Amine-functional adduct of an isocyanate-group-containing polymer with polybutadiene chains

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 a polybutadiene chain content of at least 20% by weight 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 amine-functional adduct is liquid at room temperature and storage-stable. The amine-functional adduct can be produced using a simple method and makes it possible to produce epoxy resin adhesives which have good workability, high strength and very high impact resistance.

Description

[0001] AMINE-FUNCTIONAL ADDUCT OF ISOCYANAT GROUP-CONTAINING POLYMER WITH POLYBUTADIENE CHAINS

[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 polybutadiene chain content of at least 20 wt%. The adduct according to the invention can be prepared in a simple process from readily available, inexpensive raw materials. It is stable in storage, liquid 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.

[0012] The adduct according to the invention is particularly suitable as a component of a hardener for epoxy resins. The adduct according to the invention enables good processability, high strength, and particularly high impact resistance. Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

[0013] Ways to implement the invention

[0014] The invention relates to an amine-functional adduct obtained from the reaction of

[0015] - at least one diamine of formula (I),

[0016] l_l

[0017] H2N— A— N— RO

[0018] 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,

[0019] with

[0020] - at least one isocyanate-containing polymer with an average molecular weight M n of at least 1,000 g / mol and a polybutadiene chain content of at least 20 wt% based on the isocyanate group-containing polymer,

[0021] in a ratio of the number of moles of diamine of formula (I) per mole equivalent of isocyanate groups of at least 1.3,

[0022] the amine-functional adduct is liquid at room temperature and stable during storage.

[0023] The term "molecular weight" refers to the molar mass (in grams per mole) of a molecule. The "mean molecular weight" is 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.

[0024] 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. 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 (two or three at a time), and bearing no hydrogen atom. The hydrogen atoms of primary and secondary amine groups are referred to as "amine hydrogen."

[0025] 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".

[0026] 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".

[0027] 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.

[0028] A dashed line in the formulas in this document represents the bond between a structural unit and the associated molecular residue.

[0029] A temperature of 23 °C is referred to as "room temperature".

[0030] 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.

[0031] All industry standards and norms mentioned in the document refer to the versions valid at the time of the initial application.

[0032] 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.

[0033] The amine-functional adduct is free of isocyanate groups.

[0034] 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).

[0035] In the case of a linear isocyanate group-containing polymer, the amine-functional adduct contains, in addition to unreacted diamine of formula (I), mainly the following adduct molecules of formula (II) and (III),

[0036] OO

[0037] <

[0038]

[0039] 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.

[0040]

[0041] An adduct molecule of formula (II) or (II 1The adduct molecule of formula (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). In the case of a trifunctional isocyanate-containing polymer, the monoadduct has, in particular, formula (I1a) and the diadduct has, in particular, formula (I1l), whereby in the case of R + H, the diamine of formula (I) may also be adducted via the secondary amine group.

[0042]

[0043] 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) or (Ha) and a comparatively high content of unreacted diamine of formula (I). Such an adduct is comparatively low-viscosity.

[0044] 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.

[0045] Preferably, 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, and particularly 1.7 to 7. Such an adduct is especially suitable for the described uses. It enables an advantageous combination of low viscosity and high polymer content. Preferably, the two nitrogen atoms of the diamine of formula (I) are separated from each other by at least two carbon atoms.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] Preferably, the diamine of formula (I) has a total of at least 6 carbon atoms, in particular at least 8 carbon atoms. Such a diamine is comparatively low in volatility and has little odor.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] Preferred among these are 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.

[0054] 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.

[0055] 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.

[0056] 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 adducts with particularly high reactivity towards epoxides, and allows for particularly high impact strengths. 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.

[0057] Of these, methyl, ethyl, hexyl, 2-ethylhexyl, benzyl, furfuryl or tetrahydrofurfuryl are preferred. Benzyl is particularly preferred.

[0058] 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.

[0059] Preferably, the isocyanate-containing polymer has a medium molecular weight M n from 1,000 to 15,000 g / mol, especially 1,500 to 10,000 g / mol.

[0060] Preferably, the isocyanate-containing polymer has an NCO content of 1.5 to 6 wt%, preferably 2 to 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.

