Renewable carbon-rich amine hardener

Abstract

The present invention relates to the use of a curing agent comprising at least one amine of formula (I) for curing epoxy resins. The amine of formula (I) has a high renewable carbon index (RCI) and allows for a particularly sustainable epoxy resin product. It is surprisingly easy to prepare, has a low odor, dilutes epoxy resins particularly well, and allows for a fast and problem-free curing with surprisingly low exothermic effects.

Description

[Technical field]

[0001] The present invention relates to alkylated amines high in renewable carbon and their use as curing agents for epoxy resins. [Background technology]

[0002] Amines are used in industry and construction, especially as curing agents in epoxy resin compositions. Depending on the application, the required properties include high reactivity with low exotherm and / or fast and problem-free curing at ambient temperature to obtain coatings or objects with uniform surfaces without haze, smears or craters due to brushing. The cured objects or coatings must have high hardness with low brittleness to withstand mechanical stress as much as possible, and for optically demanding applications, high gloss and low tendency to yellow. For many applications, it is important that the epoxy resin composition has a low viscosity so that it can be applied as quickly and easily as possible, has good leveling and degassing properties, and in some cases easily penetrates the substrate. Since many epoxy resins have a fairly high viscosity, efficient dilution with amine curing agents is particularly advantageous, since it allows the use of smaller amounts of diluent or solvent and / or the realization of higher filler contents to achieve the appropriate viscosity.

[0003] Currently, there is an increasing demand for sustainable epoxy resin compositions. In particular, they must contain a high content of raw materials derived from renewable biological sources, i.e., they must be bio-based to a large extent. Therefore, sustainable amine hardeners are needed. A common measure of the sustainability of chemical raw materials is the Renewable Carbon Index (RCI), which indicates the carbon content derived from renewable biological sources. It is obtained by dividing the number of carbon atoms derived from renewable resources by the total number of carbon atoms in the raw material.

[0004] Curing agents containing amines with high renewable carbon index are known, for example, from US Pat. No. 9,676,898 or WO 2015 / 124792, which describe bis(aminomethyl)furan and bisfurfurylamines and their use as curing agents for epoxy resins. However, the production of these amines is costly, difficult to carry out, prone to blushing, and their dilution effect on epoxy resins needs improvement.

[0005] European Patent No. 3,350,245 discloses sustainable hardeners containing alkylated amines with a tetrahydrofuran ring. These hardeners show incomplete curing, especially in 2D applications, and at low temperature conditions, such as 8°C, resulting in reduced final hardness.

[0006] Benzylated amines are also known, for example from EP 2731927, EP 3180383 or EP 3344677. As hardeners for epoxy resins, these amines have a good dilution effect and allow fast and problem-free curing, even in 2D applications and at low ambient temperatures. However, their biobased production is not possible. Summary of the Invention [Problem to be solved by the invention]

[0007] It is therefore an object of the present invention to provide a hardener for epoxy resins which has a high Renewable Carbon Index (RCI), is simple to prepare, has a good dilution effect of the epoxy resin and allows problem-free curing. [Means for solving the problem]

[0008] This object is surprisingly achieved by using a curing agent containing the amine of formula (I) according to claim 1. The amine of formula (I) is obtained by a simple process from the reductive alkylation of primary aliphatic amines 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 curing agent containing the amine of formula (I) allows a surprisingly high dilution. In particular, with N-furfuryl-1,2-ethanediamine, the epoxy resin is particularly efficiently diluted, even more highly diluted than with the 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 less than that of N-benzyl-1,2-ethanediamine due to its low amine equivalent weight, and is less diluting than N-benzyl-1,2-ethanediamine due to the possibility of oxygen in the furan ring and the resulting hydrogen bond formation. The curing agent according to the invention has a very low odor, which is a further great advantage for many applications. This allows a fast and problem-free curing to a high final hardness. Particularly surprising is that the exotherm during curing is significantly less than with N-benzyl-1,2-ethanediamine, and the processing time and curing speed with N-furfuryl-1,2-ethanediamine are only slightly longer / slower than with N-benzyl-1,2-ethanediamine. The low exotherm allows the use of epoxy resin products used in thick layers, such as moldings, potting compounds, or matrix resins in composites, without causing blistering, discoloration, or other inhomogeneities due to high exotherms. For two-dimensional applications, this hardener allows the realization of epoxy resin coatings that can be cured at ambient temperature, with attractive, glossy surfaces and a very low tendency to blushing. It is also particularly surprising that N-furfuryl-1,2-ethanediamine can be used in the form of less refined, particularly inexpensively producible reaction products without any appreciable adverse effects during the curing of epoxy resins.

[0010] Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention relates to a process for curing epoxy resins, comprising the steps of: [ka] (In the formula, A represents a linear alkylene group having 2 to 10 carbon atoms, and X represents H or furfuryl.) The present invention provides the use of a curing agent containing at least one amine of the formula:

[0012] "RCI" is the "Renewable Carbon Index" of a substance or substance mixture; the RCI is the ratio of the number of carbon atoms that come from biobased sources to the total number of carbon atoms of the substance or substance mixture.

[0013] A "primary amino group" refers to an amino group that is bonded to one organic group and has two hydrogen atoms; a "secondary amino group" refers to an amino group that is bonded to two organic groups and has one hydrogen atom, which may together form part of a ring; and a "tertiary amino group" refers to an amino group that has no hydrogen atoms and is bonded to three organic groups, two or three of which may be part of one or more rings.

[0014] "Amine hydrogen" refers to the hydrogen atoms of primary and secondary amine groups.

[0015] "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."

[0016] "Epoxy equivalent" refers to the mass of an epoxy-containing compound or composition that contains one molar equivalent of epoxy groups. It is expressed in units of "g / eq."

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

[0018] "Diluent" refers to a substance that is soluble in and reduces the viscosity of the epoxy resin, and that is not chemically incorporated into the epoxy resin polymer during the curing process.

[0019] "Molecular weight" refers to the molar mass (grams per mole) of a molecule. "Average molecular weight" refers to the number average M n This refers to the molecular weight distribution of the polymer, which is usually determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0020] "Pot life" refers to the maximum time between mixing the components and applying the epoxy resin composition during which the mixed composition is sufficiently free-flowing and has sufficient ability to wet the substrate surface.

[0021] "Gel time" is the time from mixing the components of an epoxy resin composition until it gels.

[0022] "Room temperature" refers to a temperature of 23°C.

[0023] All industry standards and specifications referred to herein refer to the version in effect at the date of original filing unless otherwise stated.

[0024] Weight percent (wt%) values ​​refer to the mass fraction of a component in a composition based on the entire composition, unless otherwise specified. The terms "mass" and "weight" are used interchangeably herein.

