferred embodiment of the invention, the carbon atoms of the amine of the formula H 2 NA-NH 2 also originate from a renewable source. This enables particularly sustainable amines of the formula (I), in particular with an RCI of 1.

[0037] Preferably, the amine of formula (I) has an RCI of at least 0.45, preferably at least 0.6, in particular at least 0.7, most preferably 1.

[0038] The reductive alkylation 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, especially palladium on carbon or Raney nickel.

[0039] The reductive alkylation is preferably carried out in a pressure apparatus at a hydrogen pressure of 5 to 120 bar, especially 10 to 100 bar. This can be carried out in a batch process or, preferably, in a continuous process.

[0040] The reductive alkylation is preferably carried out at a temperature in the range of 40 to 120°C, in particular 60 to 100°C.

[0041] Depending on the stoichiometry between the amine of formula H 2 NA-NH 2 and furfural, the resulting reaction mixture contains different proportions of monoalkylated amine of formula H 2 NA-NH 2 , i.e. amine of formula (I) with X = H, and dialkylated amine of formula H 2 NA-NH 2 , i.e. amine of formula (I) with X = furfuryl.

[0042] If an amine of formula (I) with X = furfuryl is to be prepared, the molar ratio of the amine of formula H 2 NA-NH 2 to furfural is preferably in the range from 0.4 to 0.7, in particular 0.5. A reaction mixture thus obtained contains a particularly high content of amine of formula (I) with X = furfuryl.

[0043] In the event that an amine of formula (I) with X = H is to be prepared, the molar ratio of the amine of formula H 2 NA-NH 2 to furfural is preferably in the range from 1 to 10, in particular 1 to 5. A reaction mixture thus obtained contains a high content of amine of formula (I) with X = H.

[0044] Excess amine of the formula H 2 NA-NH 2 is preferably removed from the reaction mixture after the reaction, in particular by distillation together with the released water.

[0045] The reaction mixture can be further purified, in particular by distillation or fractionation. The amine of formula (I) can be freed from by-products and / or the amine of formula (I) with X = H can be separated from the amine of formula (I) with X = furfuryl.

[0046] Preferably, the amine of formula (I) is used in the form of a reaction product obtained from the reductive alkylation of at least one amine of formula H 2 NA-NH 2 with furfural and hydrogen and subsequent removal of unreacted amine of formula H 2 NA-NH 2.

[0047] The reaction product is preferably not further purified, in particular distillation or fractionation of the amines of formula (I) is omitted.

[0048] Such a reaction product can be produced particularly cost-effectively. It contains a low content of amine of the formula H 2 NA-NH 2 , preferably less than 2% by weight, particularly preferably less than 1% by weight, in particular less than 0.5% by weight, of amine of the formula H 2 NA-NH 2 , based on the total reaction product.

[0049] The reaction product may contain byproducts from the reductive alkylation, particularly amines with doubly or trialkylated nitrogen atoms and amines with a hydrogenated furan ring. These amounts are preferably small.

[0050] The reaction product preferably contains amines with double or triple alkylated nitrogen atoms, in particular of the formulas , of a total of less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 2% by weight, based on the total reaction product.

[0051] The reaction product preferably has a content of amines with a hydrogenated furan ring, in particular of the formulas or , of a total of less than 20% by weight, in particular less than 15% by weight, based on the total reaction product.

[0052] In a particularly preferred embodiment of the invention, the amine of formula (I) is used in the form of a reaction product obtained from the reductive alkylation of at least one amine of formula H 2 NA-NH 2 with furfural and hydrogen and subsequent removal of unreacted amine of formula H 2 NA-NH 2, wherein the molar ratio of the amine of formula H 2 NA-NH 2 to furfural is in the range from 1 to 2, preferably 1 to 1.5. Preferably, A represents 1,2-ethylene.

[0053] The content of amine of the formula H 2 NA-NH 2 in this reaction product is preferably at most 1% by weight, particularly preferably at most 0.5% by weight, in particular at most 0.2% by weight, based on the total reaction product.

[0054] Such a reaction product contains a surprisingly high content of amine of formula (I) with X = H and surprisingly little of amine of formula (I) with X = furfuryl, and exhibits a surprisingly high reactivity toward the epoxy resin, which is hardly inferior to that of largely pure amine of formula (I) with X = H. This could not be expected from the prior art. A corresponding reaction of 1,2-ethanediamine with benzaldehyde instead of furfural, with a corresponding stoichiometry, exhibits a massively higher content of N,N'-dialkylated 1,2-ethanediamine.

[0055] Preferably, the weight ratio between the amine of formula (I) with X = H and the amine of formula (I) with X = furfuryl in the reaction product is in the range from 50 / 50 to 98 / 2, preferably 60 / 40 to 95 / 5, based on the reaction product.

[0056] A further subject of the invention is therefore the reaction product obtained from the reductive alkylation of an amine of the formula H 2 NA-NH 2 with furfural and hydrogen in a molar ratio of the amine of the formula H 2 NA-NH 2 to furfural in the range from 1 to 2, preferably 1 to 1.5, and subsequent removal of amine of the formula H 2 NA-NH 2 to a content of at most 1% by weight, preferably at most 0.5% by weight, in particular at most 0.2% by weight, based on the reaction product, where A is a linear alkylene radical having 2 to 10 C atoms, in particular 1,2-ethylene.

[0057] Preferably, A represents 1,2-ethylene and the reaction product contains 50 to 80% by weight of N-furfuryl-1,2-ethanediamine, 5 to 50% by weight, in particular 5 to 40% by weight, of N,N'-difurfuryl-1,2-ethanediamine, 0 to 20% by weight, in particular 2 to 15% by weight, of N-tetrahydrofurfuryl-1,2-ethanediamine, less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.2% by weight, of 1,2-ethanediamine and optionally further constituents, in particular further by-products from the reductive alkylation, based on the reaction product.

[0058] Such a reaction product is easy and inexpensive to produce and, without further purification, is ideally suited as a component of a hardener for curing epoxy resins, whereby it has a high reactivity towards the epoxy resin, which is hardly inferior to that of largely pure N-furfuryl-1,2-ethanediamine.

[0059] Preferably, an amine of formula (I) with X = H is used as a mixture with an amine of formula in a weight ratio between the amine of formula (I) with X = H and the amine of formula in the range from 70 / 30 to 99 / 1, preferably 80 / 20 to 98 / 2, where A has the meanings already mentioned.

[0060] Such an amine mixture is easy to produce and enables surprisingly fast and trouble-free curing of the epoxy resin.