[0061] Preferably, the isocyanate group-containing polymer has a medium isocyanate functionality of 1.8 to 4, particularly preferably 1.9 to 3, especially 2 to 3.

[0062] Preferably, the polybutadiene chain content in the isocyanate-containing polymer is 30 to 90 wt%, more preferably 30 to 70 wt%, and particularly 40 to 60 wt%. Such a polymer is particularly compatible with epoxy resin compositions and enables exceptionally high impact strength.

[0063] The polybutadiene chains contain predominantly structural elements of formula (IV) and possibly structural elements of formula (V) and / or (VI).(IV)

[0064] (V)

[0065]

[0066] (VI)

[0067] In a preferred embodiment of the invention, the isocyanate group-containing polymer contains, in addition to polybutadiene chains, polyether chains, in particular poly(oxy-1,4-butylene) chains. Such an adduct is particularly compatible with epoxy resin compositions.

[0068] A particularly preferred isocyanate group-containing polymer contains polybutadiene chains and poly(oxy-1,4-butylene) chains in a weight ratio of 30 / 70 to 70 / 30, in particular 40 / 60 to 60 / 40, and is in particular free of further polymer chains.

[0069] Preferably, the isocyanate-containing polymer is liquid at room temperature, particularly with a viscosity at 20 °C of 5 to 500 Pa s, preferably 10 to 300 Pa s, particularly 20 to 150 Pa s, measured by means of 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 .

[0070] Preferably, the isocyanate group-containing polymer is a reaction product of at least one monomeric diisocyanate with at least one polybutadiene polyol and optionally at least one further polyol in a molar NCO / OH ratio of at least 1.5, preferably at least 1.8, preferably under exclusion of moisture at 20 to 160 °C, in particular 40 to 140 °C, optionally in the presence of a suitable catalyst.

[0071] Preferably, the molar NCO / OH ratio is in the range of 1.5 / 1 to 2.5 / 1, particularly 1.8 / 1 to 2.5 / 1.

[0072] Preferably, the monomeric diisocyanate is 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)-diisocyanatocyclohexane, isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (MDI), 4(2),4'-diphenylmethane diisocyanate (MDI) and 2,4(6)-toluene diisocyanate (TDI).

[0073] HDI or IPDI is particularly preferred, IPDI is especially preferred.

[0074] A suitable polybutadiene polyol is particularly obtainable by polymerization of 1,3-butadiene and allyl alcohol in a suitable ratio, or by oxidation of suitable polybutadienes.

[0075] Preferably, the polybutadiene polyol has a medium molecular weight M n from 1,000 to 4,000 g / mol, in particular 2,500 to 3,000 g / mol. Furthermore, the polybutadiene polyol preferably exhibits a medium OH functionality of 2 to 3.

[0076] A particularly suitable polybutadiene polyol is Poly bd® R45 HTLO (from Resin Solutions).

[0077] Preferably, in the production of the isocyanate-containing polymer, in addition to at least one polybutadiene polyol, at least one further polyol is present, preferably at least one polyether polyol with an average molecular weight M. nfrom 800 to 4,000 g / mol, in particular at least one poly(oxy-1,4-butylene)diol with an average molecular weight M n from 1,500 to 2,500 g / mol.

[0078] A weight ratio between the polybutadiene polyol and the other polyol of 30 / 70 to 70 / 30, in particular 40 / 60 to 60 / 40, is preferred.

[0079] 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 5 to 70 °C, in particular 15 to 40 °C.

[0080] Preferably, the diamine of formula (I) is initially supplied 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. The reaction is preferably carried out in the presence of an organic solvent. The solvent can be supplied together with the diamine of formula (I), and / or the isocyanate-containing polymer can be added dissolved in a solvent. Preferably, the solvent is removed from the resulting adduct after the reaction, particularly by distillation, so that the adduct is ultimately largely free of organic solvents.

[0081] Suitable solvents include, in particular, acetone, methyl acetate, ethyl acetate or isopropanol.

[0082] 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.

[0083] The reaction yields the amine-functional adduct according to the invention. As already mentioned, it typically contains a mixture of unreacted diamine of formula (I) and adducted molecules in which diamines of formula (I) are adducted to isocyanate groups via urea bonds.

