Enamines as initiators in the curing of free-radically curing reactive resins for chemical fastening

Abstract

The invention describes a curing agent system for free-radically polymerizable compounds which contains an enamine and a transition metal in the form of a salt or a complex, and the use thereof for chemical fastening. Also described are a reactive resin system containing the curing agent system and a multicomponent reactive resin system containing the curing agent system, and the use thereof for chemical fastening.

Description

[0001] Principality of Liechtenstein

[0002] Enamines as initiators in the curing of radically curing reactive resins for chemical fixing

[0003] DESCRIPTION

[0004] The present invention relates to a hardener system for a reactive resin system which contains radically polymerizable compounds, wherein the hardener system comprises an enamine and a transition metal in the form of a salt or a complex, a reactive resin system containing this hardener system and a multi-component reactive resin system containing this hardener system and their use, in particular for chemical fastening.

[0005] The use of reactive resin mixtures based on radically polymerizable compounds has long been known. In the field of fastening technology, the use of reactive resin mixtures as organic binders in chemical fastening technology has become established. These are often two-component systems, with component A containing the reactive resin mixture and component B containing the curing agent. Other common ingredients such as fillers, accelerators, stabilizers, thixotropic agents, desensitizers, solvents, including reactive solvents, can be contained in one and / or the other component. By mixing the two components, the reaction is initiated through radical formation, and the resin is cured to form a thermoset.

[0006] Radically curing systems, especially those that cure at room temperature, require so-called radical initiators to trigger radical polymerization. In the field of chemical fastening technology, the hardener composition described in application DE 3226602 A1, comprising benzoyl peroxide as a radical initiator and an amine compound as an accelerator, and the hardener composition described in application EP 1586569 A1, comprising a perester as a hardener and a metal compound as an accelerator, have established themselves due to their properties. These hardener compositions allow for rapid and fairly complete curing even at very low temperatures down to -30°C. Furthermore, these systems are very robust in terms of the mixing ratios of reactive resin and hardener. This makes them suitable for use under construction conditions.

[0007] A disadvantage of these hardener compositions, however, is that in both cases, peroxides are used as radical initiators. These are thermally sensitive and react very sensitively to impurities. This leads to significant limitations in the formulation of paste-like hardener components, especially for injection mortars, with regard to storage temperatures, storage stability, and the selection of suitable components. To enable the use of peroxides such as dibenzoyl peroxide, peresters, and the like, phlegmatizing agents such as phthalates or water are added to stabilize them. However, these significantly impair the mechanical performance of reactive resin mixtures when used, for example, as reactive resin mortars for chemical bonding.

[0008] Furthermore, these known hardener compositions are disadvantageous in that they must contain peroxide concentrations of 0.5 wt.% and higher, which is problematic because peroxide-containing products with a concentration of 1% or more, such as dibenzoyl peroxide, must be labeled as sensitizing in some countries. The same applies to amine accelerators, some of which are also subject to mandatory labeling.

[0009] To date, there have been several attempts to reduce the amount of peroxide so that it falls below the labeling limit, or to completely eliminate the use of peroxides as radical initiators. DE 102010051818 B3 discloses compositions for chemical fastening in which the amount of peroxide has been reduced. The disadvantage of these compositions is that the load values ​​achievable with them are not particularly high.

[0010] DE 102011078785 A1 describes compositions for chemical fastening that use a peroxide-free curing system based on 1,3-dioxo compounds as the hardener and a manganese compound as the co-initiator. While this eliminates the need for peroxides, these compositions have the disadvantage of exhibiting a high temperature dependence during curing. While the hardener system results in good curing of the compositions at room temperature and at elevated temperatures, the curing reaction is too slow or stops completely at low temperatures, resulting in insufficient curing or even no curing at all.

[0011] Compositions for chemical fastening which also do not use peroxides as initiators are known from EP 3313896 A1, EP 3775017 A1 and WO 22 / 002567 A1.

[0012] EP 3313896 A1 describes a curing system for a synthetic resin composition with radically polymerizable compounds, which contains an activator in the form of a metal salt and, as a radical initiator, at least one aldehyde and / or ketone and at least one primary amine, and / or at least one aldimine or at least one ketimine, or a mixture of two or more of the components. This system is intended to enable the formulation of a label-free composition. However, its performance is limited, and curing is highly temperature-dependent, with the processing time of the compositions being very short at higher application temperatures and the curing time being very long at lower application temperatures.

[0013] EP 3775017 A1 describes the use of compounds known as inhibitors for radical polymerization, such as phenols, as well as triphenyl phosphite, triphenylphosphine, p-toluenesulfonic acid, N-isopropyl-N'-phenylphenylenediamine, and NH-acidic compounds, in combination with a curing system comprising an aldehyde and / or ketone and a primary amine, an aldimine, or a ketimine, or a mixture thereof, and a further activator (accelerator) in the form of a metal salt, as an initiator system for a synthetic resin composition containing radically polymerizable compounds. This is intended to accelerate radical polymerization and improve curing, particularly at low temperatures.

[0014] WO 22 / 002567 A1 describes a specific type of imine suitable as part of a curing system for radically polymerizable reactive resins and / or for polyaddition-curable reactive resins. These imines are obtainable by reacting an amino-functionalized polyoxyalkylene, whose polyoxyalkylene chains are a copolymer of oxyethylene and oxypropylene units, these polyoxyalkylene chains carrying primary amino groups, with a ketone and / or aldehyde having a hydrogen atom on the carbon atom in the α-position to the carbonyl carbon. This is intended to achieve increased reactivity compared to comparable, previously known systems as well as improved bond strengths. Furthermore, it is intended to avoid labeling, as would be required for commercially available imines and those compounds known from EP 3313896 A1 and EP 3775017 A1.

[0015] However, as tests have shown, the synthetic resin compositions known from EP 3313896 A1, EP 3775017 A1, and WO 22 / 002567 A1 have the disadvantage that, without further adjustment of the composition, their achievable load level is limited, since the adhesion of the cured mortar mass to the borehole wall is not optimal. This is demonstrated by the failure pattern in pull-out tests, in which the fastening system consisting of the anchor rod and mortar mass could be pulled out of the borehole. Therefore, further measures are required, such as the addition of additional compounds, which further increases the complexity of the system.

[0016] There is therefore a need for a hardener system for reactive resin systems based on radically polymerizable compounds for use as reaction resin mortars, in particular for chemical fixing, which does not have the disadvantages of the known hardener systems and which, however, does not negatively influence the positive properties of the reaction resin mortars.

[0017] More specifically, there is a need for a hardener system for reactive resin systems based on radically polymerizable compounds for chemical fixing, with which mortars can be provided that are label-free, whose curing is less temperature-dependent than the known hardener systems and with which a better bond of the cured mortar masses to the substrate and thus a higher load level of a fixing arrangement can be achieved.

[0018] The object of the present invention is to provide a hardener system for a reactive resin system based on radically polymerizable compounds for use in reaction resin mortars for the chemical fixing of anchoring agents, which hardener system dispenses with the use of peroxides, peresters, perketals or hydroperoxides, is therefore less critically labeled, thus allowing the formulation of label-free products, and yet has the advantageous properties of the peroxide-containing hardener systems from the prior art, such as achieving a high load level and largely temperature-independent curing.

[0019] This task is solved by providing a hardener system that contains an enamine with a metal-based activator and is free of peroxides, peresters, perketals and hydroperoxides.

[0020] Surprisingly, it has been shown that by using condensation products of secondary amines with aldehydes or ketones, the enamines, together with a metal-based activator, curing systems can be formulated that can be used as hardeners for radical-curing resins, such as those used in chemical anchors. This allows the previously used peroxides, which, among other things, lead to labeling of the mortar compounds, to be replaced with label-free compounds without having to forego the advantageous properties of the peroxides, such as use over a wide temperature range.

[0021] By eliminating the use of peroxides, peresters, perketals, or hydroperoxides, the curing systems according to the invention offer a number of additional advantages over systems known from the prior art. For example, there are no safety-related restrictions regarding the transport and storage of the components, in particular, no labeling as oxidizing agents. Furthermore, the use of phlegmatizers, which act as plasticizers and influence the mechanical performance of the cured reactive resins, can be dispensed with. Furthermore, fewer restrictions regarding the other formulation ingredients need to be considered when formulating multi-component reactive resin compositions.

[0022] Compared to the peroxide-free systems known from the prior art, the hardener systems according to the invention have the advantage that they provide a better bond between the hardened mortar masses and the substrate without having to introduce further compounds into the composition, thus making the composition less complex.

[0023] A first subject matter of the invention is a hardener system according to claim 1. A second subject matter of the invention is the use of the hardener system according to the invention as an initiator system for a reactive resin system based on radically polymerizable compounds according to claim 11. A third subject matter of the invention is a reactive resin system which contains a radically polymerizable compound as reactive resin and the hardener system according to the invention, according to claim 13. A fourth subject matter of the invention is a multi-component reactive resin system with a resin component and a hardener component according to claim 16. A fifth subject matter of the invention is the use of a reactive resin system according to the invention or a multi-component reactive resin system according to the invention as an adhesive, coating material or molding compound according to claim 18.A sixth aspect of the invention is the use of a reactive resin system according to the invention or a multi-component reactive resin system according to the invention for fixing anchoring means in substrates according to claim 19.