[0025] A preferably 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] A is particularly preferably selected from the group consisting of 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene and 1,6-hexylene, as these amines are particularly easy to obtain with high RCI and have particularly good compatibility with epoxy resins.

[0027] A most preferably represents 1,2-ethylene. Such amines of formula (I) make it possible to achieve epoxy resin compositions which cure particularly quickly and without problems, and have a particularly high RCI, even when the carbon atoms of the group A do not originate from biobased raw materials.

[0028] Preference is given to the case where X represents H. Such amines of formula (I) dilute epoxy resins particularly well, making it possible to achieve a particularly rapid cure and a particularly high final hardness.

[0029] It is preferred if 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] Among these, N-furfuryl-1,2-ethanediamine or N,N'-difurfuryl-1,2-ethanediamine is preferred, and N-furfuryl-1,2-ethanediamine is particularly preferred.

[0031] In a preferred embodiment of the invention, the amines of formula (I) are used as mixtures of amines of formula (I) where X=H with amines of formula (I) where X=furfuryl in a weight ratio ranging from 50 / 50 to 98 / 2, in particular from 60 / 40 to 95 / 5. Such mixtures are particularly inexpensive to produce and allow rapid and problem-free curing of the epoxy resin.

[0032] The amines of formula (I) are preferably prepared by carrying out a reductive alkylation of furfural and hydrogen with at least one amine of formula H2N-A-NH2.

[0033] The furfural is preferably based on renewable raw materials and has an RCI of 1. This allows the amine of formula (I) to have a high RCI.

[0034] Commercially available furfural is typically derived from bio-based raw materials. On a large industrial scale, furfural is obtained, for example, from hemicellulose derived from plant raw materials, in particular by the action of sulfuric acid on the C5 sugars present therein during dewatering, or in pulp production by the magnesium bisulfite process (liberated furfural can be extracted from the black liquor).

[0035] Preferred amines of formula H2N-A-NH2 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 amines of formula H2N-A-NH2 are also derived from renewable raw materials. This makes it possible to achieve highly sustainable amines of formula (I), in particular those with an RCI of 1.

[0037] It is preferred if 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 being palladium on charcoal (Pd / C), platinum on charcoal (Pt / C), Adams' catalyst or Raney nickel, in particular palladium on charcoal or Raney nickel.

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

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

[0041] Depending on the stoichiometry between the amine of formula H2N-A-NH2 and the furfural, the resulting reaction mixture will contain different proportions of monoalkylated amines of formula H2N-A-NH2, i.e., amines of formula (I) where X = H, and dialkylated amines of formula H2N-A-NH2, i.e., amines of formula (I) where X = furfuryl.

[0042] When an amine of formula (I) with X=furfuryl is prepared, the molar ratio of the amine of formula H2N-A-NH2 to furfural is preferably in the range from 0.4 to 0.7, in particular 0.5. The reaction mixture thus obtained contains a particularly high content of amine of formula (I) with X=furfuryl.

[0043] When an amine of formula (I) where X=H is prepared, the molar ratio of amine of formula H2N-A-NH2 to furfural is preferably in the range of 1 to 10, in particular 1 to 5. The reaction mixture thus obtained contains a high content of amine of formula (I) where X=H.

[0044] The excess amine of formula H2N-A-NH2 is preferably removed from the reaction mixture after the reaction, in particular by distillation together with the water released.

[0045] The reaction mixture can be further purified, especially by distillation / fractionation: by-products can be removed from the amine of formula (I) and / or amines of formula (I) where X=H can be separated from amines of formula (I) where X=furfuryl.

[0046] It is preferred when the amine of formula (I) is used in the form of a reaction product obtained by carrying out a reductive alkylation of furfural and hydrogen with at least one amine of formula H2N-A-NH2, and subsequently removing the unreacted amine of formula H2N-A-NH2.

[0047] The reaction product is preferably not further purified, in particular distillation / fractionation of the amine of formula (I) is avoided.

[0048] Such a reaction product can be produced particularly cheaply. It contains a low content of amines of the formula H2N-A-NH2, preferably less than 2% by weight, particularly preferably less than 1% by weight, in particular less than 0.5% by weight, based on the entire reaction product.

[0049] The reaction products may contain by-products from the reductive alkylation, particularly amines having di- or tri-alkylated nitrogen atoms and amines having hydrogenated furan rings, the proportion of which is preferably low.

[0050] The reaction product is an amine having di- or tri-alkylated nitrogen atoms, particularly an amine of the formula [ka] % in total, based on the entire reaction product, of these amines, particularly preferably less than 5% by weight and in particular less than 2% by weight.

[0051] The reaction product is an amine having a hydrogenated furan ring, particularly an amine of the formula [ka] amines in total, based on the entire reaction product, preferably less than 20% by weight, in particular less than 15% by weight.

[0052] In a particularly preferred embodiment of the invention, the amine of formula (I) is obtained in the form of a reaction product from the reductive alkylation of furfural and hydrogen with at least one amine of formula H2N-A-NH2, followed by removal of unreacted amine of formula H2N-A-NH2, the molar ratio of amine of formula H2N-A-NH2 to furfural ranging from 1 to 2, preferably from 1 to 1.5. Preference is given to the case where A represents 1,2-ethylene.

[0053] The content of amines of the formula H2N-A-NH2 in this reaction product is preferably at most 1% by weight, particularly preferably at most 0.5% by weight and in particular at most 0.2% by weight, based on the reaction product as a whole.

[0054] Such reaction products contain surprisingly high amounts of amines of formula (I) where X=H and surprisingly low amounts of amines of formula (I) where X=furfuryl, and the reaction products show surprisingly high reactivity towards epoxy resins, almost comparable to the nearly pure amines of formula (I) where X=H, which was not expected from the prior art. The corresponding reaction with 1,2-ethanediamine using benzaldehyde instead of furfural leads to a significantly higher content of N,N'-dialkylated 1,2-ethanediamine at the corresponding stoichiometry.

[0055] It is preferred if the weight ratio of the amine of formula (I) where X=H to the amine of formula (I) where X=furfuryl in the reaction product is in the range of 50 / 50 to 98 / 2, preferably 60 / 40 to 95 / 5, based on the reaction product.

[0056] The invention therefore further provides a reaction product, in which A represents a linear alkylene group having 2 to 10 carbon atoms, in particular 1,2-ethylene, obtainable by reductive alkylation of furfural and hydrogen with an amine of formula H2N-A-NH2 in a molar ratio of amine of formula H2N-A-NH2 to furfural ranging from 1 to 2, preferably from 1 to 1.5, followed by removal of the 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.

[0057] A represents 1,2-ethylene, and the reaction product is 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 containing further components, in particular further by-products from the reductive alkylation.

[0058] Such reaction products can be easily and inexpensively produced and, without further purification, are highly suitable as components of hardeners for curing epoxy resins, the products having high reactivity towards epoxy resins almost comparable to that of substantially pure N-furfuryl-1,2-ethanediamine.