[0084] Surprisingly, it has been shown that the amine-functional adduct, when used in epoxy resin compositions, enables particularly high impact strength at high strength.

[0085] 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.

[0086] In particular, the adduct has a viscosity at 25 °C of 10 to 500 Pa s, preferably 50 to 400 Pa s, as measured by 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 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.

[0087] Another object of the invention is a method for producing the amine functional adduct comprising the steps

[0088] (i) Presenting the diamine of formula (I),

[0089] (ii) Addition of the isocyanate group-containing polymer,

[0090] (iii) React until all isocyanate groups have reacted,

[0091] wherein the reaction preferably takes place in the presence of an organic solvent and the solvent is preferably removed from the reaction product obtained after the reaction by means of a suitable process, in particular by distillation.

[0092] Preferably, the isocyanate-containing polymer is slowly added in step (ii) with thorough stirring. The isocyanate-containing polymer is preferably diluted with an organic solvent.

[0093] The reaction in step (iii) preferably takes place at a temperature of 5 to 70 °C, in particular 15 to 40 °C.

[0094] In a preferred embodiment of the invention, the reaction in step (iii) takes place without the presence of organic solvents, preferably at a temperature of 80 to 140 °C, in particular 90 to 130 °C.

[0095] The amine-functional adduct is advantageously usable for curing compounds with at least two reactive groups that are reactive towards amines.

[0096] A further aspect of the invention is the use of the described amine-functional adduct as a hardener in a curable composition containing reactive groups selected from an epoxy group, an isocyanate group, a (meth)acrylate group, a 1,3-keto ester group, and a carboxylic anhydride group. Glycidyl ether groups, particularly those from commercially available epoxy resins, are preferred as the epoxy group.

[0097] The isocyanate groups preferred are aliphatic isocyanate groups, in particular those of 1,5-pentane diisocyanate (HDI), 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(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, m-xylene diisocyanate, or p-xylene diisocyanate. Oligomers of HDI are particularly preferred.

[0098] 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.

[0099] 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, derivatives of castor oil or hydroxylated vegetable oils.

[0100] Suitable carboxylic acid anhydride groups are, in particular, those of cyclic anhydrides of polycarboxylic acids, especially of pyromellitic dianhydride.

[0101] 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.

[0102] Another object of the invention is therefore a hardener for epoxy resins containing the described amine-functional adduct.

[0103] Preferably, the hardener contains at least one further amine with at least three amine hydrogens. Preferably, such further amine is different from the diamine of formula (I) which was used to prepare the adduct.

[0104] Suitable additional amines with at least three hydrogen amines are commercially available polyamines with aliphatic amine groups, such as those commonly used for curing epoxy resins.

[0105] 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)propylaminojpropylamine (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.

[0106] 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.

[0107] Particularly preferred are isophorone diamine (IPDA), 1,3-bis(aminomethyl)benzene (MXDA), 1,3-bis(aminomethyl)cyclohexane, polyetheramines and / or phenalkamines.

[0108] 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.

[0109] Preferably, the hardener for epoxy resins contains at least one further ingredient selected from curing accelerators, fillers and pigments.

[0110] Suitable accelerators for curing are in particular phenols, phenol resins or Mannich bases such as especially 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 especially calcium nitrate, tertiary amines, imidazoles, ammonium salts, amidines or guanidines.

[0111] Preferably, the hardener contains 2,4,6-tris(dimethylaminomethyl)phenol. Suitable fillers are, in particular, ground or precipitated calcium carbonate, which is optionally coated with fatty acids, especially stearates, barite, talc, quartz flour, quartz sand, silicon carbide, micaceous iron oxide, dolomite, wollastonite, kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, silica, pyrogenic silica, cement, gypsum, fly ash, soot, graphite, ground fillers from agricultural sources such as, in particular, olive kernel flour or nutshell flour, hollow spheres, in particular glass spheres, metal powders such as aluminum, copper, iron, zinc, silver or steel, or PVC powder.

[0112] Suitable pigments include, in particular, titanium dioxides, iron oxides, chromium(III) oxides, organic pigments, carbon black or corrosion protection pigments such as, in particular, phosphates, orthophosphates or polyphosphates, which contain, as a counterion, in particular chromium, zinc, aluminium, calcium, strontium or a combination of these metals.

