RU2778682C2 - Urethane methacrylate compounds and their application - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to the application of a compound of the general formula (I)

in which B means an aromatic hydrocarbon group, which is a divalent group, which is obtained by removing isocyanate groups from an aromatic diisocyanate selected from a group consisting of 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 2,4’-diphenylmethane diisocyanate, 4,4’-diphenylmethane diisocyanate and 1,5-diisocyanatonaphthalene, and each R₁ independently represents a branched or linear aliphatic alkylene group having 1-15 carbon atoms, to increase the adhesion stress of the cured fixing mass.

EFFECT: expansion of the range of methacrylate compounds.

3 cl, 11 tbl, 7 ex

Description

The invention relates to low viscosity urethane methacrylate compounds as structure-forming resins, their use in reactive resins, in particular to reduce the viscosity of reactive resins containing such compounds, and thus to reduce the extrusion forces of the reactive resin components obtained from them. In addition, the invention relates to the use of said reactive resins and components of reactive resins for building purposes, in particular for chemical anchoring.

The currently used radical-curing fixing masses are based on unsaturated polyesters, vinyl ether urethane resins and epoxy acrylates. These are two-component systems based on a reactive resin, wherein one component (component (A)) contains a resin and the other component (component (B)) contains a curing agent. Additional constituents such as organic or inorganic fillers and additives, accelerators, stabilizers, reactive diluents may be contained in one and/or the other component. When both components are mixed, the curing of the mixed components begins. When using fixing masses for fixing anchor elements in drilled holes, curing takes place in the drilled holes.

Such a fixing mass is known, for example, from the German patent application DE 3940138 A1. It describes fixing masses based on monomers having cycloaliphatic groups, which may additionally contain unsaturated polyester or vinyl ester resins. However, fixing masses of this kind have a relatively high viscosity, which limits their use, among other things, for chemical fixing technology.

Construction sites may experience relatively large temperature ranges, for example from -25°C to +45°C, depending on the time of year and/or geographic location. Therefore, the high viscosity of the curable fixing masses described at the outset and their resulting thixotropic characteristics during use can lead to problems. Therefore, high demands are placed on the field of application of such fixing masses, in particular for use in various temperature ranges.

On the one hand, in the range of low temperatures, a sufficiently low viscosity of the mass during injection must be ensured so that the mass does not have too much hydrodynamic resistance. At the same time, it must be ensured that the masses can be deposited, for example with a manual dispenser, for example introduced into a drilled hole. In particular, low viscosity is essential for perfect mixing of both components when using static mixers.

On the other hand, the mass in the higher temperature range must be stable enough to prevent the uncontrolled escape of individual components after de-energizing the dispenser, and also that the mass does not flow out of the drilled hole during overhead mounting.

Another problem caused by temperature fluctuations is the non-uniformly proceeding radical polymerization of the chain. Thus, the cured fixing mass exhibits a variable/irregular and often insufficient homogeneity, which is reflected in fluctuating load values and often also in general in low load values. For example, in the case of temperatures below 20°C, as a result of the increase in viscosity, premature curing of the fixing mass may occur. As a result, the conversion of radical polymerization of the chain is significantly reduced, which contributes to lower load values.

Since fluctuations in temperature at the construction site cannot be prevented, there is still a need for two-component reactive resin systems that provide uniformity, and the associated reproducibility of load values, both at high and at low temperatures.

In order to solve the aforementioned problems, in the case of fixing masses present on the market, the proportion of reactive thinners is increased, which ultimately leads to a decrease in the resin content in the mass. It is not uncommon for the proportion of reactive diluents to be at least 50%, based on the reactive resin.

However, an increase in the proportion of reactive thinners also leads to some disadvantages, which are especially noticeable when using a fixing mass to secure anchor fasteners in drilled holes.

A significant disadvantage is that the reduction of the high viscosity resin content, which is essential for the effectiveness of the mass, adversely affects the effectiveness of the cured fixing mass.

Another disadvantage is the large shrinkage of the fixing mass after curing, which can also adversely affect the effectiveness of the cured fixing mass. This is due to the fact that the contact between the hardened fixing mass and the internal grooves formed on the walls of the drilled hole during the creation of the hole, which occur, in particular, when using impact drills, is significantly reduced. This usually also precludes the use of fixing compounds based on radical compounds in holes made with diamond drills.

Another disadvantage is that, depending on the type of reactive diluent, the proportion of volatile organic compounds (VOCs, Volatile Organic Compounds) in the masses may increase. This can lead to fumes from the fixing mass and/or cartridge and, optionally, resulting in a sharp decrease in the effectiveness of the cured fixing mass. Some of these compounds may also be hazardous to health and/or therefore subject to mandatory labeling.

