EP4069792A1

EP4069792A1 - Michael reaction-curing hybrid system for use in chemical fastening technology

Info

Publication number: EP4069792A1
Application number: EP20819664.2A
Authority: EP
Inventors: Christian Weinelt; Martin Vogel; Ursula LINK-PFAFF; Hannah GEHRING
Original assignee: Fischerwerke GmbH and Co KG
Current assignee: Fischerwerke GmbH and Co KG
Priority date: 2019-12-04
Filing date: 2020-12-01
Publication date: 2022-10-12
Also published as: US20230002653A1; JP2023505776A; WO2021110621A1; CN114729224A; DE102020128713A1

Abstract

The invention relates to a hybrid system for use as an adhesive, coating or paint, characterized in that the hybrid system contains a) a reaction resin on the basis of α, β-unsaturated compounds, b) a reaction resin on the basis of CH-acidic methylene group-containing compounds and c) a primary amine. The invention also relates to related subject matter according to the invention.

Description

Michael addition-curing hybrid system for chemical fastening technology

The invention relates to a hybrid system (hereinafter also referred to as hybrid resin system or hybrid adhesive) for chemical fastening technology, in particular for fastening anchoring means in boreholes, which comprises a reaction resin based on α, β-unsaturated compounds, a reaction resin based on compounds containing CH-acidic methylene groups , and includes a polyamine, as well as its use and further aspects (embodiments) of the invention mentioned below.

In the field of chemical fastening technology, two different systems have become established: One based on free-radically polymerizable, ethylenically unsaturated compounds that are cured by means of peroxides, and one based on epoxy-amines. Both systems have advantages and disadvantages. Radically curing systems are characterized by rapid low-temperature curing (e.g. - 10 ° C), but show a relatively high shrinkage ("shrinkage") and not very high pull-out values. Systems based on epoxy amine, on the other hand, show a significantly slower curing rate at low temperatures (e.g. <+ 5 ° C), but have significantly less shrinkage and significantly higher pull-out values.

Efforts have long been made to combine the advantages of both systems in the field of chemical fastening technology. For this purpose, dual-curing binders have been proposed in the past, which cure both by radical polymerization and by polyaddition (epoxy + amine). This means that hybrid systems of this type are based on resin compositions which contain compounds which can be hardened according to two different types of reaction. For example, EP 2357162 A1 describes a hybrid resin system which contains a free-radically curable resin and an epoxy resin. The hardeners contain an aliphatic amine and a peroxide, especially a perester. A disadvantage of this hybrid system is that it cannot be packaged in a storage-stable manner, especially as a two-component system. This is attributed to the fact that the peresters react quickly with amines due to their reactive carbonyl group.

It is the object of the present invention to provide a hybrid system which allows rapid low-temperature curing as in the case of free-radically polymerizable Systems with significantly higher pull-out values as in polyaddition-curing systems (epoxy-amine) combined.

A further object for preferred aspects of the present invention is the provision of a fastening compound in the form of a hybrid system which avoids ingredients that are highly hazardous to health and preferably does not require labeling.

Surprisingly, it has been found that it is possible to achieve the advantages of the previous systems if - apart from the previous types of polymerization - a hybrid system is used which contains the starting materials for a Michael addition (N- and / or C- Michael- Addition) and for an enamine reaction and thus provides the reaction options mentioned below.

Systems that cure by Michael addition are known from the field of floor coatings. For example, US 2018/0134913 A1 describes a coating which contains a CH-acidic compound as component A and an activated α, ß-unsaturated compound as component B. The two components cure in the presence of a strong base.

DE 40 34279 A1 describes an enamine reaction for the production of crosslinked products for use as a coating. The enamine reaction occurs spontaneously between polyacetoacetates (reaction resin with CH-acidic methylene groups) and polyamines. However, since the corresponding systems have gel times that are far too short for practical use, DE 4034279 A1 suggests the use of primary aminosilanes. As a result, the crosslinking reaction is no longer part of the enamine reaction, but rather depends on the hydrolysis and condensation reaction of the silane.

A composition based on vinyl polymers and amines curable by aza-Michael addition (N-Michael addition) is described in EP 1 970480 A1. Advantageously, epoxy resins, which can also react with the amines, are additionally present in the curable composition.

Disadvantages of the above-mentioned disclosures include the significantly too short gel times of the enamine reaction between polyacetoacetates and polyamines and the inadequate performance of the aza-Michael addition systems in the borehole. In a first embodiment of the invention, the invention relates to a hybrid system which comprises the following components: a) reaction resin based on α, β-unsaturated compounds, b) reaction resin which contains compounds bearing CH-acidic methylene groups, and c) primary amine.

In addition, the hybrid system advantageously contains a catalyst.

The hybrid system is preferably multi-component, in particular two-component, implemented, preferably as a multi-component, such as two-component kit.

In a further embodiment, the invention also relates to the use of a multi-component, in particular two-component hybrid system composed as just described, as an adhesive, in particular for fastening anchoring means in substrates such as masonry or concrete, or furthermore for fastening fibers, scrims, fabrics or composites for Reinforcement of structures.

Corresponding processes and methods for grouting in anchoring elements in holes or crevices in which a multi-component, in particular two-component, hybrid system according to the invention (in particular multi-component or preferably two-component kit) is used for grouting (gluing in) anchoring means, the hybrid system and an anchoring means being used one after the other , in particular first the hybrid system, then the anchoring means, or (at least essentially) simultaneously, in a hole or a gap in a substrate (also in a cracked substrate, such as cracked concrete), or mixed forms with partial insertion in each case, constitute an embodiment of the invention.

Embodiments of the invention are also found in the claims, which are incorporated herein by reference.

The inventors have surprisingly found that a hybrid system based on components a), b) and c) combines the advantages found on the one hand in radical curing and, on the other hand, in chemical fastening systems curing by polyaddition, although no radical curing is involved. This is surprising insofar as the reactions taking place in parallel here have never been combined in a hybrid system for chemical fastening technology. The following reactions can occur between components a), b) and c): i. Michael addition (a, ß-unsaturated compound + CH-acidic compound) ii. Aza-Michael addition (a, ß-unsaturated compound + amine) iii. Enamine reaction (CH-acidic compound + amine).

Without wishing to be bound by these explanations, depending on the selected molar ratios between components a), b) and c), two of the reactions mentioned may take place preferentially, but it cannot be ruled out that - even if in some cases only to a small extent - all three types of reaction take place in parallel.