[0059] Amines of formula (I) where X=H and formula [ka] and an amine of formula (I) where X=H in a weight ratio of 70 / 30 to 99 / 1, preferably 80 / 20 to 98 / 2. [ka] where A is as defined above.

[0060] Such amine mixtures are easy to prepare and provide surprisingly rapid and problem-free curing of epoxy resins.

[0061] Thus, the present invention provides at least one compound of formula [ka] and at least one amine of the formula [ka] and in a weight ratio ranging from 70 / 30 to 99 / 1, preferably from 80 / 20 to 98 / 2, wherein A represents a linear alkylene group having 2 to 10 carbon atoms, in particular 1,2-ethylene.

[0062] In a preferred embodiment of the present 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 one mole of amine of formula (I) per one molar equivalent of epoxy groups.

[0063] Such adducts are in the form of a mixture of adducted molecules having at least two, typically three or four amine hydrogens derived from an amine of formula (I) and free, unadducted amines of formula (I), which allow particularly rapid curing at moderate viscosities, especially at temperatures as low as 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, especially bisphenol A, F, or A / F diglycidyl ethers or novolac epoxy resins, having an average functionality in the range of 2 to 4 are preferred. These adducts allow for particularly rapid cure and high glass transition temperatures.

[0066] Also preferred are epoxy resins containing polyoxypropylene and / or polyoxyethylene units. These are in particular the diglycidyl ethers of polypropylene glycol or the reaction products of 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.

[0067] Aromatic diepoxides are especially preferred, especially bisphenol A, F, or A / F diglycidyl ethers.

[0068] Highly preferred is bisphenol A diglycidyl ether, with an RCI of 0.28, obtained from the reaction of bisphenol A with biobased epichlorohydrin, which makes it possible to obtain a particularly sustainable adduct.

[0069] It is preferred if the addition is carried out in a stoichiometric ratio in moles of amine of formula (I) per molar equivalent of epoxy groups in the range of 1 to 10, preferably 1.2 to 5, in particular 1.4 to 3.

[0070] The curing agent preferably contains at least one additional component selected from an additional amine not according to formula (I), an accelerator, and a diluent, in particular at least one additional amine not according to formula (I).

[0071] It is preferred if the curing agent comprises at least one additional amine not according to formula (I) that is not a by-product from the preparation of the amine of formula (I).

[0072] Preferred additional amines not according to formula (I) are amines having an aliphatic amino group 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-neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2(4),4-trimethyl-1,6-hexanediamine (TMD), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino- 3,5-Dimethylcyclohexyl)methane, Bis(4-amino-3-ethyl-5-methylcyclohexyl)methane, 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 2(4)-Methyl-1,3-diaminocyclohexane, 2,5(2,6)-Bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-Bis(aminomethyl)tricyclo[5.2.1.0 2,6]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-menthanediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-bis(aminomethyl)benzene (MXDA), 1,4-bis(aminomethyl)benzene, bis(2-aminoethyl)ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,1 2-diamines, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1,13-diamine, or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofuran or other polytetrahydrofuran diamines, polyoxyalkylene di- or triamines, in particular polyoxypropylene diamines or polyoxypropylene triamines, such as Jeffamine® D-230, Jeffamine® D-400, or Jeffamine® T-4. 03 (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-aminomethyltetrahydrofuran-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), dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-aminopentyl)-1,3-pentanediamine, N5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, N,N'-bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT), N-aminoethylpiperazine, 3-dimethylaminopropylamine (DMAPA), 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), amine-functional adducts of the listed amines with epoxides, phenalkamines which are reaction products of cardanol with aldehydes, especially formaldehyde, as well as polyamines, or mixtures of two or more of these amines.

[0073] The curing agent is preferably 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, an average molecular weight M in the range of 200 to 500 g / mol. n Polyoxypropylenediamine having an average molecular weight M in the range of 300 to 500 g / mol n The compound includes at least one amine selected from the group consisting of polyoxypropylene triamine having the formula: 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 phenalkamine.

[0074] Among these, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, particularly 1,3-bis(aminomethyl)cyclohexane, is preferred, as this allows particularly rapid curing.

[0075] Among these, IPDA is further preferred, which allows a particularly high glass transition temperature to be achieved and therefore a particularly good robustness to high application temperatures. It is particularly preferred to use IPDA with a high RCI from bio-based acetone, which allows the realization of a sustainable hardener.

[0076] Of these, MXDA is more preferred, as it provides a fast curing rate and particularly high strength.

[0077] Among these, N-benzyl-1,2-ethanediamine is more preferred. Such a hardener allows for particularly low viscosity epoxy resin products with particularly attractive surfaces.

[0078] Among these, 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, particularly 2,5-bis(aminomethyl)furan, are more preferred, which makes it possible to realize a particularly sustainable curing agent.

[0079] The curing agent may in particular contain two or more additional amines not conforming to formula (I).

[0080] The hardener particularly preferably comprises, as additional amine not according to formula (I), at least one amine with an RCI of 1, in particular an amine 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.

[0081] It is preferred if the hardener contains additional amines not according to formula (I) in an amount such that 5% to 95%, preferably 10% to 80%, in particular 15% to 60% of all amine hydrogens are attributable to amines of formula (I). When the amines of formula (I) are present in the form of adducts with the epoxy resin, the amine hydrogens of such adducts are likewise counted as amine hydrogens of the amines of formula (I).

[0082] Suitable accelerators are in particular acids or compounds hydrolysable with 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, in particular phosphoric acid; or mixtures of the abovementioned acids and acid esters; nitrates, in particular calcium nitrate; tertiary amines, in particular 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine; in particular N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole. 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, in particular 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, or polymers made from phenol, formaldehyde and N,N-dimethylpropane-1,3-diamine; phosphites, in particular di- or triphenylphosphite; or compounds containing a mercapto group.

[0083] 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.

[0084] 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 ... ethers, 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 (Exxon), alkylphenols, for example tert-butylphenol, nonylphenol, dodecylphenol, cardanol, styrenated phenols, bisphenols, aromatic hydrocarbon resins, especially those types which contain phenolic groups, alkoxylated phenols, especially ethoxylated or propoxylated phenols, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organophosphates, or sulfonates, or sulfonamides.

[0085] Among these, diluents having a boiling point above 200° C. are particularly preferred, in particular benzyl alcohol, styrenated phenols, ethoxylated phenols, aromatic hydrocarbon resins containing phenolic groups, such as in particular Novares® grades LS500, LX200, LA300 or LA700 (from Ruetgers), diisopropyl naphthalene or cardanol, in particular benzyl alcohol.

[0086] Phenol-containing diluents are also useful as accelerators.

[0087] Among these, aromatic diluents, particularly xylene, which have a particularly high dilution effect, are also preferred.