The number of usable reactive diluents is also small, as there are currently only a few reactive diluents available on the market. The reactive diluents available, apart from the radically curable functional groups, have no or very limited other functional groups and therefore often have little effect on the properties of the cured fixing mass. This has the effect that fixing masses are usually designed for specific applications, such as specified temperature ranges, or for use on specific substrates. This indicates a huge development effort to enable new and wider applications to be explored with the fixing masses.

So far, special products have been produced whose formulations are adapted to specific application temperatures. Although there are products that are designed for a wide temperature range, they have the same properties throughout the range. Directly in the border areas, i.e. at low and high temperatures, deteriorations in processing, in curing the mass, or in relation to the properties of the cured mass, are to be expected. No fixing mass is known that would cover a very wide temperature range without having to put up with losses in the border areas.

Therefore, there is a need for fixing masses whose effectiveness and properties can be influenced not by the use of reactive diluents, but by resin ingredients.

It is an object of the present invention to influence the properties of the reactive resin masterbatch, as well as the reactive resin derived from it, solely by the structure of the structurant resin, and not by the presence of additional compounds such as, for example, reactive diluents or additives. Basically, the object of the present invention is to control the properties of a two- or multi-component reactive resin system with the aid of the structurant resin present. In particular, it is an object of the present invention to provide fixing masses, such as two- or multi-component systems based on reactive resins, the viscosity of which is less dependent on the application temperature of the fixing mass, which in particular have a low viscosity at low temperatures, for example, less than 20° C and therefore allow the provision of reactive resin systems which, at application temperatures of less than 20°C, in particular at application temperatures of less than 10°C, are characterized by reduced extrusion forces and therefore are more user-friendly than conventional fixing systems.

Another object of the invention is to provide a fixing mass which has reduced extrusion forces of the reactive resin component and at the same time higher load values of the cured fixing mass than conventional masses.

Yet another object of the present invention is to provide a fixing mass that dispenses with highly hazardous ingredients in the reactive resin component and, if necessary, is also not subject to mandatory labelling. In particular, it is an object to reduce the content of reactive diluents in reactive chemical fixing resins without having to sacrifice their function or functions and positively affect the cured fixing mass.

Yet another object of the present invention is to provide a fixative mass which is characterized by good processability, curing properties and negligible shrinkage over a wide temperature range.

These tasks are solved using the compounds according to paragraph 1 and their use according to paragraphs 5-8, the reactive resin according to paragraph 9 and the reactive resin component according to paragraph 10 of the claims.

Surprisingly, it has been found that by using certain low-viscosity urethane methacrylate compounds as the structurant resin, it is possible to increase the temperature range in which the viscosity of the reactive resin containing these compounds and the reactive resin component obtained therefrom remains not significantly affected by temperatures.

Advantageously, the present invention provides, at low application temperatures, reduced extrusion forces for reactive resin systems compared to conventional systems. Thus, by using low viscosity urethane methacrylate compounds as a structurant resin in reactive resins, it has been possible to reduce the extrusion forces of the reactive resin system both at 20°C and at lower temperatures, for example, at temperatures below 10°C, preferably below 5°C, without the need for this high content of reactive diluents.

In addition, it has been found that by using certain low viscosity urethane methacrylate compounds, it is possible to reduce the content of reactive diluents in reactive chemical anchor resins, without having to sacrifice their function or functions and benefit the cured fixative mass, since the content of structurant resin can be increased. As a result, it becomes possible, on the one hand, to increase the load values of the hardened mass, and on the other hand, at higher temperatures, for example at 80° C., to achieve higher load values with the same content of structurant resin.

The invention is based on the discovery that it is possible to replace the high viscosity resins hitherto used in fixing masses with shorter, low viscosity builder resins in order to reduce the content of reactive diluents without having to sacrifice their functionality.

For a better understanding of the essence of the present invention, explanations are given below regarding the method for producing a reactive resin and the terminology used.

The method for producing a reactive resin, which is illustrated here by the example of MDI-based urethane methacrylate, usually proceeds as follows:

1. Preparation of structurant resin/reactive resin masterbatch

Methane diphenyl diisocyanate (MDI) and hydroxypropyl methacrylate (HPMA) are reacted in the presence of a catalyst and an inhibitor (which serves to stabilize the structurant resin resulting from the polymerization, often also referred to as a stabilizer or process stabilizer). This forms a structure-forming resin.

The reaction mixture obtained after completion of the reaction is called the reactive resin master batch. It is not processed further, i.e. structure-forming resin is not isolated.

2. Obtaining a reactive resin

To the masterbatch of the reactive resin after completion of the reaction for obtaining the structure-forming resin, a system of inhibitors and accelerators is added, i.e. a combination of one or more additional inhibitors and one or more accelerators, and optionally a reactive diluent.

As a result, a reactive resin is obtained.