[0024] For the purposes of the invention, the terms used mean:

[0025] - ‘Inhibitor’ means a substance which suppresses undesired radical polymerisation during the synthesis or storage of a resin or resin-containing composition (these substances are also referred to as ‘stabilisers’ in specialist circles) or which delays radical polymerisation of a resin after the addition of an initiator (usually in conjunction with an accelerator or activator) (these substances are also referred to as ‘inhibitors’ in specialist circles; the respective meaning of the term can be deduced from the context);

[0026] - ‘initiator’, ‘curing agent’ or ‘hardener’ means a substance which (usually in combination with an activator) forms reaction-initiating radicals;

[0027] - ‘activator’ means a substance which reacts with the initiator so that large quantities of radicals are produced by the initiator even at low temperatures, or which catalyzes the decomposition reaction of the initiator;

[0028] - “Co-activator” means a substance whose presence enhances the reaction of the hardener with the activator.

[0029] - “hardener system”, a combination of the actual hardener (initiator) and activator and, if necessary, another activator (co-activator);

[0030] - "hardener component" means a liquid or viscous mixture of the hardener, optionally other components, e.g. co-activator, fillers, additives; typically the hardener composition is one of the two components of a two-component reactive resin system for chemical fixing (in a multi-component system also referred to as "hardener composition"); "peroxide-free" means that no peroxides, peresters, perketals or hydroperoxides are added;

[0031] - "reactive resin" means a usually solid or highly viscous "radically polymerisable", i.e. curable, compound which hardens by polymerisation and forms a resin matrix; the reactive resin is the reaction product of a bulk reaction itself; this also includes the reaction mixture for producing the backbone resin after the reaction has ended, which mixture is present without isolation of the product and can therefore contain, in addition to the radically polymerisable compound, the reactive resin, a reactive diluent, a stabiliser and a catalyst, if used;

[0032] - "Reactive diluents" are liquid or low-viscosity monomers and backbone resins which dilute other backbone resins or the reactive resin masterbatch and thereby impart the viscosity necessary for their application, contain functional groups capable of reacting with the reactive resin, and become predominantly a component of the cured mass (e.g., mortar) during polymerization (curing); reactive diluents are also called co-polymerizable monomers;

[0033] - “Reactive resin mixture” a liquid mixture of reactive resin, reactive diluents and optionally other components, such as activators and inhibitors, which is formulated by adding fillers and other additives, e.g. rheology aids to the reactive resin component.

[0034] - ‘Reactive resin component’ means a liquid or viscous mixture of reactive resin, fillers, optionally at least one reactive diluent and optionally further components, e.g. additives such as rheology additives, adhesion promoters, activators and / or inhibitors; typically, the reactive resin component is one of the two components of a two-component reactive resin system for chemical fastening (also referred to as ‘reactive resin composition’);

[0035] - "Reactive resin system" means a liquid or viscous mixture of reactive resin, optionally at least one reactive diluent, fillers, and optionally other components as described for the reactive resin composition. In addition, the reactive resin system contains the hardener, optionally at least one reactive or non-reactive diluent, as well as fillers and additives such as rheology additives, adhesion promoters, (co-)activators, and / or inhibitors.

[0036] - ‘two-component reactive resin system’ means a reactive resin system comprising two components stored separately from one another, a reactive resin component (A) and a hardener component (B), so that the backbone resin contained in the reactive resin component is only cured after the two components have been mixed;

[0037] - ‘multi-component system’ or ‘multi-component reactive resin system’ means a reactive resin system comprising several components stored separately from one another, including a reactive resin component (A) and a hardener component (B), so that the reactive resin contained in the reactive resin component only hardens after all components have been mixed;

[0038] - "(Meth)acrylic... / ...(meth)acrylic...'' means both the "methacrylic... / ...methacrylic..." and the "acrylic... / ...acrylic..." compounds; preferably, in the present invention, "methacrylic... / ...methacrylic..." compounds are meant;

[0039] - ‘Epoxy(meth)acryla’ means a compound containing acrylate or methacrylate groups and being substantially free of epoxy groups;

[0040] - "Alkyl" means a saturated hydrocarbon radical which may be branched or unbranched; preferably a Ci-C?-alkyl, particularly preferably a Ci-C4-alkyl, i.e. an alkyl selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl; methyl, ethyl, and tert-butyl are particularly preferred, and methyl is most preferably used;

[0041] 'Hydroxyalkyl' means an alkyl which carries at least one hydroxyl group as a substituent; - 'Alkenyl' means an unsaturated hydrocarbon radical having at least one double bond, which may be branched or unbranched; preferably a C2-C20 alkenyl, particularly preferably a C2-C8 alkenyl, i.e. an alkenyl selected from the group consisting of ethenyl, propenyl, butenyl, pentenyl and hexenyl; ethenyl, propenyl and butenyl are particularly preferred, and ethenyl is very particularly preferred;

[0042] - "cold-curing" means that a reactive resin system can fully cure at room temperature;

[0043] - "a", "an", "another" as an article before a chemical compound class, e.g., before the word "enamine," indicates that one or more compounds falling within this chemical compound class, e.g., various enamines, may be meant. In a preferred embodiment, this article refers to only a single compound;

[0044] - "at least one," "at least one," "at least one," numerically "one or more." In a preferred embodiment, this term means numerically "one," "an," "another";

[0045] - "contain," "comprise," and "include" indicate that, in addition to the components mentioned, further components may be present. These terms are meant inclusively and therefore also include "consist of." "Consist of" is meant conclusively and means that no further components may be present. In a preferred embodiment, the terms "contain," "comprise," and "include" mean the term "consist of."

[0046] - “approximately” or “circa” or “ca.” before a numerical value means a range of ± 10% of this value, preferably ± 2% of this value, more preferably ± 1% of this value, particularly preferably ± 0% of this value (i.e. exactly this value).

[0047] All standards mentioned in this text (e.g., DIN standards) were used in the current version as of the filing date of this application.

[0048] A first subject of the invention is a hardener system for a reactive resin system which contains radically polymerizable compounds, wherein the hardener system a) comprises a compound of formula (I) wherein

[0049] R 1 , R 2 and R 3 each independently of one another represents a hydrogen atom, a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl group may each optionally contain at least one heteroatom and / or be substituted,

[0050] R 4 and R 5each independently of one another is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl groups may each contain at least one heteroatom and / or be substituted, or

[0051] R 1 and R 2 , R 1 and R 3 , R 2 and R 3 and R 4 and R 5 together each independently form a cycloalkylene or cycloalkenyl group, each of which may also contain heteroatoms in or on the ring and / or may be substituted, and b) a transition metal in the form of a salt or a complex. The compound of formula (I) is an enamine wherein

[0052] R 1 , R 2 and R 3each independently of one another represents a hydrogen atom, a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl group may each optionally contain at least one heteroatom and / or be substituted,

[0053] R 4 and R 5 each independently of one another is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl groups may each contain at least one heteroatom and / or be substituted, or

[0054] R 1 and R 2 , R 1 and R 3 , R 2 and R 3 and R 4 and R 5together, independently of one another, form a cycloalkylene or cycloalkenyl group, which may each also contain heteroatoms in or on the ring and / or may be substituted.

[0055] R 1 , R 2 and R 3 are independently of one another a hydrogen atom, a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl group may each optionally contain at least one heteroatom and / or be substituted. R 1 and R 2 , independently of one another, are a linear or branched alkyl group, more preferably a Ci-Cw-alkyl group, even more preferably a Ci-Ce-alkyl group, and most preferably a Ci-Ca-alkyl group. R is most preferably 1 a methyl or ethyl group and R 2a methyl, ethyl or propyl group.

[0056] Preferred is R 3 a hydrogen atom, a linear or branched alkyl group, more preferably a hydrogen atom or a linear or branched Ci-Ce alkyl group, and most preferably a hydrogen atom.

[0057] Alternatively, R 1 and R 2 , R 1 and R 3 and R 2 and R 3 together form a cycloalkylene or cycloalkenyl group, which may also contain at least one heteroatom and / or be substituted, where two or more heteroatoms may be the same or different and may preferably be selected from oxygen (O), nitrogen (N), and sulfur atoms (S), more preferably from oxygen (O) and nitrogen atoms (N). The cycloalkenyl or cycloalkenyl group may be substituted. The heteroatoms may be present in or as a substituent on the ring.

[0058] R 4 and R 5 are independently of one another a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl group may each contain at least one heteroatom and / or be substituted.

[0059] Alternatively, R 4 and R 5 together form a cycloalkylene or cycloalkenyl group, which may also contain at least one heteroatom. If two or more heteroatoms are present, the heteroatoms may be the same or different and may preferably be selected from oxygen (O), nitrogen (N), and sulfur atoms (S), more preferably oxygen (O) and nitrogen atoms (N). The cycloalkenyl or cycloalkenyl group may be substituted. The heteroatoms may be present in or as a substituent on the ring. R preferably form 4 and R5 together an alkylene or cycloalkylene group which also contains at least one heteroatom, preferably one or two heteroatom(s), more preferably a cycloalkylene group having two heteroatoms, more preferably a Cs-Cs cycloalkylene group having two heteroatoms, even more preferably a Cs-Cs cycloalkylene group having one heteroatom or two heteroatoms, and most preferably a Cs cycloalkenyl group having two heteroatoms, wherein the heteroatoms are nitrogen atoms (N).

[0060] In a preferred embodiment, R 1 , R 2 and R 3 independently of one another, a hydrogen atom, a linear or branched alkyl, cycloalkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkenyl or aryl group, each of which may be optionally substituted, and R 4 and R 5together an alkylene or cycloalkylene unit which also contains at least one heteroatom, preferably one or two heteroatoms.

