Amine-functional adduct of an isocyanate-group-containing polymer with low monomer content

Abstract

The invention relates to an amine-functional adduct obtained from the reaction of at least one diamine of formula (I) with at least one isocyanate-group-containing polymer having an average molecular weight Mn of at least 1000 g / mol in a ratio of the number of moles of diamine of formula (I) per mole equivalent of isocyanate groups of at least 1.3, wherein the isocyanate-group-containing polymer has a content of monomeric diisocyanates of less than 0.5% by weight. The adduct is easy to produce, stable in storage, and makes it possible to produce epoxy resin adhesives which have good workability, rapid curing and good elasticity while also having high strength and / or high impact resistance.

Description

[0001] AMIN-FUNCTIONAL ADDUCT OF ISOCYANAT GROUP-CONTAINING POLYMER WITH LOW MONOMER CONTENT

[0002] Technical field

[0003] The invention relates to amine-functional adducts from the reaction of diamines with isocyanate group-containing polymers and their use in curable compositions, in particular in adhesives with high impact strength.

[0004] State of the art

[0005] Epoxy adhesives offer high bond strength on various substrates. However, they are typically not very elastic and have low impact strength. For applications requiring high impact strength or where strong vibrations and movements occur, conventional epoxy adhesives are often too brittle. For such applications, impact-modified (toughened) epoxy products have been developed, for example, for bonding in vehicle bodies requiring high crash resistance. In these products, the cured adhesive contains finely dispersed, flexible polymers bonded to the epoxy matrix as an impact modifier or toughener. These polymers absorb mechanical energy during a crash and can thus significantly reduce crack propagation in the adhesive.For example, functionalized liquid rubber, such as ATBN (amine-terminated butadiene-acrylonitrile copolymer) or ETBN (epoxy-terminated butadiene-acrylonitrile copolymer), is known as a toughener, but these are highly viscous and expensive and have disadvantages in terms of low-temperature flexibility.

[0006] US 2021 / 0198537 describes metals bonded using a toughened epoxy resin adhesive. Among the impact modifiers (tougheners) described are polyurethanes, particularly isocyanate-containing polymers, which are blocked with an epoxy resin or with cardanol. Such adhesives exhibit high cold flexibility. However, the epoxy-blocked tougheners are very viscous, and in the case of cardanol-blocked tougheners, cardanol is released during curing, which can have an undesirable softening effect in the cured adhesive and migrate out of the adhesive. US 2016 / 0280844 describes amine-functional adducts resulting from the reaction of polyether aminobenzoates with monomeric diisocyanates and their use as hardeners for epoxy resins.

[0007] US 3,248,424 describes amine-functional adducts resulting from the reaction of diamines with isocyanate-containing polyether polymers and mentions their use as hardeners for isocyanates.

[0008] US 7,001,972 describes amine-functional adducts of polyamines with isocyanate-containing polymers whose isocyanate groups are blocked by phenol-containing resins. Such adducts contain the phenol-containing resins released during this process, which is undesirable for toxicological reasons and due to migration problems.

[0009] Description of the invention

[0010] The object of the present invention is to provide a hardener that can be used as an impact modifier for epoxy resin adhesives and that overcomes the disadvantages of the prior art with regard to high viscosity and released releasers.

[0011] Surprisingly, this problem is solved with an amine-functional adduct as described in claim 1. The adduct is obtained from the reaction of at least one diamine of formula (I) with an isocyanate-containing polymer having a particularly low content of monomeric diisocyanates.

[0012] The adduct according to the invention can be produced in a simple process from readily available, inexpensive raw materials. It is stable during storage and is liquid, particularly at room temperature, and easy to handle. It is therefore particularly easy to use as a hardener and / or impact modifier for epoxy resin compositions, as well as a hardener for compositions with other reactive groups that are reactive towards amines, such as, in particular, isocyanate groups or acetoacetate groups.

[0013] The adduct according to the invention contains particularly few reaction products of diamine of formula (I) and monomeric diisocyanate. Surprisingly, it has been shown that such an adduct enables the production of epoxy resin products with particularly high strength combined with excellent elongation and / or high impact strength. The low content of monomeric diisocyanates in the isocyanate-containing polymer also allows for the production of adducts derived from highly reactive aromatic monomeric diisocyanates, such as diphenylmethane diisocyanate (MDI), whereas corresponding adducts could not be produced with a high content of monomeric MDI, as they gelled during production.

[0014] The adduct according to the invention enables epoxy resin products with very good processability, fast curing, high strength and good elongation and / or impact strength.

[0015] Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of dependent claims.

[0016] Ways to implement the invention

[0017] The invention relates to an amine-functional adduct obtained from the reaction of

[0018] - at least one diamine of formula (I),

[0019] l_l

[0020] H2N— A— N— RO

[0021] where A represents a divalent hydrocarbon residue with 2 to 25 C atoms, optionally containing ether oxygen, and R represents H or a monovalent hydrocarbon residue with 1 to 12 C atoms, optionally containing oxygen atoms,

[0022] with

[0023] - at least one isocyanate-containing polymer with an average molecular weight M n of at least 1,000 g / mol,

[0024] in a ratio of the number of moles of diamine of formula (I) per mole equivalent of isocyanate groups of at least 1.3,

[0025] wherein the isocyanate-containing polymer has a content of monomeric diisocyanates of the formula OCN—D—NCO, based on the isocyanate-containing polymer, of less than 0.5 wt%, preferably less than 0.2 wt%, and particularly less than 0.1 wt%, and D represents a divalent organic residue with 4 to 15 carbon atoms. The term "molecular weight" refers to the molar mass (in grams per mole) of a molecule. The term "mean molecular weight" refers to the number-average molecular weight M. n A polydisperse mixture of oligomers or polymeric molecules. It is determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0026] The "NCO content" refers to the percentage of isocyanate groups by weight. Substance names beginning with "poly," such as polyol, polyepoxide, or polyacetoacetate, denote substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0027] A "primary amine group" is an amine group bonded to a single organic residue and bearing two hydrogen atoms; a "secondary amine group" is an amine group bonded to two organic residues, which may also be part of a ring, and bearing one hydrogen atom; and a "tertiary amine group" is an amine group bonded to three organic residues, which may also be part of one or more rings in pairs or groups of three, and bearing no hydrogen atom. The hydrogen atoms of primary and secondary amine groups are referred to as "amine hydrogen."

[0028] The term "ammonium hydrogen equivalent weight" refers to the mass of an amine or an amine-containing composition that contains one mole equivalent of ammonium hydrogen. It is expressed in the unit "g / eq".

[0029] The term "epoxide equivalent weight" refers to the mass of an epoxy compound or composition containing one mole equivalent of epoxy groups. It is expressed in the unit "g / eq".

[0030] An adduct or composition is described as "storage-stable" if it can be stored at room temperature in a suitable container for a longer period of time, typically at least 3 months up to 6 months or more, without its application or usage properties being altered by storage to an extent relevant to its use.

[0031] Room temperature is defined as a temperature of 23 °C. The term "liquid at room temperature" means that a substance or composition exists as a liquid at 23 °C and an ambient pressure of 1 bar.

[0032] All industry standards and norms mentioned in the document refer to the versions valid at the time of the initial application.

[0033] Weight percent (wt%) denotes the mass fraction of a component of a composition or molecule, relative to the entire composition or molecule, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0034] The amine-functional adduct is free of isocyanate groups.

[0035] The amine-functional adduct is storage-stable and preferably liquid at room temperature.

[0036] The reaction product obtained from the reaction of the diamine of formula (I) with the isocyanate-containing polymer is referred to in this document as the amine-functional adduct. It typically contains a mixture of the amine-functional polymer and unreacted diamine of formula (I) and only a very small amount of reaction products of the diamine of formula (I) with monomeric diisocyanates.

[0037] In the case of a linear isocyanate group-containing polymer, the amine-functional adduct mainly contains the following polymeric adduct molecules of formula (II) and (III),

[0038] OOH JL H (II) R— N— A— NN — P — NN— A— N— R

[0039] HHHH

[0040]

[0041] where P represents the remainder of the isocyanate-containing polymer after removal of two isocyanate groups, and A and R have the meanings already mentioned. In the case of R + H, the diamine of formula (I) can also be added via the secondary amine group and, for example, form (II). 1 exhibit.