[0113] Additionally, the hardener may contain other components, in particular

[0114] - 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,

[0115] - Compounds containing mercapto groups,

[0116] - further impact modifiers such as, in particular, amine-functional butadienes, - surfactant additives, in particular defoamers, deaerators, wetting agents, dispersants or leveling agents,

[0117] - Solvents or thinners, in particular benzyl alcohol, styrene-based phenol, 2-phenoxyethanol, 2-benzyloxyethanol, aromatic hydrocarbon resins containing phenol groups, diisopropylnaphthalene, isopropyl biphenyls, cardanol or phenol-formaldehyde novolacs. Preferably, the hardener for epoxy resins 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 hardener.

[0118] Preferably, the hardener for epoxy resins contains less than 10% water by weight based on the total hardener.

[0119] 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.

[0120] 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.

[0121] The hardener for epoxy resins enables epoxy resin products with good processability, fast curing, high strength and particularly high impact resistance.

[0122] Another 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.

[0123] A suitable epoxy resin is obtained in particular from the reaction of epichlorohydrin with polyols, polyphenols or amines, or from the oxidation of olefins.

[0124] Aromatic epoxy resins are preferred, in particular the glycidyl ethers of bisphenol A, bisphenol F or bisphenol A / F, where A stands for acetone and F for formaldehyde, which served as starting materials for the production of these bisphenols. In the case of bisphenol-F, positional isomers may also be present, in particular derived from 2,4'- or 2,2'-hydroxyphenylmethane, dihydroxybenzene derivatives such as resorcinol, hydroquinone or 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,.

[0125] - 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,

[0126] - 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).

[0127] Other suitable epoxy resins are aliphatic or cycloaliphatic poly-epoxides, in particular

[0128] - 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;

[0129] - a hydrogenated bisphenol A, F or A / F liquid resin, or the glycidylation products of hydrogenated bisphenol A, F or A / F;

[0130] - an N-glycidyl derivative of amides or heterocyclic nitrogenous bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin.

[0131] - Epoxy resins from the oxidation of olefins, such as in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene.

[0132] 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.

[0133] Preferably, the epoxy resin is a liquid resin or a mixture containing two or more liquid epoxy resins.

[0134] The term "epoxy liquid resin" refers to a technical polyepoxide with a glass transition temperature below 25°C.

[0135] If necessary, additional amounts of epoxy resin may be used.

[0136] 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.

[0137] Aromatic liquid epoxy resins with an average epoxy equivalent weight of 150 to 250 g / eq are preferred, in particular bisphenol A and / or bisphenol F diglycidyl ethers. In addition to the epoxy resin, at least one epoxy-containing reactive diluent may be included.

[0138] 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.

[0139] Preferred reactive diluents include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, or p-tert-butylphenyl glycidyl ether.

[0140] The epoxy resin composition may contain other components, in particular

[0141] - 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,

[0142] - other reactive diluents, in particular epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, butyrolactone, carbonates, aldehydes, isocyanates or silicones containing reactive groups,

[0143] - Fillers, especially those already mentioned,

[0144] - Pigments, especially those already mentioned,

[0145] - surface-active additives, in particular defoamers, deaerators, wetting agents, dispersants, leveling agents or dispersed paraffin waxes,

[0146] - Solvents or thinners, especially those already mentioned,

[0147] - 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,

[0148] - Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers,

[0149] - Nanofillers, especially carbon nanotubes,

[0150] - Rheology modifiers, especially thickeners or anti-settling agents,

[0151] - Adhesion improvers, especially organoalkoxysilanes,

[0152] - 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,

[0153] - Stabilisers against oxidation, heat, light or UV radiation or biocides.

[0154] Preferably, the epoxy resin composition 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 epoxy resin composition.

[0155] Preferably, the epoxy resin composition contains less than 5% by weight of water based on the total epoxy resin composition. 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, particularly 0.8 to 1.2.

[0156] 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.

[0157] Preferably, the epoxy resin composition comprises a resin component and a hardener component, each of which is independently stable and stored in separate containers. To use the epoxy resin composition, the resin and hardener components are mixed together shortly before or during application, at which point the curing process begins.