[0088] Among these, diluents with an RCI of 1 are particularly preferred, in particular cardanol, which make it possible to achieve a particularly sustainable hardener.

[0089] The curing agent preferably contains only a small amount of diluent, particularly 0 to 50% by weight, preferably 0 to 30% by weight of diluent based on the total weight of the curing agent.

[0090] The curing agent contains preferably 1 wt % to 99 wt %, more preferably 5 wt % to 90 wt %, more preferably 10 wt % to 80 wt %, and particularly preferably 15 wt % to 70 wt % of the amine of formula (I) based on the total weight of the curing agent.

[0091] The curing agent may be water-based and contains water in the range of 15% to 90% by weight, preferably 20% to 80% by weight.

[0092] 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 hardener is particularly suitable for non-aqueous epoxy resin products.

[0093] The hardener may in particular comprise the following additional components: additional 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 is removed by distillation after the reaction, Monoamines, in particular benzylamine or furfurylamine, polyamidoamines, in particular the reaction products of monobasic 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, 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, 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, Surfactants, in particular defoamers, degassing agents, wetting agents, dispersing agents or levelling agents, or · Stabilizers, especially those against oxidation, heat, light or UV radiation.

[0094] The present invention further comprises: a resin component comprising at least one epoxy resin; a hardener component comprising a hardener containing at least one amine of formula (I) above; The present invention provides an epoxy resin composition comprising:

[0095] Suitable epoxy resins are obtainable in known manner, in particular from the reaction of epichlorohydrin with polyols, polyphenols or amines.

[0096] Suitable epoxy resins are in particular aromatic epoxy resins, in particular the glycidyl ethers of: Bisphenol A, bisphenol F or bisphenol A / F (A stands for acetone and F for formaldehyde used as reactant in the production of these bisphenols). In the case of bisphenol F, positional isomers may also be present, more specifically those derived from 2,4'- or 2,2'-hydroxyphenylmethane; Dihydroxybenzene derivatives such as resorcinol, hydroquinone, or catechol; 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 (bis additional bisphenols or polyphenols such as 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, 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).

[0097] Further suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular Saturated or unsaturated, branched or unbranched, cyclic or open-chain, di-, tri- or tetra-functional C2-C 30 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 reaction products of epichlorohydrin with hydantoins; It is.

[0098] Further suitable epoxy resins are those with high RCI, especially those obtained from the reaction of bio-based hydroxy-functional raw materials with epichlorohydrin. Vanillin-based epoxy resins, especially the diglycidyl ether of vanillin alcohol, and glycerol-based epoxy resins, especially the bio-based triglycidyl ether of glycerol, are particularly preferred.

[0099] The epoxy resin is preferably a liquid resin or a mixture containing two or more liquid epoxy resins.

[0100] "Liquid epoxy resin" refers to commercial polyepoxides having a glass transition temperature below 25°C.

[0101] The resin component optionally further contains a percentage of a solid epoxy resin.

[0102] The epoxy resin is in particular a liquid resin based on bisphenol or novolac and has in particular an average epoxy equivalent weight in the range of 156 to 210 g / eq.

[0103] Particularly suitable are bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether, such as those commercially 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 resin or novolac epoxy resin.

[0104] Highly preferred is bisphenol A diglycidyl ether, with an RCI of 0.28, obtained from the reaction of bisphenol A with biobased epichlorohydrin, which makes it possible to achieve particularly sustainable epoxy resin compositions.

[0105] Also particularly suitable are phenol-formaldehyde novolac glycidyl ethers, in particular 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, in particular bisphenol A diglycidyl ether or bisphenol F diglycidyl ether.

[0106] Also particularly suitable are the diglycidyl ethers of vanillin alcohol or the triglycidyl ethers of glycerol, in particular the diglycidyl ethers of vanillin alcohol.

[0107] The resin component may include a reactive diluent.

[0108] Preferred reactive diluents are those 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 ~C 14 Or C 13 ~C 15 It is an alkyl glycidyl ether.

[0109] It is preferred that the epoxy resin composition contains at least one additional component selected from the group consisting of diluents, accelerators, fillers, pigments, and surfactants.

[0110] Suitable diluents or promoters include, inter alia, those mentioned hereinabove.

[0111] Suitable fillers are in particular ground or precipitated calcium carbonate, optionally coated with fatty acids, in particular stearates, barite, talc, quartz flour, 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 powders or hollow beads. Among these, calcium carbonate, barite, quartz flour, talc, aluminum powder or combinations thereof are preferred.

[0112] Suitable pigments include, in particular, titanium dioxide, iron oxide, chromium(III) oxide, organic pigments, carbon black, or anticorrosive pigments, especially phosphates, orthophosphates, or polyphosphates, especially those containing chromium, zinc, aluminum, calcium, strontium, or combinations of these metals as counterions. Titanium dioxide is particularly suitable.

[0113] Suitable surfactants are especially antifoaming agents, degassing agents, wetting agents, dispersing agents, leveling agents and / or dispersing paraffin wax.

[0114] The epoxy resin composition may optionally contain additional auxiliaries and additives, in particular: reactive diluents, 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, homopolymers or copolymers of unsaturated monomers, in particular unsaturated homopolymers or copolymers 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, metal, ceramic or polymer fibres, such as polyamide or polyethylene fibres; · Nanofillers, especially carbon nanotubes; Rheology modifiers, in particular thickeners or anti-settling agents; Adhesion promoters, especially organoalkoxysilanes; flame retardant substances, in particular the already mentioned aluminium hydroxide or magnesium hydroxide fillers, 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, phosphate esters, 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 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(dibromonobornanedicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadieno)cyclooctane, or chloroparaffins; or Stabilizer against oxidation, heat, light, UV rays or biocides.

[0115] The epoxy resin composition preferably contains only a small amount of diluent, preferably less than 20% by weight, particularly preferably less than 10% by weight, in particular less than 5% by weight, most preferably less than 1% by weight.

[0116] The epoxy resin composition may contain water.

[0117] 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.

[0118] However, the epoxy resin composition preferably contains only small amounts of water, preferably less than 5% by weight, in particular less than 1% by weight of water. Such non-aqueous epoxy resin compositions are particularly versatile and particularly water resistant.

[0119] Preferred are epoxy resin compositions comprising: a resin component comprising at least one epoxy resin and, in particular, optional additional components such as epoxy-containing reactive diluents, diluents, fillers, pigments, and / or surfactants, and A hardener component comprising at least one amine of formula (I) and optionally further components such as in particular further amines, accelerators and / or diluents.

[0120] The resin component and the hardener component of the epoxy resin composition are stored in separate containers.

[0121] Suitable containers for storing the resin or hardener components are in particular vats, hobs, bags, buckets, cans, cartridges or tubes. The components are storable, meaning that they can be stored for several months up to a year or more before use without changing their respective properties to an extent relevant for use.