[0061] In a further preferred embodiment, R 1 , R 2 and R 3 , independently of one another, represent a hydrogen atom, a linear or branched alkyl group, more preferably a Ci-Cw-alkyl group, even more preferably a Ci-Cs-alkyl group, and form R 4 and R 5 together a Cs-Cs cycloalkylene unit having two heteroatoms, more preferably a Cs-Cs cycloalkylene unit having one heteroatom or two heteroatoms.

[0062] In a further preferred embodiment, R 1 and R 2 independently of one another, a linear or branched alkyl group, more preferably a C1-C10 alkyl group, even more preferably a Ci-Ce alkyl group, R 3 a hydrogen atom and form R 4 and R 5together a Cs-Cs cycloalkylene unit having two heteroatoms, more preferably a Cs-Cs cycloalkylene unit having one heteroatom or two heteroatoms.

[0063] In a particularly preferred embodiment, R 1 and R 2 independently of one another a Ci-Cs-alkyl group, most preferably a methyl group, R 3 a hydrogen atom and form R 4 and R 5 together a cycloalkylene unit which carries a nitrogen atom (N) and optionally a further nitrogen atom and / or oxygen atom (O) as heteroatoms.

[0064] In a particularly preferred embodiment, in the compound of formula (I) R 1 and R 2 a methyl, ethyl or propyl group, R 3 a hydrogen atom and form R 4 and R 5a 5-membered heterocycle with one nitrogen atom or a 6-membered heterocycle with one oxygen atom and one nitrogen atom or with two nitrogen atoms as heteroatoms, in particular a pyrrolidine, piperidine, piperazine or morpholine residue.

[0065] The described enamines are obtainable by condensation reaction of an aldehyde or a ketone, each carrying a hydrogen atom on the carbon atom in the a-position to the carbonyl carbon, with an amine having at least one secondary amino group.

[0066] The usable or suitable aldehydes or ketones are in particular those of the formula (II) (II), wherein:

[0067] R 1 , R 2 and R 3 which have the meaning as described above for formula (I).

[0068] The aldehydes and / or ketones are preferably compounds which have at least one or more (primary and / or secondary) hydrogen atoms on the a-carbon atom adjacent to the carbonyl group. Examples of such aldehydes are acetaldehyde, propanal (propionaldehyde), 2-methylpropanal (isobutyraldehyde), 2,2-dimethylpropanal (pivalaldehyde, trimethylacetaldehyde), butanal, 2-methylbutanal (2-methylbutyraldehyde), 2-ethylbutanal, n-pentanal (valeraldehyde), iso-pentanal (isovaleraldehyde), 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,3-dimethylpentanal, hexanal, 2-ethylhexanal, heptanal, octanal, nonanal, decanal, undecanal, 2-methylundecanal, dodecanal, or methoxyacetaldehyde, or 3,7-dimethyl-6-octenal (Citronellal), Malondialdehyde (Propandial), Succinaldehyde (butanedial), glutaraldehyde (pentandial), adipaldehyde (hexanedial) or 3,7-dimethyl-7-hydroxyoctanal (hydroxycitronellal).

[0069] More preferably, the aldehydes and / or ketones are compounds that have a branch and / or double bond at the α-carbon atom adjacent to the carbonyl group. As a result, the more preferred aldehydes and / or ketones have only one (tertiary) hydrogen atom at the α-carbon atom adjacent to the carbonyl group. Examples of particularly preferred aldehydes are isobutyraldehyde, 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, 2-methylvaleraldehyde, 2,3-dimethylvaleraldehyde, 2,6-dimethyl-5-heptenal, cyclopentanecarbaldehyde, cyclohexanecarbaldehyde, 2-methylcyclopentanone 4-formyltetrahydropyran, 2-phenyl-propionaldehyde or 3,7-dimethyl-2,6-octadienal (Citral), 3-(4-tert-butylphenyl)-2-methylpropanal (Lilial, Lysmeral), tetrahydrofuran-3-carboxaldehyde, tetrahydro-2-furancarboxaldehyde, 4-formyltetrahydropyran,

[0070] Tetrahydro-2H-pyran-2-carbaldehyde or tetrahydropyran-3-carbaldehyde. Other preferred ketones include diisopropyl ketone, 3-methyl-2-pentanone, 2-methylcyclohexanone, and ionone.

[0071] Aldehydes with a branch at the a-carbon atom adjacent to the carbonyl group are particularly preferred.

[0072] Even more preferably, these are aldehydes with a branch and a hydrogen atom at the a-carbon adjacent to the carbonyl group.

[0073] Also particularly preferred are the aldehydes mentioned in the examples and mixtures of two or more thereof.

[0074] Isobutyraldehyde, 2-methylbutanal, 2-ethylbutanal, and 2-methylpentanal are particularly preferred. The usable or suitable secondary amines are, in particular, those of the formula (III)

[0075] NHR 4 R 5 (III), wherein

[0076] R 4and R 5 which have the meaning as described above for formula (I).

[0077] Preferably, R 4 and R 5 together an alkylene or cycloalkylene group which also contains at least one heteroatom, preferably one or two heteroatom(s), further preferably a cycloalkylene group having two heteroatoms, more preferably a Cs-Cs cycloalkylene unit having two heteroatoms, even more preferably a Cs-Ce cycloalkylene unit having one heteroatom or two heteroatoms, and most preferably a Cs cycloalkenyl group having two heteroatoms, wherein the heteroatoms are nitrogen atoms (N).

[0078] Suitable secondary amines are, for example, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 4-(1-pyrrolidinyl)piperidine, piperazine, 1-methylpiperazine, 2,5- and 2,6-dimethylpiperazine, 2,3,5,6-tetramethylpiperazine, 1-(2-methoxyethyl)piperazine, pyrrolidine, morpholine, thiomorpholine, 3-phenylthiomorpholine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-isobutylamine, di-tert-butylamine, diethanolamine, and the like, N-benzylmethylamine, dibenzylamine, N,N'-dimethylethylenediamine, N,N'-dimethyldiethylenetriamine, N,N'-

[0079] Diisopropylethylenediamine, N,N'-dibutylethylenediamine, N,N'-dimethyldipropylenetriamine, N,N-bis-[3-(methylamino)propyl]methylamine, N,N'-di-tert-butylethylenediamine, tris[2-(methylamino)ethyl]amine, N,N,N'-trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N'-dimethyl-1,6-hexanediamine, N,N-diethyl-2-(1-piperazinyl)ethanamine, as well as homologues of piperazine, such as 1,4,7-triazacyclononane,

[0080] 1.4.7.10-Tetraazacyclododecane, 1,4,8,11-Tetraazacyclotetradecane, or 1,7-Dioxa-

[0081] 4,10-diazacyclododecane.

[0082] The amines mentioned in the examples or mixtures of two or more thereof are also particularly preferred. The initiation of polymerization and thus the curing of the reactive resins is based on a reaction of the at least one enamine with an activator. Suitable activators are transition metals in the form of salts and compounds, including oxides and complexes.

[0083] The transition metals in the form of a metal salt, which also includes metal complexes and metal oxides, are preferably one or more metal salts or in particular one or more salts of organic and / or inorganic acids with metals, e.g. selected from copper, iron, vanadium, manganese, cerium, cobalt, zirconium, or bismuth, or mixtures of two or more thereof. In particular, the metal salts are selected from the group consisting of vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid residues, such as sulfate and / or carbonate residues and / or organic acid residues, for example carboxylate residues, wherein the organic acids are straight-chain or branched and preferably saturated, such as carboxylates with CH3, C2-C2o-alkyl, a Ce-C24-aryl residue or CyCso-aralkyl residue, for example octoate, e.g. 2-ethylhexanoate (isooctanoate), neodecanoate, or acetylacetonate.Particularly preferred are salts that are soluble in organic media, such as carboxylates, e.g., octanoates, naphthenates, acetylacetonates, acetates, and quinolates. Manganese, vanadium, cobalt, and copper carboxylates are especially preferred.

[0084] The transition metals have varying degrees of reactivity. Their reactivity depends on various factors, such as their oxidation potential, the salts and compounds used, and possibly also on the form in which the transition metals are present, for example in solutions, whereby the solvent can also influence their reactivity. When using less reactive transition metal salts and compounds that have a lower activity, such as iron and copper salts and compounds, an additional activator (co-activator) is required to ensure that the initiator system has sufficient activity to initiate radical polymerization under construction site conditions. Under conditions such as those that prevail when reactive resins are used as mortar for chemical fixing, particularly in basic environments and with widely varying orDue to fluctuating temperatures, the enamines are not reactive enough in combination with an activator alone. Therefore, they are activated by adding a co-activator.

[0085] For the hardener system according to the invention, in particular when using copper as activator, phenols such as butylhydroxytoluene, hydroquinone, catechol and their alkylated or etherified derivatives (e.g. tert-butylcatechol or hydroquinone monomethyl ether), phosphites such as triethyl or triphenyl phosphate), phthalimide, saccharin and the like are suitable co-activators for the enamine-based hardener system according to the invention.

[0086] Saccharin can preferably be used as a co-activator.