[0158] 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.

[0159] 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 any significant change in their respective properties. Suitable containers for storing the resin or hardener components include, in particular, a drum, pail, bag, bucket, can, cartridge, or tube.

[0160] 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.

[0161] The components are mixed using a suitable method, in particular a static mixer or a dynamic mixer. Mixing can be continuous or batch-wise.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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. Curing can take place at ambient conditions, particularly at 5 to 45 °C, preferably at 10 to 35 °C, or it can be accelerated and / or completed by heating, particularly by heating to a temperature of 50 to 130 °C, preferably 70 to 120 °C, preferably for 5 minutes to 24 hours, and particularly for 30 minutes to 4 hours.

[0166] The epoxy resin composition is preferably applied to at least one substrate.

[0167] Suitable substrates include in particular

[0168] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, gypsum or natural stones such as granite or marble;

[0169] - Repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

[0170] - 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;

[0171] - Asphalt or bitumen;

[0172] - 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;

[0173] - 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;

[0174] - fiber-reinforced plastics, such as carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GFRP), natural fiber reinforced plastics (NFRP) and sheet moulding compounds (SMC);

[0175] - 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, - coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

[0176] - Coatings, paints or varnishes.

[0177] 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.

[0178] Two identical or two different substrates can be bonded together.

[0179] The application and curing process yields the hardened epoxy resin composition. This is characterized by good workability, high strength, and particularly high impact resistance.

[0180] The epoxy resin composition is suitable for a wide variety of uses. It is particularly suitable as an adhesive, casting resin, coating, or filler.

[0181] The epoxy resin composition is particularly suitable as an adhesive.

[0182] Such an epoxy resin adhesive is particularly suitable for bonding applications where high strength and high impact resistance or crash resistance are required.

[0183] The epoxy resin adhesive preferably has a paste-like consistency.

[0184] 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. The amine-functional adduct enables epoxy resin compositions, especially epoxy resin adhesives, with good processability and high impact strength combined with high tensile strength.

[0185] Examples

[0186] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described embodiments.

[0187] A temperature of 23+1 °C and a relative humidity of 50+5% is referred to as "standard climate" ("NC").

[0188] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH.

[0189] "AHEW" stands for amine hydrogen equivalent weight

[0190] "EEW" stands for epoxy equivalent weight.

[0191] Description of the measurement methods:

[0192] 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.

[0193] 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 ).

[0194] Substances and abbreviations used:

[0195] 1922A: Polyetheramine, AHEW 55 g / eq (4,7,10-trioxatridecane-1,13-diamine,

[0196] Ancamine® 1922A, from Evonik)

[0197] EC-280: Polyetheramine, AHEW 51 g / eq (4,9-dioxadodecane-1,12-diamine, Baxxodur® EC 280, from BASF)

[0198] TMD: 2,2(4),4-Trimethylhexamethylenediamine, AHEW 39.6 g / eq (Vestamin® TMD, from Evonik) BAC: 1,3-Bis(aminomethyl)cyclohexane, AHEW 35.5 g / eq (from Mitsubishi Gas Chemical)

[0199] D-230: Polyoxypropylenediamine, medium molecular weight M n approx. 240 g / mol, AHEW 60 g / eq (Jeffamine® D-230, from Huntsman) MXDA: 1,3-bis(aminomethyl)benzene, 136.2 g / mol, AHEW 34 g / eq (from Mitsubishi Gas Chemical)

[0200] B-EDA: N-Benzyl-1,2-ethanediamine, AHEW 50.1 g / eq, prepared as described below

[0201] BADGE: Bisphenol A diglycidyl ether (Araldite® GY-250, EEW 188 g / eq, from Huntsman)

[0202] 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.

[0203] Production of isocyanate group-containing polymers:

[0204] Polymer P-1:

[0205] 300 g polybutadiene polyol (Poly bd® R45 HTLO, average molecular weight M) n approx.

[0206] 2,800 g / mol, average OH functionality approx. 2.5, OH number 47 mg KOH / g, from Resin Solutions), 300 g poly(oxy-1,4-butylene)diol (polyTHF, Terathane® 2000, OH number 56 mg KOH / g, from Invista) and 137.8 g 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 97.9 Pa s and an NCO-Ge content of 3.0 wt%. It has a calculated polybutadiene chain content of 40.7 wt%. Polymer P-2:

[0207] 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), yielding a polymer with a viscosity of 17.4 Pa s at 20 °C and an NCO content of 1.8 wt%.