The system of inhibitors and accelerators is used to adjust the reactivity of the reactive resin, i.e. to control the time during which the reactive resin after adding the initiator is not yet fully cured and, therefore, until which point the wood putty mixed with the reactive resin remains suitable for processing after mixing with the initiator.

The inhibitor in the inhibitor/accelerator system may be the same as the inhibitor in the formation of the structurant resin if it is also able to control the reactivity, or be a different inhibitor if it does not perform both functions. For example, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL) can be used as a stabilizer and as an inhibitor to control reactivity.

3. Preparation of the reactive resin component

In order to use the reactive resin for building purposes, in particular for chemical anchoring, one or more inorganic auxiliaries such as additives and/or fillers are added after the reactive resin has been prepared.

As a result, a reactive resin component is obtained.

In the context of the present invention, the terms used mean:

"structural resin" means a generally hard or highly viscous radical polymerizable resin which is cured by polymerization (eg after the addition of an initiator in the presence of an accelerator) and usually does not contain a reactive diluent and is not further purified and thus may contain impurities;

- "reactive resin masterbatch" - the reaction product of obtaining a structure-forming resin, that is, a mixture of a structure-forming resin, reactive diluents and, if necessary, other components of the reaction mixture;

- "reactive resin" - a mixture of a reactive resin masterbatch, at least one accelerator and at least one inhibitor (also called an accelerator and inhibitor system), at least one reactive diluent and, if necessary, additional additives; the reactive resin is typically liquid or viscous and can be further processed into a reactive resin component; in the present description, the reactive resin is also referred to as "resin mixture";

- "inhibitor" means a substance that inhibits unwanted radical polymerization during the synthesis or storage of a resin or resin-containing composition (these substances are also referred to in the art as a "stabilizer") or, accordingly, slow down the radical polymerization of the resin after the addition of an initiator (usually in combination with an accelerator) (these substances are referred to in the art as "inhibitor" - the appropriate meaning of each term is obvious from the context);

- "accelerator" - a chemical reagent that reacts with the initiator, so that already at low temperatures the initiator provides a large amount of free radicals, or which catalyzes the decomposition reaction of the initiator;

- “reactive diluents” - liquid or low-viscosity monomers and structurant resins that dilute another structurant resin or reactive resin masterbatch, and thereby impart the viscosity necessary for their use, contain functional groups capable of reacting with the structurant resin, and during polymerization ( curing) for the most part become an ingredient in the cured mass (for example, mortar); the reactive diluent is also referred to as a copolymerizable monomer;

- "reactive resin component" means a liquid or viscous mixture of reactive resin and fillers and, if necessary, other components, such as additives; typically, the reactive resin component is one of two components of a two-component reactive resin system for chemical anchoring;

- "initiator" - a substance that forms (usually in combination with an accelerator) radicals initiating the reaction;

- "curing agent component" means a composition containing an initiator for the polymerization of a structure-forming resin; the hardener component may be solid or liquid and may contain, in addition to the initiator, a solvent, as well as fillers and/or additives; typically, the hardener component, in addition to the reactive resin component, is the other of the two components of the two-component reactive resin system for chemical fixing;

"mortar mass/fixing mass" means a composition which is obtained by mixing a reactive resin component with a hardener component and as such can be directly used for chemical fixing;

- "reactive resin system" - in general, means a system that includes components stored separately from each other, so that the curing of the structure-forming resin contained in the component occurs only after mixing the components;

- "two-component system" or respectively "two-component reactive resin system" means a reactive resin system that includes two components stored separately from each other, a reactive resin component (A) and a hardener component (B), so that the curing of the structure-forming resin , contained in the reactive resin component, occurs only after mixing these two components;

- "multi-component system" or, respectively, "multi-component reactive resin system" means a reactive resin system that includes several components stored separately from each other, among others, a reactive resin component (A) and a hardener component (B), so that curing structure-forming resin contained in the reactive resin component occurs only after mixing all the components;

- "construction purposes" means any use for the manufacture, maintenance or respectively repair of structural parts and structures, such as polymer concrete, polymer resin coating or cold curing road markings; in particular the strengthening of structural parts and structures such as walls, ceilings or floors, the fastening of structural parts such as slabs or blocks, e.g. made of stone, glass or plastic, to structural parts and structures, for example by gluing (construction bonding) and especially chemically anchoring anchoring means such as anchor rods, bolts or the like in recesses such as drilled holes;

- "chemical fixing" means the fixing of anchoring means such as anchor rods, bolts, steel reinforcement, screws and the like in recesses such as drilled holes, in particular in drilled holes in various substrates, in particular mineral substrates such as as substrates based on concrete, aerated concrete, brick, lime-sand brick, sandstone, natural stone, glass and the like, and metal substrates such as steel;