The types of reactions i. to iii. are, each on their own, from the field of Beschich lines, specifically as a floor coating, known (see the above-mentioned ent speaking patents). Since the forces occurring in the borehole are completely different from those of a (floor) coating, it was not obvious to the person skilled in the field of fastening technology for anchoring means that the reaction types i. to iii. to be considered on its own, or in particular as a hybrid system, for chemical fastening systems for use. From a macroscopic point of view, for example, enormous shear stresses occur in the borehole when subjected to axial loading, which the system has to withstand, whereas a (floor) coating should withstand rather high compressive strengths and abrasion resistance.

It was also found that a hybrid system based on components a), b) and c) fulfills the criteria applicable to usability under construction site conditions. These include, on the one hand, sufficient stability at high temperatures (<45 ° C) to prevent running on and / or running out of the borehole, and on the other hand, a sufficiently low viscosity at low temperatures (> - 25 ° C) ) in order to ensure that they can be pressed out by hand from cartridges or the like.

Above and below, more general terms or features can be replaced by more specific (in particular below) specified definitions individually, in several or all, which leads to specific, particularly preferred, embodiments of the invention.

Where "a" or "an" is used, this is to be understood primarily as the indefinite article (unless otherwise indicated, for example by prefixing "at least") and includes "one (in numbers: 1) or more" like just one (in numbers: 1). In other words, “a” or “an” means “a” (“1”) or “one or more, for example two or three or four”.

Above and below, proportions or content data in percent mean weight percent (“% by weight”) or the relative weight proportion, unless otherwise stated, based on all ingredients of a hybrid system according to the invention (without packaging material), unless otherwise stated or evident.

“Contain” or “comprise” means that, in addition to the components or features mentioned, others may also be present, so it stands for a non-exhaustive list, in contrast to “consist (d) of”, which is a final list of the means components or features listed when it is used. In embodiments of the invention, “include” or “comprise” may be replaced by “consist (d) of”.

Where the attribute “further” is mentioned, it means that characteristics without this attribute may be more preferred.

“And / or” means that the features / substances mentioned can each be present alone or in combination of two or more of the features / substances mentioned in each case.

In a reaction resin based on α, β-unsaturated compounds, the α, β-unsaturated compound generally contains an ethylenically unsaturated compound in which the carbon double bond is activated by an electron-withdrawing group (for example a carbonyl group in a-position). In particular, it is to be understood as meaning a reaction resin that contains or (considered as a reaction resin in itself) consists of a compound which has at least one, preferably 2 or more, fumarate, maleate, itaconate or, in particular, acrylate group (s) (H2C = CH-CO-) carries, such as an acrylic acid ester or acrylamide, such as a mono- or, in particular, di-, tri-, tetra- or higher polyacrylate, in particular selected from hydroxy-C2-Cioalkyl-acrylate, such as hydroxyethyl-, -propyl- or -butyl acrylate, ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol acrylate, poly (butanediol) diacrylate, polybutadiene diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, diethyleneglycol diacrylate, tetrapylene glycol

T riethylenglykoldiacrylat, riisopropylenglykoldiacryalat T, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated or propoxylated neopentylglycol diacrylate, tripropylene glycol diacrylate, bisphenol A, bisphenol F, bisphenol AF or bisphenol-S diglycidyl ether diacrylate, bisphenol-A-polyethoxydiacrylat, bisphenol F polyethoxydiacrylat, Polyethylene glycol, polypropylene glycol diacrylate, trimethylolpropane triacrylate, di- trimethylolpropane tetraacrylate, Trimethylolpropanpolyethoxytriacrylat, ethoxylated or propoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxylated or propoxylated glycerol triacrylate, tris (2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, Pentaerythritolmonohydroxytriacrylat, Pentaerythritoltriethoxytriacrylat, pentaerythritol tetraacrylate, ethoxylated or propoxylated pentaerythritol tetraacrylate, DITRi - methylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol polyhexanolide hexaacrylate, dipentaerythritol hexaacrylate, T ris (hydroxyethyl) isocyanuratopolyhexanolide triacrylate, T ris (2-hydroxyethyl) isocyanuratotriacrylate, 2-dimethyl-2-diacrylate, tricyclodiacrylate-1,1-diacrylate, tricyclodiacylate-1,1-methyl-triacrylate, tricyclodiacrylate-1,1 ethyl-5-acryloyloxymethyl-1,3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenylsulfide diacrylate, polytetraethylene glycol col diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, dimethylol propane tetraacrylate, cresol epoxy acrylate, novolak “poly“ acrylate, oligomers containing acrylate groups or polymers from the reaction of polyepoxides with acrylic acid (or reactive derivatives thereof, such as Acid halides or active esters) or from the reaction of polyester polyols with acrylic acid (or reactive derivatives thereof, in particular as just mentioned), or urethane acrylates (obtainable e.g. by reacting isocyanates with an acrylate containing OH groups, such as hydroxyethyl, hydroxypropyl, Hydroxybutyl or pentaerythritol tri-acrylate, and polyester acrylate resins, for example tetrafunctional polyester acrylates). Acrylic-functional alkoxysilanes or organopolysiloxanes are also possible (cf. WO2006 / 087079 A1), such as acrylatomethyl-trimethoxysilane, -methyldimethoxysilane, -dimethylmethoxysilane, -triethoxysilane or -methyldiethoxysilane, acryl-amidomethyl-trimethoxysilane, -methoxysilane, -trimethoxysilane, -methoxysilane, -trimethoxysilane, -methoxysilane, -trimethoxysilane, -methoxy - methyldiethoxysilane, or -methyl-dimethylethoxysilane.

Alternatively, a reaction resin based on α, β-unsaturated compounds can also be understood as a polyester resin based on maleic and / or fumaric and / or itaconic acid, as well as their anhydride. Polyester, polyurethane, polyether and / or alkyd resins which carry activated, ethylenically unsaturated groups are also to be understood as such reaction resins. Acrylates (particularly preferred), fumarates, itaconates and maleates, particularly characterized as preferred in the present disclosure, are preferred reactive resins.

The compounds mentioned can also be present as mixtures of two or more thereof. Mono-acrylates are also possible. However, because of their chain-breaking effect, these are less preferred or are present as admixtures with di- or polyacrylates. Commercially available acrylates and / or fumarates and / or maleates and / or itaconates can be used. Examples of representatives of the mono-acrylates are tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate and / or cyclic trimethylolpropane formal acrylate. The more preferred mono-acrylates include acrylated amines, available from Sartomer, for example. The monoacrylates, monoacrylates, maleates and / or itaconates can also be mixed with di- or polyacrylates, fumarates, maleates and / or itaconates.