[0042]

[0043] An adduct molecule of formula (II) or (II 1 (III) is also called a "monoadduct". It contains only one P residue. An adduct molecule of formula (III) is also called a "diadduct". It contains two P residues. Additionally, the adduct also contains smaller proportions of more highly adducted components, in which more than two P residues are adducted via diamines of formula (I).

[0044] A high ratio of moles of diamine of formula (I) per mole equivalent of isocyanate groups corresponds to a high excess of diamine of formula (I) and favors a high content of monoadduct of formula (II) and a comparatively high content of unreacted diamine of formula (I). Such an adduct is comparatively low-viscosity.

[0045] A lower ratio of moles of diamine of formula (I) per mole equivalent of isocyanate groups corresponds to a lower excess of diamine of formula (I) and favors a higher content of more highly adducted components and a lower content of unreacted diamine of formula (I). Such an adduct is comparatively more viscous.

[0046] The amine-functional adduct contains only a very low content of reaction products of the diamine of formula (I) with monomeric diisocyanates. This enables the production of products with particularly high strength combined with excellent ductility and / or high impact strength, as well as the preparation of adducts derived from highly reactive aromatic diisocyanates such as diphenylmethane diisocyanate (MDI). Preferably, the ratio of the number of moles of diamine of formula (I) per mole equivalent of isocyanate groups is 1.5 to 15, more preferably 1.6 to 10, and particularly 1.7 to 7. Such an adduct is particularly suitable for the described uses. It allows for an advantageous combination of low viscosity and high polymer content.

[0047] Preferably, the two nitrogen atoms of the diamine of formula (I) are separated from each other by at least two carbon atoms.

[0048] The amine groups of the diamine of formula (I) are preferably each bonded to an aliphatic carbon atom. Such amines are particularly advantageous from a toxicological point of view.

[0049] Preferably, A represents an alkylene residue with 2 to 13 C atoms, optionally containing cyclic or aromatic components, or a polyether residue with 6 to 25 C atoms, preferably 9 to 15 C atoms.

[0050] Particularly preferably, A represents an alkylene residue with 6 to 13 C atoms, preferably 8 to 12 C atoms, or a polyether residue with 6 to 25 C atoms, preferably 9 to 15 C atoms.

[0051] Preferably, the diamine of formula (I) has a total of at least 6 carbon atoms, and in particular at least 8 carbon atoms. Such a diamine is comparatively low in volatility and has little odor.

[0052] In the event that the diamine of formula (I) has fewer than 6 C atoms, unreacted portions of the diamine of formula (I) are preferably removed from the obtained adduct, in particular by distillation.

[0053] However, adducts of diamines of formula (I) with a total of at least 6 C atoms, in particular at least 8 C atoms, are preferred, in which unreacted parts of the diamine of formula (I) have not been removed.

[0054] Preferably, the diamine of formula (I) is selected from the list consisting of 1,5-diamino-2-methylpentane (MPMD), 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2,5-dimethyl-1,6-hexanediamine, 1,9-nonanediamine, 2,2(4),4-trimethyl-hexane-1-6-diamine (TMD), 1,10-decanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine (IPDA), 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-Bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), Bis(4-aminocyclohexyl)methane, 1,3-Bis(aminomethyl)benzene (MXDA), 3,6-Dioxaoctane-1,8-diamine, 4,7-Dioxadecane-1,10-diamine, 4,9-Dioxadodecane-1,12-diamine, 4,7,10-Tri-oxatridecane-1,13-diamine, Medium molecular weight polyoxypropylenediamines M n from 200 to 500 g / mol, N-Benzyl-1,2-ethanediamine, N-Furfuryl-1,2-ethanediamine, N-Tetrahydrofurfuryl-1,2-ethanediamine, N-Benzyl-1,3-bis(aminomethyl)benzene and N-Cyclohexyl-1,3-propanediamine.

[0055] Preferred among these is 1,8-octanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2(4),4-trimethylhexane-1-6-diamine (TMD), 1,3-bis(aminomethyl)cyclohexane, 1,2-diaminocyclohexane, isophoronediamine (IPDA), 2(4)-methyl-1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 1,3-bis(aminomethyl)benzene (MXDA), 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, and polyoxypropylenediamines with medium molecular weight M. n from 200 to 300 g / mol, Benzyl-1,2-ethanediamine, N-Furfuryl-1,2-ethanediamine or N-Tetrahydrofurfuryl-1,2-ethanediamine.

[0056] Particularly preferred as the diamine of formula (I) is 2,2(4),4-trimethylhexane-1,6-diamine (TMD), 1,3-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene (MXDA), 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine or polyoxypropylenediamines with medium molecular weight M nfrom 200 to 300 g / mol such as Jeffamine D-230 (from Huntsman) or corresponding types from BASF or Nitroil.

[0057] In a particularly preferred embodiment of the invention, the diamine of formula (I) is free of cyclic structures, in particular selected from 2, 2(4), 4-trimethylhexane-1-6-diamine (TMD), 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxa-tridecane-1,13-diamine and polyoxypropylenediamine with medium molecular weight M n from 200 to 300 g / mol. Such diamines of formula (I) enable a particularly high impact strength. In a particularly preferred embodiment of the invention, the diamine of formula (I) is a polyetheramine, in particular selected from the list consisting of 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine and polyoxypropylenediamines with medium molecular weight M nfrom 200 to 500 g / mol. A polyetheramine as a diamine of formula (I) enables a particularly high impact strength.

[0058] A polyoxypropylenediamine with medium molecular weight M is particularly preferred as a diamine of formula (I). n from 200 to 300 g / mol. This results in epoxy resin adhesives with particularly high impact strength.

[0059] In a preferred embodiment of the invention, R in formula (I) represents H. Such a diamine has two primary amine groups. It is particularly readily available, enables the formation of adducts with particularly high reactivity towards epoxides, and allows for particularly high impact strengths.

[0060] In a further embodiment of the invention, R in formula (I) represents a monovalent hydrocarbon residue, optionally containing oxygen atoms and having 1 to 12 carbon atoms. Preferably, R is selected from the list consisting of methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, benzyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, furfuryl, tetrahydrofurfuryl, and naphthylmethyl.

[0061] Of these, methyl, ethyl, hexyl, 2-ethylhexyl, benzyl, furfuryl or tetrahydrofurfuryl are preferred. Benzyl is particularly preferred.

[0062] Such a diamine possesses a primary and a secondary amine group. It enables the production of adducts with particularly low viscosity and / or particularly high polymer content.

[0063] Preferably, the isocyanate-containing polymer has a medium molecular weight M nfrom 1,000 to 20,000 g / mol, especially 1,000 to 10,000 g / mol. The preferred diisocyanate is the formula OCN— D— NCO selected from the list consisting of 1,5-pentane diisocyanate (PDI), 1,6-hexane diisocyanate (HDI), 2,2(4),4-trimethyl-1,6-hexane diisocyanate (TMDI), 1-methyl-2,4(6)-diisocyano-natocyclohexane, isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane, 4(2),4'-diphenylmethane diisocyanate (MDI) and 2,4(6)-toluene diisocyanate (TDI).

[0064] HDI, IPDI, or MDI are preferred.

[0065] IPDI is particularly preferred. Such an adduct is especially low-viscosity and allows for particularly good ductility combined with high strength.

[0066] The most preferred adduct is diphenylmethane diisocyanate (MDI), especially 4,4'-diphenylmethane diisocyanate. Such an adduct enables particularly high impact strength.

[0067] Preferably, the isocyanate-containing polymer has an NCO content of 1 to 9 wt%, more preferably 1.5 to 6.5 wt%. The NCO content is determined in particular by reacting the isocyanate groups with an excess of dibutylamine and back-titration of the unreacted dibutylamine with aqueous hydrochloric acid.

[0068] Preferably, the isocyanate group-containing polymer has a medium isocyanate functionality of 1.5 to 4, particularly preferably 1.7 to 3, particularly 1.8 to 2.5, most preferably 1.9 to 2.0.

[0069] Preferably, the isocyanate group-containing polymer contains a polyether, polyester or hydrocarbon backbone, particularly preferably a polyether or a hydrocarbon backbone, most preferably a polyether backbone.