- "aromatic hydrocarbon group" - a planar cyclic hydrocarbon group with an aromatic system, which, due to its delocalized electronic system, is energetically more favorable than its non-aromatic mesomers, and therefore is chemically more stable (PAC, 1995, 67, 1307; Glossary of class names of organic compounds and reactivity intermediates based on structure (IUPAC 1995 Recommendations), p. 1319);

- "Aromatic diisocyanate" means that two isocyanate groups are connected directly to the aromatic hydrocarbon skeleton;

- “(meth)acryl…/…(meth)acryl…” should be understood as “methacryl…/…methacryl…”- and “acryl…/…acryl…”-compounds; preferably in the context of this invention means "methacryl.../...methacryl..."-compounds;

- "one", "one", "one" as an article before a certain class of chemical compounds, for example, before the word "urethane methacrylate", means that at least one can be meant, i.e. one or more of the compounds belonging to this class of chemical compounds, for example, various urethane methacrylates; in a preferred embodiment, the given article refers to one particular compound.

- "at least one", "at least one", "at least one" in numerical terms means "one or more"; in the preferred embodiment, the term in numerical terms means "one", "one", "one".

- "contains" and "includes" means that, in addition to the ingredients mentioned, additional ingredients may be present. These terms refer to "open type" and therefore include "consists of". "Consists of" refers to "closed type" and means that no other ingredients may be present. In a preferred embodiment, the terms "comprises" and "includes" mean the term "consists of";

- "about" or "approximately" in front of a numerical value means a range of ±5% of this value, preferably ±2% of this value, more preferably ±1% of this value, particularly preferably ±0% of this value (that is, this meaning);

- numerically limited range means that both extreme values and each value in this range are disclosed individually.

All standards referred to in this text (for example, DIN standards) have been used in the edition current at the date of filing of this application.

The first object of the invention is a compound of general formula (I),

wherein

B is an aromatic hydrocarbon group, and

each R ₁ is independently a branched or linear aliphatic alkylene group having 1-15 carbon atoms.

The second object is its use for obtaining a reactive resin or a reactive resin component for building purposes. A third object is its use for reducing the viscosity of a reactive resin or reducing the extrusion force of a reactive resin component or a reactive resin system for building purposes. The fourth object is its use to increase the load values of the cured fixing mass. The fifth object is a reactive resin containing a compound of general formula (I), an inhibitor, an accelerator and, if necessary, a reactive diluent. The sixth object is a reactive resin component for a reactive resin system containing a reactive resin. A seventh aspect is a reactive resin system comprising a reactive resin component and a curing agent component containing an initiator. An eighth object is the use of a reactive resin or a reactive resin system for building purposes.

According to the invention, the low viscosity urethane methacrylate compound is a compound of general formula (I),

in which B represents an aromatic hydrocarbon group, and each R ₁ independently of one another represents a branched or linear aliphatic alkylene group having 1-15 carbon atoms.

The aromatic hydrocarbon group is divalent and preferably has 6 to 20 carbon atoms and more preferably 6 to 14 carbon atoms. The aromatic hydrocarbon group may have substituents, in particular alkyl radicals, among which alkyl radicals with one to four carbon atoms are preferred.

In one embodiment, the aromatic hydrocarbon group contains a benzene ring, which may have substituents.

In an alternative embodiment, the aromatic hydrocarbon group contains two fused benzene rings or two benzene rings linked through an alkylene group, such as a methylene or ethylene group. Both the benzene rings and the alkylene bridge may have substituents, preferably alkyl groups.

The aromatic hydrocarbon group is derived from aromatic diisocyanates, with "aromatic diisocyanate" meaning that two isocyanate groups are connected directly to the aromatic hydrocarbon backbone;

Suitable aromatic hydrocarbon groups are divalent groups which are obtained by removing isocyanate groups from an aromatic diisocyanate, for example divalent phenylene group from benzene diisocyanate, methylphenylene group from toluene diisocyanate (TDI) or ethylphenylene group from ethylbenzene diisocyanate, divalent methanediphenylene group from methanediphenyl diisocyanate (MDI) or divalent a naphthyl group from naphthalene diisocyanate (NDI).

Particularly preferably B is obtained from 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate or 1,5-diisocyanatonaphthalene.

R ₁ in each case independently of each other represents a branched or linear aliphatic alkylene group having 1-15 carbon atoms, which may have substituents. R ₁ is derived from hydroxyalkyl methacrylates and includes divalent alkylene groups obtained by removing hydroxyl groups and a methacrylate group.

In one embodiment, the alkylene group R ₁ is divalent.

In an alternative embodiment, however, it may also have three or more valences, so that the compound of formula (I) may also have more than two methacrylate groups, even though this is not immediately apparent from formula (I).