[0061] A further subject of the invention is thus an amine mixture containing at least one amine of the formula and at least one amine of the formula in a weight ratio in the range from 70 / 30 to 99 / 1, preferably 80 / 20 to 98 / 2, where A is a linear alkylene radical having 2 to 10 C atoms, in particular 1,2-ethylene.

[0062] In a preferred embodiment of the invention, the amine of formula (I) is used partially or completely in the form of an amine-functional adduct with at least one epoxy resin or monoepoxide in a stoichiometric ratio of at least 1 mol of amine of formula (I) to 1 mol equivalent of epoxy groups.

[0063] Such an adduct exists as a mixture of adducted molecules with at least two, typically 3 or 4, amine hydrogens derived from the amine of formula (I) and free, non-adducted amine of formula (I). It enables particularly rapid curing with moderate viscosity, especially at low temperatures (8 °C).

[0064] The epoxy resin preferably has an average epoxy equivalent weight in the range of 150 to 500 g / eq, preferably 156 to 250 g / eq.

[0065] Aromatic epoxy resins with an average functionality in the range of 2 to 4 are preferred, especially a bisphenol A, F, or A / F diglycidyl ether or a novolak epoxy resin. These adducts enable particularly rapid curing and high glass transition temperatures.

[0066] Also preferred are epoxy resins containing polyoxypropylene and / or polyoxyethylene units. 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 particularly suitable as components of water-based curing agents for epoxy resins. Aromatic diepoxides, in particular a bisphenol A, F, or A / F diglycidyl ether, are particularly preferred.

[0067] A bisphenol A diglycidyl ether with an RCI of 0.28, derived from the reaction of bisphenol A with bio-based epichlorohydrin, is particularly preferred. This results in particularly sustainable adducts.

[0068] The adducting is preferably carried out in a stoichiometric ratio in the range from 1 to 10, preferably 1.2 to 5, in particular 1.4 to 3, mol of amine of the formula (I) per molar equivalent of epoxide groups.

[0069] The hardener preferably contains at least one further constituent selected from further amines which do not correspond to formula (I), accelerators and diluents, in particular at least one further amine which does not correspond to formula (I).

[0070] The hardener preferably contains at least one further amine which does not correspond to formula (I) and which is not a by-product from the preparation of the amine of formula (I).

[0071] As further amines which do not correspond to formula (I), preference is given to amines having aliphatic amino groups and at least three amine hydrogens, in particular N-benzyl-1,2-ethanediamine, N-benzyl-1,2-propanediamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-1,3-bis(aminomethyl)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-neo-diamine), 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-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatri-decane-1,13-diamine or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofurans or other polytetrahydrofurandiamines, polyoxyalkylenedi- or triamines, especially polyoxypropylenediamines or polyoxypropylenetriamines such as Jeffamine®< D-230, Jeffamine®< D-400 or Jeffamine®< T-403 (all from Huntsman), furan-based amines such as 2,5-bis(aminomethyl)furan, 2,5-bis(aminomethyl)tetrahydrofuran, bis(5-aminomethylfuran-2-yl)methane,Bis(5-aminomethyl-tetrahydrofuran-2-yl)methane, 2,2-bis(5-aminomethylfuran-2-yl)propane or 2,2-bis(5-aminomethyltetrahydrofuran-2-yl)propane, or diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), Dipropylene triamine (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-amino-pentyl)-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, bis(hexamethylene)triamine (BHMT), N-aminoethylpiperazine, 3-dimethylaminopropylamine (DMAPA), 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), amine-functional adducts of the above-mentioned amines with epoxides, phenalkamines, which are reaction products of cardanol with aldehydes, especially formaldehyde, and polyamines,or a mixture of two or more of these amines.,

[0072] The hardener preferably contains at least one amine selected from the group consisting of N-benzyl-1,2-ethanediamine, N,N'-dibenzyl-1,2-ethanediamine, MPMD, TMD, 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 having an average molecular weight M n in the range from 200 to 500 g / mol, polyoxypropylenetriamines having an average molecular weight M n in the range from 300 to 500 g / mol, 2,5-bis(aminomethyl)furan, 2,5-bis(aminomethyl)tetrahydrofuran, bis(5-aminomethylfuran-2-yl)methane, bis(5-aminomethyltetrahydrofuran-2-yl)methane, 2,2-bis(5-aminomethylfuran-2-yl)propane, 2,2-bis(5-aminomethyltetrahydrofuran-2-yl)propane and phenalkamines.

[0073] Preferred among these is 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, especially 1,3-bis(aminomethyl)cyclohexane. This enables particularly rapid curing.

[0074] IPDA remains the preferred material. This achieves particularly high glass transition temperatures, enabling exceptional robustness at high operating temperatures. IPDA with a high RCI made from bio-based acetone is particularly preferred, allowing for particularly sustainable hardeners.

[0075] MXDA remains the preferred material, achieving high curing speeds and particularly high strength.

[0076] Of these, N-benzyl-1,2-ethanediamine is still preferred. This type of hardener enables particularly low-viscosity epoxy resin products with particularly attractive surfaces.

[0077] Further preferred among these are 2,5-bis(aminomethyl)furan, 2,5-bis(aminomethyl)tetrahydrofuran, bis(5-aminomethylfuran-2-yl)methane, bis(5-aminomethyltetrahydrofuran-2-yl)methane, 2,2-bis(5-aminomethylfuran-2-yl)propane, or 2,2-bis(5-aminomethyltetrahydrofuran-2-yl)propane, especially 2,5-bis(aminomethyl)furan. This enables particularly sustainable hardeners.

[0078] In particular, the hardener may contain more than one further amine which does not correspond to formula (I).

[0079] The curing agent particularly preferably contains, as a further amine which does not correspond to formula (I), at least one amine having an RCI of 1, in particular selected from 2,5-bis(aminomethyl)furan, 2,5-bis(aminomethyl)tetrahydrofuran, bis(5-aminomethylfuran-2-yl)methane, bis(5-aminomethyltetrahydrofuran-2-yl)methane, 2,2-bis(5-aminomethylfuran-2-yl)propane and 2,2-bis(5-aminomethyltetrahydrofuran-2-yl)propane.

[0080] The hardener preferably contains an amount of other amines that do not correspond to formula (I) such that 5 to 95%, preferably 10 to 80%, in particular 15 to 60%, of all amine hydrogens present originate from amines of formula (I). If the amine of formula (I) is present in adducted form with an epoxy resin, the amine hydrogens of such adducts are also counted as amine hydrogens of the amine of formula (I).

[0081] Suitable accelerators are, in particular, acids or compounds hydrolyzable to 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 aforementioned 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-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.