[0208] Polymer P-3:

[0209] 725 g of ethylene oxide-terminated polyoxypropylenetriol (Desmophen® 5031 BT, OH number 28.0 mg KOH / g, OH functionality approx. 2.3, from Covestro) and 275 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 unreacted 4,4'-diphenylmethane diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180 °C, pressure 0.1 to 0.005 mbar), yielding a polymer with a viscosity of 25.1 Pa s at 20 °C and an NCO content of 1.6 wt%.

[0210] Polymer P-4:

[0211] 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 and an NCO content of 1.9 wt%. Polymer P-5:

[0212] 500 g polybutadiene polyol (Poly bd® R45 HTLO, average molecular weight M) n approx.

[0213] 2,800 g / mol, average OH functionality approx. 2.5, OH number 47 mg KOH / g, from Resin Solutions), and 90.6 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 90 °C according to a known procedure to form a polymer that is liquid at room temperature with an NCO content of 2.8 wt%.

[0214] Polymer P-1 is an isocyanate-containing polymer with a calculated polybutadiene chain content of 40.7 wt%. Polymer P-5 is an isocyanate-containing polymer with a calculated polybutadiene chain content of 84 wt%. Polymers P-2, P-3, and P-4 are free of polybutadiene chains and serve as a comparison.

[0215] Production of amine-functional adducts:

[0216] Adducts N-1 to N-7 and R-1 to R-6:

[0217] The amount (in parts by weight) of the specified diamine, as indicated in Tables 1 and 2, was reacted at room temperature in the presence of 700 ml of ethyl acetate with the specified amount (in parts by weight) of the specified isocyanate-containing polymer until no more isocyanate groups were detectable by IR spectroscopy. The ethyl acetate was then removed by rotary evaporator.

[0218] The properties of the adducts are given in Tables 1 and 2.

[0219] The AHEW of the adducts was calculated, assuming that for adducts of polyamines with one primary and one secondary amine group, approximately half of the number of reacted amine groups were primary amine groups and the other half were secondary amine groups.

[0220] The adducts R-1 to R-6, designated with "(Ref.)", are comparative examples without polybutadiene chains.

[0221] Adducts N-8 and N-9:

[0222] The amount (in parts by weight) of the specified diamine given in Table 1 was placed in the solution and heated to a temperature of 120 °C. Then, 75 parts by weight of polymer P-5 were slowly added at a temperature of 100 °C and reacted until no more isocyanate groups were detectable by IR spectroscopy.

[0223] The properties of the obtained adducts are given in Table 1.

[0224] The AHEW of the adducts was calculated, assuming that for adducts of diamines with a primary and a secondary amine group, only primary amine groups reacted with NCO groups.

[0225]

[0226] Table 1: Amine-functional adducts N-1 to N-9.

[0227]

[0228] Table 2: Amine-functional adducts R-1 to R-6.

[0229] Use in epoxy resin compositions:

[0230] Composition Z1 to Z4:

[0231] For each composition, the amount of bisphenol A diglycidyl ether (in parts by weight) specified in Table 3 was used as the resin component. Furthermore, the adduct and MXDA specified in Table 3 were mixed in the indicated amounts (in parts by weight), stored in a dry place, and used as the hardener component.

[0232] Subsequently, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer and immediately tested as follows:

[0233] The viscosity (5') was measured 5 min after mixing the resin and hardener components.

[0234] 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.

[0235] The mechanical properties tensile strength, elongation at break, and Young's modulus (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). These were then removed from the mold and tested according to EN ISO 527 at a tensile speed of 10 mm / min. Prior to testing, the mixed composition was either stored for 7 days under standard climate conditions, or it was stored for 24 hours under standard climate conditions followed by 24 hours at 80 °C, followed by 3 days under standard climate conditions. The results are marked accordingly with the suffix "7d NK" or "24h NK + 24h 80°C". The Tg value (glass transition temperature) was determined by DSC on specimens cured as described above for the determination of the 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).