Preferably, the alkylene group R ₁ is a divalent linear or branched C 1 -C 15 alkylene group, preferably a C 1 -C 6 alkylene group, and particularly preferably a C 1 -C 4 alkylene group. These include, in particular, methylene, ethylene, propylene, isopropylene, n-butylene, 2-butylene, sec-butylene, tert-butylene, n-pentylene, 2-pentylene, 2-methylbutylene, 3-methylbutylene, 1,2 -dimethylpropylene, 1,1-dimethylpropylene, 2,2-dimethylpropylene, 1-ethylpropylene, n-hexylene, 2-hexylene, 2-methylpentylene, 3-methylpentylene, 4-methylpentylene, 1,2-dimethylbutylene, 1,3-dimethylbutylene , 2,3-dimethylbutylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutylene, 1,1,2-trimethylpropylene, 1,2,2-trimethylpropylene, 1-ethylbutylene, 2-ethylbutylene, 1 -ethyl-2-methylpropylene, n-heptylene, 2-heptylene, 3-heptylene, 2-ethylpentylene, 1-propylbutylene or octylene group, among which ethylene, propylene and isopropylene group are more preferred. In a particularly preferred embodiment of the present invention, both R ₁ groups are the same and represent an ethylene, propylene or isopropylene group.

The low viscosity urethane methacrylate compound of the invention is prepared by reacting two equivalents of hydroxyalkyl methacrylate with at least one equivalent of a diisocyanate. The diisocyanate and hydroxyalkyl methacrylate are reacted in the presence of a catalyst and an inhibitor which serves to stabilize the resulting compound.

Suitable hydroxyalkyl methacrylates are those having alkylene groups of 1-15 carbon atoms, the alkylene groups being linear or branched. Preferred are hydroxyalkyl methacrylates having from 1 to 10 carbon atoms. More preferred are hydroxyalkyl methacrylates having two to six carbon atoms, among which 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate (2-HPMA), 3-hydroxypropyl methacrylate (3-HPMA) and glycerol-1,3-dimethacrylate are particularly preferred. Most preferred is 2-hydroxypropyl methacrylate (2-HPMA) or 3-hydroxypropyl methacrylate (3-HPMA).

Preferred aromatic diisocyanates are those having aromatically bonded isocyanate groups, such as diisocyanatobenzene, toluene diisocyanates (TDI), diphenylmethane diisocyanates (MDI), diisocyanatonaphthalenes. These compounds may be present both in the form of pure compounds and as optical isomers or mixtures of isomers of various compositions, which, if necessary, can be separated in the usual way.

Particularly preferred aromatic diisocyanates are 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate or 1,5-diisocyanatonaphthalene.

Preferably the compound of formula (I) is a compound of general formula (II) or (III)

in which each R ₁ is independently the same as defined above.

Most preferably, the compound of formula (I) is a compound of formula (IV) or (V):

The structures shown in formulas (I), (II), (III), (IV) and (V) are intended to represent the compounds according to the invention by way of example only, since the diisocyanates used for their preparation can be used both in the form of isomerically pure compounds, and in the form of mixtures of different isomers, in each case of different composition, i.e. in various quantitative ratios. Therefore, the structures shown should not be considered limiting.

Therefore, the compounds according to the invention may be present as isomeric pure compounds or as isomeric mixtures of various compositions, which, if necessary, can be separated in the usual way. Both pure isomers and isomeric mixtures are the subject of the present invention. Mixtures with different content of isomeric compounds are also the object of the invention.

In the event that not all of the isocyanate groups are reacted in the preparation of the compounds according to the invention or some of the isocyanate groups are converted into other groups as a result of a side reaction before the reaction, compounds are formed that can be present in the masterbatch of the reaction resin either as basic compounds or as impurities. These compounds, insofar as they can be used for the purposes of the invention, are also covered by the invention.

The compounds of formula (I) are used according to the invention to obtain a reactive resin. As a result, the viscosity of the reactive resin thus obtained can be reduced without the need for a high content of reactive diluents, as is the case with commercially available masses, and without the problems associated with a high content of reactive diluents, such as a decrease in the achievable loads of the cured mass. . Thus, a reduction in the extrusion forces of the reactive resin system which contains the compounds according to the invention can be achieved. In addition, by using the compounds according to the invention, the load values of the cured fixing mass can be increased.

The reactive resin according to the invention contains a compound of formula (I) as described above as a structurant resin, an inhibitor, an accelerator and, if appropriate, a reactive diluent. Since the structurant resin after its preparation is usually used without isolation to obtain a reactive resin, as a rule, additional components are also present in the reactive resin that are present in addition to the structurant resin in the reactive resin masterbatch, for example, a catalyst.

The proportion of compounds of General formula (I) in the reactive resin according to the invention is from 25% wt. up to 65% wt., preferably from 30% wt. up to 45% wt., particularly preferably 35% wt. up to 40% wt., most preferably from 33 to 40% wt. in terms of the total weight of the reactive resin.