Also a, b-unsaturated compounds with a biogenic component (characterized by the ¹⁴ C content, which is higher relative to the total carbon content than with fossil materials) belong to the preferred compounds of this class, i.e. in particular those that are caused by (preferably biogenic) acrylic acid, for example via OH- or SH- or amino (NH2-) or imino (-NH-) contained in the (preferably also biogenic) complementary educts (raw materials) (at least part of the acrylic acid and / or the complementary educts being biogenic) -Groups, or two or more of these groups, are functionalized, in particular those that contain hydroxyl groups and are thus functionalized to (correspondingly fully or at least partially biogenic) acrylic acid esters, such as acrylates (preferably with a biogenic acrylate content) of hydroxy-containing vegetable oils, such as castor oil or soybean oil, wholly or at least partially biogenic (eg C1-C10) alkane (mono-, di-, tri-, tetra-, pe nta or hexa, or poly) ol acrylates, partly or preferably entirely biogenic polyglycerol acrylates, wholly or partly biogenic acrylates of sugar alcohols, such as mannitol, xylitol or sorbitol, wholly or partly biogenic acrylated fusel oils, wholly or partly biogenic 5- or 6 Ring heterocyclyl acrylates (in particular with one or two heteroatoms selected from O, N and S in the ring), or partially or preferably entirely biogenic glycerol or polyglycerol acrylates, wholly or partially biogenic saccharide acrylates. Particularly preferred are epoxidized Sojabohnenölacrylat, 1,10-Decandiol- diacrylate, nylacrylat tetrahydrofuryl acrylate, isobornyl acrylate, Sorbitolacrylat, lauryl (meth) acrylate, behenyl, propoxylated glyceryl triacrylate, pentaerythritol triacrylate, Pentaerythritoltetra- acrylate, di-Pentaerythritolpentaacrylat, tetrahydrofurfuryl methacrylate, polyethylene glycol di methacrylate, polyester , acrylated fusel oil, or biogenic glycerol triacrylate or such in which at least the acrylate component is biogenic. Biogenic urethane acrylates (obtainable, for example, by reaction of isocyanates (such as: Desmodur Eco N 7300) with an acrylate containing OH groups, such as hydroxyethyl, hydroxypropyl, hydroxybutyl or pentaerythritol tri-acrylate, and polyester acrylate resins, e.g. tetrafunctional, are also particularly preferred Polyester acrylates). The proportion of bio-based carbon is carried out on the basis of ASTM 6866 (Standard Test Method for Determining the Biobased Content of Solid, Liquid and Gaseous Samples Using Radiocarbon Analysis, using the ¹⁴ C content (ASTM International, D6866: 2008 Method A).

Where acrylates are mentioned above and below, this also includes, alternatively or in combination, the corresponding methacrylates (in the case of the more specific, to be realized by adding (“meth” before “acrylate”).

A mixture of two or more (in particular the abovementioned) α, β-unsaturated compounds is also possible.

The proportion of the reaction resin based on α, β-unsaturated compounds is preferably 1 to 80% by weight, in particular 2 to 60% by weight.

A reaction resin which contains compounds bearing (one or more) CH-acidic methylene groups (activated methylene groups) includes, in particular, a malonic acid or malonic acid ester, such as malonic acid dimethyl ester, malonic acid diethyl ester, malonic acid di-n-propyl ester, malonic acid diisopropyl ester, malonic acid dibutyl ester -di (2-ethylhexyl) ester or malonic acid dilauryl ester; Cyanoacetic acid esters, such as 2-ethylhexyl cyanoacetate, butyl cyanoacetate, octyl cyanoacetate, 2-methoxyethyl cyanoacetate; Diones, such as pentane-2,4-dione, hexane-2,4-dione, heptane-2,4-dione, 1-methoxy-2,4-pentanedione, 1-phenyl-1,3-butanedione, 1 , 3-diphenylo-1,3-propanedione, 4,6-dioxoheptanoic acid methyl ester, 5,7-dioxooctanoic acid methyl ester; Acetoacetates, such as methyl, ethyl or butyl benzoylacetoacetate, methyl, ethyl or butyl propionylacetate, methyl butyroylacetate, methyl acetoacetate, ethyl, isopropyl, n-butyl, isobutyl or tert-butyl ester, 2-methoxyethyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, 2-acetoacetatoethyl acrylate, benzyl acetoacetate,

1,4-butanediol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentylglycol diacetoacetate, 2-ethyl-2-butyl1,3-propanediol diacetoacetate, cyclohexanedimethanol diacetoacetate, free or ethoxylated bisphenol A-, -F-, -AF- or -S-trimethyl diacetoacetate, Pentaerythritol tri- or tetraacetoacetate, ditrimethylolpropane tetraacetoacetate, dipentaerythritol hexaacetoacetate, oligomers bearing acetoacetate groups or polymers which can be obtained, for example, by transesterification of acetoacetic acid (eg ethyl) esters, acetoacetate copolymers, ethyl acetate groups, obtainable from acrylate methyl methacrylates or polymers bearing ethyl acetate are, oligomers or polymers obtainable from dialkyl malonates and diols, or acetoacetylated novolaks, or a mixture of two or more thereof; to understand. The reaction resin bearing CH-acidic methylene groups is very particularly preferably an acetoacetate with at least 2 or more acetoacetate groups. As already indicated above (in the list of possible compounds listed purely by way of example), the acetoacetates can be aliphatic, heteroaliphatic, cyclic, heterocyclic, cycloaliphatic and / or araliphatic.

The proportion of the CH-acidic compound (s) is preferably 1 to 80% by weight, in particular 2 to 60% by weight.

A mixture of two or more (in particular the aforementioned) CH-acidic compounds is also possible.

CH-acidic compounds with methylene groups (-CH2-) are, since they carry two hydrogens, to be regarded as mono- or difunctional.

A primary amine is to be understood as meaning any common amine hardener that could be used to crosslink epoxy resins.

For example, primary diamines or polyamines are preferred (where “poly” also includes “oligo”). The amine can be either linear or branched. The amine molecular structure can contain aliphatic, heteroaliphatic, alicyclic, heterocyclic, aromatic, aliphatic aromatic and silane / siloxane molecular structures or two or more independently selected thereof. Furthermore, the primary amine from the group of the aminoamides, polyaminoamides, Mannich bases and the amine adducts (such as in particular epoxy-amine adducts as described, for example, in EP 0 387418 A2, isocyanate-amine adducts, Bucherer adducts and Michael Addition adducts) must be selected.