[0122] 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 epoxy reactive 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 of the resin component to the hardener component is typically in the range of 1:2 to 20:1.

[0123] The components are mixed continuously or batchwise in any suitable manner, taking care not to let too much time pass between mixing and coating, and that coating occurs within the pot life. Mixing and coating can be carried out at ambient temperature, typically in the range of about 5° C. to 40° C., preferably in the range of about 10° C. to 35° C., or at elevated temperatures, particularly in the range of 40° C. to 150° C., preferably 50° C. to 120° C.

[0124] Once the components are mixed, a chemical reaction begins to cure the epoxy resin composition. 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.

[0125] Curing typically takes from a few hours to a few days, the duration depending on factors such as temperature, the reactivity of the components, their stoichiometry, and the presence / amount of accelerators.

[0126] In the freshly mixed state, the epoxy resin composition has a low viscosity. Five minutes after mixing the resin and hardener components at 20°C, the viscosity is 10s -1 When measured using a cone and plate viscometer at a shear rate of 0.1 to 20 Pa·s, preferably 0.2 to 10 Pa·s, and particularly preferably 0.3 to 5 Pa·s.

[0127] The epoxy resin composition is applied to at least one substrate and / or at least one mold.

[0128] Suitable substrates are in particular Glass, glass ceramics, concrete, mortar, cement screed, fibre cement, brick, tile, stucco or natural stone such as granite or marble; · Repair or levelling compounds based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar); · metals or alloys such as aluminium, iron, steel, copper and other non-ferrous metals (including metals or alloys with a surface finish such as zinc-plated or chrome-plated metals); Asphalt or bitumen; Leather, textiles, paper, wood, wood-based materials bonded with resins (e.g. phenolic, melamine or epoxy resins), resin-textile composites or further polymer composites; Plastics such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy, phenolic, PUR, POM, TPO, PE, PP, EPM or EPDM, either untreated or surface treated, for example by plasma, corona or flame; Fiber-reinforced plastics such as carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GFRP) and sheet molding compounds (SMC); Thermal insulation foams, especially those made from EPS, XPS, PUR, PIR, rock wool, mineral wool or foamed 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 further overcoated with a coating, paint or varnish, especially a floor covering layer; It is.

[0129] The substrate can, if necessary, be pretreated prior to application, in particular by physical and / or chemical cleaning methods or the application of an activator or primer.

[0130] The substrates are in particular joined by coating and / or gluing.

[0131] A suitable mold is a device into which the mixed liquid epoxy resin composition can be poured and cured, and from which it can be demolded or removed after curing, such that the cured composition forms a molded body.

[0132] The mold is preferably made at least of a material whose surface allows the cured epoxy resin composition to be released again without being damaged, in particular made of metal, ceramic, plastic or silicone, and optionally provided with a non-stick coating, in particular a non-stick coating of Teflon, silicone or wax.

[0133] The present invention further provides a cured composition obtained from the epoxy resin composition described herein after mixing the resin component and the hardener component.

[0134] The epoxy resin composition is preferably used as a coating, primer, adhesive, sealant, potting compound, casting resin, impregnating resin or as a moulding or as a matrix for composite materials, such as in particular CFRP (containing carbon fibres) or GFRP (containing glass fibres) or wood composites.

[0135] This use results in the formation of an article that includes a cured composition comprised of the described epoxy resin composition.

[0136] The article is in particular a floor coating, a wall coating, a component coating, a pipe coating, a roof coating or an anti-corrosion coating, or an adhesively bonded article or molding, in particular a composite material. EXAMPLES

[0137] Below are exemplary embodiments intended to more specifically illustrate the described invention, the invention being of course not limited to these described exemplary embodiments.

[0138] "AHEW" stands for amine hydrogen equivalent weight.

[0139] "EEW" stands for epoxy equivalent weight.

[0140] "Standard Climatic Conditions" ("SCC") refers to a temperature of 23±1°C and a relative atmospheric humidity of 50±5%.

[0141] Unless otherwise stated, chemicals used were obtained from Sigma-Aldrich Chemie GmbH.

[0142] Measurement method description: Viscosity was measured using a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone-tip-plate distance 0.05 mm, shear rate 10 s -1 ) for viscosity less than 100 mPa s. -1 The measurements were performed at a shear rate of .

[0143] Amine values ​​were determined by titration (0.1 N HClO4 in acetic acid for crystal violet).

[0144] Gas chromatograms (GC) were measured in the temperature range from 60 to 320 °C with a heating rate of 15 °C / min and a hold 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) with a gas flow rate of 1.5 ml / min. Detection was performed by flame ionization (FID).

[0145] Infrared spectra (FT-IR) were measured as undiluted films on a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal ATR measurement unit with a diamond crystal. Absorption bands are expressed in wavenumbers (cm -1 ) will be reported.

[0146] 1 H NMR spectra were recorded on a Bruker Ascend 400 type spectrometer at 400.14 MHz. Chemical shifts δ are reported in ppm relative to tetramethylsilane (TMS). True and pseudo-coupling patterns were not distinguished.

[0147] Substances and abbreviations used: Araldite® GY 250: Bisphenol A diglycidyl ether, EEW approx. 187 g / eq (Huntsman) Araldite® DY-E:C 12 ~C 14 Monoglycidyl ether of alcohol, EEW approx. 290g / eq (Huntsman) DEN® 438: Phenol-formaldehyde novolac glycidyl ether, EEW about 179 g / eq, average functionality about 3.6 (Olin) IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6g / eq (Vestamin® IPD, Evonik) MXDA: 1,3-bis(aminomethyl)benzene, AHEW 34g / eq (Mitsubishi Gas Chemical) Ancamine® K54 2,4,6-tris(dimethylaminomethyl)phenol (Evonik).

[0148] Preparation of amines: Reaction Product P-1: (Contains N-furfuryl-1,2-ethanediamine; 1:1 stoichiometry) At room temperature, 30.05 g (0.5 mol) of ethane-1,2-diamine was initially placed in a round-bottom flask under nitrogen atmosphere. With good stirring, 48.05 g (0.5 mol) of furfural (furan-2-carbaldehyde, RCI=1) was added and stirred for another hour at 40 °C. The reaction mixture was mixed with 1000 ml of isopropanol and then hydrogenated in a continuous hydrogenation apparatus equipped with a Raney nickel fixed bed catalyst at a hydrogen pressure of 70 bar, a temperature of 70 °C and a flow rate of 5.5 ml / min. To monitor the reaction, IR spectroscopy was used to measure the peak at approximately 1665 cm. -1It was confirmed whether the imine band of the hydrogenated amine disappeared or not. Then, the hydrogenated solution was concentrated on a rotary evaporator at 65° C. to remove 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 of 10 mPa·s at 20°C, and a GC content of about 57.9 wt% N-furfuryl-1,2-ethanediamine (retention time 7.3 min), about 8.2 wt% N-tetrahydrofurfuryl-1,2-ethanediamine (retention time 8.0 min), about 31.6 wt% N,N'-difurfuryl-1,2-ethanediamine (retention time 11.9 min), and about 2.3 wt% furan ring hydrogenated N,N'-difurfuryl-1,2-ethanediamine (retention time 12.5 min). 58.9 g / eq AHEW was used for further use.