[0236] The results are shown in Table 3.

[0237]

[0238] Table 3: Composition and properties of Z1 to Z4.

[0239] Compositions Z5 to Z17: (epoxy resin adhesives)

[0240] 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.

[0241] 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.

[0242] 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 4.

[0243] Subsequently, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer in the mixing ratio specified in Table 4, and this liquid was immediately tested as follows:

[0244] 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.

[0245] The dynamic resistance was determined in an impact peel test according to ISO 11343 as a measure of impact toughness. For this purpose, 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. The results are given in Table 4.

[0246] The compounds marked with "(Ref.)" are comparative examples.

[0247]

[0248] Table 4: Composition and properties of Z5 to Z16.

[0249] 1Resin component / hardener component (weight)

[0250]

[0251] Table 4: (continued)

[0252] Table 4 shows that compositions Z5 to Z11, each with an adduct according to the invention, exhibited high impact peel strength, especially after curing for 1 hour at 80 °C, compared to compositions Z12 (Ref.) to Z17 (Ref.) with adducts without polybutadiene chains.

[0253] Use as a hardener for acetoacetates:

[0254] Composition Z18:

[0255] 100 parts by weight of adduct N-1 were mixed with 31.5 parts by weight of triacetoacetate-1, the preparation of which is described below, using a centrifugal mixer and tested as follows:

[0256] 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.

[0257] The Shore hardness was determined according to DIN 53505 on test specimens (diameter 20 mm, thickness 5 mm) hardened for 7 days in standard climate.

[0258] The gelling time was 10 minutes.

[0259] The Shore A hardness was 25.

[0260] The hardened composition was rubbery and solid, with a non-sticky surface.

[0261] 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

1. 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 and a polybutadiene chain content of at least 20 wt% based on the isocyanate group-containing polymer in a ratio of the number of moles of diamine of formula (I) per mole equivalent of isocyanate groups of at least 1.3, the amine-functional adduct is liquid at room temperature and stable during storage.

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 one of claims 1 to 3, characterized in that R in formula (I) stands for H.

5. Adduct according to one of claims 1 to 4, characterized in that the isocyanate group-containing polymer has an NCO content of 1.5 to 6 wt%, preferably 2 to 5 wt%.

6. Adduct according to any one of claims 1 to 5, characterized in that the isocyanate group-containing polymer is a reaction product of at least one monomeric diisocyanate with at least one polybutadiene polyol and optionally at least one further polyol in a molar NCO / OH ratio of at least 1.5, preferably at least 1.

8.

7. Adduct according to claim 6, characterized in that the polybutadiene polyol has an average molecular weight M n from 1'000 to 4'000 g / mol, preferably 2'500 to 3'000 g / mol, and has a mean OH functionality of 2 to 3.

8. Adduct according to one of claims 6 or 7, characterized in that, in addition to at least one polybutadiene polyol, at least one further polyol is present, preferably at least one polyether polyol with an average molecular weight M n from 800 to 4,000 g / mol, in particular at least one poly(oxy-1,4-butylene)diol with an average molecular weight M n from 1,500 to 2,500 g / mol.

9. Adduct according to any one of claims 1 to 8, characterized in that the adduct has an average hydrogen amine equivalent weight of 80 to 800 g / eq, preferably 120 to 600 g / eq, in particular 140 to 400 g / eq.

10. Method for producing the adduct according to any one of claims 1 to 9, 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 preferably takes place in the presence of an organic solvent and the solvent is preferably removed from the reaction product obtained after the reaction by means of a suitable process, in particular by distillation.

11. Use of the adduct according to any one of claims 1 to 9 as a hardener in a hardenable composition comprising reactive groups selected from epoxide group, isocyanate group, (meth)acrylate group, 1,3-ketoester group and carboxylic anhydride group.

12. Hardener for epoxy resins containing the adduct according to any one of claims 1 to 9.

13. Hardener according to claim 12, characterized in that at least one further amine with at least three amine hydrogens is contained.

14. Hardener according to one of claims 12 or 13, characterized in that it contains at least one further ingredient selected from accelerators for curing, in particular 2,4,6-tris(dimethylaminomethyl)phenol, fillers and pigments.

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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