Particularly suitable amines, without restricting the scope of the invention, are, for example, from the group of the alkylamines (such as: 1,2-diaminoethane, 2-methylpentanediamine, 2,2-dimethyl-1,3-propanediamine, 2,2, 4- or 2,4,4-trimethylhexamethylene diamine), the heteroalkylamines (such as 1,13-diamino-4,7,10-trioxatridecane, commercially available amine-functionalized polyoxyalkylenes [Jeffamine] from Huntsman Corp, triethylenetetramine and / or higher homologues of the cycloalkylamines (such as, for example: isophoronediamine, 1,3- and / or 1,4-bisaminomethylcyclohexane, TCD-diamine, 1,2- and 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, norbornanediamine, diaminodicyclohexylmethane, 2,2-bis (4-aminocyclohexyl) propane), the heterocyloalkylamines (such as, for example: aminoethylpiperazine) and the aliphatic-aromatic amines (such as 1,3- or 1,4-benzenedimethanamine), or it is a mixture of two or more of these compounds.

A possible preferred amine is in particular a di- or polyamine, preferably 2-methylpentanediamine (DYTEKA), 1,2-diaminocyclohexane (DCH), 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1, 3-benzenedimethanamine (MXDA), 1,4-benzenedimethanamine (PXDA), 1,6-diamino-2,2,4-trimethylhexane (TMD), triethylenetetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), N- aminoethylpiperazine (AEP), 1,3-bis (aminomethyl) cyclohexane (1,3-BAC), TCD-diamine, Jeffamine from Huntsman, dipropylenetriamine, N, N ^{'-Dicyclohexyl-1,6-hexanediamine,} N, ^N' - dimethyl-1,3-diaminopropane, N, N ^{'-diethyl-1,3-diaminopropane,} N, N-dimethyl-1,3-diaminopropane, secondary polyoxypropylene triamine and 2,5-diamino-2, 5-dimethylhexane, bis- (aminomethyl) tricyclopentadiene, 1,8-diamino-p-menthane, or bis- (4-amino-3,5-dimethyl-cyclohexyl) methane, or a mixture of two or more of these compounds.

An aminoalkylsilane that contains at least one hydrolyzable group, such as alkoxy, e.g. methoxy or ethoxy - bonded to silicon - is also of particular interest as a primary amine. This can hydrolyze and condense (for example through water of reaction or water added) and thus form oligomers that carry several amino groups and meet the REACH definition for polymers. A preferred aminoalkylsilane of this type is selected, for example, from the group comprising one or more of the following compounds: aminoalkyltri- or -dialkoxysilanes, such as 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropylethyldiethoxysilane , 4-aminobutyltiethoxysilane, 4-aminobutylethyldiethoxysilane, and N- (aminoalkyl) -amino-alkyltri- or -dialkoxysilanes, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane . A copolymer of one or more of the aforementioned and furthermore other silanes is also of particular interest. Examples of this are the Dynasilanes (such as Dynasilan 1146) from Evonik and the amino-functional organopolysiloxanes with the brand name Silres from Wacker (such as Silres HP 2000).

The proportion of (poly) amines is preferably 0.2 to 60% by weight, in particular 1 to 40% by weight. A mixture of two or more (in particular those mentioned above) amines is also possible.

One (or two or more) selected from the following catalysts can advantageously be included as a catalyst for a hybrid system according to the invention:

Strongly basic catalysts (especially with a pKa of 11 or higher) such as alkali metal hydroxides (e.g. sodium or potassium hydroxide), alkali metal alkoxides (e.g.

Sodium or potassium (m) ethoxide), quaternary ammonium compounds (e.g. tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium carbonate), tertiary amines (e.g. diazabicyclooctane (also referred to as DABCO) and guanicidines / amidines (e.g. tetramethylguanidines) 5.4.0] undec-7-en, 1,5-diazabicyclo [4.3.0.] Non-5-en), silicates (e.g. sodium silicate) and metal oxides (e.g. calcium oxide); phosphine catalysts, e.g. tricyclohexylphosphine (particularly preferred) , Tricyclopentylphosphine, tri-n-hexylphosphine, tris (2,4,4-trimethylpentyl) phosphine, tris (2-ethylhexyl) phosphine, tri-n-octylphosphine (particularly preferred), tri-n-decylphosphine, tri -ndodecylphosphine (particularly preferred), tristearylphosphine and triphenylphosphine.

A further suitable catalyst (resulting after mixing the components of a hybrid system according to the invention) is a mixture of an epoxide (with epoxy groups as (preferably as low molecular weight) glycidyl esters, glycidyl ethers, such as the diglycidyl ether of bisphenol A, or epoxidation products of alpha-olefins) with one or several tertiary amines (in particular triethylenediamine, Mannich reaction products, or the acrylated amines already mentioned above (available from Sartomer)), as described in EP 0 326723 (hereinafter also referred to as epoxy / tert-amine catalysts). The epoxide can advantageously be accommodated in the component with the a, b-unsaturated compound or the CH-acidic compound or both, the tertiary amine in the component with the a, b-unsaturated compound. Salts of strong bases (or small amounts of the strong bases themselves) such as tetramethylguanidine, DABCO (1,8-diazabicyclo (5.4.0) undec-7-en) or quaternary ammonium hydroxides can also be added, for example divided in such a way that the starch Base part in one component (preferably not the one with the CH-acidic compound), the epoxide is contained in another component. The ingredients react when mixed and form a strong catalytically active base.

Possible catalysts are also carbon dioxide-blocked strong bases, such as quaternary alkyl ammonium bi- or alkyl carbonates, which, however, are less preferred because they contain CO2 release, except for applications where this is not bothersome or even desirable, for example heat-insulating coatings.

It can also contain two or more of the catalysts mentioned.

The catalysts are preferably added in 0.01 to 15% by weight, in particular 0.1 to 10% by weight.