[0087] As co-activators, optionally additionally conceivable are also the amines commonly used in fastening systems, such as dimethylamine, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, diisopropylamine, triisopropylamine, di-n-butylamine, diisobutylamine, tri-isobutylamine, diisopentylamine, diethanolamine, triethanolamine, dimethyl(2-chloroethyl)amine, bis(2-chloroethyl)amine, bis(2-ethylhexyl)amine, N-methylstearylamine, dialkylamines, N,N'-dimethylethylenediamine, permethyldiethylenetriamine, trimethylhexamethylenediamine, N,N-dimethylaminoethanol, 2-(2-diethylaminoethoxy)ethanol, tris-[2-(2-hydroxy-ethoxy)-ethyl]amine, 3-dimethylamino-1-propanol, 1-diethylamino-2-propanol,

[0088] Diisopropanolamin, Methyl-bis(2-hydroxypropyl)amin, Tris(2-hydroxypropyl)amin, 5- Diethylamino-2-pentanon, 3-Methylaminopropionsäurenitril, N-Methylcyclohexylamin, N,N-Dimethylcyclohexylamin, Dicyclohexylamin, N-Ethylcyclohexylamin, N-(2- Hydroxyethyl)-cyclohexylamin, N,N-Bis-(2-hydroxyethyl)-cyclohexylamin, N- Methylanilin, N,N-Dimethylanilin, N,N-Diethylanilin, N,N-Di-propylanilin, Diphenylamin, N-Hydroxyethylanilin, Bis(N-hydroxyethyl)anilin, Dibenzylamin, Tribenzylamin, Methyldibenzylamin, N,N-Diisopropylanilin, N-Dodecylanilin, N-Methylaminonaphthalin, N,N-Dimethylaminonaphthalin, N,N-Dibenzylnaphthalin, Morpholin, N-Methylmorpholin, N-Phenylmorpholin, Hydroxyethylmorpholin, N-Methylpyrrolidin, Pyrrolidin, Piperidin, Hydroxyethylpiperidin, Pyrrole, Pyridine, Chinoline, Indole, Indolenine, Carbazole, Pyrazole, Imidazole, Thiazole, Pyrimidine, Chinoxaline, Dimorpholinethan, [2,2,2]- Diazabicyclooctan und N,N-Dimethyl-p-toluidin.

[0089] It has been shown that for the purposes of chemical fixing, in particular for the chemical fixing of anchoring means in boreholes, by means of radically curing mortar systems, a hardener system based on copper in the form of salts and compounds, in particular carboxylates, enamine and saccharin, is particularly preferred, since they can provide compositions that are storage-stable compared to hardener systems that contain other, more reactive metals, in particular vanadium and cobalt.

[0090] The hardener system according to the invention contains the enamine in an amount of 30 to 99.9 wt.%, preferably 40 to 99 wt.%, particularly preferably 40 to 95 wt.% and very particularly preferably 50 to 95 wt.%, in each case based on the total weight of the hardener system.

[0091] If the hardener system contains a metal-based activator, it is contained in an amount of 0.001 to 50 wt.%, preferably 0.05 to 50 wt.% and particularly preferably 0.3 to 40 wt.%, in each case based on the total weight of the hardener system.

[0092] If the hardener system contains a co-activator, such as saccharin, this is contained in an amount of 0.01 to 50 wt.%, preferably 0.1 to 40 wt.% and particularly preferably 0.1 to 30 wt.%, in each case based on the total weight of the hardener system.

[0093] The hardener system according to the invention is suitable as an initiator for radical polymerization and thus for the curing of reactive resin systems based on radically curing compounds, so-called reactive resins.

[0094] The hardener system according to the invention makes it possible to provide a reactive resin system that, in addition to the hardener system according to the invention, contains a reactive resin and can also contain additives and fillers as additional components. It is peroxide-free, thus requiring less critical and, in the best case, no longer requiring corresponding labeling. This reactive resin system is particularly suitable for chemical fastening, in particular the chemical fastening of anchoring materials in boreholes, as it enables higher load values, even in damp boreholes.

[0095] Thus, a further object of the invention is the use of the hardener system according to the invention as a peroxide-free initiator system for a reactive resin system with radically polymerizable compounds, in particular for chemical fixing.

[0096] Reactive resin system

[0097] Furthermore, a further subject matter of the invention is a reactive resin system which contains the hardener system according to the invention, at least one radically polymerizable compound, at least one reactive diluent and optionally organic and / or inorganic additives and fillers.

[0098] The reactive resin system preferably contains, dissolved or dispersed in the reactive resin, at least one activator and optionally at least one co-activator of the hardener system. Suitable activators and co-activators are described above as components of the hardener system.

[0099] The reactive resin system contains the enamine in the hardener system in an amount of 0.1 to 30 wt.%, preferably 0.2 to 25 wt.%, particularly preferably 0.5 to 25 wt.% and very particularly preferably 0.5 to 20 wt.%, in each case based on the total weight of the reactive resin system.

[0100] If the reactive resin system contains a metal-based activator, it is present in an amount of 0.001 to 10 wt.%, preferably 0.005 to 5 wt.%, and particularly preferably 0.01 to 2 wt.%, based in each case on the total weight of the reactive resin system. If the reactive resin system contains a co-activator, such as saccharin, it is present in an amount of 0.001 to 10 wt.%, preferably 0.05 to 10 wt.%, and particularly preferably 0.01 to 3 wt.%, based in each case on the total weight of the reactive resin system.

[0101] The reactive resin system contains at least one radically polymerizable compound as reactive resin.

[0102] Suitable radically polymerizable compounds, the reactive resin, are compounds based on urethane (meth)acrylate, compounds based on epoxy (meth)acrylate, methacrylates of alkoxylated bisphenols, compounds based on other ethylenically unsaturated compounds and combinations thereof, as known to the person skilled in the art.

[0103] Particularly suitable and preferred vinyl ester resins are (meth)acrylate-functionalized resins, which are obtained, for example, by reacting di- and / or higher-functional isocyanates with suitable acrylic compounds, optionally with the assistance of hydroxy compounds containing at least two hydroxyl groups, as described, for example, in DE 3940309 A1. The urethane methacrylate resins described in DE 102011017626 B4 (also referred to as vinyl ester urethane resins) are particularly suitable and preferred.

[0104] Aliphatic (cyclic or linear) and / or aromatic di- or higher-functional isocyanates or prepolymers thereof can be used as isocyanates. The use of such compounds serves to increase wettability and thus improve adhesion properties. Aromatic di- or higher-functional isocyanates or prepolymers thereof are preferred, with aromatic di- or higher-functional prepolymers being particularly preferred. Examples include tolylene diisocyanate (TDI), diisocyanatodiphenylmethane (MDI), and polymeric diisocyanatodiphenylmethane (pMDI) for increasing chain stiffening, as well as hexane diisocyanate (HDI) and isophorone diisocyanate (IPDI), which improve flexibility, among which polymeric diisocyanatodiphenylmethane (pMDI) is particularly preferred.

[0105] Suitable acrylic compounds include acrylic acid and hydrocarbon-substituted acrylic acids such as methacrylic acid, hydroxyl-containing esters of acrylic or methacrylic acid with polyhydric alcohols, pentaerythritol tri(meth)acrylate, glycerol di(meth)acrylate such as trimethylolpropane di(meth)acrylate, and neopentyl glycol mono(meth)acrylate. Hydroxyalkyl esters of acrylic or methacrylic acid, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyoxyethylene (meth)acrylate, and polyoxypropylene (meth)acrylate, are preferred. The corresponding methacrylates are particularly preferred, since the steric hindrance leads to better alkali stability compared to acrylates.

[0106] Also suitable are compounds that are at least partially based on a recycled compound, in particular (meth)acrylic acid esters. Particular preference is given to a (meth)acrylic acid ester obtained from recycled methyl (meth)acrylate. Suitable compounds include hydroxyl-containing esters of acrylic or methacrylic acid with polyhydric alcohols, pentaerythritol tri(meth)acrylate, glycerol di(meth)acrylate, such as trimethylolpropane di(meth)acrylate, and neopentyl glycol mono(meth)acrylate, preferably acrylic or methacrylic acid hydroxyalkyl esters, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyoxyethylene (meth)acrylate, and polyoxypropylene (meth)acrylate, each of which can be obtained from recycled methyl (meth)acrylate.

[0107] Suitable hydroxy compounds which may be used optionally are dihydric or higher alcohols, for example derivatives of ethylene or propylene oxide, such as ethanediol, di- or triethylene glycol, propanediol, dipropylene glycol, other diols, such as 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethanolamine, further bisphenol A or F or their ethoxylation / propoxylation and / or hydrogenation or halogenation products, higher-hydric alcohols, such as glycerol, trimethylolpropane, hexanetriol and pentaerythritol, hydroxyl-containing polyethers, for example oligomers of aliphatic or aromatic oxiranes and / or higher cyclic ethers, such as ethylene oxide, propylene oxide, styrene oxide and furan, polyethers which contain aromatic structural units in the main chain, such as those of bisphenol A or F, hydroxyl-containing polyesters based on the above-mentioned alcohols or polyethers and dicarboxylic acids or their anhydrides, such as adipic acid, phthalic acid, tetra- orHexahydrophthalic acid, hetic acid, maleic acid, fumaric acid, itaconic acid, sebacic acid, and the like. Particularly preferred are hydroxy compounds with aromatic structural units for chain stiffening of the resin; hydroxy compounds containing unsaturated structural units, such as fumaric acid, for increasing the crosslinking density; branched or star-shaped hydroxy compounds, in particular trihydric or higher-hydric alcohols and / or polyethers or polyesters containing their structural units; and branched or star-shaped urethane (meth)acrylates for achieving lower viscosity of the resins or their solutions in reactive diluents and higher reactivity and crosslinking density.

[0108] The vinyl ester resin preferably has a molecular weight Mn in the range of 500 to 3000 Daltons, more preferably 500 to 1500 Daltons (according to ISO 13885-1). The vinyl ester resin has an acid value in the range of 0 to 50 mg KOH / g resin, preferably in the range of 0 to 30 mg KOH / g resin (according to ISO 2114-2000).