[0082] 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.

[0083] Suitable thinners 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, 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, styrenated phenol, bisphenols, aromatic hydrocarbon resins, in particular types containing phenol groups, alkoxylated phenol, in particular ethoxylated or propoxylated phenol, in particular 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphoric or sulfonic acid esters or sulfonamides.

[0084] Preferred among these are thinners with a boiling point above 200 °C, especially benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenol groups, such as the Novares® types LS 500, LX 200, LA 300, or LA 700 (from Rütgers), diisopropylnaphthalene, or cardanol, especially benzyl alcohol. Phenol-containing thinners also act as accelerators. Also preferred are aromatic thinners with a particularly high diluting effect, especially xylene.

[0085] Of these, thinners with an RCI of 1, especially cardanol, are particularly preferred. These enable a particularly sustainable hardener.

[0086] The hardener preferably contains only a small amount of thinners, in particular 0 to 50% by weight, preferably 0 to 30% by weight, of thinner based on the total hardener.

[0087] The hardener preferably contains 1 to 99% by weight, more preferably 5 to 90% by weight, more preferably 10 to 80% by weight, particularly preferably 15 to 70% by weight, of amines of the formula (I) based on the total hardener.

[0088] The hardener may be water-based and contain water in the range of 15 to 90% by weight, preferably 20 to 80% by weight.

[0089] The hardener is preferably not water-based. It preferably contains less than 15% by weight, especially less than 10% by weight, of water, based on the total hardener. Such a hardener is particularly suitable for non-aqueous epoxy resin products.

[0090] The hardener may contain other ingredients, 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 polybasic 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, 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, 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, surface-active additives, in particular defoamers, deaerators, wetting agents, dispersants or leveling agents, or stabilizers, in particular stabilizers against oxidation, heat, light or UV radiation.

[0091] Another object of the invention is an epoxy resin composition comprising a resin component comprising at least one epoxy resin and a hardener component comprising the hardener containing at least one amine of formula (I), as described above.

[0092] A suitable epoxy resin is obtained in a known manner, in particular from the reaction of epichlorohydrin with polyols, polyphenols or amines.

[0093] Suitable epoxy resins are in particular aromatic epoxy resins, in particular 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 pyrocatechol; 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, 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)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 phenol or cresols with formaldehyde orParaformaldehyde 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).

[0094] 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 C 2 - to C 30 -alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythrol, 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 nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin.

[0095] Other suitable epoxy resins are epoxy resins with a high RCI, especially those obtained from the reaction of bio-based hydroxy-functional raw materials with epichlorohydrin. Vanillin-based epoxy resins, such as diglycidyl ethers of vanillin alcohol, and glycerol-based epoxy resins, such as triglycidyl ethers of bio-based glycerol, are particularly preferred.

[0096] Preferably, the epoxy resin is a liquid resin or a mixture containing two or more epoxy liquid resins.

[0097] An "epoxy liquid resin" is a technical polyepoxide with a glass transition temperature below 25 °C.

[0098] If necessary, the resin component also contains portions of solid epoxy resin.

[0099] The epoxy resin is in particular a liquid resin based on a bisphenol or novolak, in particular with an average epoxy equivalent weight in the range of 156 to 210 g / eq.

[0100] Bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether, such as those commercially available from Olin, Huntsman, or Momentive, are particularly suitable. These liquid resins have a low viscosity for epoxy resins and enable rapid curing and high hardness. They can contain portions of bisphenol A solid resin or novolak epoxy resins.

[0101] A bisphenol A diglycidyl ether with an RCI of 0.28, derived from the reaction of bisphenol A with bio-based epichlorohydrin, is particularly preferred. This enables a particularly sustainable epoxy resin composition.

[0102] Also particularly suitable are phenol-formaldehyde novolak glycidyl ethers, in particular with an average 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.

[0103] Also particularly suitable are diglycidyl ethers of vanillin alcohol or triglycidyl ethers of glycerol, in particular diglycidyl ethers of vanillin alcohol.

[0104] The resin component may contain a reactive diluent.

[0105] Preferred reactive diluents are reactive diluents 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, pn-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 C 8 - to C 10 - or C 12 - to C 14 - or C 13 - to C 15 -alkyl glycidyl ethers.

[0106] The epoxy resin composition preferably contains at least one further component selected from the group consisting of thinners, accelerators, fillers, pigments and surface-active additives.

[0107] The ones already mentioned are particularly suitable as thinners or accelerators.

[0108] Suitable fillers include, in particular, ground or precipitated calcium carbonate, optionally coated with fatty acids, especially stearates, barite (barite), talc, quartz powder, quartz sand, silicon carbide, iron mica, 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, metal powders such as aluminum, copper, iron, zinc, silver, or steel, PVC powder, or hollow spheres. Preferred fillers are calcium carbonate, barite, quartz powder, talc, aluminum powder, or a combination thereof.

[0109] Suitable pigments include, in particular, titanium dioxide, iron oxide, chromium(III) oxide, organic pigments, carbon black, or anticorrosive pigments, especially phosphates, orthophosphates, or polyphosphates, which contain, in particular, chromium, zinc, aluminum, calcium, strontium, or a combination of these metals as counterions. Titanium dioxide is particularly suitable.

[0110] Suitable surface-active additives are in particular defoamers, deaerators, wetting agents, dispersants, leveling agents and / or dispersed paraffin waxes.

[0111] The epoxy resin composition may contain other auxiliary substances and additives, 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, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers; nanofillers,in particular carbon nanotubes; rheology modifiers, in particular thickeners or anti-settling agents; adhesion promoters, in particular organoalkoxysilanes; flame-retardant substances, in particular the fillers already mentioned: aluminium 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, 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(dibromonorbornane dicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadieno)cyclooctane or chlorinated paraffins; or stabilizers against oxidation, heat, light or UV radiation or biocides.

[0112] The epoxy resin composition preferably contains only a low content of thinners. It preferably contains less than 20% by weight, more preferably less than 10% by weight, especially less than 5% by weight, and most preferably less than 1% by weight of thinner.

[0113] The epoxy resin composition may contain water.

[0114] In one embodiment, the epoxy resin composition is water-based. The epoxy resin is preferably emulsified in water in an amount of 50 to 85% by weight, and the hardener component preferably contains 20 to 80% by weight of water.

[0115] Preferably, however, the epoxy resin composition contains only a low water content, preferably less than 5% by weight, in particular less than 1% by weight. Such a non-water-based epoxy resin composition is particularly versatile and particularly water-resistant.