A multi-component kit (or set) is to be understood as meaning, in particular, a two-component kit, preferably a two- or further multi-chamber device, in which the components that are reactive with one another are contained in such a way that they cannot lead to undesired reactions during storage, preferably such that the components that are reactive with one another do not come into contact with one another before use. Cartridges are possible. Particularly suitable, however, are cartridges or foil bags with two or more chambers, or containers such as buckets or tubs with several chambers or sets (e.g. bundles) of two or more such containers, with two or more components of the respective curable hybrid system, in particular two components, in each case spatially separated from one another as a kit or set, in which the contents after mixing or mixing on the application site (in particular using devices for application such as spatulas or brushes or a static mixer), for example a surface for attaching fibers, scrims, fabrics, Composites or the like, or in particular in a recess, preferably in front of a borehole, in particular rods for fastening anchoring means such as anchors or the like, is brought; as well as multi-component or in particular two-component cartridges, in the chambers of which the several or preferably two components for a hybrid system according to the invention are contained, especially for fastening purposes with the above and below mentioned components for storage before use, with a static mixer preferably also belonging to the corresponding kit. In the case of foil bags and multi-component cartridges, the multi-component kit can also include a device for emptying (for example a pressure pistol), but this can preferably also be made up or offered independently of the kit (for example for multiple use).

The reactive constituents of a hybrid system according to the invention (this primarily means constituents a), b) and c) and the catalyst) are distributed among the components of the multicomponent system, in particular multicomponent kits, in such a way that constituents that are reactive with one another prior to use (especially during manufacture , Storage and transport) do not come into contact with each other (the components are separated from each other in a reaction-inhibiting manner). Corresponding divisions are readily apparent to those skilled in the art.

In a possible preferred variant of a multicomponent kit according to the invention, components a) and b) are contained in one component (K1), while component c) is contained together with the catalyst in another component (K2) (immiscible in storage, ie separated) is, it being possible for one or more further additional ingredients to be optionally present in each case.

If the catalyst is an epoxy / tert-amine catalyst, it can also be divided between the two components. In this case, in a possible preferred variant of a multicomponent kit according to the invention, the components a), b) and the epoxy part of an epoxy / tert-amine catalyst are included in one component (K1), and the component c) is included together with the tert -Amin part of an epoxy / tert-amine catalyst in another component (K2), it being possible for one or more additional ingredients to be optionally present here as well.

In addition to the components already mentioned, a hybrid system according to the invention preferably contains one or more further additives, in particular selected from fillers, rheological auxiliaries, thixotropic agents, plasticizers, coloring additives and adhesion promoters, as well as solvents and / or reactive thinners.

Customary rheological aids which cause thixotropy can be used as thixotropic agents, such as pyrogenic silica, bentonites, alkyl and methyl celluloses, castor oil derivatives or the like. For example, they can be added in a weight proportion of 0.01 to 50% by weight, in particular 0.5 to 20% by weight, for example 0.1 to 5% by weight.

As fillers, conventional fillers with a fine (e.g. medium grain d50 at 50 μm or less, in particular at 40 μm or less, preferably at 30 μm or less, preferably at 25 μm or less, e.g. preferably at 20 μm or less) can be used preferably at 10 pm or less, primarily 5 pm or less, first and foremost 1 pm or less) or larger medium grain size, in particular chalk, sand, quartz sand, quartz flour, rock flour, glass, porcelain, corundum, ceramics, Silicates, clays, barite, aluminum hydroxide, calcium carbonate or the like, which can be added as powder, in larger form or in the form of shaped bodies, use, or others, such as core or shell flour from plants, which increases the bio-genic carbon content, such as olive seed meal, coconut shell meal or walnut shell meal, or hydraulic fillers such as gypsum, quicklime or cement (e.g. clay or Portland cement) , Water glasses or active aluminum hydroxides, or niches of two or more of them, wherein the fillers can further or in particular also be silanized. The fillers can be present in one or more components of a multi-component hybrid adhesive according to the invention, for example one or both components of a corresponding two-component kit; the proportion of fillers is preferably 0 to 90% by weight, for example 10 to 70% by weight (although the covering material (e.g. broken glass or splintered plastic), for example shards, is destroyed when anchoring elements are introduced from cartridges, which can or is preferably counted as filler).

The mean grain d50 is defined as the grain size at which 50% by weight of the particles is smaller than the specified particle size d50. There are different and technically generally recognized methods for determining the d50, e.g. by means of classifying grading curves with sieves or for example (especially for smaller particles with a diameter of less than 1 μm) by laser granulometry. In the case of commercially available fillers, the medium grain size may correspond to the manufacturer's specifications.

As adhesion promoters, there are silane coupling agents with functional groups such as amino, mercapto, epoxy, vinyl, or halogen, such as g-aminopropylmethyldimethoxysilane, g-aminopropylmethyldiethoxysilane, Y- (2-aminoethyl) aminopropyltrimethoxysilane, g-aminopropyl trimethoxysilane (2 -minoethyl) aminopropylmethyldiethoxysilane, Y- (2-aminoethyl) aminopropyltriisopropoxysilane, g-ureidopropyltrimethoxysilane, N-phenyl- g-aminopropyltrimethoxysilane, N-benzyl- g-aminopropyltrimethoxysilane, g-trimethoxinopropylsilicon, g-trimethoxinopropylsilaptyl- g-mercaptopropyl-triethoxysilane, g-mercaptopropylmethyl-dimethoxysilane, g-mercaptopropylmethyldimethoxysilane, g-glycidyloxypropyltrimethoxysilane, g-glycidylpropyltriethoxysilane, g-glycidyloxypropyl-hexylane, 3,4-glycidyloxypropylmethyl-dimethoxcoxysilane, 3,4-glycidyloxypropyl-hexoxy-3, 4-oxyloxypropylmethyldimethoxcoxysilane, 3,4-ethoxy-3, 4-oxyloxypropyl-hexoxy-3, 4-oxy-hexylane, epoxy-3, 4, 4, 6-dimethoxy ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, g-acryloyloxypropylmethyltriethoxysilane, g-chloropropyltrimethoxysilane, or like; modified derivatives thereof, such as amino-modified silyl polymers, silylated aminopolymers, unsaturated aminosilane complexes, phenylamino-alkylsilanes, aminosilylated silicones, or silylated polyesters, or a mixture of two or more of them. Other additives can also be added, such as plasticizers, non-reactive diluents, flexibilizers, stabilizers, rheological aids, wetting agents and dispersants, coloring additives such as dyes or, in particular, pigments, for example for different coloring of the components for better control of them Mixing, or the like, or a mixture of two or more of them. Such further additives can preferably be added in a total of 0 to 90% by weight, for example from 0 to 40% by weight.

All components of hybrid systems according to the invention are known, obtainable by processes known per se (for example from the patents mentioned at the beginning as prior art or with regard to urethane acrylates DE 4 111 828 A1), or are commercially available.