[0149] Reaction Product P-2: (Contains N-furfuryl-1,2-ethanediamine; 2:1 stoichiometry) At room temperature, 60.1 g (1 mol) of ethane-1,2-diamine was initially placed in a round-bottom flask under nitrogen atmosphere. With good stirring, 48.05 g (0.5 mol) of furfural (furan-2-carbaldehyde, RCI=1) was added and stirred for another hour at 40 °C. The reaction mixture was mixed with 1000 ml of isopropanol and then hydrogenated in a continuous hydrogenation apparatus equipped with a Raney nickel fixed bed catalyst at a hydrogen pressure of 70 bar, a temperature of 70 °C and a flow rate of 5.5 ml / min. To monitor the reaction, IR spectroscopy was used to measure the peak at approximately 1665 cm -1It was checked whether the imine band of 1,2-ethanediamine disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C to remove unreacted 1,2-ethanediamine, water, and isopropanol. The reaction mixture so obtained was a clear, slightly yellowish liquid with an amine value of 772 mg KOH / g, a viscosity of 11 mPa·s at 20 °C, and a GC content of about 78.2 wt% N-furfuryl-1,2-ethanediamine (retention time 7.3 min), about 12.3 wt% N-tetrahydrofurfuryl-1,2-ethanediamine (retention time 8.0 min), and about 9.1 wt% N,N'-difurfuryl-1,2-ethanediamine (retention time 11.9 min). 56.6 g / eq AHEW was used for further use.

[0150] Reaction Product P-3: (Contains N-furfuryl-1,2-ethanediamine; 3:1 stoichiometry) At room temperature, 60.1 g (1 mol) of ethane-1,2-diamine was initially placed in a round-bottom flask under nitrogen atmosphere. With good stirring, 32.0 g (0.33 mol) of furfural (furan-2-carbaldehyde, RCI=1) was added and stirred for another hour at 40°C. The reaction mixture was mixed with 1000 ml of isopropanol and then hydrogenated in a continuous hydrogenation apparatus equipped with a Raney nickel fixed bed catalyst at a hydrogen pressure of 65 bar, a temperature of 65°C and a flow rate of 5.5 ml / min. To monitor the reaction, IR spectroscopy was used to measure the peak at approximately 1665 cm. -1It was confirmed whether the imine band of the hydrogenated amine disappeared or not. Then, the hydrogenated solution was concentrated on a rotary evaporator at 65° C. to remove unreacted 1,2-ethanediamine, water, and isopropanol. The reaction mixture thus obtained was a clear, slightly yellowish liquid having an amine value of 757 mg KOH / g, a viscosity of 10 mPa·s at 20°C, and a GC content of about 86.1 wt% N-furfuryl-1,2-ethanediamine (retention time 7.3 min), about 3.3 wt% N-tetrahydrofurfuryl-1,2-ethanediamine (retention time 8.0 min), about 2.8 wt% N,N'-difurfuryl-1,2-ethanediamine (retention time 11.9 min), about 1.5 wt% furan ring hydrogenated N,N'-difurfuryl-1,2-ethanediamine (retention time 12.5 min), and about 6.0 wt% N,N,N'-trisfurfuryl-1,2-ethanediamine (retention time 14.2 min). For further use, 51.6 g / eq of AHEW was used.

[0151] Reaction product P-4: (containing N-furfuryl-1,2-ethanediamine; 3.5:1 stoichiometry, Pd / C) At room temperature, 105.2 g (1.75 mol) of ethane-1,2-diamine was initially placed in a round-bottom flask under nitrogen atmosphere. With good stirring, a solution of 48.05 g (0.5 mol) of furfural (furan-2-carbaldehyde, RCI=1) in 200 ml of isopropanol was added and stirred for another hour at 40° C. The reaction mixture was mixed with an additional 1000 ml of isopropanol and then hydrogenated in a continuous hydrogenation apparatus equipped with a Pd / C fixed bed catalyst at a hydrogen pressure of 80 bar, a temperature of 80° C. and a flow rate of 5 ml / min. To monitor the reaction, IR spectroscopy was used to measure the peak at approximately 1665 cm -1It was confirmed whether the imine band disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 °C to remove unreacted 1,2-ethanediamine, water, and isopropanol. The reaction mixture thus obtained had an amine value of 691 mg KOH / g, a viscosity of 13.5 mPa·s at 20 °C, and a GC measurement of about 72.8 wt% N-furfuryl-1,2-ethanediamine (retention time 7.3 min), about 7.8 wt% N-tetrahydrofurfuryl-1,2-ethanediamine (retention time 8.0 min), and about 3.3 wt% N,N'-difurfuryl-1,2-ethanediamine (retention time 10 min). The fraction was a clear, slightly yellowish liquid with a retention time of 11.9 min, a fraction of furan ring hydrogenated N,N'-difurfuryl-1,2-ethanediamine of about 3.0 wt% (retention time 12.5 min), a fraction of N,N,N'-trisfurfuryl-1,2-ethanediamine of about 9.9 wt% (retention time 14.2 min), and a fraction of furan ring hydrogenated N,N,N'-trisfurfuryl-1,2-ethanediamine of about 3.2 wt% (retention time 14.7 min). 55 g / eq of AHEW was used for further use.

[0152] N-Furfuryl-1,2-ethanediamine (F-EDA): 41.2 g of reaction product P-4, prepared as described above, was vacuum distilled at 70° C., collecting 25.6 g of distillate at a vapor temperature of about 50° C. and 0.1 bar. This gave a colorless liquid with an amine number of 802 mg KOH / g, an AHEW of about 46.7 g / eq, an RCI of 0.71, a viscosity at 20° C. of 3.2 mPa·s, and a GC content of about 94.6 wt. % N-furfuryl-1,2-ethanediamine (retention time 7.3 min) and about 5.3 wt. % N-tetrahydrofurfuryl-1,2-ethanediamine (retention time 8.0 min), which was used hereafter as F-EDA. 1H NMR(CDCl3):7.33(d,1H,Ar-H),6.27(m,1H,Ar-H),6.14(m,1H,Ar-H),3.76(s,2H,Ar-CH2),2.78(m,2H,NHCH2CH2),2.65(m,2H,CH2NH2),1.52(br s,3H,NH and NH2). FT-IR:3284,3043,2945,2838,1567,1504,1455,1382,1306,1219,1146,1108,1073,1009,916,883,806,738.