[0070] A polyether backbone preferably consists of poly(oxy-1,4-butylene), poly(oxy-1,3-propylene), or poly(oxy-1,2-propylene), optionally containing oxy-1,2-ethylene units, particularly at the chain ends. A poly(oxy-1,2-propylene) backbone, optionally with oxy-1,2-ethylene units at the chain ends, is particularly preferred.

[0071] Preferably, the isocyanate-containing polymer is liquid at room temperature, particularly with a viscosity at 20 °C of 0.5 to 75 Pa s, preferably 1 to 50 Pa s, particularly 2 to 30 Pa s, measured using a cone-plate viscometer with a cone diameter of 10 mm, a cone angle of 1°, a cone tip-plate distance of 0.05 mm and a shear rate of 10 s'. 1 .

[0072] Preferably, the isocyanate group-containing polymer is a reaction product of at least one monomeric diisocyanate of the formula OCN— D— NCO with at least one polymeric polyol in a molar NCO / OH ratio of 3 / 1 to 10 / 1, preferably 4 / 1 to 8 / 1, and subsequent removal of the monomeric diisocyanate by means of a suitable separation process down to a content based on the isocyanate group-containing polymer of less than 0.5 wt%, preferably less than 0.2 wt%, in particular less than 0.1 wt%.

[0073] The reaction preferably takes place in the absence of moisture at 20 to 160 °C, particularly 40 to 140 °C, optionally in the presence of a suitable catalyst.

[0074] Preferably, the monomeric diisocyanate is removed by thin-film distillation or short-path distillation under vacuum.

[0075] The isocyanate-containing polymer has a particularly narrow molecular weight distribution and a particularly low viscosity. It enables adducts according to the invention with a particularly low content of reaction products from diamines of formula (I) and monomeric diisocyanate.

[0076] Preferred polymeric polyols for the production of the isocyanate group-containing polymer are polyether polyols, in particular polyoxyalkylene diols or polyoxyalkylene triols, especially polymerization products of 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, oxetane or tetrahydrofuran, optionally with the use of ethylene oxide, wherein these are optionally polymerized by means of a starter molecule with two or more active hydrogen atoms.

[0077] Preferred polyether polyols are poly(oxy-1,4-butylene)diols, also called polytetrahydrofurans, poly(oxy-1,3-propylene)diols, poly(oxy-1,2-propylene)diols, poly(oxy-1,2-propylene)triols, or ethylene oxide-terminated (EO-endcapped) poly(oxy-1,2-propylene)diols or triols. The latter are obtained by further alkoxylating poly(oxy-1,2-propylene)diols or triols with ethylene oxide after completion of the polypropoxylation reaction, thereby ultimately giving them primary hydroxyl groups. They contain, in particular, up to 25 wt% oxy-1,2-ethylene units based on the total polyol.

[0078] Preferred polyether polyols have a degree of unsaturation of less than 0.02 mEq / g, in particular less than 0.01 mEq / g.

[0079] - Polyester polyols from the polycondensation of dicarboxylic acids with di- or trihydric alcohols, in particular adipic acid, sebacic acid, dodecanedicacarboxylic acid or a dimer fatty acid, with di- and / or trioiums such as in particular 1,6-hexanediol, neopentyl glycol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerol or castor oil.

[0080] - Polyhydroxy functional fats or oils, especially natural fats or oils, such as castor oil, derivatives of castor oil or vegetable oil-based polyols, such as those available under the trade name Sovermol® (from BASF).

[0081] - Polyetherpolyesterpolyols.

[0082] - Polyhydrocarbon polyols, especially hydrogenated polybutadiene polyols.

[0083] Liquid polymeric polyols at room temperature are preferred.

[0084] Preferably, the polymeric polyol has an OH number of 12 to 175 mg KOH / g, preferably 18 to 120 mg KOH / g, and particularly 25 to 60 mg KOH / g. The polymeric polyol is preferably selected from the list consisting of polyether polyols, polyester polyols, and hydrocarbon polyols.

[0085] Preferred are polyether polyols, in particular poly(oxy-1,4-butylene)diols, poly(oxy-1,3-propylene)diols, poly(oxy-1,2-propylene)diols, poly(oxy-1,2-propylene)triols or ethylene oxide-terminated poly(oxy-1,2-propylene)diols or triols.

[0086] Particularly preferred are poly(oxy-1,2-propylene)diols, poly(oxy-1,2-propylene)triols or ethylene oxide-terminated poly(oxy-1,2-propylene)triols.

[0087] Poly(oxy-1,2-propylene)diols are most preferred.

[0088] The reaction of the diamine of formula (I) with the isocyanate group-containing polymer to form the adduct according to the invention preferably takes place at a temperature of 10 to 50 °C, in particular 15 to 30 °C.

[0089] Preferably, the diamine of formula (I) is initially taken and the isocyanate-containing polymer is slowly added with thorough stirring. Alternatively, the reaction to form the adduct can be carried out in a continuous process.

[0090] Preferably, the reaction is carried out in the presence of an organic solvent. The solvent can be added together with the diamine of formula (I), and / or the isocyanate-containing polymer is added dissolved in a solvent. Preferably, the solvent is removed from the resulting adduct after the reaction, in particular by distillation, so that the adduct is ultimately largely free of organic solvents.

[0091] Suitable solvents include, in particular, acetone, methyl acetate, ethyl acetate or isopropanol.

[0092] The reaction is complete when the reaction product is free of isocyanate groups. The decrease in the isocyanate group content can be monitored, in particular, by titrimetric analysis or infrared spectroscopy.

[0093] The reaction yields the amine-functional adduct according to the invention.

[0094] Preferably, the amine-functional adduct has an average amine hydrogen equivalent weight of 80 to 800 g / eq, preferably 120 to 600 g / eq, and particularly 140 to 400 g / eq. The amine hydrogen equivalent weight can be calculated from the diamine of formula (I) and the NCO content of the isocyanate-containing polymer.

[0095] Preferably, the adduct is liquid at room temperature. In particular, the adduct has a viscosity at 25 °C of 1 to 200 Pa s, preferably 1 to 100 Pa s, and more preferably 1 to 50 Pa s, measured using a cone-plate viscometer with a cone diameter of 10 mm, a cone angle of 1°, a cone-tip-plate distance of 0.05 mm, and a shear rate of 10 s⁻¹. -1

[0096] Preferably, the adduct contains less than 5 parts by weight, preferably less than 1 part by weight, in particular less than 0.5 parts by weight, organic solvents with a boiling point at normal pressure of less than 250 °C, based on 100 parts by weight of reaction product of diamine of formula (I) and isocyanate group-containing polymer.

[0097] Another object of the invention is a method for producing the amine functional adduct comprising the steps

[0098] (i) Presenting the diamine of formula (I),

[0099] (ii) Addition of the isocyanate group-containing polymer,

[0100] (iii) React until all isocyanate groups have reacted,

[0101] wherein the reaction may optionally take place in the presence of an organic solvent and the solvent is preferably removed from the reaction product obtained after the reaction by a suitable process, in particular by distillation.

[0102] Preferably, the isocyanate-containing polymer is slowly added in step (ii) with thorough stirring. Optionally, the isocyanate-containing polymer is diluted with an organic solvent.

[0103] The reaction in step (iii) preferably takes place at a temperature of 5 to 70 °C, particularly 15 to 40 °C. In a preferred embodiment of the process, the reaction in step (iii) takes place at a temperature in the range of 80 to 120 °C, preferably without the presence of an organic solvent. In this step, the diamine of formula (I) is preferably introduced in step (i) at a temperature in the range of 80 to 120 °C, and the isocyanate-containing polymer is added in step (ii) at a temperature in the range of 80 to 120 °C.

[0104] In the adduct according to the invention, the content of reaction products from diamines of formula (I) and monomeric diisocyanates is particularly low. Reaction products from diamines of formula (I) and monomeric diisocyanates have, in particular, formula (IV), where A, D, and R have the meanings already mentioned.

[0105] OOHLH (IV)

[0106] R— N— A— NN — D — NN— A— N— R

[0107] HHHH

[0108] Surprisingly, it has been shown that the adduct according to the invention, with its particularly low content of reaction products of formula (IV), exhibits particularly good elongation combined with high strength when used in epoxy resin compositions. The elongation and strength are significantly higher than with a corresponding adduct based on an isocyanate-containing polymer with a high content of monomeric diisocyanate, as a comparison of compositions Z1 and Z2 (Ref.) in the examples demonstrates.