Alkyl preferably denotes a linear or mono- or multiply branched saturated (acyclic) hydrocarbon radical with up to 20 carbon atoms, for example C C -C -alkyl, in particular C 1 -C 4 -alkyl, such as in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , tert-butyl, or the like. Where CrC4-alkyl is mentioned, the number 1-4 always refers to the alkyl group itself (and does not include adjacent parts of the molecule, such as -carbonyl or -carbonylmethyl).

Parameters ("material-specific properties"), insofar as they are presented in the context of the present application, are determined using methods known to the person skilled in the art, in particular as follows:

For pull-out tests with threaded rods M12, according to ETAG 001 PART 5 (publisher DIBt, Berlin 2008), proceed as follows:

First, drill holes (diameter 14 mm; depth 60 mm) are made in a horizontal concrete test body (concrete type C20 / 25) with a hammer drill and a hammer drill. The drill holes are cleaned with a hand blower and a hand brush. The drill holes are then filled to two thirds with the respective hardenable compound to be tested for fastening purposes. A threaded rod is pressed in by hand for each borehole. The excess mortar is removed with a spatula. After 24 hours at room temperature, the threaded rod is pulled until failure while measuring the failure load. The gel time is determined from a 30 g mixture in a plastic beaker at 23 ° C. by means of manual stirring. When the gelation point is reached, the previously liquid mixture becomes highly viscous and gel-like, which is noticeable through the formation of lumps. At this point, the clock started after the test started will be stopped. The gel time can be read off directly.

The onset or glass transition temperature (Tg) (an indirect measure, among other things, for heat resistance) is measured using dynamic differential calorimetry (DSC) based on ISO 11357-2 (2013) on samples that are cured for 24 hours.

Examples: The following examples serve to illustrate the invention without restricting its scope:

Table 1: Components and abbreviations used

Example 1: Composition and pull-out tests from concrete of hybrid systems according to the invention (RMA + AMA preferred)

Setting tests are carried out in accordance with the aforementioned methods for determining parameters for “pull-out tests from concrete”. Table 2 shows the components used and the bond stresses determined. The amount of primary amines used or the primary amino groups (-NH2) present therefrom in the system are balanced out by additional acrylate groups, whereby the reactions i. and ii. can run preferentially.

Table 2: Recipes for the setting tests and the bond stresses determined

In Examples B1.1 to B1.3 the molar ratio of the primary amino groups to acrylate groups is 1: 1 (NH2: C = C = 1: 1), whereas in Examples B1.4 and B1.5 a 1: 2 ratio (NH: C = C = 1: 1) was chosen between primary amino groups and acrylate groups. The bond stresses listed in Table 2 demonstrate the enormous efficiency of the hybrid system according to the invention. Table 2 also shows the robustness of the hybrid system, since both the primary amine content and the molar ratios between amino groups and acrylate groups can be varied over a wide range without suffering a loss in performance.

Example 2: Compositions and pull-out tests from concrete with different primary amines (RMA + AMA preferred)

In order to make it clear that all primary amines can be used in the hybrid systems according to the invention, one representative is selected from each of the aforementioned groups of primary amines, and setting tests are carried out according to the aforementioned parameters.

Table 3: Recipes for amine screening and determined bond stresses

It can be seen from Table 3 that all primary amines can be used in the hybrid systems according to the invention. Table 3 also shows that the hybrid systems according to the invention can combine the advantages of the systems previously used in chemical fastening technology: a fast one Curing as with radically curing systems, with the high bond stresses of epoxy systems. This is confirmed by the gel times and bond stresses determined. Example B2.1 is mixed again with half the amount of TMG. The resulting gel time is 07:20 [mm: ss]. This experiment shows that the gel time can be controlled with the aid of the amount of catalyst used and set to a desired gel time.

Example 3: Compositions and pull-out tests from concrete of hybrid systems according to the invention (RMA + En preferred)

The following table 4 shows the constituents used and the determined composite tensions of hybrid systems according to the invention, in which the amount of primary amines used or the primary amino groups (-NH2) present in the system from them are balanced by CH-acidic methylene groups (-CH2-), whereby the reactions i. and iii. can run preferentially.

Table 4: Recipes for the setting tests and the bond stresses determined

Table 4 further illustrates the enormous performance of the hybrid systems according to the invention already shown in Table 2, as well as their robustness.

Example 4: Pull-out tests from concrete with mixtures of the components a, b and c

In order to show that different mixtures of ingredients of constituents a, b and c can also be used in the hybrid systems according to the invention, setting tests according to ETAG 001 PART 5 are carried out. Table 5 lists the components used and the bond stresses determined.

Table 5: Recipes with mixtures a, b, c and determined bond stresses

In example E4.1, the additional primary amino groups are saturated by acrylate groups (RMA + AMA preferred), whereas in examples E4.2 and B4.3 the amino groups are saturated by CH-acidic methylene groups (-CH2-) (RMA + En preferred). The high bond tensions prove that one can also use varying mixtures of ingredients of constituents a, b and c for the formulation of hybrid systems according to the invention.

The very high bond stresses of Examples B3.5, B3.6 and B4.3, in which the silane AMMO is used, are striking. Without wishing to be bound by this theory, one possible reason for the very high performance is that the enamine reaction of the primary amine with the CH-acidic methylene group (-CH2-) -bearing compound produces water. This in turn causes a hydrolysis and condensation reaction of the silane AMMO. Together with the Michael addition (Real Michael addition / C-Michael addition) between the α, ß-unsaturated compound and the CH-acidic methylene group-bearing compound, this creates a strongly interlinked and close-knit network, which explains the very high bond stresses would be.

Example 5: reference experiments

In order to underline the enormous efficiency of the hybrid systems according to the invention again, reference tests were carried out and the subsequent bond stresses were determined.

Table 6: Reference experiments in comparison of hybrid systems according to the invention

From Table 6 it can be seen that neither the reference experiment Ref1 (acrylate - amine / N-Michael addition) nor the reference experiment Ref2 (classic epoxy - amine reaction) achieve the high bond stresses of the hybrid systems according to the invention, despite the similar chemical structure of the starting materials.

Example 6: Composition and determination of the onset or glass transition temperatures of hybrid systems according to the invention

When the glass transition temperature is exceeded, a solid polymer changes to a rubbery to viscous state. In other words, the glass transition temperature is a measure of the strength under the influence of heat. Since, depending on the weather, high temperatures can occur on construction sites, the aim is to develop systems with correspondingly high glass transition temperatures. Table 7 below shows the onset or glass transition temperatures of hybrid systems according to the invention in comparison with a standard epoxy-amine system.