[0109] Preferred vinyl ester resins are (meth)acrylate-functionalized resins and resins obtained by reacting an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid, and optionally with a chain extender, such as diethylene glycol or dipropylene glycol. Examples of such compounds are known from applications US 3297745 A, US 3772404 A, US 4618658 A, GB 2217722 A1, DE 3744390 A1, and DE 4131457 A1.

[0110] The epoxy (meth)acrylate resins are obtained by reacting an organic compound containing epoxy groups with acrylic acid or methacrylic acid, so that the resins necessarily have acryloxy groups or methacryloxy groups at the molecular ends and hydroxyl groups in the 2-position to the formed acryloxy or methacryloxy group (hereinafter also referred to as α-hydroxyl groups) in the main chain of the molecule. Advantageously, 0.7 to 1.2 carboxyl equivalents of (meth)acrylic acid are used per epoxy equivalent. The organic compounds containing epoxy groups and the (meth)acrylic acid are preferably used in approximately stoichiometric ratios, i.e., approximately one equivalent of (meth)acrylic acid is used per epoxy equivalent of the organic compound. The reaction takes place in the presence of suitable catalysts known to those skilled in the art, such as quaternary ammonium salts.

[0111] As organic compounds containing epoxide groups, it is advisable to use those with a molecular weight that corresponds to a number average molecular weight M n in the range of 129 to 2,400 g / mol and which contain on average at least one, preferably 1.5 to 2, epoxy groups per molecule. Particular preference is given to epoxy groups of the glycidyl ether or glycidyl ester type, which are obtained by reacting an epihalohydrin, in particular epichlorohydrin, with a mono- or multifunctional aliphatic or aromatic hydroxy compound, thiol compound or carboxylic acid or a mixture thereof. The resulting organic compound containing epoxy groups has an epoxy equivalent mass (EEW) preferably in the range of 87 to 1,600 g / equivalent, more preferably in the range of 160 to 800 g / equivalent, and most preferably in the range of 300 to 600 g / equivalent.

[0112] Examples of suitable compounds containing epoxy groups are polyglycidyl ethers of polyhydric phenols such as pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane, 2,2-(4,4'-dihydroxydiphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane (bisphenol F), 4,4'-dihydroxydiphenylsulfone (bisphenol S), 4,4'-dihydroxydiphenylcyclohexane, tris-(4-hydroxyphenyl)methane, novolaks (ie from reaction products of mono- or polyhydric phenols with aldehydes, in particular formaldehyde, in the presence of acidic catalysts), such as phenol novolak resin, cresol novolak resin.

[0113] Furthermore, the following may be mentioned by way of example, but not by way of limitation: glycidyl ethers of monoalcohols, such as n-butanol or 2-ethylhexanol; or glycidyl ethers of polyhydric alcohols, such as 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerol, benzyl alcohol, neopentyl glycol, ethylene glycol, cyclohexanedimethanol, trimethylolpropane, pentaerythritol and polyethylene glycols, triglycidyl isocyanurate; polyglycidyl thioethers of polyhydric thiols, such as bismercaptomethylbenzene; or glycidyl esters of monocarboxylic acids, such as versatic acid; or glycidyl esters of polybasic, aromatic and aliphatic carboxylic acids, for example phthalic acid diglycidyl ester,

[0114] Diglycidyl isophthalate, diglycidyl terephthalate,

[0115] Diglycidyl tetrahydrophthalate, diglycidyl adipic acid and

[0116] Hexahydrophthalic acid diglycidyl ester.

[0117] As organic compounds containing epoxide groups, diglycidyl ethers of divalent hydroxy compounds of the general formula (VI) are particularly preferred in which R is an unsubstituted or substituted aliphatic or aromatic group, preferably an aromatic group, more preferably an aromatic group having 6 to 24 carbon atoms and the average value for n is 0 to 3. R is particularly preferably a bisphenol-type group, such as bisphenol A, bisphenol F or bisphenol S, or of the novolak type, with a bisphenol-type group being very particularly preferred. The average value for n is preferably about 0.1, about 1 or about 2. For the purposes of the present invention, compounds in which n is ~ 0.1 are referred to as monomeric and compounds in which n is ~ 1 or 2 are referred to as polymeric.

[0118] The polymeric compounds have the advantage over the monomeric compounds that the reactive resin content in the reactive resin composition can be significantly reduced, which makes the reactive resin composition more economical to produce, as this can reduce the production costs.

[0119] For the purposes of the invention, vinyl ester resins are oligomers or polymers with at least one (meth)acrylate end group, so-called (meth)acrylate-functionalized resins, which primarily include epoxy (meth)acrylates.

[0120] Vinyl ester resins that have unsaturated groups only in the terminal position are obtained, for example, by reacting epoxy oligomers or polymers (e.g., bisphenol A digylcidyl ether, phenol novolak-type epoxides, or tetrabromobisphenol A-based epoxy oligomers) with, for example, (meth)acrylic acid or (meth)acrylamide. Preferred vinyl ester resins are (meth)acrylate-functionalized resins and resins obtained by reacting an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid. Examples of such compounds are known from the applications US 3297745 A, US 3772404 A, US 4618658 A, GB 2217722 A1, DE 3744390 A1, and DE 4131457 A1. In this context, reference is made to application US 2011 / 071234.

[0121] The vinyl ester resin preferably has a molecular weight Mn in the range of 500 to 3000 Daltons, more preferably 500 to 1500 Daltons (according to ISO 13885-1). The vinyl ester resin has an acid value in the range of 0 to 50 mg KOH / g resin, preferably in the range of 0 to 30 mg KOH / g resin (according to ISO 2114-2000).

[0122] Particularly suitable as vinyl ester resins are ethoxylated bisphenol A di(meth)acrylate with a degree of ethoxylation of 2 to 10, preferably 2 to 4, difunctional, trifunctional or higher-functional urethane (meth)acrylate oligomers or mixtures of these polymerizable components.

[0123] Examples of such epoxy(meth)acrylates are those of formula (V)

[0124] (V), where n is a number greater than or equal to 1 (if mixtures of different molecules with different n values ​​are present and are represented by formula (V), non-integer numbers are also possible as the average value). Further examples of the propoxylated or, in particular, ethoxylated aromatic diols, such as bisphenol A, bisphenol F, or novolak (in particular di-)(meth)acrylates, are those of formula (VI)

[0125] (VI), wherein a and b each independently represent a number greater than or equal to 0, with the proviso that preferably at least one of the values ​​is greater than 0, preferably both are 1 or greater (if mixtures of different molecules with different (a and b) values ​​are present and are represented by the formula (VI), non-integer numbers are also possible as the mean value).

[0126] Particularly suitable are the known reaction products of di- or polyisocyanates and hydroxyalkyl methyl acrylates, as described, for example, in DE 2312559 A1, adducts of (di)isocyanates and 2,2-propanebis-[3-(4-phenoxy)-1,2-hydroxypropane-1-methacrylate] according to US Pat. No. 3,629,187, and the adducts of isocyanates and methacryloyl alkyl ethers, alkoxybenzenes, or alkoxycycloalkanes, as described in EP 44352 A1. In this context, reference is made to DE 2312559 A1, DE 19902685 A1, EP 0684906 A1, DE 4111828 A1, and DE 19961342 A1. Of course, mixtures of suitable monomers can also be used.

[0127] All of these resins, which can be used with preference according to the invention, can be modified according to methods known to those skilled in the art, for example, to achieve lower acid numbers, hydroxide numbers, or anhydride numbers, or to make them more flexible by incorporating flexible units into the backbone, and the like. Furthermore, the reactive resin can contain other reactive groups that can be polymerized with a radical initiator, such as peroxides, for example, reactive groups derived from itaconic acid, citraconic acid, and allylic groups, and the like, as described, for example, in WO 2010 / 108939 A1 (itaconic acid esters).

[0128] The reactive resin system may contain suitable reactive diluents, as described in applications EP 1 935 860 A1 and DE 195 31 649 A1. The reactive resin composition preferably contains a (meth)acrylic acid ester as reactive diluent, with particular preference being given to selecting aliphatic or aromatic C5-C15-(meth)acrylates. Suitable examples include: 2-,3-hydroxypropyl (meth)acrylate (HP(M)A), 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,

[0129] Trimethylolpropane tri(meth)acrylate, phenethyl(meth)acrylate,

[0130] Tetrahydrofurfuryl(meth)acrylat, / V, / V-Dimethylaminoethyl(meth)acrylat, / V, / V- Dimethylaminomethyl(meth)acrylat, Acetoacetoxyethyl(meth)acrylat, lsobornyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, Methoxypolyethylenglykol- mono(meth)acrylat, T rimethylcyclohexyl(meth)acrylat, 2-Hydroxyethyl(meth)acrylat, Dicyclopentenyloxyethyl(meth)acrylat und / oder T ricyclopentadienyldi(meth)acrylat, Bisphenol-A-(meth)acrylat, Novolakepoxidi(meth)acrylat, Di-[(meth)acryloyl-maleoyl]- tricyclo-5.2.1 .0. 2 6 -decan, Dicyclopentenyloxyethylcrotonat, 3-(Meth)acryloyl-oxymethyl- tricylo-5.2.1.0. 2 6 -decan, 3-(Meth)cyclopentadienyl(meth)acrylat, und Decalyl-2- (meth)acrylat; Glycerolformal(meth)acrylat; Solketal(meth)acrylat,