[0109] Furthermore, the low content of monomeric diisocyanates in the isocyanate-containing polymer surprisingly also enables the formation of adducts derived from the highly reactive diphenylmethane diisocyanate (MDI) as a monomeric diisocyanate, as a comparison of adducts N-2 and R-2 in the examples shows. Adduct N-2 according to the invention was readily producible, whereas the reference adduct R-2, based on the corresponding isocyanate-containing polymer with a high content of monomeric MDI, gelled during preparation and could not be used. The amine-functional adduct is advantageously used for curing compounds with at least two reactive groups that are reactive towards amines.

[0110] Another object of the invention is the use of the described amine-functional adduct as a hardener in a hardenable composition containing reactive groups selected from epoxide group, isocyanate group, (meth)acrylate group, 1,3-ketoester group and carboxylic anhydride group.

[0111] Preferred epoxy groups are glycidyl ether groups, especially those from commercially available epoxy resins.

[0112] The isocyanate groups preferred are aliphatic isocyanate groups, in particular those of 1,5-pentane diisocyanate (PDI), 1,6-hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), perhydro-2,4(6)-toluene diisocyanate (HeTDI), perhydro-4,4'-diphenylmethane diisocyanate (H12MDI), 2,2(4),4-trimethyl-1,6-hexane diisocyanate (TMDI), cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1,3-bis(isocyano-natomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, m-xylene diisocyanate, or p-xylene diisocyanate. Oligomers of HDI are particularly preferred.

[0113] Preferred (meth)acrylate groups are those of multifunctional acrylates and methacrylates, in particular acrylates and methacrylates of aliphatic polyethers, polyesters, novolacs, phenols, aliphatic or cycloaliphatic alcohols, glycols and polyester glycols, as well as mono- and polyalkoxylated derivatives of the aforementioned compounds, for example ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate. Dipentaerithritol tetra(meth)acrylate, dipentaerithritol penta(meth)acrylate, dipentaerithritol hexa(meth)acrylate, as well as tris-(2-hydroxyethyl)-isocyanurate tri(meth)acrylate, tris-(2-hydroxyethyl)-cyanurate tri(meth)acrylate or N,N',N"-Tris-(meth)acryloyl-perhydrotriazine, as well as adducts of epoxy resins with acrylic and methacrylic acid or (meth)acrylate-terminated polyurethane polymers.

[0114] Preferred 1,3-keto ester groups are acetoacetate groups, in particular polyacetoacetates of commercially available diols, triols or tetroyls such as, in particular, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, 1,10-decanediol, 1,12-dodecanediol, polytetrahydrofurandiols, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, propoxylated and / or ethoxylated glycerol, propoxylated and / or ethoxylated 1,1,1-trimethylolpropane, poly(oxy-1,2-propylene)diols, EO-terminated poly(oxy-1,2-propylene)diols, di- or trimer fatty acid-based polyester polyols, castor oil, castor oil derivatives or hydroxylated vegetable oils.

[0115] Suitable carboxylic acid anhydride groups are, in particular, those of cyclic anhydrides of polycarboxylic acids, especially of pyromellitic dianhydride.

[0116] The amine-functional adduct is particularly preferred for use as a hardener in a curable composition containing epoxy groups. It enables the production of epoxy resin products with good processability at ambient temperatures, high strength, and particularly high impact resistance.

[0117] Another object of the invention is therefore a hardener for epoxy resins containing the described amine-functional adduct.

[0118] Preferably, the hardener contains at least one further amine with at least three hydrogen amines. Preferably, such a further amine is different from the diamine of formula (I) used to prepare the adduct. Suitable further amines with at least three hydrogen amines are commercially available polyamines with aliphatic amine groups, such as those commonly used for curing epoxy resins.

[0119] Preferred are the aforementioned diamines of formula (I), as well as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)1,2-ethanediamine (N4-amine), bis(1,6-hexylene)triamine (BHMT), N-2-benzylaminoethyl-N'-2-aminoethyl-1,2-ethanediamine, N-3-benzylaminopropyl-N'-3-aminopropyl-1,2-ethanediamine, 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), phenalkamines or phenalkamides, which are reaction products of cardanol with aldehydes, in particular formaldehyde, and polyamines, and amine-functional adducts of these amines with Epoxides, as well as combinations of two or more of these amines.

[0120] Particularly preferred are isophorone diamine (IPDA), 1,3-bis(aminomethyl)benzene (MXDA), 1,3-bis(aminomethyl)cyclohexane, N-benzyl-1,2-ethanediamine, N-2-benzyl-aminoethyl-N'-2-aminoethyl-1,2-ethanediamine, N-3-benzylaminopropyl-N'-3-amino-propyl-1,2-ethanediamine, polyetheramines, phenalkamines and / or an amine-functional adduct of N-benzyl-1,2-ethanediamine with a bisphenol AD ​​glycidyl ether.

[0121] Particularly preferred are isophorone diamine (IPDA), 1,3-bis(aminomethyl)benzene (MXDA), 1,3-bis(aminomethyl)cyclohexane, polyetheramines and / or phenalkamines.

[0122] Preferably, the hardener for epoxy resins contains more than one additional amine, in particular two or three additional amines with at least three hydrogen amines.

[0123] Preferably, the hardener for epoxy resins contains at least one further ingredient selected from curing accelerators, fillers, and pigments. Suitable curing accelerators are, in particular, phenols, phenolic resins, or Mannich bases such as, in particular, 2,4,6-tris(dimethylaminomethyl)phenol; organic carboxylic acids such as salicylic acid or 2-nitrobenzoic acid; organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, or 4-dodecylbenzenesulfonic acid; nitrates such as, in particular, calcium nitrate; tertiary amines; imidazoles; ammonium salts; amidines; or guanidines.

[0124] Preferably, the hardener contains 2,4,6-tris(dimethylaminomethyl)phenol

[0125] Suitable fillers include, in particular, ground or precipitated calcium carbonate, which may be coated with fatty acids, especially stearates; barite; talc; quartz flour; quartz sand; silicon carbide; ferrous mica; dolomite; wollastonite; kaolin; mica (potassium aluminum silicate); molecular sieves; aluminum oxide; zinc oxide; aluminum hydroxide; magnesium hydroxide; silicic acid; pyrogenic silica; cement; gypsum; fly ash; soot; graphite; ground fillers from agricultural sources, such as olive kernel flour or nutshell flour; hollow spheres, especially glass spheres; metal powders such as aluminum, copper, iron, zinc, silver, or steel; or PVC powder.

[0126] Suitable pigments include in particular titanium dioxides, iron oxides, chromium(III) oxides, organic pigments, carbon black or corrosion protection pigments such as phosphates, orthophosphates or polyphosphates, which contain as a counterion in particular chromium, zinc, aluminium, calcium, strontium or a combination of these metals.

[0127] Additionally, the hardener may contain other components, in particular

[0128] - other amines, in particular amines with two hydrogen amines such as N,N'-dibenzyl-1,2-ethanediamine, monoamines such as benzylamine or furfurylamine, polyamidoamines such as reaction products of dimer fatty acids with DETA, TETA or TEPA, Mannich bases or aromatic polyamines such as 4(2),4'-diaminodiphenylmethane or 2,4(6)-toluenediamine,

[0129] - Compounds containing mercapto groups, - further impact modifiers such as, in particular, amine-functional butadienes, - surfactant additives, in particular defoamers, deaerators, wetting agents, dispersants or leveling agents,

[0130] - Solvents or thinners, in particular benzyl alcohol, styrene-ized phenol, 2-phenoxyethanol, 2-benzyloxyethanol, aromatic hydrocarbon resins containing phenol groups, diisopropylnaphthalene, isopropyl biphenyls, cardanol or phenol-formaldehyde novolacs.

[0131] Preferably, the hardener for epoxy resins contains less than 5 wt%, in particular less than 1 wt%, organic solvents with a boiling point at normal pressure of less than 250 °C based on the total hardener.

[0132] Preferably, the hardener for epoxy resins contains less than 10% water by weight based on the total hardener.

[0133] Preferably, the hardener for epoxy resins has an amine hydrogen equivalent weight of 50 to 140 g / eq, preferably 60 to 130 g / eq, and in particular 80 to 120 g / eq, based on the total weight of all amine hydrogen-containing components.