[0153] N,N'-Difurfuryl-1,2-ethanediamine (BisF-EDA) At room temperature, 11.12 g (0.185 mol) of 1,2-ethanediamine in 200 ml of isopropanol was initially placed in a round-bottom flask under nitrogen. With good stirring, 35.0 g (0.37 mol) of furfural (furan-2-carbaldehyde, RCI=1) was added and the mixture was stirred for another hour at 40°C. The reaction mixture was mixed with another 800 ml of isopropanol and then hydrogenated in a continuous hydrogenation apparatus equipped with a Raney nickel fixed bed catalyst at a hydrogen pressure of 65 bar, a temperature of 65°C and a flow rate of 5.5 ml / min. To monitor the reaction, IR spectroscopy was used to measure the peak at approximately 1665 cm. -1It was checked whether the imine band of 1,2-ethanediamine disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65°C to remove unreacted 1,2-ethanediamine, water, and isopropanol. This gave a clear, slightly yellowish liquid, which was vacuum distilled at 110°C-130°C and the distillate was collected at a vapor temperature of 105°C-110°C and 0.15 bar. This gave a colorless liquid with an amine value of 502 mg KOH / g, an AHEW of 110 g / eq, a viscosity of 28 mPa·s at 20°C, and a GC content of about 79.0 wt% N,N'-difurfuryl-1,2-ethanediamine (retention time 11.9 min), about 11.9 wt% furan ring hydrogenated N,N'-difurfuryl-1,2-ethanediamine (retention time 12.4-12.5 min), about 4.4 wt% N,N,N'-trisfurfuryl-1,2-ethanediamine (retention time 14.2 min), and about 3.7 wt% furan ring hydrogenated N,N,N'-trisfurfuryl-1,2-ethanediamine (retention time 14.6-14.7 min). This was used as BisF-EDA below.

[0154] N-Tetrahydrofurfuryl-1,2-ethanediamine (THF-EDA): At room temperature, 60.1 g (1 mol) of ethane-1,2-diamine was initially placed in a round-bottom flask under nitrogen atmosphere. A solution of 32.0 g (0.33 mol) of furfural in 200 ml of isopropanol was slowly added dropwise with good stirring, and stirring was continued for another hour at 40° C. An additional 300 ml of isopropanol was mixed with the reaction mixture, which was then hydrogenated in a continuous hydrogenation apparatus equipped with a Raney nickel fixed bed catalyst at a hydrogen pressure of 90 bar, a temperature of 110° C., and a flow rate of 5 ml / min. To monitor the reaction, IR spectroscopy was used to measure the peak at approximately 1665 cm -1 It was confirmed whether the imine band of 1,2-ethanediamine disappeared or not, and then the hydrogenated solution was concentrated on a rotary evaporator at 65° C. to remove unreacted 1,2-ethanediamine, water, and isopropanol.

[0155] This gave a clear, slightly yellowish liquid which was vacuum distilled at 70 °C, collecting 35.6 g of distillate at a vapor temperature of about 50 °C and 0.1 bar. This gave a colorless liquid 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 about 97 wt% N-tetrahydrofurfuryl-1,2-ethanediamine by GC (retention time 8.0 min), which was used hereafter as THF-EDA.

[0156] N-Benzyl-1,2-ethanediamine (B-EDA): 180.3 g (3 mol) of 1,2-ethanediamine was initially charged at room temperature and mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol, stirred for 2 hours, then hydrogenated in a continuous hydrogenation apparatus equipped with a Pd / C fixed bed catalyst at 80° C., 80 bar hydrogen pressure and a flow rate of 5 ml / min, and the hydrogenated solution was concentrated in a rotary evaporator at 65° C. to remove unreacted 1,2-ethanediamine, water and isopropanol. The reaction mixture thus obtained was a clear, pale yellowish liquid with a content of N-benzyl-1,2-ethanediamine of about 81% by weight (retention time 8.5 min) and a content of N,N'-dibenzylethane-1,2-diamine of about 14% by weight (retention time 14.3 min) as measured by GC. The mixture was purified by vacuum distillation at 80° C. This gave a colorless liquid with an AHEW of 50.1 g / eq and >97% N-benzyl-1,2-ethanediamine content by GC, which was used subsequently as B-EDA.

[0157] Preparation of the adduct: Addendum A1: 51.3 g of N-furfuryl-1,2-ethanediamine (F-EDA, 0.366 mol) was heated to 70°C and 45.0 g of Araldite® GY250 (0.241 mol of EP groups) was added slowly with good stirring while maintaining the temperature of the reaction mixture between 70°C and 90°C. The reaction mixture was stirred at this temperature range for 1 hour and then cooled. This gave 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.

[0158] Addendum A2: 58.6 g of N-furfuryl-1,2-ethanediamine (F-EDA, 0.418 mol) was heated to 70°C and 37.3 g of DEN® 438 (0.208 mol of EP groups) was added slowly with good stirring while maintaining the temperature of the reaction mixture between 70°C and 90°C. The reaction mixture was stirred at this temperature range for 1 hour and then cooled. This gave 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.

[0159] Addendum A3 (reference): 55.0 g of N-benzylethane-1,2-diamine (B-EDA, 0.366 mol) was heated to 70°C and 45.0 g of Araldite® GY250 (0.241 mol of EP groups) was added slowly with good stirring while maintaining the temperature of the reaction mixture between 70°C and 90°C. The reaction mixture was held in this temperature range for 1 hour and then cooled. This gave 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.

[0160] Preparation of epoxy resin composition: Examples Z-1 and Ref-1 to Ref-3 For each example, the resin and hardener components specified in Table 1 were separately heated to a temperature of 60° C. These preheated components were then used to prepare a total of 20 g of epoxy resin composition by mixing the components in the weight ratios specified in Table 1 for 15 seconds using a centrifugal mixer (SpeedMixer™ DAC150, FlackTek Inc.), and immediately thereafter tested as follows.

[0161] The mixed composition was placed in a test tube thermostated at 60°C using a water bath and a temperature sensor was placed in the center of the mixed material. This was used to determine the time it took for the mixed material to reach its maximum temperature (reported in the table as time to peak exotherm) and the maximum temperature level (peak exotherm temperature). The values ​​shown in Table 1 are the average values ​​from three measurements.

[0162] The Tg values ​​(glass transition temperature) were measured by DSC on the samples cured from the center of the test tube from the above mentioned measurements. These samples were further stored for 14 days at standard climatic conditions before the measurements. The measurements were carried out using 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).

[0163] The results are reported in Table 1.

[0164] Epoxy resin composition Z-1 is an example of the present invention, and epoxy resin compositions Ref-1 to Ref-3 are comparative examples.