[0131] Cyclohexyl (meth)acrylate, phenoxyethyl di(meth)acrylate, methoxyethyl (meth)acrylate, tert-butyl (meth)acrylate, and norbornyl (meth)acrylate. Methacrylates are preferred over acrylates. Particularly preferred are 2- and 3-hydroxypropyl methacrylate (HPMA), 1,2-ethanediol dimethacrylate, 1,4-butanediol dimethacrylate (BDDMA), 1,3-butanediol dimethacrylate, trimethylolpropane trimethacrylate, acetoacetoxyethyl methacrylate, isobornyl methacrylate, bisphenol A methacrylate, trimethylcyclohexyl methacrylate, 2-hydroxyethyl methacrylate, PEG200 or PEG400 dimethacrylate, and norbornyl methacrylate. Particularly preferred are 1,4-butanediol dimethacrylate and a mixture of 2- and 3-hydroxypropyl methacrylate (HPMA), or a mixture of these three methacrylates. A mixture of 2- and 3-hydroxypropyl methacrylate (HPMA) is most preferred.In principle, other conventional radically polymerizable compounds, alone or mixed with the (meth)acrylic acid esters, can also be used as reactive diluents, e.g., styrene, α-methylstyrene, alkylated styrenes such as tert-butylstyrene, divinylbenzene, and vinyl and allyl compounds, with preference being given to those not subject to labeling. Examples of such vinyl or allyl compounds are hydroxybutyl vinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, mono-, di-, tri-, tetra-, and polyalkylene glycol vinyl ether, mono-, di-, tri-, tetra-, and polyalkylene glycol allyl ether, divinyl adipate, trimethylolpropane diallyl ether, and trimethylolpropane triallyl ether.

[0132] The reactive diluents are preferably present in an amount of up to about 80% by weight, particularly preferably from about 10 to about 60% by weight, even more preferably from about 30 to about 60% by weight, based on the reactive resin.

[0133] One or more inhibitors may be present in the reactive resin system according to the invention both to stabilize the reactive resin or the reactive resin composition containing the reactive resin and to adjust the resin reactivity.

[0134] Suitable inhibitors for this purpose are the inhibitors commonly used for radically polymerizable compounds, as known to those skilled in the art. These inhibitors are preferably selected from non-phenolic inhibitors, especially phenothiazines.

[0135] Suitable non-phenolic inhibitors are preferably phenothiazines, such as phenothiazine and / or derivatives or combinations thereof, or stable organic radicals, such as galvinoxyl and / V-oxyl radicals, in particular of the piperidinyl-A / -oxyl or tetrahydropyrrole- / V-oxyl type, such as aluminum-ZV-nitrosophenylhydroxylamine, diethylhydroxylamine, oximes, such as acetaldoxime, acetone oxime, methyl ethyl ketoxime, salicyloxime, benzoxime, glyoximes, dimethylglyoxime, acetone-O-(benzyloxycarbonyl)oxime, 4-hydroxy-TEMPO, (TEMPOL), 4-acetyl-TEMPO, TEMPO and the like. Furthermore, pyrimidinol or pyridinol compounds substituted in the para position to the hydroxyl group, as described in patent DE 10 2011 077 248 B1, can be used as inhibitors.

[0136] Stable / V-oxyl radicals that can be used include those described in DE 199 56 509 A1 and DE 195 31 649 A1. Such stable nitroxyl radicals are of the piperidinyl-AZ-oxyl or tetrahydropyrrole- / V-oxyl type, or a mixture thereof.

[0137] Preferred stable nitroxyl radicals are selected from the group consisting of 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (also referred to as TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one (also referred to as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine (also referred to as 4-carboxy-TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine (also referred to as 3-carboxy-PROXYL) and mixtures of two or more of these compounds, wherein 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-ol (TEMPOL) is particularly preferred.

[0138] Preferably, the inhibitor(s) are selected from the group consisting of / V-oxyl radicals, catechols, catechol derivatives, and phenothiazines, and a mixture of two or more thereof. Particularly preferred is the inhibitor(s) selected from the group consisting of tempol, catechols, and phenothiazines. The inhibitors used in the examples are very particularly preferred, preferably in approximately the amounts specified in the examples.

[0139] Depending on the desired properties of the reactive resin, the inhibitors can be used either alone or in combination with two or more of them. A combination of phenolic and non-phenolic inhibitors is preferred.

[0140] The inhibitor or the inhibitor mixture is added in amounts customary in the art or is already contained in the raw materials used, preferably in an amount of about 0.0005 to about 2 wt.%, more preferably from about 0.001 to about 1 wt.%, even more preferably from about 0.005 to about 0.5 wt.%, in each case based on the reactive resin.

[0141] The reactive resin system may contain fillers and / or additives commonly used for chemical bonding. It should be noted that some substances can be used both as fillers and, possibly in modified form, as additives. For example, fumed silica in its polar, untreated form serves more as a filler, while its apolar, post-treated form serves more as an additive. In cases where the exact same substance can be used as a filler or additive, its total amount should advantageously not exceed the upper limit for fillers specified herein.

[0142] For the formulation of the reactive resin system according to the invention, conventional fillers can be used, preferably mineral or mineral-like fillers, such as quartz, glass, sand, quartz sand, quartz flour, porcelain, corundum, ceramics, talc, silica (e.g. fumed silica, in particular polar, non-treated fumed silica), silicates, aluminum oxides (e.g. alumina), clay, titanium dioxide, chalk, barite, feldspar, basalt, aluminum hydroxide, granite or sandstone, polymeric fillers, such as thermosets, hydraulically curable fillers, such as gypsum, quicklime or cement (e.g. aluminate cement (often also referred to as alumina cement) or Portland cement), metals, such as aluminum, carbon black, furthermore wood, mineral or organic fibers, or the like, or mixtures of two or more thereof. The fillers can be in any desired form, for example as powder or flour, or as shaped bodies, e.g.in cylindrical, ring, spherical, platelet, rod, saddle, or crystalline form, or further in fiber form (fibrillar fillers), and the corresponding base particles preferably have a maximum diameter of about 10 mm and a minimum diameter of about 1 nm. That is, the diameter is about 10 mm or any value less than about 10 mm but more than about 1 nm. Preferably, the maximum diameter is about 5 mm, more preferably about 3 mm, even more preferably about 0.7 mm. A maximum diameter of about 0.5 mm is very particularly preferred. The more preferred minimum diameter is about 10 nm, even more preferably about 50 nm, even more preferably about 100 nm. Diameter ranges resulting from a combination of these maximum and minimum diameters are particularly preferred. However, globular, inert substances (spherical shape) have a preferred and significantly more enhancing effect.Core-shell particles, preferably in spherical form, can also be used as fillers.

[0143] Preferred fillers are selected from the group consisting of cement, silica, quartz, quartz sand, quartz flour, and mixtures of two or more thereof. For the purposes of chemical fastening, particularly preferred fillers are selected from the group consisting of cement, fumed silica, especially untreated polar fumed silica, quartz sand, quartz flour, and mixtures of two or more thereof.

[0144] The use of at least one powdered recycling material according to the previously unpublished European patent application EP 21 207137.7 (filing date 09.11.2021) as a filler is also suitable.

[0145] Further conceivable additives are rheology additives, such as optionally organically or inorganically post-treated pyrogenic silica (if it is not already used as a filler), in particular apolar post-treated pyrogenic silica, bentonites, alkyl and methyl celluloses, castor oil derivatives or the like, plasticizers such as phthalic acid or sebacic acid esters, stabilizers, antistatic agents, thickeners, flexibilizers, curing catalysts, rheology aids, wetting agents, coloring additives such as dyes or in particular pigments, for example for differently coloring the components to better control their mixing, or the like, or mixtures of two or more thereof. Furthermore, agents for regulating the pH value, such as inorganic and / or organic acids according to DE 102010008971 A1, in particular copolymers with acidic groups, e.g. esters of phosphoric acid, can be used.Non-reactive diluents (solvents) may also be present, preferably in an amount of up to 30% by weight, based on the respective component (reactive resin mortar, hardener), for example from 1 to 20% by weight, such as lower alkyl ketones, e.g. acetone, di-lower alkyl-lower alkanoylamides, such as dimethylacetamide, lower alkylbenzenes, such as xylenes or toluene, phthalic acid esters or paraffins, or water, or glycols. In addition, agents for improving the compatibility between resin and hardener components, such as ionic, non-ionic or amphoteric surfactants; soaps, wetting agents, detergents; polyalkylene glycol ethers; salts of fatty acids, mono- or diglycerides of fatty acids, sugar glycerides, lecithin; alkanesulfonates, alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol polyglycol ethers,.

[0146] Fatty alcohol ether sulfates, sulfonated fatty acid methyl esters; fatty alcohol carboxylates; alkyl polyglycosides, sorbitan esters, N-methylglucamides, sucrose esters; alkylphenols, alkylphenol polyglycol ethers, alkylphenol carboxylates; quaternary ammonium compounds, esterquats, carboxylates of quaternary ammonium compounds.

[0147] In one embodiment, the reactive resin system can additionally contain a bonding agent. The use of a bonding agent improves the cross-linking of the borehole wall with the anchoring compound, thus increasing the adhesion in the cured state. This is important for the use of a anchoring compound, for example, in boreholes drilled with a diamond drill, and increases the bond failure stress. Suitable bonding agents are selected from the group of silanes, which are functionalized with other reactive organic groups and can be incorporated into the polymer network. This group includes, for example,3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxymethyltrimethoxysilane, 3-(meth)acryloyloxymethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, functionalized tetraethoxysilane, functionalized tetramethoxysilane, functionalized tetrapropoxysilane, functionalized ethyl or propyl polysilicate, and mixtures of two or more thereof. In this regard, reference is made to application DE 10 2009 059210.