[0134] Preferably, the hardener is used in such an amount that the molar ratio of the hydrogen amines to the epoxy groups is in the range of 0.5 to 1.5, in particular 0.8 to 1.2.

[0135] The hardener for epoxy resins enables epoxy resin products with good processability, fast curing, high strength and particularly high impact resistance.

[0136] A further object of the invention is an epoxy resin composition comprising at least one epoxy resin and at least the described amine-functional adduct, or the described hardener for epoxy resins containing the described amine-functional adduct. A suitable epoxy resin is obtained in particular from the reaction of epichlorohydrin with polyols, polyphenols, or amines, or from the oxidation of olefins.

[0137] Aromatic epoxy resins are preferred, in particular the glycidyl ethers of bisphenol A, bisphenol F, or bisphenol A / F, where A represents acetone and F represents 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 those derived from 2,4'- or 2,2'-hydroxyphenylmethane.

[0138] - Dihydroxybenzene derivatives such as resorcinol, hydroquinone or catechin, - 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.bu- tylphenyl)propan, 2,2-Bis(4-hydroxyphenyl)butan (Bisphenol B), 3,3-Bis(4- hydroxyphenyl)pentan, 3,4-Bis(4-hydroxyphenyl)hexan, 4,4-Bis(4-hydroxy- phenyl)heptan, 2,4-Bis(4-hydroxyphenyl)-2-methylbutan, 2,4-Bis(3,5-dimethyl-4- hydroxyphenyl)-2-methylbutan, 1 , 1 -Bis(4-hydroxyphenyl)cyclohexan (Bisphenol Z), 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan (Bisphenol TMC), 1,1- Bis(4-hydroxyphenyl)-1 -phenylethan, 1 ,4-Bis[2-(4-hydroxyphenyl)-2-propyl]- benzol (Bisphenol P), 1 ,3-Bis[2-(4-hydroxyphenyl)-2-propyl]benzol (Bisphenol M), 4,4'-Dihydroxydiphenyl (DOD), 4,4'-Dihydroxybenzophenon, Bis(2-hydroxy- naphth-1-yl)methan, Bis(4-hydroxynaphth-1-yl)methan, 1 ,5-Dihydroxynaph- thalin, Tris(4-hydroxyphenyl)methan, 1 ,1 ,2,2-Tetrakis(4-hydroxyphenyl)ethan, Bis(4-hydroxyphenyl)ether oder Bis(4-hydroxyphenyl)sulfon,.

[0139] - Novolaks, which are in particular condensation products of phenol or cresols with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde or 2-ethylhexanal or benzaldehyde or furfural,

[0140] - aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi-(N-methyl)amine, 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline (Bisaniline P) or 4,4'-[1,3-phenylene-bis(1-methylethylidene)]bisaniline (Bisaniline M). Other suitable epoxy resins are aliphatic or cycloaliphatic poly-epoxides, in particular

[0141] - Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2 to Cso 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;

[0142] - a hydrogenated bisphenol A, F or A / F liquid resin, or the glycidylation products of hydrogenated bisphenol A, F or A / F;

[0143] - an N-glycidyl derivative of amides or heterocyclic nitrogenous bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin.

[0144] - Epoxy resins from the oxidation of olefins, such as in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene.

[0145] Other suitable epoxy resins are those produced from the reaction of bio-based hydroxy-functional raw materials with epichlorohydrin, in particular vanillin-based epoxy resins such as diglycidy leather of vanillin alcohol, or glycerol-based epoxy resins.

[0146] Preferably, the epoxy resin is a liquid resin or a mixture containing two or more liquid epoxy resins.

[0147] The term "epoxy liquid resin" refers to a technical polyepoxide with a glass transition temperature below 25°C.

[0148] If necessary, additional amounts of epoxy resin may be used.

[0149] Preferred epoxy resins are aromatic liquid epoxy resins, in particular bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, or phenol formalaldehyde novolac glycidyl ether, or mixtures thereof, especially a mixture of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether. Such epoxy resins are highly reactive, hydrophobic, and exhibit a low viscosity for epoxy resins. They offer good processability, rapid curing, and high adhesive strength.

[0150] Aromatic epoxy liquid resins with a mean epoxy equivalent weight of 150 to 250 g / eq are preferred, in particular bisphenol A and / or bisphenol F diglycidyl ethers.

[0151] In addition to the epoxy resin, at least one epoxy group-containing reactive diluent may be included.

[0152] Suitable for this purpose are, in particular, 1,4-butanediol diglycidyl ethers, 1,6-hexanediol diglycidyl ethers, trimethylolpropane di- or triglycidyl ethers, phenylglycidyl ethers, cresyl glycidyl ethers, guaiacol glycidyl ethers, 4-methoxyphenyl glycidyl ethers, pn-butylphenyl glycidyl ethers, p-tert-butylphenyl glycidyl ethers, 4-nonylphenyl glycidyl ethers, 4-dodecylphenyl glycidyl ethers, cardanol glycidyl ethers, benzyl glycidyl ethers, allyl glycidyl ethers, butyl glycidyl ethers, hexyl glycidyl ethers, 2-ethylhexyl glycidyl ethers, or glycidyl ethers of natural alcohols such as, in particular, Cs to C10, C12 to C14, or C13 to cis alkyl glycidyl ethers.

[0153] Preferred reactive diluents include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, or p-tert-butylphenyl glycidyl ether.

[0154] The epoxy resin composition may contain other components, in particular

[0155] - further impact modifiers such as, in particular, reaction products of hydrophobic polyols or isocyanate group-containing polymers with epoxy resins or isocyanate group-containing polymers with blocked isocyanate groups, especially with cardanol-blocked isocyanate groups,

[0156] - other reactive diluents, in particular epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, butyrolactone, carbonates, aldehydes, isocyanates or silicones containing reactive groups,

[0157] - Fillers, especially those already mentioned,

[0158] - Pigments, in particular those already mentioned, - surfactant additives, in particular defoamers, deaerators, wetting agents, dispersants, leveling agents or dispersed paraffin waxes,

[0159] - Solvents or thinners, especially those already mentioned,

[0160] - 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,

[0161] - Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers,

[0162] - Nanofillers, especially carbon nanotubes,

[0163] - Rheology modifiers, especially thickeners or anti-settling agents,

[0164] - Adhesion improvers, especially organoalkoxysilanes,

[0165] - Flame-retardant substances, in particular the fillers already mentioned: aluminum hydroxide or magnesium hydroxide, antimony trioxide, antimony pentoxide, boric acid (B(OH)3), zinc borate, zinc phosphate, melamine borate, melamine cyanurate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, polybrominated diphenyl oxides or diphenyl ethers, phosphates such as, in particular, diphenylcresyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol diphosphate oligomer, tetraphenylresorcinol dihosphite, ethylenediamine diphosphate, bisphenol A bis(diphenyl phosphate), tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, Tris(dichloroisopropyl) phosphate, Tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, tetrabromobisphenol A, bis(2,3-dibromopropyl ether) of bisphenol A, brominated Epoxy resins, ethylene bis(tetrabromophthalimide), ethylene bis(dibromonorbornanedicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane,Bis(hexachlorocyclopentadieno)cyclooctane or chlorinated paraffins, or,

[0166] - Stabilisers against oxidation, heat, light or UV radiation or biocides. Preferably, the epoxy resin composition contains less than 5% by weight, in particular less than 1% by weight, organic solvents with a boiling point at normal pressure of less than 250 °C based on the total epoxy resin composition.

[0167] Preferably, the epoxy resin composition contains less than 5% by weight of water based on the total epoxy resin composition.

[0168] Preferably, the molar ratio of the hydrogen amines to the epoxy groups in the epoxy resin composition is in the range of 0.5 to 1.5, in particular 0.8 to 1.2.

[0169] Preferably, the weight ratio between the amine-functional adduct and epoxy resins in the epoxy resin composition is in the range of 5 / 95 to 70 / 30, more preferably 7 / 93 to 50 / 50, and particularly 10 / 90 to 35 / 65. Such an epoxy resin composition has high strength and high impact resistance.

[0170] Preferably, the epoxy resin composition comprises a resin component and a hardener component, each of which is independently stable and stored in separate containers. For use, the resin and hardener components are mixed together shortly before or during application, at which point the curing process begins.