[0116] Preferably, an epoxy resin composition comprising a resin component containing at least one epoxy resin and optionally further components such as in particular reactive diluents containing epoxy groups, thinners, fillers, pigments and / or surface-active additives, and a hardener component containing at least one amine of the formula (I) and optionally further components such as in particular further amines, accelerators and / or thinners.

[0117] The resin and hardener components of the epoxy resin composition are stored in separate containers.

[0118] A suitable container for storing the resin or hardener components is, in particular, a drum, a hobbock, 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 intended use.

[0119] The resin and hardener components are mixed shortly before or during application. The mixing ratio is preferably selected such that the molar ratio of the groups reactive toward epoxy 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.

[0120] The components are mixed continuously or batchwise using a suitable process, ensuring that there is not too much time between mixing the components and application and that application occurs within the pot life. Mixing and application can take place at ambient temperature, which is typically in the range of about 5 to 40°C, preferably about 10 to 35°C, or at elevated temperature, in particular in the range of 40 to 150°C, preferably 50 to 120°C.

[0121] With the mixing of the components, the curing of the epoxy resin composition begins through a chemical reaction. Primary and secondary amino groups, and any other epoxy-reactive groups present, react with the epoxy groups, causing their ring opening. As a result of these reactions, the composition polymerizes and thus cures.

[0122] Curing typically takes several hours to several days. The duration depends, among other things, on the temperature, the reactivity of the components, their stoichiometry, and the presence or amount of accelerators.

[0123] In the freshly mixed state, the epoxy resin composition has a low viscosity. The viscosity 5 minutes after mixing the resin and hardener components at 20°C is preferably in the range of 0.1 to 20 Pa s, preferably 0.2 to 10 Pa s, particularly preferably 0.3 to 5 Pa s, measured using a cone-and-plate viscometer at a shear rate of 10 s -1< .

[0124] The epoxy resin composition is applied to at least one substrate and / or into at least one casting mold.

[0125] Particularly suitable as substrates are: Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, plaster or natural stones such as granite or marble; repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-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, wood materials bonded with resins, for example phenolic, melamine or epoxy resins, resin-textile composites or other so-called polymer composites; Plastics such as rigid and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, each untreated or surface-treated, for example by means of plasma, corona or flames;Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GRP) and sheet molding compounds (SMC); insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass); 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 another floor covering layer.

[0126] If necessary, the substrates may be pretreated before application, in particular by physical and / or chemical cleaning processes or the application of an activator or a primer.

[0127] The substrates are in particular coated and / or glued.

[0128] A suitable casting mold is a device into which the mixed, liquid epoxy resin composition is poured and cured therein and, after curing, can be demolded or removed therefrom, whereby the cured composition forms a molded body.

[0129] The casting mold preferably consists, at least on the surface, of a material from which the cured epoxy resin composition can be removed again without damage, in particular of metal, ceramic, plastic or silicone, which may optionally be provided with a non-stick coating, in particular of Teflon, silicone or a wax.

[0130] A further object of the invention is a cured composition obtained from the described epoxy resin composition after mixing the resin and hardener components.

[0131] 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.

[0132] The use results in an article containing the cured composition of the described epoxy resin composition.

[0133] The article is in particular a floor coating, wall coating, component coating, pipe coating, roof coating or a corrosion protection coating, or a bonded article, or a shaped body, in particular a composite material. Examples

[0134] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described exemplary embodiments.

[0135] "AHEW" stands for amine hydrogen equivalent weight.

[0136] "EEW" stands for epoxy equivalent weight.

[0137] The "standard climate" ("NK") is defined as a temperature of 23±1°C and a relative humidity of 50±5%.

[0138] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH. Description of the measurement methods:

[0139] The viscosity was measured on a thermostatted Rheotec RC30 cone-and-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-to-plate distance 0.05 mm, shear rate 10 s -1< ). Viscosities of less than 100 mPa s were measured at a shear rate of 100 s -1<.

[0140] The Amine number was determined by titration (with 0.1N HClO 4 in acetic acid against crystal violet).

[0141] Gas chromatograms (GC) were measured in the temperature range from 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 was used (L = 30 m, ID = 0.25 mm, dj = 0.5 µm) at a gas flow of 1.5 ml / min. Detection was performed by flame ionization (FID).

[0142] Infrared spectra (FTIR) were measured on undiluted films using a Thermo Scientific Nicolet iS5 FTIR instrument equipped with a horizontal diamond crystal ATR measurement unit. Absorption bands are given in wavenumbers (cm -1< ).

[0143] 1< H-NMR spectrawere measured 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. Substances and abbreviations used:

[0144] Araldite ®< GY 250: Bisphenol A diglycidyl ether, EEW approx. 187 g / eq (from Huntsman) Araldite ®< DY-E: Monoglycidyl ether of C 12 to C 14 alcohols, EEW approx. 290 g / eq (from Huntsman) DEN ®< 438: Phenol-formaldehyde novolak glycidyl ether), EEW approx. 179 g / eq, average functionality approx. 3.6 (from Olin) IPDA 3-Aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g / eq (Vestamin ®< IPD, from Evonik) MXDA: 1,3-Bis(aminomethyl)benzene, AHEW 34 g / Eq (from Mitsubishi Gas Chemical) Ancamine ®< K54 2,4,6-Tris(dimethylaminomethyl)phenol (from Evonik) Production of amines: Reaction product P-1: (containing N-furfuryl-1,2-ethanediamine; 1:1 stoichiometry)

[0145] 30.05 g (0.5 mol) of 1,2-ethanediamine were placed in a round-bottom flask under a nitrogen atmosphere at room temperature. 48.05 g (0.5 mol) of furfural (furan-2-carbaldehyde, RCI = 1) were added with vigorous stirring, and the mixture was stirred for 1 hour at 40 °C. The reaction mixture was treated with 1,000 ml of isopropanol, and the mixture was then hydrogenated at a hydrogen pressure of 70 bar, a temperature of 70 °C, and a flow rate of 5.5 ml / min on a continuously operating hydrogenation apparatus with a Raney nickel fixed-bed catalyst. To monitor the reaction, IR spectroscopy was used to check whether the imine band at approximately 1665 cm -1 had disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C, removing unreacted 1,2-ethanediamine, water and isopropanol.The reaction mixture thus obtained was a clear, slightly yellowish liquid with an amine number of 695 mg KOH / g, a viscosity at 20 °C of 10 mPa s and a content of N-furfuryl-1,2-ethanediamine of approximately 57.9 wt% (retention time 7.3 min), N-tetrahydrofurfuryl-1,2-ethanediamine of approximately 8.2 wt% (retention time 8.0 min), N,N'-difurfuryl-1,2-ethanediamine of approximately 31.6 wt% (retention time 11.9 min) and proportions of N,N'-difurfuryl-1,2-ethanediamine hydrogenated on the furan ring of approximately 2.3 wt% (retention time 12.5 min), determined by GC. For further use, an AHEW of 58.9 g / eq was used. Reaction product P-2: (containing N-furfuryl-1,2-ethanediamine; 2:1 stoichiometry)