[0148] In a particularly preferred embodiment, the components of the reactive resin system are one or more of the components mentioned in the examples according to the invention. Reactive resin and / or hardener compositions that contain the same components or consist of the same components as mentioned in the individual examples according to the invention, preferably in approximately the proportions mentioned therein, are very particularly preferred.

[0149] The reactive resin system according to the invention is preferably present as a multi-component reactive resin system, which also includes a two-component reactive resin system. A multi-component system is understood, in particular, to mean a two-component system in which the mutually reactive components are contained in such a way that they cannot lead to undesirable reactions during storage. In a two-component system, this means, for example, that the system is a two-chamber device, i.e., the components (reactive resin component and hardener component) are located in spatially separate chambers.

[0150] A further subject of the invention is therefore a multi-component reactive resin system containing the reactive resin system according to the invention, wherein the constituents of the reactive resin system are distributed among the components in such a way that they do not react with each other. Only when the components are mixed do the components react, causing the reactive resin to cure. This means that the constituents of the hardener system according to the invention are distributed among different components.

[0151] The preferred two-component reactive resin system consists of a reactive resin component (also reactive resin composition) and a hardener component (also hardener composition).

[0152] The reactive resin component comprises a reactive resin, a reactive diluent, optionally an activator, and optionally a co-activator. One or more of these components may be present in each case. Furthermore, the reactive resin component may comprise inorganic and / or organic additives and fillers. Therefore, in a preferred embodiment, the reactive resin component comprises a reactive resin, at least one reactive diluent, an activator, optionally a co-activator, and inorganic and / or organic additives and fillers.

[0153] If the hardener system and thus the multi-component reactive resin system contains a metal-based activator, it is contained in an amount of 0.001 to 10 wt.%, preferably 0.01 to 5 wt.% and particularly preferably 0.05 to 2 wt.%, in each case based on the total weight of the reactive resin component.

[0154] If the hardener system contains a co-activator, such as saccharin, this is contained in an amount of 0.01 to 10 wt.%, preferably 0.01 to 5 wt.% and particularly preferably 0.1 to 5 wt.%, in each case based on the total weight of the reactive resin component.

[0155] The hardener component comprises an enamine, optionally at least one activator, and optionally at least one co-activator. Furthermore, the hardener component can comprise at least one reactive or non-reactive diluent, inorganic and / or organic additives, and fillers.

[0156] The at least one activator can be contained in the hardener component and / or the reactive resin component. However, it is preferably contained in the reactive resin component to increase the storage stability of the multi-component reactive resin system.

[0157] The at least one co-activator can be contained in the hardener component and / or the reactive resin component. However, it is preferably contained in the hardener component to increase the storage stability of the multi-component reactive resin system.

[0158] The constituents of the reactive resin component and the hardener components of the multi-component reactive resin system according to the invention are as described above. Furthermore, the hardener component can contain at least one reactive or non-reactive diluent. Suitable non-reactive diluents are liquid, organic substances that do not contain ethylenically unsaturated double bonds; typically, but not exclusively, ethers or esters; preferably low-viscosity and high-boiling substances with a viscosity of less than 2000 mPas and a boiling point above 80°C.

[0159] Preferred non-reactive diluents are diesters of bifunctional carboxylic acids, such as adipates or (also hydrogenated) phthalates. Benzoates or esters of inorganic acids, such as organic phosphates, are also suitable. Also preferred are liquid polyalkylene glycols of suitable chain length (polyethylene glycols, polypropylene glycols, and mixed polyalkylene glycols or mixtures thereof) that bear OH groups at the chain ends or are etherified or esterified.

[0160] Preferred are dialkyl adipates, dialkyl maleates or dialkyl succinates as well as di- or trialkyl citrates or optionally hydrogenated dialkyl phthalates; e.g. 1,2-

[0161] Cyclohexanedicarboxylic acid diisononyl ester (DINCH) or mixtures of these or other plasticizers.

[0162] Also preferred are reactive diluents mentioned in EP 1352002 A1.

[0163] Further preferred are reactive diluents containing ethylenically unsaturated double bonds. Examples include (meth)acrylic acid esters, styrene, α-methylstyrene, alkylated styrenes such as tert-butylstyrene, divinylbenzene, and vinyl and allyl compounds, with preference given to the non-labeling-required representatives.

[0164] Particularly preferred are non-radically homopolymerizable reactive diluents, such as vinyl or allyl compounds. Examples of these particularly preferred reactive diluents are hydroxybutyl vinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, mono-, di-, tri-, tetra-, and polyalkylene glycol vinyl ether, mono-, di-, tri-, tetra-, and polyalkylene glycol allyl ethers that carry OH groups at the chain ends or are etherified or esterified, divinyl adipate, trimethylolpropane diallyl ether, and trimethylolpropane triallyl ether, as well as mixtures of such substances with one another or with non-reactive diluents.

[0165] The proportion of the reactive resin in the reactive resin component is preferably from about 10 to about 70 wt.%, more preferably from about 10 to about 60 wt.%, even more preferably from about 10 to about 40 wt.%, based on the reactive resin component.

[0166] The reactive diluent(s) are preferably present in the reactive resin in an amount of up to about 70% by weight, particularly preferably from about 5 to about 60% by weight, even more preferably from about 10 to about 50% by weight, based on the reactive resin component.

[0167] The adhesion promoter is advantageously contained in amounts of about 1 to about 10 wt.% based on the total weight of the reactive resin component.

[0168] The proportion of the enamine in the hardener component is preferably from about 1 to about 70 wt.%, more preferably from about 2 to about 50 wt.%, even more preferably from about 5 to about 30 wt.%, based on the total weight of the hardener component.

[0169] If the hardener system and thus the multi-component reactive resin system contains a metal-based activator, it is contained in an amount of 0.01 to 10 wt.%, preferably 0.1 to 5 wt.% and particularly preferably 0.2 to 2 wt.%, in each case based on the total weight of the hardener composition.

[0170] If the hardener system contains a co-activator, e.g. saccharin, this is contained in an amount of 0.01 to 20 wt.%, preferably 0.1 to 10 wt.% and particularly preferably 0.5 to 10 wt.%, in each case based on the total weight of the hardener composition.

[0171] The proportion of the at least one reactive or non-reactive diluent in the hardener component is preferably from about 5 to about 70 wt.%, more preferably from about 10 to about 50 wt.%, even more preferably from about 20 to about 50 wt.%, based on the total weight of the hardener component.

[0172] It is also possible to divide the reactive resin system into three or more components. In this case, a multi-component reactive resin system results.

[0173] The mixing ratio of reactive resin and hardener components is in the range of 1:1 to 20:1 based on the volume of the components. Mixing ratios between 3:1 and 10:1 are preferred, with mixing ratios between 5:1 and 10:1 being particularly preferred.

[0174] The multi-component reactive resin system according to the invention can be in the form of a cartridge system, a cartridge system, or a foil bag system. When used as intended, the components are pressed out of the cartridges, cartridges, or foil bags either under the action of mechanical forces or gas pressure, mixed together, preferably with the aid of a static mixer through which the components are passed, and introduced into the borehole. Afterward, the devices to be secured, such as threaded anchor rods and the like, are inserted into the borehole filled with the curing reactive resin and adjusted accordingly.

[0175] The reactive resin system according to the invention is used primarily in the construction sector, for example for the repair of concrete, as polymer concrete, as a synthetic resin-based coating compound, or as a cold-curing road marking. It is particularly suitable for the chemical fastening of anchoring elements, such as anchors, reinforcing bars, screws, and the like, in boreholes, in particular in boreholes in various substrates, in particular mineral substrates such as those based on concrete, aerated concrete, brickwork, sand-lime brick, sandstone, natural stone, glass, and the like, and metallic substrates such as those made of steel. In one embodiment, the substrate of the borehole is concrete, and the anchoring element is made of steel or iron. In another embodiment, the substrate of the borehole is steel, and the anchoring element is made of steel or iron.The reactive resin system according to the invention is used in particular for securing anchoring means in boreholes in various substrates and for structural bonding. In one embodiment, the substrate of the borehole is concrete, and the anchoring means is made of steel or iron. In another embodiment, the substrate of the borehole is steel, and the anchoring means is made of steel or iron. The steel borehole preferably has grooves.

[0176] The invention is explained in more detail below using a series of examples. All examples and illustrations support the scope of the claims. However, the invention is not limited to the specific embodiments shown in the examples and illustrations.

[0177] EXAMPLES OF IMPLEMENTATION

[0178] Unless otherwise stated, all components of the compositions listed here are commercially available and were used in commercially usual quality.

[0179] All percentages given in the examples refer to the total weight of the described composition as a calculation basis, unless otherwise stated.

[0180] Table 1 : Raw materials used in the reactive resin components (A)

[0181] Production of enamines

[0182] Depending on the consistency of the raw materials, the condensation was carried out either in substance or in aqueous solution.

[0183] Example Morpholine / Isobutyraldeh yd

[0184] 8.7 g of morpholine were initially introduced, and 7.2 g of isobutyraldehyde were added portionwise while stirring. The addition rate should not be too high to avoid excessive heat evolution. The reaction mixture was stirred overnight. In this case, the water formed remained in the resulting enamine.