[0171] The resin component comprises at least one epoxy resin, optionally at least one epoxy-group-containing reactive diluent, and optionally further components reactive with amine hydrogens. The hardener component comprises the amine-functional adduct and optionally further components reactive with epoxy groups, in particular further amines with at least three amine hydrogens. Other components of the epoxy resin composition, such as fillers, pigments, accelerators, or surfactant additives, may be present as components of the resin or the hardener component, or as components of both. The resin and hardener components of the epoxy resin composition are stored in separate containers.The components are shelf-stable, 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 use.

[0172] A suitable container for storing the resin or hardener component is in particular a barrel, a pail, a bag, a bucket, a can, a cartridge or a tube.

[0173] The resin and hardener components are mixed shortly before or during application. The mixing ratio is preferably chosen such that the molar ratio of the epoxy-reactive groups to the epoxy groups is in the range of 0.5 to 1.5, particularly 0.8 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.

[0174] The components are mixed using a suitable method, in particular a static mixer or a dynamic mixer. Mixing can be continuous or batch-wise.

[0175] Mixing and application can take place at ambient temperature, which is typically in the range of 5 to 45 °C, preferably 10 to 35 °C.

[0176] If the components are mixed before application, care must be taken to ensure that not too much time elapses between mixing the components and the application, and that the application takes place within the pot life.

[0177] The curing of the epoxy resin composition begins with the mixing of the ingredients or components through a chemical reaction. The hydrogen amines from the adduct according to the invention, and any other amines and any other groups reactive towards epoxy groups, react with the epoxy groups, causing their rings to open. As a result primarily of these reactions, the composition polymerizes and thus cures. The curing process typically extends over several hours to several days. The duration depends, among other things, on the temperature, the reactivity of the components, their stoichiometry, and any accelerators present.

[0178] The curing can take place at ambient conditions, in particular at 5 to 45 °C, preferably at 10 to 35 °C, or it can be accelerated and / or completed by heating, in particular by heating to a temperature of 50 to 130 °C, preferably 70 to 120 °C, preferably for 5 minutes to 24 hours, particularly for 30 minutes to 4 hours.

[0179] The epoxy resin composition is preferably applied to at least one substrate.

[0180] Suitable substrates include in particular

[0181] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, gypsum or natural stones such as granite or marble;

[0182] - Repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

[0183] - Metals or alloys such as aluminium, iron, steel, copper, other non-ferrous metals, including surface-treated metals or alloys such as galvanised or chromium-plated metals;

[0184] - Asphalt or bitumen;

[0185] - Leather, textiles, paper, wood, with resins, for example phenolic, melamine or epoxy resins, bonded wood materials, resin-textile composites or other so-called polymer composites;

[0186] - Plastics such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, either untreated or surface-treated, for example by means of plasma, corona or flames;

[0187] - Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GFRP), natural fiber-reinforced plastics (NFRP) and sheet molding compounds (SMC); - Insulating materials, in particular foams, especially made of EPS, XPS, PUR, PIR, aerogel or foamed glass (Foamglas), or fibers made of rock wool or glass wool,

[0188] - coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

[0189] - Coatings, paints or varnishes.

[0190] The substrates can be pretreated before application if necessary, in particular by physical and / or chemical cleaning processes or by applying an activator or a primer.

[0191] Two identical or two different substrates can be bonded together.

[0192] The application and curing process yields the hardened epoxy resin composition. This is characterized by good workability, high strength combined with good elongation, and / or high impact resistance.

[0193] The epoxy resin composition is suitable for a wide variety of uses. It is particularly suitable as an adhesive, casting resin, coating, or filler.

[0194] The epoxy resin composition is particularly suitable as an adhesive.

[0195] Such an epoxy resin adhesive is particularly suitable for bonding applications where high strength and high impact resistance or crash resistance are required.

[0196] Preferably, the epoxy resin adhesive comprises

[0197] - a resin component containing at least one epoxy resin, and

[0198] - a hardener component containing the described amine-functional adduct and at least one further amine with at least three amine hydrogens. Suitable further amines with at least three amine hydrogens include those already mentioned above, in particular isophorone diamine (IPDA), 1,3-bis(aminomethyl)benzene (MXDA), 1,3-bis(aminomethyl)cyclohexane, N-benzyl-1,2-ethanediamine, N-2-benzylaminoethyl-N'-2-aminoethyl-1,2-ethanediamine, N-3-benzyl-aminopropyl-N'-3-aminopropyl-1,2-ethanediamine, polyetheramines, phenalkamines and / or an amine-functional adduct of N-benzyl-1,2-ethanediamine with a bisphenol A diglycidyl ether. The further amine with at least three amine hydrogens is preferably different from the diamine of formula (I), which was used to prepare the amine-functional adduct.

[0199] Such an epoxy resin adhesive exhibits high impact strength combined with high strength (tensile strength and modulus of elasticity).

[0200] Preferably, such an epoxy resin adhesive has a tensile strength of at least 15 MPa, particularly preferably at least 18 MPa, and in particular at least 20 MPa, determined according to EN ISO 527 on dumbbell-shaped test specimens with a thickness of 2 mm, a length of 75 mm, a web length of 30 mm and a web width of 4 mm, cured for 24 h in standard climate followed by 24 h at 80 °C followed by 3 days in standard climate.

[0201] Preferably, such an epoxy resin adhesive has a modulus of elasticity at 0.05 to 0.25% elongation of at least 1,500 MPa, particularly at least 1,700 MPa, determined according to EN ISO 527 on dumbbell-shaped test specimens with a thickness of 2 mm, a length of 75 mm, a web length of 30 mm, and a web width of 4 mm, cured for 24 hours in standard climate conditions followed by 24 hours at 80 °C followed by 3 days in standard climate conditions. Preferably, such an epoxy resin adhesive has high impact strength.

[0202] The epoxy resin adhesive preferably has a paste-like consistency.

[0203] Preferably, the adhesive can be applied from a dual cartridge with separate chambers for the resin and hardener components using an attached static mixer. It is advantageous if the adhesive has a low viscosity. Furthermore, such an adhesive preferably has a mixing ratio by volume between the resin and hardener components of approximately 1:1. Such an adhesive is particularly easy to process using a dual cartridge and attached static mixer.

[0204] The amine-functional adduct enables epoxy resin compositions, especially epoxy resin adhesives, with good processability at ambient temperatures, high strength with good elongation and / or high impact strength.

[0205] Examples

[0206] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described embodiments.

[0207] A temperature of 23+1 °C and a relative humidity of 50+5% is referred to as "standard climate" ("NC").

[0208] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH.

[0209] "AHEW" stands for amine hydrogen equivalent weight

[0210] "EEW" stands for epoxy equivalent weight.

[0211] Description of the measurement methods:

[0212] Viscosity was measured on a thermostatically controlled cone-plate viscometer Rheotec RC30 (cone diameter 10 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s). _1 ) measured.

[0213] Infrared spectra (FT-IR) were measured as undiluted films on a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal ATR measuring unit with a diamond crystal. The absorption bands are given in wavenumbers (cm⁻¹). -1 ).

[0214] The content of monomeric diisocyanate was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivation using N-propyl-4-nitrobencylamine. Substances and abbreviations used:

[0215] B-EDA: N-Benzyl-1,2-ethanediamine, 150.2 g / mol, AHEW 50.1 g / eq, prepared as described below

[0216] MXDA: 1,3-bis(aminomethyl)benzene, 136.2 g / mol, AHEW 34 g / eq (from Mitsubishi Gas Chemical)

[0217] D-230: Polyoxypropylenediamine, medium molecular weight M napprox. 240 g / mol, AHEW 60 g / eq (Jeffamine® D-230, from Huntsman) BADGE: Bisphenol A diglycidyl ether (Araldite® GY-250, EEW 188 g / eq, from Huntsman)

[0218] B-EDA (N-benzyl-1,2-ethanediamine) was prepared by mixing 180.3 g of 1,2-ethanediamine with a solution of 106.0 g of benzaldehyde in 1200 ml of isopropanol, stirring for 2 hours at room temperature, and then hydrogenating the mixture at 80°C, 80 bar hydrogen pressure, and a flow rate of 5 ml / min on a continuous hydrogenation apparatus with a Pd / C fixed-bed catalyst. The hydrogenated solution was then concentrated by rotary evaporation, removing unreacted 1,2-ethanediamine, water, and isopropanol. The resulting reaction mixture was purified by distillation at 80°C under vacuum, yielding a colorless liquid with an N-benzyl-1,2-ethanediamine content of > 97%, as determined by GC.