[0146] 60.1 g (1 mol) of 1,2-ethanediamine were placed in a round-bottom flask under a nitrogen atmosphere at room temperature. 48.05 g (0.5 mol) of furfural (furan-2-carbaldehyde, RCI = 1) were added with vigorous stirring, and the mixture was stirred for 1 hour at 40 °C. The reaction mixture was treated with 1,000 ml of isopropanol, and the mixture was then hydrogenated at a hydrogen pressure of 70 bar, a temperature of 70 °C, and a flow rate of 5.5 ml / min on a continuously operating hydrogenation apparatus equipped with a Raney nickel fixed-bed catalyst. IR spectroscopy was used to monitor the reaction to determine whether the imine band at approximately 1665 cm -1 had disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C, removing unreacted 1,2-ethanediamine, water, and isopropanol.The resulting reaction mixture was a clear, slightly yellowish liquid with an amine number of 772 mg KOH / g, a viscosity at 20 °C of 11 mPa s, and a content of N-furfuryl-1,2-ethanediamine of approximately 78.2 wt% (retention time 7.3 min), N-tetrahydrofurfuryl-1,2-ethanediamine of approximately 12.3 wt% (retention time 8.0 min), and N,N'-difurfuryl-1,2-ethanediamine of approximately 9.1 wt% (retention time 11.9 min), determined by GC. An AHEW of 56.6 g / eq was used for further processing. Reaction product P-3: (containing N-furfuryl-1,2-ethanediamine, 3:1 stoichiometry)

[0147] 60.1 g (1 mol) of 1,2-ethanediamine were placed in a round-bottom flask under a nitrogen atmosphere at room temperature. 32.0 g (0.33 mol) of furfural (furan-2-carbaldehyde, RCI = 1) were added with vigorous stirring, and the mixture was stirred for 1 hour at 40 °C. The reaction mixture was treated with 1,000 ml of isopropanol, and the mixture was then hydrogenated at a hydrogen pressure of 65 bar, a temperature of 65 °C, and a flow rate of 5.5 ml / min on a continuously operating hydrogenation apparatus equipped with a Raney nickel fixed-bed catalyst. IR spectroscopy was used to monitor the reaction to determine whether the imine band at approximately 1665 cm -1 had disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C, removing unreacted 1,2-ethanediamine, water, and isopropanol.The reaction mixture thus obtained was a clear, slightly yellowish liquid with an amine number of 757 mg KOH / g, a viscosity at 20 °C of 10 mPa s and a content of N-furfuryl-1,2-ethanediamine determined by GC of approximately 86.1 wt% (retention time 7.3 min), N-tetrahydrofurfuryl-1,2-ethanediamine of approximately 3.3 wt% (retention time 8.0 min), N,N'-difurfuryl-1,2-ethanediamine of approximately 2.8 wt% (retention time 11.9 min), proportions of N,N'-difurfuryl-1,2-ethanediamine hydrogenated on the furan ring of approximately 1.5 wt% (retention time 12.5 min) and N,N,N'-trisfurfuryl-1,2-ethanediamine of approximately 6.0 wt% (retention time 14.2 min). For further use, an AHEW of 51.6 g / eq was used. Reaction product P-4: (containing N-furfuryl-1,2-ethanediamine; 3.5:1 stoichiometry, Pd / C)

[0148] 105.2 g (1.75 mol) of 1,2-ethanediamine were placed in a round-bottom flask under a nitrogen atmosphere at room temperature. A solution of 48.05 g (0.5 mol) of furfural (furan-2-carbaldehyde, RCI = 1) in 200 mL of isopropanol was added with vigorous stirring, and the mixture was stirred for 1 hour at 40 °C. A further 1,000 mL of isopropanol was added to the reaction mixture, and the mixture was then hydrogenated at a hydrogen pressure of 80 bar, a temperature of 80 °C, and a flow rate of 5 mL / min on a continuously operating hydrogenation apparatus with a Pd / C fixed-bed catalyst. To monitor the reaction, IR spectroscopy was used to check whether the imine band at approximately 1665 cm -1 had disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C, removing unreacted 1,2-ethanediamine, water, and isopropanol. The resulting reaction mixture was a clear, slightly yellowish liquid with an amine number of 691 mg KOH / g and a viscosity of 13 at 20 °C.5 mPa s and a content of N-furfuryl-1,2-ethanediamine of approximately 72.8 wt.% (retention time 7.3 min), N-tetrahydrofurfuryl-1,2-ethanediamine of approximately 7.8 wt.% (retention time 8.0 min), N,N'-difurfuryl-1,2-ethanediamine of approximately 3.3 wt.% (retention time 11.9 min), proportions of N,N'-difurfuryl-1,2-ethanediamine hydrogenated on the furan ring of approximately 3.0 wt.% (retention time 12.5 min), N,N,N'-trisfurfuryl-1,2-ethanediamine of approximately 9.9 wt.% (retention time 14.2 min) and proportions of N-furfuryl-1,2-ethanediamine hydrogenated on the furan ring N,N,N'-Trisfurfuryl-1,2-ethanediamine at approximately 3.2 wt% (retention time approximately 14.7 min). For further use, an AHEW of 55 g / eq was used. N-Furfuryl-1,2-ethanediamine (F-EDA):

[0149] 41.2 g of the reaction product P-4,prepared as described above, were distilled at 70 °C under vacuum, collecting 25.6 g of distillate at a vapor temperature of approximately 50 °C and 0.1 bar. A colorless liquid was obtained with an amine number of 802 mg KOH / g, an AHEW of approximately 46.7 g / eq, an RCI of 0.71, a viscosity of 3.2 mPa s at 20 °C, and a content of N-furfuryl-1,2-ethanediamine of 94.6 wt% (retention time 7.3 min) and N-tetrahydrofurfuryl-1,2-ethanediamine of 5.3 wt% (retention time 8.0 min), which is hereinafter referred to as F-EDA was used.