[0185] Example Piperazine / Isobutyraldehyde

[0186] 43g of piperazine were dissolved in 50g of water at approximately 50°C, and 72g of isobutyraldehyde were slowly added at this temperature. The temperature was maintained at 80°C for two hours while stirring. After cooling, the organic phase (enamine) was separated from the aqueous phase in a separatory funnel and used for curing experiments.

[0187] Other enamines (diethanolamine / isobutyraldehyde; morpholine / glutaraldehyde; piperazine / glyoxalaldehyde) were prepared analogously. Depending on the reactivity of the reactants, longer heating may be necessary. It is advisable, but often not necessary, to separate the water formed from the organic phase—for example, by azeotropic distillation using a water separator. In this case, the aldehyde was added in excess and distilled off after the reaction. Conducting the curing experiments

[0188] To test the suitability of components of the initiator system, a few grams of a resin mixture (urethane methacrylate with reactive diluents) were placed in a crimp-neck vial, metal salt (solid or in solution) was added, and homogenized on a magnetic stirrer. When using non-pre-dissolved resins, the mixture was heated to approximately 50°C, leaving any incompletely dissolved residue in the resin. After cooling to room temperature, the additives listed in Table 2 and the enamine were added, if necessary, the vial was sealed, and shaken. The consistency of the contents was checked approximately every 5 minutes, and the time until solidification (t(gel)) was recorded. The results are shown in Tables 2 to 5.

[0189] Where low-soluble reactants (such as saccharin) were used in the resin, the resin was thickened with a small amount of silica (Cab-O-Sil® TS720) to prevent settling.

[0190] The results shown in Table 2 clearly show that enamines are generally suitable as curing agents for methacrylates. However, without additional co-activators, metal compounds with high redox potential are required.

[0191] The results shown in Table 3 show that various co-activators are suitable for enabling the initiation of polymerization even with metals with low redox potential.

[0192] Table 4 shows that different metal compounds can be used to ensure curing by enamines with a suitable co-activator.

[0193] The results shown in Table 5 demonstrate that various enamines are suitable for use as curing agents. Table 2: Composition of the reactive resin compositions according to the invention and results of the curing tests (determination of t(gel))

[0194] *) Petr Vanysek; CRC handbook of chemistry and physics; 69 th Edition 1988-1989

[0195] Table 2 (Continued 1):

[0196] Table 2 (continued 2):

[0197] Table 2 (continued 3):

[0198] Production of two-component mortars

[0199] Production of the reactive resin components

[0200] All components of the respective reactive resin components listed in Table 6, as well as activators and inhibitors, were placed in a plastic beaker and stirred on a magnetic stirrer at 50°C until the mixture was homogeneous. After adding the silica and fillers, the mixture was briefly stirred manually using a wooden spatula and homogenized in a dissolver (PC Laborsystem) for 8 minutes at 3500 μl / min under vacuum (80 mPa).

[0201] Production of the hardener components

[0202] The hardener components used in the examples were prepared by combining all of the respective hardener components listed in Table 5 and mixing them together in a dissolver (type LDV) for 8 minutes at 3500 rpm in vacuum at a pressure of 80 mPa.

[0203] Production of mortar masses

[0204] To produce the mortar mixtures, the reactive resin and hardener components were filled into hard cartridges in the specified volume ratio according to Tables 6 and 7 and applied into the borehole via a static mixer (HIT-RE-M, Hilti).

[0205] Production of the comparison reactive resin components and hardener components

[0206] The comparative reactive resin components and comparative hardener components were prepared based on EP 3313896 B1, EP 3775017 A1, and WO 2022002567 A1. Since the additives used there were not disclosed, commercially available thickeners were added.

[0207] Measurement of the gelling time

[0208] The gel time of the resulting mixture of reactive resin and hardener components was determined using a commercially available device (GELNORM® Gel Timer) at a temperature of 25°C. For this purpose, the reactive resin and hardener components were mixed in the specified volume ratio, and the temperature of the sample was measured immediately after mixing. The sample itself was placed in a test tube with an air jacket in a silicone bath maintained at 25°C.

[0209] Determination of load values

[0210] To determine the load values ​​of the cured mass, a high-strength anchor threaded rod M12 was used, which was doweled into a borehole with a diameter of 14 mm and a borehole depth of 72 mm in C20 / 25 concrete after cleaning with compressed air (blown out twice at 6 bar) and a suitable steel brush (brushed twice) and blown out again (twice at 6 bar) with the respective chemical mortar mass at approx. 20°C.

[0211] The mean failure load (R1) was determined by centrally pulling out the anchor threaded rod with close support. Five anchor threaded rods were inserted into each of the anchors, and after a curing time of 24 hours at room temperature, the load values ​​were determined. The mean load values ​​determined (average of the five measurements) are listed in Table 6 (below).

[0212] The determination of the failure load in wet concrete (B7) was carried out analogously, with the drill holes being drilled in concrete that had been submerged for four weeks. The concrete block was only briefly removed from the water for the test. Cleaning was performed after drilling by blowing it out, brushing it with a steel brush, and then blowing it out again with 6 bar compressed air.

[0213] Table 3: Composition of the reactive resin components

[0214] Table 3 (continued):

[0215] Table 4: Composition of the hardener components and the comparison hardener components*)

[0216] * Comparative examples based on EP 3 313 896 B1 , EP3775017 A1 and W02022002567A1

[0217] Table 4 (continued)

[0218] Table 5: Composition of the mortar masses and results of the load value determinations

[0219] 5 Table 5 (continued)

Claims

PATENT CLAIMS 1. Hardener system for a reactive resin system which contains radically polymerizable compounds, wherein the hardener system a) comprises a compound of formula (I) (I), wherein R 1 , R 2 and R 3 each independently of one another represents a hydrogen atom, a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl group may each optionally contain at least one heteroatom and / or be substituted, R 4 and R 5each independently of one another is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl groups may each contain at least one heteroatom and / or be substituted, or R 1 and R 2 , R 1 and R 3 , R 2 and R 3 and R 4 and R 5 together each independently form a cycloalkylene or cycloalkenyl group, each of which may also contain heteroatoms in or on the ring and / or may be substituted, and b) a transition metal in the form of a salt or a compound / complex.

2. Hardener system according to claim 1, wherein R 1 , R 2 and R 3 are independently a hydrogen atom or a linear or branched alkyl group.

3. Hardener system according to claim 2, wherein R 1 and R 2 independently of one another are a linear or branched Ci-Cw-alkyl group, in particular a linear Ci-Ce-alkyl group and R 3 a hydrogen atom or Ci-Ce alkyl group.

4. Hardener system according to claim 3, wherein R 1 and R 2 are independently a Ci-Cs-alkyl group and R 3 is a hydrogen atom.

5. Hardener system according to one of the preceding claims, wherein R 4 and R 5 together form an alkylene, cycloalkylene or cycloalkenyl group, optionally containing at least one heteroatom.

6. Hardener system according to claim 5, wherein R 4 and R 5 together form a heterocyclic cycloalkylene group with one heteroatom or two heteroatoms.

7. Hardener system according to claim 6, wherein R 4 and R 5a Cs-Ce cycloalkylene group carrying a nitrogen atom (N) and / or an oxygen atom (O) as heteroatoms.

8. Hardener system according to one of the preceding claims, wherein the transition metal is selected from the group consisting of copper, iron, vanadium, manganese, cerium, cobalt, zirconium, or bismuth, or mixtures of two or more thereof.

9. Hardener system according to one of the preceding claims, wherein the transition metal in the form of a compound is a transition metal carboxylate.

10. Hardener system according to one of the preceding claims, further comprising a co-activator, in particular saccharin.

11. Use of a hardener system according to one of claims 1 to 10 as an initiator system for a reactive resin system based on radically polymerizable compounds.

12. Use according to claim 11, wherein the reactive resin system is one for chemical fastening.

13. Reactive resin system comprising a hardener system according to any one of claims 1 to 10 and a radically polymerizable compound as reactive resin.

14. Reactive resin system according to claim 13, wherein the radically polymerizable compound is selected from the group consisting of urethane (meth)acrylate-based compounds, epoxy (meth)acrylate-based compounds, methacrylates of alkoxylated bisphenols, compounds based on other ethylenically unsaturated compounds, and combinations thereof.

15. Reactive resin system according to one of claims 13 or 14, further comprising organic and / or inorganic additives and / or fillers.

16. Multi-component reactive resin system comprising a resin component and a hardener component, wherein the resin component contains a radically polymerizable compound, a reactive diluent and a transition metal in the form of a salt or a compound / complex, and the hardener component contains a compound of formula (I) wherein R 1 , R 2 and R 3 each independently of one another represents a hydrogen atom, a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl group may each optionally contain at least one heteroatom and / or be substituted, R 4 and R 5each independently of one another is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkylene, cycloalkyl, cycloalkenyl or ar(alk)yl group, where the cycloalkyl, cycloalkenyl and ar(alk)yl groups may each contain at least one heteroatom and / or be substituted, or R 1 and R 2 , R 1 and R 3 , R 2 and R 3 and R 4 and R 5 together each independently form a cycloalkylene or cycloalkenyl group, each of which may also contain heteroatoms in or on the ring and / or may be substituted.

17. Multi-component reactive resin system according to claim 16, wherein the reactive resin component and / or the hardener components further contain inorganic and / or organic additives and fillers.

18. Use of a reactive resin system according to one of claims 13 to 15 or of a multi-component reactive resin system according to one of claims 16 or 17 as an adhesive, coating material or molding compound.

19. Use of a reactive resin system according to any one of claims 13 to 15 or a multi-component reactive resin system according to any one of claims 16 or 17 for fixing anchoring means in substrates.

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