[0219]

[0220] Polymer P-1:

[0221] 600 g of polyoxypropylenediol (Voranol® 1010 L, OH number 112 mg KOH / g, from Dow) were reacted with 533.3 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) at 80 °C according to a known procedure to form a reaction mixture with an NCO content of 15.6 wt%. Subsequently, the volatile components, in particular unreacted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160 °C, pressure 0.1 to 0.005 mbar), yielding a polymer with a viscosity at 20 °C of 10.7 Pa s, an NCO content of 5.0 wt%, and a monomeric isophorone diisocyanate content of 0.03 wt%. Polymer P-2:

[0222] 600 g of polyoxypropylenediol (Voranol® 1010 L, OH number 112 mg KOH / g, from Dow) and 266.6 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80 °C according to a known process to form a polymer with a viscosity at 20 °C of 26.5 Pas, an NCO content of 5.1 wt% and a content of monomeric isophorone diisocyanate (IPDI) of more than 1 wt%.

[0223] Polymer P-3:

[0224] 727 g of polyoxypropylenediol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro) and 273 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted at 80 °C according to a known procedure to form a reaction mixture with an NCO content of 7.6 wt%. Subsequently, the volatile components, in particular monomeric 4,4'-diphenylmethane diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180 °C, pressure 0.1 to 0.005 mbar, condensation temperature 47 °C), yielding a polymer with a viscosity at 20 °C of 17.4 Pa s, an NCO content of 1.8 wt% and a monomeric 4,4'-diphenylmethane diisocyanate (MDI) content of 0.08 wt%.

[0225] Polymer P-4:

[0226] 400 g of polyoxypropylenediol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro) and 52 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted at 80 °C according to a known process to form a polymer with a viscosity at 20 °C of 43.6 Pa s, an NCO content of 1.8 wt% and a content of monomeric 4,4'-diphenylmethane diisocyanate (MDI) of 2.3 wt%.

[0227] Polymer P-5:

[0228] 818 g of polyoxypropylenediol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro) and 227 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80 °C according to a known procedure to form a reaction mixture with an NCO content of 6.6 wt%. Subsequently, the volatile components, in particular unreacted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160 °C, pressure 0.1 to 0.005 mbar), yielding a polymer with a viscosity at 20 °C of 12.7 Pa s, an NCO content of 1.9 wt%, and a monomeric isophorone diisocyanate (IPDI) content of 0.03 wt%.

[0229] Production of amine-functional adducts:

[0230] Adducts N-1 to N-5 and R-1 to R-2:

[0231] The amount (in parts by weight) of the specified diamine, as indicated in Table 1, was reacted at room temperature in the presence of 200 ml of solvent with the specified amount (in parts by weight) of the specified isocyanate-containing polymer until no isocyanate groups were detectable by IR spectroscopy. The solvent was then removed by rotary evaporator. Isopropanol was used as the solvent for the preparation of adducts N-1, R-1, and N-3. Ethyl acetate was used as the solvent for the preparation of adducts N-2, R-2, N-4, and N-5.

[0232] Adduct N-6:

[0233] The amount (in parts by weight) of diamine specified in Table 1 was placed at a temperature of 100 °C. The isocyanate-containing polymer specified in Table 1 was preheated to 100 °C and slowly added to the diamine in the specified amount (in parts by weight) and reacted until no more isocyanate groups were detectable by IR spectroscopy.

[0234] The properties of the adducts are given in Table 1.

[0235] The AHEW of the adducts was calculated, assuming that for adducts of polyamines with one primary and one secondary amine group, primary and secondary amine groups were each converted at half their number.

[0236] The adducts R-1 and R-2, designated with "(Ref.)", are comparative examples. They are each based on an isocyanate-containing polymer with a high content of monomeric diisocyanate.

[0237] >

[0238]

[0239] Table 1: Amine-functional adducts N-1 to N-6 and R-1 to R-2.

[0240] Adduct R-2 (Ref.), based on polymer P-4 with a content of 2.3 wt% monomeric MDI, gelled during preparation and was therefore unsuitable for use in an epoxy resin composition. In contrast, adduct N-2, based on polymer P-3 with a content of only 0.08% monomeric MDI, was readily producible. It exhibited a manageable viscosity and was advantageously suited for use in an epoxy resin composition.

[0241] Use in epoxy resin compositions:

[0242] Composition C1 to C6:

[0243] For each composition, the amount of bisphenol A diglycidyl ether (in parts by weight) specified in Table 2 was used as the resin component. The adduct and, if applicable, MXDA, also specified in Table 2, were used as the hardener component in the indicated amounts (in parts by weight). Subsequently, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer and immediately tested as follows:

[0244] The viscosity (5') was measured 5 min after mixing the resin and hardener components.

[0245] The gelling time was determined by stirring a freshly mixed quantity of approximately 3 g at regular intervals with a spatula under standard climate conditions until the mixture gelled.

[0246] The mechanical properties tensile strength, elongation at break, and modulus of elasticity (0.5–1%) were determined by curing the mixed composition in a silicone mold to form dumbbell-shaped specimens (2 mm thick, 75 mm long, 30 mm web length, 4 mm web width) for 24 hours under standard climate conditions, followed by 24 hours at 80 °C, and then for 3 days under standard climate conditions. These specimens were then removed from the mold and tested according to EN ISO 527 at a tensile speed of 10 mm / min. The glass transition temperature (Tg) was determined by DSC on samples cured as described above for the determination of mechanical properties. The measurement was performed using a Mettler Toledo DSC 3+ 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).

[0247] The results are shown in Table 2.

[0248] The composition marked "(Ref.)" is a comparative example.

[0249]

[0250] Table 2: Composition and properties of C1 to C6.

[0251] "nb" stands for "not determined"

[0252] Table 2 shows that compositions C1 and C3 to C6, each containing an adduct according to the invention, exhibited high elongation at break combined with high strength (tensile strength and modulus of elasticity). A comparison between composition C1 and composition C2 (Ref.) shows that the adduct N-1 according to the invention, based on polymer P-1 with a content of only 0.03 wt.% monomeric IPDI, exhibited significantly higher elongation at break combined with higher strength (tensile strength and modulus of elasticity) compared to adduct R-1, based on the corresponding polymer with a high content of > 1 wt.% monomeric IPDI. This is surprising, as one would expect a high content of monomeric IPDI to result in higher strength. Furthermore, compositions with higher elongation would typically be expected to have lower strength.

[0253] Compositions C7 to C9: (epoxy resin adhesives)

[0254] A resin component was prepared by mixing the following ingredients in the specified amounts (in parts by weight, wt) and storing them under exclusion of moisture: 40 wt bisphenol A diglycidyl ether (Epikote® 828 LVEL, from Westlake Epoxy), 16 wt bisphenol F diglycidyl ether (Epikote® 862, from Westlake Epoxy), 6 wt butanediol diglycidyl ether (Araldite® DY-D, from Huntsman), 20 wt reaction product U1, prepared as described below, 1 wt 3-glycidoxypropyltrimethoxysilane, 12 wt fillers, and 5 wt pyrogenic silica.

[0255] The reaction product U1 was prepared by reacting 5687 g of polyetherdiol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro) and 712 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) at 80 °C until a constant NCO content of 1.9 wt.% was reached, followed by reaction with Cardanol (Cardolite® NC-700, from Cardolite) for 2 h at 80 °C until no isocyanate groups were detectable by FT-IR.

[0256] Furthermore, one hardener component each was prepared by mixing the following ingredients in the specified amounts (in parts by weight, wt) and storing them under exclusion of moisture: 14 wt modified polyamine (Ancamine® 2712M, AHEW 95 g / eq, from Evonik), 6 wt polyetheramine (Jeffamine® D-230, AHEW 60 g / eq, from Huntsman), 6 wt phenalkamine (Cardolite® LITE 2002, AHEW 104 g / eq, from Cardolite), 5 wt 2,4,6-tris(dimethylaminomethyl)phenol (Ancamine® K54, from Evonik), 44 wt fillers, 6 wt pigments, 4 wt pyrogenic silica and 15 wt of the adduct specified in Table 3.