Suitable inhibitors are the stable radicals commonly used for radically polymerizable compounds, such as N-oxyl radicals, which are known to the person skilled in the art.

The inhibitor may, on the one hand, serve to suppress unwanted radical polymerization during the synthesis of the structure-forming resin or the storage of the reactive resin and the reactive resin component. It can also serve - optionally additionally - to retard the radical polymerization of the structurant resin after addition of the initiator and thus control the processing time of the reactive resin or reactive resin component after mixing with the curing agent.

As stable N-oxyl radicals, for example, those described in German patent applications DE 199 56 509 A1 and DE 195 31 649 A1 can be used. Such stable nitroxyl radicals are of the piperidinyl-N-oxy or tetrahydropyrrole-N-oxy type, or mixtures thereof.

Suitable 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-carboxypiperidine (also referred to as 4-carboxy-TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2,2,5,5-tetramethyl-3-carboxypyrrolidine (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 preferred. TEMPOL is preferably the TEMPOL used in the examples.

In addition to the nitroxy radical of the piperidinyl-N-oxy or tetrahydropyrrole-N-oxy type, one or more additional inhibitors may be present both to further stabilize the reactive resin or the reactive resin component of the reactive resin (A), or other reactive resin-containing compositions, and to control resin reactivity.

Inhibitors commonly used for radically polymerizable compounds, which are known to the person skilled in the art, are suitable for this. Preferably, said additional inhibitors are selected from phenolic compounds, non-phenolic compounds and/or phenothiazines.

Suitable phenolic inhibitors are phenols such as 2-methoxyphenol, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-trimethylphenol, 2, 4,6-tris(dimethylaminomethyl)phenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidenediphenol, 6,6'-ditretbutyl-4,4'-bis(2,6 -di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2'-methylenedi-p-cresol, catechins such as catechol, and catechin derivatives such as butyl pyrocatechins, for example 4-tert-butyl pyrocatechol, 4,6-di-tert-butyl pyrocatechol, hydroquinones such as hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, methylbenzoquinone, 2,6-dimethylbenzoquinone, naphthoquinone, or mixtures of two or more of these. These inhibitors are often ingredients of commercial radical-curable reactive resin components.

Preferred non-phenolic inhibitors are phenothiazines such as phenothiazine and/or derivatives or combinations thereof, or stable organic radicals such as galvinoxy and N-oxyl radicals, but not piperidinyl-N-oxy or tetrahydropyrrole of the N-oxy type such as N aluminum-nitrosophenylhydroxylamine, diethylhydroxylamine, oximes such as acetaldoxime, acetone oxime, methylethylketoxime, salicyloxime, benzoxime, glyoximes, dimethylglyoxime, acetone-O-(benzyloxycarbonyl)oxime and the like.

In addition, pyrimidinol or pyridinol compounds substituted in the para-hydroxyl position with respect to the hydroxyl group, such as are described in German patent DE 102011 077 248 B1, can also be used as inhibitors.

Preferably the additional inhibitors are selected from the group of catechins, catechin derivatives, phenothiazines, tert-butyl catechin, TEMPOLa, or a mixture of two or more of these. Particularly preferred are additional inhibitors selected from the group of catechins and phenothiazines. Most preferred are the additional inhibitors used in the examples, preferably in the approximate amounts indicated in the examples.

Depending on the desired properties of the reactive resin, additional inhibitors can be used either alone or as a combination of two or more of them.

The inhibitor or mixture of inhibitors is added in the usual amounts known in the art, preferably in an amount of from about 0.0005 to about 2% wt. (in terms of the final obtained reactive resin), more preferably from about 0.01 to about 1% wt. (in terms of reactive resin), even more preferably from about 0.05 to about 1% wt. (in terms of reactive resin), even more preferably from about 0.2 to about 0.5% wt. (in terms of reactive resin).

As a rule, the curing of the compound of general formula (I), in particular when used in reactive resins and reactive resin components for chemical anchoring and structural bonding, is carried out with peroxides as curing agent. The peroxides are preferably initiated by the accelerator so that polymerization occurs even at low application temperatures. The accelerator is already present in the reactive resin.

Suitable accelerators are known to the person skilled in the art and are, for example, amines, preferably tertiary amines, and/or metal salts.