[0165] [Table 1]

[0166] Examples Z-2 to Z-11 and Ref-4 to Ref-8 For each example, the raw materials of the resin components reported in Tables 2 to 4 were mixed in the specified amounts (parts by weight) using a centrifugal mixer (SpeedMixer™ DAC150, FlackTek Inc.), and stored with the exclusion of moisture.

[0167] The raw materials for the hardener components specified in Tables 2-4 were also processed and stored.

[0168] The two components of each composition were then processed using a centrifugal mixer to obtain a homogenous liquid, which was then immediately tested as follows.

[0169] Viscosity was measured as indicated at a temperature of 20° C., 5 minutes after mixing the resin and hardener components.

[0170] Gel time was determined at standard climatic conditions by moving a freshly mixed amount of about 3 g with a spatula at regular intervals until the mass gelled.

[0171] The Shore D hardness was determined according to DIN 53505 on two cylindrical test specimens (diameter 20 mm, thickness 5 mm), one stored under standard climatic conditions and the other stored at 8 °C and 80% relative humidity, the hardness was measured in each case after 1 day (after 24 hours) and after 2 days.

[0172] Furthermore, a film was applied to a glass plate with a layer thickness of 500 μm and stored / cured under standard climatic conditions. The König hardness (König pendulum hardness according to DIN EN ISO 1522) was determined for this film after 1 day, 2 days, 7 days and 14 days (1d SCC), (2d SCC), (7d SCC), (14d SCC). After 14 days, the appearance (SCC) of the film was evaluated. Transparent films with a glossy, non-sticky surface and without structure were described as "attractive". "Structure" refers to any kind of pattern or texture on the surface.

[0173] Further films were applied to glass plates with a layer thickness of 500 μm and stored / cured immediately after application at 8 ° C and 80% relative humidity for 7 days and then for 2 weeks at standard climatic conditions. 24 hours after application, a polypropylene bottle lid with a moist sponge underneath was placed on the film. After another 24 hours, the sponge and bottle lid were removed and placed in a new position on the film, and after another 24 hours they were removed and replaced, a total of 4 times. The appearance of the film was then evaluated in the same way as described for appearance (SCC) (referred to in the table as "Appearance (8 ° / 80%)"). Here, the number and nature of visible marks formed on the film as a result of placing the moist sponge or bottle lid on top were also reported in each case. The number of whitened spots means "brushing". Faintly whitened spots were marked "(1)". Clearly whitened spots were marked "1". If a ring-shaped mark was present 24 hours after application due to the sinking of the first bottle lid applied, it was reported with the term "ring". Such a ring-shaped mark indicates that the coating was not yet walkable. The König hardness of the thus cured films was then determined after 7 days at 8°C and 80% relative humidity (König (7d 8° / 80%)), and then after 2 further days at SCC (König (+2d SCC)), or after 7 days at SCC (König (+7d SCC)), or after 14 days at SCC (König (+14d SCC)).

[0174] The results are shown in Tables 2 to 4.

[0175] Epoxy resin compositions Z-2 to Z-10 are examples of the present invention, while epoxy resin compositions Ref-4 to Ref-8 are comparative examples.

[0176] [Table 2]

[0177] [Table 3]

[0178]

Table 4

Claims

1. Use of a curing agent containing at least one amine of formula (I) 【Chemical 1】 (wherein A represents a linear alkylene group having 2 to 10 carbon atoms, and X represents H or furfuryl) for curing an epoxy resin.

2. Use according to claim 1, characterized in that A represents a group 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 claim 1 or 2, characterized in that A represents 1,2-ethylene.

4. Use according to claim 1 or 2, characterized in that X represents H.

5. The amine of formula (I) has an RCI of at least 0.45, preferably at least 0.6, particularly at least 0.7, and most preferably 1, and the RCI is the ratio of the number of carbon atoms derived from bio-based raw materials to the total number of carbon atoms of the amine of formula (I). Use according to claim 1 or 2, characterized thereby.

6. The amine of formula (I) is used in the form of a reaction product obtained by subjecting furfural and hydrogen to reductive alkylation with at least one amine of the formula H ２ N-A-NH ２ and subsequently removing the unreacted amine of the formula H ２ N-A-NH ２ The use according to claim 1 or 2, characterized in that it is used in the form of a reaction product obtained from.

7. The molar ratio of the amine of the formula H ２ N-A-NH ２ to fulural is in the range of 1 to 2, preferably 1 to 1.5, and the use according to claim 6 is characterized by this.

8. X represents H, and the curing agent additionally contains the amine of formula 【Chemical 2】 in a weight ratio of the amine of formula (I) to the amine of formula 【Chemical Formula 3】 in the range of 70 / 30 to 99 / 1, preferably 80 / 20 to 98 / 2. Use according to claim 1 or 2, characterized thereby.

9. 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 mole of the amine of formula (I) per 1 mole equivalent of epoxy groups. Use according to claim 1 or 2, characterized thereby.

10. The curing agent contains at least one additional component selected from additional amines, accelerators, and diluents not according to formula (I), particularly at least one additional amine not according to formula (I). Use according to claim 1 or 2, characterized thereby.

11. The hardener contains at least one amine in which RCI is 1 as an additional amine not conforming to formula (I), in particular 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, and the RCI is a ratio of the number of carbon atoms derived from a biobased raw material to the total number of carbon atoms of the amine, The use according to claim 10, characterized in that.

12. A resin component containing at least one epoxy resin, A hardener component containing the hardener according to claim 1 or 2, An epoxy resin composition containing.

13. After mixing the resin component and the hardener component, a cured epoxy resin composition obtained from the epoxy resin composition according to claim 12.

14. Furfural and hydrogen and the reductive alkylation with an amine of the formula H ２ N-A-NH ２ are carried out at a molar ratio of the amine of the formula H ２ N-A-NH ２ in the range of 1 to 2, preferably 1 to 1.5, and subsequently the amine of the formula H ２ N-A-NH ２ is removed to a content of at most 1% by weight, preferably at most 0.5% by weight, particularly at most 0.2% by weight, based on the reaction product, and A in the formula represents a straight-chain alkylene group having 2 to 10 carbon atoms, particularly 1,2-ethylene, to obtain a reaction product.

15. A represents 1,2-ethylene, and the reaction product is based on the reaction product 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 components, in particular further by-products from the reductive alkylation, The reaction product according to claim 14, characterized in that it contains.

16. At least one formula 【Chemical Formula 4】 Of amine and at least one formula 【Chemical Formula 5】 Of amine, an amine mixture containing in a weight ratio in the range of 70 / 30 to 99 / 1, preferably 80 / 20 to 98 / 2, wherein A represents a straight-chain alkylene group having 2 to 10 carbon atoms, in particular 1,2-ethylene, Amine mixture.

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