[0257] Subsequently, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer in the mixing ratio specified in Table 3, and this liquid was immediately tested as follows:

[0258] The mechanical properties tensile strength, elongation at break and modulus of elasticity 0.25% (at 0.05 to 0.25% elongation) were determined by curing the mixed composition in a silicone mold for 7 days under standard climatic conditions to form dumbbell-shaped test specimens (thickness 1 mm, length 75 mm, web length 30 mm, web width 4 mm), then removing them from the mold and testing them according to EN ISO 527 at a tensile speed of 2 mm / min.

[0259] The dynamic resistance was determined in an impact peel test according to ISO 11343 as a measure of impact toughness. For this test, specimens were produced with two bonded, electrolytically zinc-plated DC04 steel plates measuring 90 x 20 x 0.8 mm, with a bonding area of ​​20 x 30 mm and an adhesive thickness of 0.3 mm. Curing was carried out either for 7 days in standard climate conditions (indicated in Table 3 as "7d NK"), or for 1 hour in standard climate conditions followed by 1 hour at 80 °C, followed by 1 day in standard climate conditions (indicated in Table 3 as "1h 80°C"). The impact peel resistance was measured at an impact velocity of 2 m / s.

[0260] The results are shown in Table 3.

[0261]

[0262] Table 3: Composition and properties of C7 to C9.

[0263] 1 Resin component / hardener component (weight)

[0264] Table 3 shows that compositions C7 to C9 had very good impact strength combined with high strength (tensile strength and modulus of elasticity).

[0265] Use as a hardener for acetoacetates:

[0266] Composition C10:

[0267] 100 parts by weight of adduct N-3 were mixed with 60.3 parts by weight of triacetoacetate-1, the preparation of which is described below, using a centrifugal mixer and tested as follows: The gelling time was determined by moving a freshly mixed quantity of approximately 3 g at regular intervals with a spatula under standard climate conditions until the mass gelled.

[0268] The Shore A hardness was determined according to DIN 53505 on test specimens (diameter 20 mm, thickness 5 mm) hardened for 7 days in standard climate.

[0269] The gelling time was 10 minutes.

[0270] The Shore A hardness was 68.

[0271] The hardened composition was glass-like and solid, with a non-sticky surface.

[0272] Triacetoacetate-1 was prepared by reacting 50 g (0.49 mol OH) propoxylated 1,1,1-trimethylolpropane (Desmophen® 4011 T, OH number 550 mg KOH / g, from Covestro) with 67 g (0.52 mol) ethyl acetoacetate and 0.1 g tetra-n-butyl titanate (Tyzor® TnBT, from Dorf Ketal) under vacuum and removal of volatile components at a temperature of 80 to 140 °C. A clear, colorless liquid with a viscosity of 0.8 Pa s at 20 °C and a calculated acetoacetate equivalent weight of 186 g / eq was obtained.

Claims

Patent claims:

1. Amine-functional adduct obtained from the reaction of - at least one diamine of formula (I), l_l H2N— A— N— R 0) where A represents a divalent hydrocarbon residue with 2 to 25 C atoms, optionally containing ether oxygen, and R represents H or a monovalent hydrocarbon residue with 1 to 12 C atoms, optionally containing oxygen atoms, with - at least one isocyanate-containing polymer with an average molecular weight M n of at least 1,000 g / mol, in a ratio of the number of moles of diamine of formula (I) per mole equivalent of isocyanate groups of at least 1.3, wherein the isocyanate group-containing polymer has a content of monomeric diisocyanates of the formula OCN— D— NCO based on the isocyanate group-containing polymer of less than 0.5 wt%, preferably less than 0.2 wt%, in particular less than 0.1 wt%, and D represents a divalent organic residue with 4 to 15 C atoms.

2. Adduct according to claim 1, characterized in that the ratio of the number of moles of diamine of formula (I) per mole equivalent of isocyanate groups is 1.5 to 15, preferably 1.6 to 10, in particular 1.7 to 7.

3. Adduct according to one of claims 1 or 2, characterized in that the diamine of formula (I) is selected from the list consisting of 1,5-diamino-2-methylpentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2,5-dimethyl-1,6-hexanediamine, 1,9-nonanediamine, 2,2(4),4-trimethylhexane-1,6-diamine, 1,10-decanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-Bis(aminomethyl)bicyclo[2.2.1]heptane, Bis-(4-aminocyclohexyl)methane, 1,3-Bis(aminomethyl)benzene, 3,6-Dioxaoctane-1,8-diamine, 4,7-Dioxadecane-1,10-diamine, 4,9-Dioxadodecane-1,12-diamine, 4,7,10-Trioxatridecane-1,13-diamine, Polyoxypropylenediamines with medium molecular weight M nfrom 200 to 500 g / mol, N-Benzyl-1,2-ethanediamine, N-Furfuryl-1,2-ethanediamine, N-Tetrahydrofurfuryl-1,2-ethanediamine, N-Benzyl-1,3-bis(aminomethyl)benzene and N-Cyclohexyl-1,3-propanediamine.

4. Adduct according to any one of claims 1 to 3, characterized in that the diamine of formula (I) is a polyetheramine, in particular selected from the list consisting of 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine and polyoxypropylenediamines with average molecular weight M n from 200 to 500 g / mol.

5. Adduct according to any one of claims 1 to 4, characterized in that the monomeric diisocyanate of formula OCN— D— NCO is selected from the list consisting of 1,5-pentane diisocyanate, 1,6-hexane diisocyanate, 2,2(4),4-trimethyl-1,6-hexane diisocyanate, 1-methyl-2,4(6)-diisocyanatocyclohexane, isophorone diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 4(2),4'-diphenylmethane diisocyanate and 2,4(6)-toluene diisocyanate.

6. Adduct according to any one of claims 1 to 5, characterized in that the monomeric diisocyanate of formula OCN— D— NCO is a diphenylmethane diisocyanate, in particular 4,4'-diphenylmethane diisocyanate.

7. Adduct according to any one of claims 1 to 6, characterized in that the isocyanate group-containing polymer has an NCO content of 1 to 9 wt%, preferably 1.5 to 6.5 wt%.

8. Adduct according to any one of claims 1 to 7, characterized in that the isocyanate group-containing polymer is a reaction product of at least one monomeric diisocyanate of the formula OCN— D— NCO with at least one polymeric polyol in a molar NCO / OH ratio of 3 / 1 to 10 / 1 and subsequent removal of the monomeric diisocyanate by means of a suitable separation process down to a content based on the isocyanate group-containing polymer of less than 0.5 wt%, preferably less than 0.2 wt%, in particular less than 0.1 wt%.

9. Adduct according to claim 8, characterized in that the polymeric polyol is selected from the list consisting of polyether polyols, polyester polyols and hydrocarbon polyols.

10. Adduct according to any one of claims 1 to 9, characterized in that the adduct has an average amine hydrogen equivalent weight of 80 to 800 g / eq, preferably 120 to 600 g / eq, in particular 140 to 400 g / eq.

11. Method for producing the adduct according to any one of claims 1 to 10, comprising the steps (i) Presenting the diamine of formula (I), (ii) Addition of the isocyanate group-containing polymer, (iii) React until all isocyanate groups have reacted, wherein the reaction may optionally take place in the presence of an organic solvent and the solvent is preferably removed from the reaction product obtained after the reaction by a suitable process, in particular by distillation.

12. Use of the adduct according to any one of claims 1 to 10 as a hardener in a hardenable composition containing reactive groups selected from epoxide group, isocyanate group, (meth)acrylate group, 1,3-ketoester group and carboxylic anhydride group.

13. Hardener for epoxy resins containing the adduct according to any one of claims 1 to 10.

14. Hardener according to claim 13, characterized in that it contains at least one further amine with at least three hydrogen amines.

15. Epoxy resin composition comprising at least one epoxy resin and at least one adduct according to any one of claims 1 to 9 or the hardener for epoxy resins according to any one of claims 12 to 14.

16. Epoxy resin composition according to claim 15, characterized in that the weight ratio between the amine-functional adduct and epoxy resins is in the range of 5 / 95 to 70 / 30, preferably 7 / 93 to 50 / 50, in particular 10 / 90 to 35 / 65.

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