Suitable amines are selected from the following compounds: dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, isobutylamine, t-butylamine, di -n-butylamine, diisobutylamine, triisobutylamine, pentylamine, isopentylamine, diisopentylamine, hexylamine, octylamine, dodecylamine, laurylamine, stearylamine, aminoethanol, diethanolamine, triethanolamine, aminohexanol, ethoxyaminoethane, dimethyl(2-chloroethyl)amine, 2-ethylhexylamine, bis(2 -chloroethyl)amine, 2-ethylhexylamine, bis(2-ethylhexyl)amine, N-methylstearylamine, dialkylamines, ethylenediamine, N,N'-dimethylethylenediamine, tetramethylenediamine, diethylenetriamine, permethyldiethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminopropane, dipropylenetriamine, tripropylenetetramine, 1,4-diaminobutane, 1,6-diaminohexane, 1,4-amino-1-diethylaminopentane, 2,5-diamino-2,5-dimethylhexane, trimethylhexamethylenediamine, N,N-dimethylaminoethanol, 1,2- (2-diethyl-aminoethoxy) ethanol, bis(2-hydroxyethyl)-oleylamine, tris[2-(2-hydroxy-ethoxy)ethyl]amine, 3-amino-1-propanol, methyl(3-aminopropyl) ether, ethyl(3-aminopropyl) simple ether, 1,4-butanediolbis(3-aminopropyl ether), 3-dimethylamino-1-propanol, 1-amino-2-propanol, 1-diethylamino-2-propanol, diisopropanolamine, methylbis(2-hydroxypropyl)amine, tris -(2-hydroxypropyl)amine, 4-amino-2-butanol, 2-amino-2-methylpropanol, 2-amino-2-methylpropanediol, 2-amino-2-hydroxymethylpropanediol, 5-diethylamino-2-pentanone, nitrile 3 -methylaminopropionic acid, 1,6-aminohexanoic acid, 11-aminoundecanoic acid, 6-aminohexanoic acid ethyl ester, 11-aminohexanoic acid isopropyl ester, cyclohexylamine, N-methylcyclohexylamine, N,N-dimethylcyclohexylamine, dichlorhexylamine, N-ethylcyclohexylamine, N-(2-hydroxyethyl)-cyclohexylamine, N,N-bis(2-hydroxyethyl)cyclohexylamine, N-(3-aminopropyl)cyclohexylamine, aminomethylcyclohexane, hexahydrotoluidine, hexahydrobenzylamine, anili n, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, isobutylaniline, toluidines, diphenylamine, hydroxyethylaniline, bis(hydroxyethyl)aniline, chloraniline, aminophenols, aminobenzoic acids and their esters, benzylamine , dibenzylamine, tribenzylamine, methyldibenzylamine, α-phenylethylamine, xylidine, diisopropylaniline, dodecylaniline, aminonaphthalene, N-methylaminonaphthalene, N,N-dimethylaminonaphthalene, N,N-dibenzylnaphthalene, diaminocyclohexane, 4,4'-diaminodicyclohexyl-methane, diaminodimethyldicyclohexylmethane, phenylenediamine, xylylenediamine, diaminodiphenyl, naphthalenediamines, toluidines, benzidines, 2,2-bis(aminophenyl)propane, aminoanisols, aminothiophenols, aminodiphenyl oxide, aminocresols, morpholine, N-methylmorpholine, N-phenyl-morpholine, hydroxyethylmorpholine, N-methylpyrrolidine, pyrrolidine, piperidine, hydroxyethylpiperidine, pyrroles, pyridines, quinolines, indoles, indolenines, carbazoles, pyrazoles, imidazoles, thiazoles, pyrimidines, quinoxalines, aminomorpholine, dimorpholinethane, [2,2,2]-diazabicyclooctane and N,N-dimethyl-p-toluidine.

According to the invention, diisopropanol-p-toluidine or N,N-bis(2-hydroxyethyl)-m-toluidine is used as an accelerator.

Preferred amines are aniline derivatives and N,N-bisalkylarylamines, e.g. N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-bis(hydroxyalkyl)arylamines, N,N- bis(2-hydroxyethyl)anilines, N,N-bis(2-hydroxyethyl)toluidine, N,N-bis(2-hydroxypropyl)aniline, N,N-bis(2-hydroxypropyl)toluidine, N,N-bis( 3-methacryloyl-2-hydroxypropyl)-p-toluidine, N,N-dibutoxyhydroxypropyl-p-toluidine and 4,4'-bis(dimethylamino)diphenylmethane. Particularly preferred is diisopropanol-p-toluidine.

Suitable accelerators are also polymeric amines obtained, for example, by the polycondensation of N,N-bis(hydroxyalkyl)aniline with dicarboxylic acids or by the polyaddition of ethylene oxide or other epoxides and the indicated amines.

Suitable metal salts are, for example, cobalt octoate or cobalt naphthenoate, as well as vanadium, potassium, calcium, copper, manganese or zirconium carboxylates. Other suitable metal salts are the tin catalysts described below.

If an accelerator is used, it is used in an amount of 0.01 to 10% by weight, preferably 0.2 to 5% by weight, based on the reactive resin.