Table 7: onset and glass transition temperatures of hybrid systems according to the invention

FIS EM 390 ^S® (fischerwerke GmbH & Co. KG, Waldachtal, Germany) is a successful, well-established example on the market of a two-component injection mortar system for grouting in anchoring elements based on an epoxy-amine reaction. Table 7 shows that the onset temperatures of the hybrid systems according to the invention are comparable to an established injection mortar system and even exceed this in the second run in terms of the glass transition temperature. The hybrid systems according to the invention accordingly also have the necessary heat resistance, as required under construction site conditions.

Claims

Expectations:

1. Hybrid system for use as an adhesive, coating or paint, characterized in that the hybrid system a) a reaction resin based on a, ß-unsaturated compounds, b) a reaction resin based on CH-acidic methylene groups containing compounds and c) a primary Amine includes.

2. Hybrid system according to claim 1 as an adhesive for chemical fastening technology, in particular for fastening anchoring means in boreholes, which contains a reaction resin based on α, β-unsaturated compounds, a reaction resin based on compounds containing CH-acidic methylene groups, and a primary amine .

3. Hybrid system according to claim 1 or 2 in the form of a multi-component, in particular two-component system.

4. Hybrid system according to one of claims 1 to 3 in the form of a two-component kit.

5. Hybrid system according to one of claims 1 to 4, further comprising a catalyst.

6. Hybrid system according to one of claims 1 to 5 in the form of a multi-component kit, wherein

(i) the constituents a) and b) are contained in one component, while the constituent c) is contained together with a catalyst in another component which is immiscible in the storage state, it being possible for one or more further ingredients to be optionally present in each case; or

(ii) Components a), b) and the epoxy part of an epoxy / tert-amine. Catalyst is contained in one component and component c) together with the tertiary amine part of an epoxy / tertiary amine catalyst is contained in another component, it being possible for one or more additional ingredients to be optionally present in each case.

7. Hybrid system according to one of claims 1 to 6, wherein the reaction resin based on α, β-unsaturated compounds is such a reaction resin that contains or consists of an α, β-unsaturated compound, which contains at least one fumarate, maleate, Itaconate or acrylate group or preferably two or carries more of it, such as an acrylic acid ester or acrylamide, for example a mono- or, in particular, di-, tri-, tetra- or higher polyacrylate, in particular selected from hydroxy-C2-Cioalkyl-acrylate, such as hydroxyethyl-, -propyl- or -butyl acrylate, Ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol acrylate, poly (butanediol) diacrylate, polybutadiene diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripylene glycol, triethylene glycol diacrylate, Triisopropylenglykoldiacryalat, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated or propoxylated neopentylglycol diacrylate, tripropylene glycol diacrylate, bisphenol A, bisphenol F, bisphenol AF or bisphenol-S-diglycidyl ether diacrylate, bisphenol-A-polyethoxydiacrylate, bis phenol F-polyethoxy diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylol propane triacrylate, di-trimethylol propane tetraacrylate, trim ethylol propane polyethoxy triacrylate, ethoxylated or propoxylated trimethylol propane triacrylate, glycerol triacrylate, ethoxylated or propoxylated glycerol triacrylate,

T ris (2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, Pentaerythritolmono- hydroxytriacrylat, Pentaerythritoltriethoxytriacrylat, pentaerythritol tetraacrylate, ethoxylated or propoxylated pentaerythritol tetraacrylate, Ditrimethylolpropan- tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritolpolyhexanolidhexaacrylat, dipentaerythritol hexaacrylate, tris (hydroxyethyl) isocyanuratopolyhexanolidtriacrylat,

Tris (2-hydroxyethyl) isocyanuratotriacrylat, Tricyclodecandimethyloldiacrylat, Esterdioliacrylat, 2- (2-Acryloyloxy-1,1-dimetrhyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, Tetrabromobisphenol-A-diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide diacrylate, poly- tetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, dimethylolpropane tetraacrylate, cresol epoxy acrylate, novolak “poly“ acrylate, oligomers containing acrylate groups or polymers from the reaction of polymers - epoxides with acrylic acid or reactive derivatives thereof, such as acid halides or active esters or from the reaction of polyester polyols with acrylic acid or reactive derivatives thereof, in particular as just mentioned, or urethane acrylates (obtainable e.g. by reaction of isocyanates with an acrylate containing OH groups, such as hydroxyethyl, hydroxypropyl, hydroxybutyl or pentaerythritol tri-acrylate, and polyester acrylate resins, for example tetrafunctional polyester acrylates); an acrylic-functional alkoxysilane or organopolysiloxane as Acrylatomethyl trimethoxysilane, --methyldimethoxysilan, -dimethylmethoxysilan, ethoxysilane triethoxysilane or -methyldi-, acrylamidomethyl-trimethoxysilane, -methyldimethoxysilan, dimethyl methoxy silane, triethoxysilane, or methyl diethoxysilane, methyl-dimethylethoxysilane ; or a polyester resin based on maleic, fumaric or itaconic acid or in each case an anhydride thereof; or a polyester, polyurethane, polyether and / or alkyd resin which carries activated, ethylenically unsaturated groups; or an α, ß-unsaturated compound with a biogenic component, in particular an acrylate, preferably with a biogenic acrylate component of hydroxy-containing vegetable oils, such as castor oil or soybean oil, a wholly or at least partially biogenic (e.g. C1-C10) alkane (mono-, preferably di- , tri-, tetra-, penta- or hexa-, or poly) ol acrylate, a partially or preferably completely biogenic polyglycerol acrylate, a completely or partially biogenic acrylate of one or more sugar alcohols, such as mannitol, xylitol or sorbitol, a completely or partially biogenic one acrylated fusel oil, a fully or partially biogenic 5- or 6-ring heterocyclyl acrylate (in particular with one or two heteroatoms selected from O, N and S in the ring), or a partially or preferably fully biogenic glycerol or polyglycerin acrylate, or a completely or partially biogenic saccharide acrylate; or the corresponding methacrylates; or a mixture of two or more of the abovementioned α, β-unsaturated compounds.