[0150] 1<H-NMR (CDCl 3 ): 7.33 (d, 1 H, Ar-H), 6.27 (m, 1 H, Ar-H), 6.14 (m, 1 H, Ar-H), 3.76 (s, 2 H, Ar-CH 2 ), 2.78 (m, 2 H, NHC H 2 CH 2 ), 2.65 (m, 2 H, C H 2 NH 2 ), 1.52 (br s, 3 H, NH and NH 2 ).

[0151] FT-IR: 3284, 3043, 2945, 2838, 1567, 1504, 1455, 1382, 1306, 1219, 1146,1108, 1073, 1009, 916, 883, 806, 738. N,N'-Difurfuryl-1,2-ethanediamine (BisF-EDA)

[0152] In a round-bottom flask, 11.12 g (0.185 mol) of 1,2-ethanediamine in 200 mL of isopropanol were placed under a nitrogen atmosphere at room temperature. 35.0 g (0.37 mol) of furfural (furan-2-carbaldehyde, RCI = 1) were added with vigorous stirring, and the mixture was stirred for 1 hour at 40 °C. A further 800 mL of isopropanol was added to the reaction mixture, and the mixture was then hydrogenated at a hydrogen pressure of 65 bar, a temperature of 65 °C, and a flow rate of 5.5 mL / min on a continuously operating hydrogenation apparatus with a Raney nickel fixed-bed catalyst. To monitor the reaction, IR spectroscopy was used to check whether the imine band at approximately 1665 cm -1 had disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C, removing unreacted 1,2-ethanediamine, water and isopropanol.A clear, slightly yellowish liquid was obtained, which was distilled at 110 to 130 °C under vacuum, with the distillate being collected at a vapor temperature of 105 to 110 °C and 0.15 bar. A colorless liquid was obtained with an amine number of 502 mg KOH / g, an AHEW of approximately 110 g / eq, a viscosity of 28 mPa s at 20 °C, and a content of N,N'-difurfuryl-1,2-ethanediamine of 79.0 wt.% (retention time 11.9 min), a proportion of N,N'-difurfuryl-1,2-ethanediamine hydrogenated at the furan ring of approximately 11.9 wt.% (retention time 12.4 to 12.5 min), N,N,N'-trisfurfuryl-1,2-ethanediamine of approximately 4.4 wt.% (retention time 14.2 min), and a proportion of N,N,N'-trisfurfuryl-1,2-ethanediamine hydrogenated at the furan ring of approximately 3.7 Weight-% (retention time approx. 14.6 to 14.7 min), which is referred to below as . BisF-EDA was used. N-Tetrahydrofurfuryl-1,2-ethanediamine (THF-EDA):

[0153] 60.1 g (1 mol) of 1,2-ethanediamine were placed in a round-bottom flask under a nitrogen atmosphere at room temperature. A solution of 32.0 g (0.33 mol) of furfural in 200 ml of isopropanol was slowly added dropwise with vigorous stirring, and the mixture was stirred for 1 hour at 40 °C. A further 300 ml of isopropanol was added to the reaction mixture, and the mixture was then hydrogenated at a hydrogen pressure of 90 bar, a temperature of 110 °C, and a flow rate of 5 ml / min on a continuously operating hydrogenation apparatus equipped with a Raney nickel fixed-bed catalyst. IR spectroscopy was used to monitor the reaction to determine whether the imine band at approximately 1665 cm -1 had disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C, removing unreacted 1,2-ethanediamine, water, and isopropanol.

[0154] A clear, slightly yellowish liquid was obtained, which was distilled at 70 °C under vacuum, collecting 35.6 g of distillate at a vapor temperature of approximately 50 °C and 0.1 bar. A colorless liquid was obtained with a viscosity of 4.3 mPa s at 20 °C, an amine number of 728 mg KOH / g, an AHEW of 48.1 g / eq, and a content of N-tetrahydrofurfuryl-1,2-ethanediamine of 97% by weight (retention time 8.0 min), which was determined by GC and is referred to below as THF-EDA was used. N-Benzyl-1,2-ethanediamine (B-EDA):

[0155] 180.3 g (3 mol) of 1,2-ethanediamine were initially charged at room temperature, mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol, stirred for 2 hours and then hydrogenated at 80°C, 80 bar hydrogen pressure and a flow rate of 5 ml / min on a continuously operating hydrogenation apparatus with Pd / C fixed bed catalyst and the hydrogenated solution was concentrated on a rotary evaporator at 65°C, whereby unreacted 1,2-ethanediamine, water and isopropanol were removed. The resulting reaction mixture was a clear, slightly yellowish liquid with a content of approximately 81 wt% (retention time 8.5 min) of N-benzyl-1,2-ethanediamine and approximately 14 wt% (retention time 14.3 min) of N,N'-dibenzyl-1,2-ethanediamine, determined by GC. It was purified by distillation at 80°C under vacuum. A colorless liquid with an AHEW of 50 was obtained.1 g / eq and a content of N-benzyl-1,2-ethanediamine of > 97% determined by GC, which is referred to below as . B-EDA was used. Production of adducts: Adduct A1:

[0156] 51.3 g of N-furfuryl-1,2-ethanediamine (F-EDA, 0.366 mol) were heated to 70 °C, and 45.0 g of Araldite®< GY 250 (0.241 mol of EP groups) were slowly added with vigorous stirring, maintaining the reaction temperature between 70 and 90 °C. The reaction mixture was stirred within this temperature range for one hour and then cooled. A clear, slightly yellowish liquid with a viscosity at 20 °C of 124 Pa s, an amine number of 419 mg KOH / g, and a calculated AHEW of 112.3 g / eq was obtained. Adduct A2:

[0157] 58.6 g of N-furfuryl-1,2-ethanediamine (F-EDA, 0.418 mol) were heated to 70 °C, and 37.3 g of DEN ®< 438 (0.208 mol of EP groups) were slowly added with vigorous stirring, maintaining the reaction temperature between 70 and 90 °C. The reaction mixture was stirred within this temperature range for one hour and then cooled. A clear, slightly yellowish liquid with a viscosity at 20 °C of 40.8 Pa s, an amine number of 492 mg KOH / g, and a calculated AHEW of 91.6 g / eq was obtained. Adduct A3 (Ref.):

[0158] 55.0 g of N-benzyl-1,2-ethanediamine (B-EDA, 0.366 mol) were heated to 70 °C, and 45.0 g of Araldite®< GY 250 (0.241 mol of EP groups) were slowly added with vigorous stirring, maintaining the reaction mixture temperature between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid with a viscosity at 20 °C of 262 Pa s, an amine number of 408 mg KOH / g, and a calculated AHEW of 116.3 g / eq was obtained. Production of epoxy resin compositions: Examples Z-1 and Ref-1 to Ref-3

[0159] For each example, the resin and hardener components listed in Table 1 were heated separately to a temperature of 60 °C. Using these preheated components, a total of 20 g of epoxy resin composition was then prepared by mixing the components in the weight ratios listed in Table 1 using a centrifugal mixer (SpeedMixer™< DAC 150, FlackTek Inc.) for 15 seconds and then immediately testing them as follows: The mixed composition was placed in a test tube thermostatted to 60 °C using a water bath, and a thermocouple was placed in the center of the mixed material. This determined the time until the maximum temperature was reached (specified in the table as time to peak exotherm) and the height of the maximum temperature (peak exothermic temperature) in the mixed material. The values ​​given in Table 1 are averages of three measurements.

[0160] The Tg value (glass transition temperature) was measured by DSC on cured samples taken from the center of the test tube from the determination described above. These samples were additionally stored under standard 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).

[0161] The results are shown in Table 1.

[0162] In the epoxy resin compositions Z-1 This is an example according to the invention. The epoxy resin compositions Ref-1 until Ref-3 These are comparative examples. Z-1 Ref-1 Ref-2. Table 1: Composition and properties from and to Example Z-1 Ref-1 Ref-2 Ref-3 Resin comp.: Araldite ®< GY 250 187.0 187.0 187.0 187.0 Hardener comp.: F-EDA 46.7 - - - B-EDA - 50.1 - - MXDA - - 34.0 - IPDA - - - 42.6 time to peak exotherm [min] 14 12 12 21 peak exotherm temperature 106 °C 201 °C 150 °C 74 °C Tg 1st / 2nd run [°C] 50 / 90 53 / 88 93 / 100 76 / 155 Examples Z-2 to Z-11 and Ref-4 to Ref-8

[0163] For each example, the resin component ingredients listed in Tables 2 to 4 were mixed in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™< DAC 150, FlackTek Inc.) and stored under exclusion of moisture.

[0164] Likewise, the ingredients of the hardener component listed in Tables 2 to 4 were processed and stored.

[0165] The two components of each composition were then processed into a homogeneous liquid using the centrifugal mixer and immediately tested as follows: viscosity was measured 5 minutes after mixing the resin and hardener components as described at a temperature of 20 °C.

[0166] The Setting timewas determined by moving a freshly mixed amount of approximately 3 g in standard conditions with a spatula at regular intervals until the mass gelled.

[0167] The Shore D Hardness was determined according to DIN 53505 on two cylindrical test specimens (diameter 20 mm, thickness 5 mm), one stored in standard climate and one at 8 °C and 80% relative humidity, and the hardness was measured after 1 day (24 h) and after 2 days.

[0168] Furthermore, a film with a thickness of 500 µm was applied to a glass plate and stored and cured in a standard climate. King's hardness (Pendulum hardness according to König according to DIN EN ISO 1522) after 1 day, 2 days, 7 days and after 14 days (1d NK), (2d NK), (7d NK), (14d NK). After 14 days the Aspect (NK)of the film. A clear film was defined as having a glossy, non-sticky surface without any texture. "Texture" refers to any type of pattern or design on the surface.

[0169] Another film was applied to a glass plate with a layer thickness of 500 µm. Immediately after application, this film was stored for 7 days at 8 °C and 80% relative humidity and then cured for 2 weeks under standard conditions. 24 hours after application, a polypropylene bottle cap was placed on the film, underneath which a moist sponge was placed. After another 24 hours, the sponge and cap were removed and placed on a new part of the film, where they were removed and re-placed after 24 hours, a total of 4 times. The appearance of this film was then assessed (in the tables with "Aspect (8° / 80%)"(referred to as "blushing"), in the same way as described for aspect (NK). The number and type of visible marks caused by the damp sponge or the applied lid were also recorded. "Blushing" was the number of white stains. "(1)" was a faint, white stain. "1" was a distinct, white stain. "Ring" indicated whether a ring-shaped mark was present due to the sinking of the first lid applied 24 hours after application. Such a ring-shaped mark indicates that the coating is not yet walkable. The Königs hardness was again determined on the cured films, each after 7 days at 8 °C and 80% relative humidity. (Royal H. (7d 8° / 80%) ), then after another 2 days in the NK (Royal H. (+2d NK) ) or 7 days in NK (Royal H. (+7d NK) ) or 14d in NK (Royal H. (+14d NK) ).

[0170] The results are shown in Tables 2 to 4.