8. Hybrid binder according to one of claims 1 to 7, wherein the reaction resin, which carries one or more CH-acidic methylene groups, one comprising malonic acid or a malonic acid ester, such as dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, dibutyl malonate, di-malonate - (2-ethylhexyl) ester or malonic acid dilauryl ester, cyanoacetic acid ester, such as 2-ethylhexyl cyanoacetate, butyl cyanoacetate, octyl cyanoacetate, 2-methoxyethyl cyanoacetate, a dione such as pentane-2,4-dione, hexane-2,4-dione, heptane -2,4-dione, 1-methoxy-2,4-pentanedione, 1-phenyl-1,3-butanedione, 1,3-diphenylo-1,3-propanedione, 4,6-dioxoheptanoic acid methyl ester, 5.7 -Dioxooctanoic acid methyl ester, an acetoacetate, such as benzoylacetoacetate, methyl, ethyl or butyl ester, methyl, ethyl or butyl propionylacetate, methyl butyroylacetate, methyl acetoacetate, ethyl, isopropyl, - n-butyl, isobutyl or tert-butyl ester, acetoacetic acid (2-methox ethyl) ester, acetoacetic acid (2-ethylhexyl) ester, acetoacetic acid lauryl ester, 2-acetoacetatoethyl acrylate, acetoacetic acid benzyl ester, 1,4-butanediol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentylglycol diacetoacetate, 2-propentylglycol diacetoacetate, 2-butanediol diacetate, 2-propylene diacetate , Cyclohexanedimethanol diacetoacetate, free or ethoxylated bisphenol A-, -F-, -AF- or -S-diacetoacetate, trimethylolpropane triacetoacetate, pentaerythritol tri- or tetraacetoacetate, ditrimethylolpropane tetraacetoacetate, or a polymeric acetoacetate, eg is obtainable by transesterification of acetoacetic acid (e.g. ethyl) esters, an oligomer or polymer bearing acetoacetate groups that is obtainable by copolymerization of acetoacetoxyethyl methacrylate, an oligomer or polymer that is obtainable from dialkyl malonates and diols, or an acetoacetylated novolak, or a mixture of is two or more of them.

9. Hybrid binder system according to one of claims 1 to 8, wherein the primary amine is a primary di- or polyamine, the aliphatic, heteroaliphatic, alicyclic, heterocyclic, aromatic, aliphatic-aromatic and silane / siloxane molecule structures or two or more independently selected thereof contains, in particular selected from the group of amino amides, polyamino amides, Mannich bases and amine adducts, isocyanate-amine adducts, Bucherer adducts and Michael adducts, in particular selected from the group of alkyl amines such as 1,2-diaminoethane, 2-methylpentanediamine, 2,2-dimethyl-1,3-propanediamine,

2.2.4- or 2,4,4-trimethylhexamethylenediamine), the heteroalkylamines such as 1,13-diamino-4,7,10-trioxatridecane, the commercially available amine-functionalized polyoxyalkylenes, triethylenetetramine and / or higher homologues, the cycloalkylamines, such as isophoronediamine, 1,3- and / or 1,4-bisaminomethylcyclohexane, TCD-diamine, 1,2- or 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl ) methane, norbornanediamine, diaminodicyclohexylmethane or 2,2-bis (4-aminocyclohexyl) propane, the heterocyloalkylamines, such as: aminoethylpiperazine and the aliphatic-aromatic amines, such as 1,3- or 1,4-benzenedimethanamine; or a mixture of two or more of these compounds; in particular selected from 2-methylpentanediamine, 1,2-diaminocyclohexane, 1-amino-3-aminomethyl-

3.5.5-trimethylcyclohexane, 1,3-benzenedimethanamine, 1,4-benzenedimethanamine, 1,6-diamino-2,2,4-trimethylhexane, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, N-aminoethylpiperazine, 1,3-bis ( aminomethyl) cyclohexane, TCD diamine, Jeffamines, dipropylenetriamine, N, N ^{'-Dicyclohexyl-1,6-hexanediamine,} N, ^N' - dimethyl-1,3-diaminopropane, N, N ^{'-diethyl-1,3-diaminopropane} , N, N-dimethyl-1,3-diaminopropane, secondary polyoxypropylenedi- and triamines, 2,5-diamino-2,5-dimethylhexane, bis- (aminomethyl) tricyclopentadiene, 1,8-diamino-p-menthane and bis- (4-amino-3,5-dimethylcyclohexyl) methane, or an aminoalkylsilane that contains at least one hydrolyzable group, such as alkoxy, for example methoxy or ethoxy - bonded to silicon -, in particular selected from the group that includes one or more of the following compounds includes: aminoalkyltri- or dialkoxysilanes, such as 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmetrhyldiethoxysilane, 3-aminopropylethyldietho xysilane, 3-aminopropylphenyldiethoxysilane, 4-aminobutyl- tiethoxysilane, 4-aminobutylethyldiethoxysilane, and N- (aminoalkyl) -amino-alkyltri- or -dialkoxysilanes, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; or a copolymer of one of the aforementioned silanes or another silane; or a mixture of two or more of the mentioned (poly) amines.

10. Hybrid system according to one of claims 1 to 9, which has a catalyst or two or more thereof, selected from strongly basic catalysts, such as alkali metal hydroxides, alkali metal alkoxides, quaternary ammonium compounds, tertiary amines, guanidines, amidines; Silicates; Metal oxides; Phosphine catalysts, e.g. tricyclohexylphosphine (particularly preferred),

Tricyclopentylphosphine, tri-n-hexylphosphine, tris (2,4,4-trimethylpentyl) phosphine, tris (2-ethylhexyl) phosphine, tri-n-octylphosphine (particularly preferred), tri-n-decylphosphine, tri-n -dodecylphosphine (particularly preferred), tristearylphosphine and triphenylphosphine; and catalysts in the form of mixtures of an epoxide with one or more tertiary amines, it being possible for salts of strong bases or small amounts of the strong bases themselves to be additionally added; or a mixture of two or more of the named catalysts.

11. Hybrid system according to one of claims 1 to 10, containing one or more further additives, in particular selected from fillers, rheological auxiliaries, thixotropic agents, plasticizers, coloring additives, adhesion promoters, solvents and reactive thinners.

12. Use of a multi-component, in particular two-component hybrid system composed as in one of claims 1 to 11 as an adhesive, in particular for fastening anchoring means in substrates such as masonry or concrete, or furthermore for fastening fibers, scrims, fabrics or composites to reinforce Structures.

13. A method or method for grouting anchoring elements in holes or gaps, in which a multi-component, in particular two-component, hybrid system according to one of claims 1 to 11 is used for grouting (of anchoring means, the hybrid system and an anchoring means successively, in particular first the Hybrid system, then the anchoring means, or - at least substantially - simultaneously, are introduced into a hole or a gap in a substrate.