[0171] For epoxy resin compositions Z-2 until Z-10 are examples according to the invention. The epoxy resin compositions Ref-4 until Ref-8 These are comparative examples. Z-2 Z-4 Ref-4 Ref-6. Table 2: Composition and properties of up to and up to 1< not measurable (too soft) Example Z-2 Ref-4 Ref-5 Z-3 Z-4 Ref-6 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: F-EDA 46.7 - - - - - THF-EDA - 48.1 - - - - B-EDA - - 50.1 - - - Adduct A1 - - - 112.3 - - Adduct A2 - - - - 91.6 - Adduct A3 - - - - - 116.3 Viscosity (10') [Pa·s] 0.20 0.20 0.22 13.8 5.3 14.6 Setting time (h:min) 5:00 >5:30 5:15 2:30 2:30 2:30 Shore D (1d NK) 75 67 75 74 80 73 (2d NK) 78 73 76 76 82 75 Shore D (1d 8° / 80%) nm 1< nm 1< nm 1< 61 56 63 (2d 8° / 80%) 61 49 62 74 70 76 King's hardness [s] (1d NK) 41 24 116 162 137 175 (2d NK) 63 43 148 192 182 204 (7d NK) 119 91 190 203 203 (14d NK) 167 111 197 Aspect (NK) nice nice nice nice nice nice Royal H. [s] (7d 8° / 80%) 12 nm 1< 29 50 35 109 (+2d NK) 25 nm 1< 67 102 59 190 (+7d NK) 52 nm 1< 90 164 83 195 (+14d NK) 61 6 104 171 124 197 Aspect (8° / 80%) nice structure nice nice nice nice Blushing 1 4 (1) (1) (1) no ring 1 2 no no no no Z-5 Z-6 Ref-7 Ref-8. Table 3: Composition and properties of to and to Example Z-5 Ref-7 Z-6 Ref-8 Resin component: Araldite ®< GY-250 167.2 167.2 167.2 167.2 Araldite ®< DY-E 31.8 31.8 31.8 31.8 Hardener component: F-EDA 33.1 - 14.5 - B-EDA - 35.1 - 15.0 Adduct A1 33.1 - 33.1 - Adduct A3 - 35.1 - 35.1 IPDA - - 17.0 17.0 Benzyl alcohol - - 20.0 20.0 Ancamine ®< K54 - - 2.0 2.0 Viscosity (10') [Pa·s] 0.66 0.75 0.82 0.92 Setting time (h:min) 3:40 3:40 3:10 3:20 Shore D (1d NK) 79 78 75 77 (2d NK) 80 79 77 78 Shore D (1d 8° / 80%) 23 38 31 38 (2d 8° / 80%) 58 66 67 71 King's hardness [s] (1d NK) 94 136 55 66 (2d NK) 133 181 101 108 (7d NK) 153 198 136 155 (14d NK) 199 209 167 168 Aspect (NK) nice nice nice nice Royal H. [s] (7d 8° / 80%) 15 45 21 29 (+2d NK) 46 130 95 119 (+7d NK) 64 146 119 153 (+14d NK) 83 152 129 155 Aspect (8° / 80%) nice nice nice nice Blushing (1) (1) (1) (1) ring no no no no Z-7 Z-11. Table 4: Composition and properties of to 1< not measurable (too soft) 2< not measurable (sticky) Example Z-7 Z-8 Z-9 Z-10 Z-11 Resin component: Araldite ®< GY-250 167.2 167.2 167.2 167.2 167.2 Araldite ®< DY-E 31.8 31.8 31.8 31.8 31.8 Hardener component: reaction product P-1 58.9 - - - - reaction product P-2 - 56.6 - - - reaction product P-3 - - 51.6 - - reaction product P-4 - - - 55.0 - BisF-EDA - - - - 110.0 Viscosity (10') [Pa·s] 0.22 0.18 0.23 0.28 0.17 Setting time (h:min) 6:25 5:05 5:10 > 7:00 > 7:00 Shore D (1d NK) 67 74 74 40 nm 1< (2d NK) 74 77 79 50 nm 1< Shore D (1d 8° / 80%) nm 1< nm 1< nm 1< nm 1< nm 1< (2d 8° / 80%) 59 70 67 48 nm 1< King's hardness [s] (1d NK) 31 49 29 8 nm 2< (2d NK) 60 56 39 15 3 (7d NK) 81 96 77 84 8 (14d NK) 113 118 102 96 8 Aspect (NK) nice nice nice nice nice

Claims

1. Use of a hardener containing at least one amine of formula (I) for curing of epoxy resins, wherein A represents a linear alkylene radical having 2 to 10 carbon atoms and X represents H or furfuryl.

2. Use according to Claim 1, characterized in that A represents a radical selected from the group consisting of 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene and 1,6-hexylene.

3. Use according to either of Claims 1 or 2, characterized in that A represents 1,2-ethylene.

4. Use according to any of Claims 1 to 3, characterized in that X represents H.

5. Use according to any of Claims 1 to 4, characterized in that the amine of formula (I) has an RCI of at least 0.45, preferably at least 0.6, in particular at least 0.7, most preferably of 1, wherein the RCI is the ratio of the number of carbon atoms from biobased sources to the total number of carbon atoms of the amine of formula (I).

6. Use according to any of Claims 1 to 5, characterized in that the amine of formula (I) is employed in the form of a reaction product obtained from the reductive alkylation of at least one amine of formula H2N-A-NH2 with furfural and hydrogen and subsequent removal of unreacted amine of formula H2N-A-NH2.

7. Use according to Claim 6, characterized in that the molar ratio of the amine of formula H2N-A-NH2 to furfural is in the range from 1 to 2, preferably 1 to 1.5.

8. Use according to any of Claims 1 to 7, characterized in that X represents H and the hardener additionally contains an amine of formula in a weight ratio between the amine of formula (I) and the amine of formula in the range from 70 / 30 to 99 / 1, preferably 80 / 20 to 98 / 2.

9. Use according to any of Claims 1 to 8, characterized in that the amine of formula (I) is present partially or completely in the form of an amine-functional adduct with at least one epoxy resin or monoepoxide in a stoichiometric ratio of at least 1 mol of amine of formula (I) to 1 mol equivalent of epoxy groups.

10. Use according to any of Claims 1 to 9, characterized in that the hardener contains at least one further constituent selected from further amines which do not conform to formula (I), accelerators and diluents, in particular at least one further amine which does not conform to formula (I).

11. Use according to Claim 10, characterized in that the hardener contains as a further amine which does not conform to formula (I) at least one amine having an RCI of 1, in particular selected from 2,5-bis(aminomethyl)furan, 2,5-bis(aminomethyl)tetrahydrofuran, bis(5-aminomethylfuran-2-yl)methane, bis(5-aminomethyltetrahydrofuran-2-yl)methane, 2,2-bis(5-aminomethylfuran-2-yl)propane and 2,2-bis(5-aminomethyltetrahydrofuran-2-yl)propane, wherein the RCI is the ratio of the number of carbon atoms from biobased sources to the total number of carbon atoms of the amine.

12. Epoxy resin composition comprising - a resin component comprising at least one epoxy resin and - a hardener component comprising the hardener as described in any of Claims 1 to 11.

13. Cured epoxy resin composition obtained from the epoxy resin composition according to Claim 12 after the mixing of the resin component and the hardener component.

14. Reaction product obtained from the reductive alkylation of an amine of formula H2N-A-NH2 with furfural and hydrogen in a molar ratio of the amine of formula H2N-A-NH2 to furfural in the range from 1 to 2, preferably 1 to 1.5, and subsequent removal of amine of formula H2N-A-NH2 to a content of at most 1% by weight, preferably at most 0.5% by weight, in particular at most 0.2% by weight, based on the reaction product, wherein A represents a linear alkylene radical having 2 to 10 carbon atoms, in particular 1,2-ethylene.

15. Reaction product according to Claim 14, characterized in that A represents 1,2-ethylene and the reaction product contains 50% to 80% by weight of N-furfuryl-1,2-ethanediamine, 5% to 50% by weight, in particular 5% to 40% by weight, of N,N'-difurfuryl-1,2-ethanediamine, 0% to 20% by weight, in particular 2% to 15% by weight, of N-tetrahydrofurfuryl-1,2-ethanediamine, less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.2% by weight, of 1,2-ethanediamine and optionally further constituents, in particular further byproducts from the reductive alkylation, based on the reaction product.

16. Amine mixture containing at least one amine of formula and at least one amine of formula in a weight ratio in the range from 70 / 30 to 99 / 1, preferably 80 / 20 to 98 / 2, wherein A represents a linear alkylene radical having 2 to 10 carbon atoms, in particular 1,2-ethylene.