If desired, the reactive resin may still contain a reactive diluent. In this case, an excess of hydroxy-functionalized (meth)acrylate, optionally used in the preparation of the structurant resin, can act as a reactive diluent. In addition, if hydroxy-functionalized (meth)acrylate is used in approximately equimolar amounts with an isocyanate group, or additionally if an excess of hydroxy-functionalized (meth)acrylate is used, additional reactive diluents that are structurally different from hydroxy-functional can be added to the reaction mixture. functionalized (meth)acrylate.

Suitable reactive diluents are low viscosity, radical copolymerizable compounds, preferably label free compounds, which are added inter alia to adjust the viscosity of the urethane methacrylate or its precursors during its preparation, if necessary.

Suitable reactive diluents are described in European patent application EP 1 935 860 A1 and German patent application DE 195 31 649 A1. Preferably, the reactive resin (resin mixture) contains a (meth)acrylic acid ester as a reactive diluent, with aliphatic or aromatic (meth)acrylates having 5 to 15 carbon atoms being particularly preferred. Suitable examples are: 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 1,2-ethanedioldi(meth)acrylate, 1,3-propanedioldi(meth)acrylate, 1,3-butanedioldi(meth)acrylate, 1,4-butanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate, phenethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl triglycol (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl ( meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, acetoacetoxyethyl(meth)acrylate, isobornyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, tert-butylcyclohexyl(meth)acrylate, benzyl(meth)acrylate, methyl( meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, 3-trimethoxysilylpropyl(meth)acrylate, isodecyl(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, trimethylcyclohexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate and/or tricyclopentadienyldi-(meth)acrylate, bisphenol-A-(meth)acrylate, novolakepoxydi(meth)acrylate, di-[(meth) acryloylmaleo yl]tricyclo-5.2.1.0. ^2.6 -decane, 3-(meth)acryloyloxymethyltricyclo-5.2.1.0. ^2.6 -decane, 3-(meth)cyclopentadienyl(meth)acrylate and decalyl-2-(meth)acrylate; PEG di(meth)acrylates such as PEG-200-di(meth)acrylate, tetraethylene glycol di(meth)acrylate, solketal(meth)acrylate, cyclohexyl(meth)acrylate, phenoxyethyl di(meth)acrylate, 2-phenoxyethyl( meth)acrylate, hexanediol-1,6-di(meth)acrylate, 1,2-butanedioldi(meth)acrylate, methoxyethyl(meth)acrylate, butyldiglycol(meth)acrylate, t-butyl(meth)acrylate and norbornyl(meth) acrylate. Methacrylates are preferred over acrylates.

Especially preferred are 2- and 3-hydroxypropyl methacrylate, 1,2-ethanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, glycerol dimethacrylate, trimethylol propane trimethacrylate, acetoacetoxyethyl methacrylate, isobornyl methacrylate, bisphenol-A-dimethacrylate, ethoxylated bisphenol-A-methacrylates, such as E2BADMA or E3BADMA, trimethylcyclohexyl methacrylate, 2-hydroxyethyl methacrylate, PEG200-dimethacrylate and norbornyl methacrylate, and most preferred is a mixture of 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate and 1,4-butanediol dimethacrylate or a mixture of these three methacrylates.

Highly preferred is a mixture of 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate. In principle, other conventional radically polymerizable compounds can also be used as reactive diluents, individually or as a mixture with (meth)acrylic acid esters, e.g. methacrylic acid, styrene, α-methylstyrene, alkylated styrenes such as tert-butyl -styrene, divinylbenzene, as well as vinyl and allyl compounds, with preferred being the representatives of the above compounds that are not subject to mandatory labeling. Examples of such vinyl or allyl compounds are hydroxybutyl vinyl ether, ethylene glycol divinyl ether, 1,4-butanedioldivinyl ether, trimethylol propane divinyl ether, trimethylol propane trivinyl ether, mono-, di-, tri-, tetra- and polyalkylene-picolvinyl ethers, mono- , di-, tri-, tetra- and polyalkylene glycol allyl ethers, adipic acid divinyl ether, trimethylol propane diallyl ether and trimethylol propane triallyl ether.

The reactive diluent or reactive diluents are added in an amount of up to 65% by weight, preferably up to 60% by weight, more preferably up to 55% by weight, particularly preferably in amounts of less than 50% by weight, based on the reactive resin.

An exemplary reactive resin contains a compound of general formula (I),

in which B represents an aromatic hydrocarbon group, and each R ₁ independently of each other represents a branched or linear aliphatic alkylene group having 1-15 carbon atoms, as a structure-forming resin, a stable nitroxyl radical as an inhibitor, substituted toluidine as an accelerator and, if necessary, a reactive diluent.

A preferred reactive resin contains (a) a compound of formula (II) or (III)

in which each R ₁ is independently a branched or linear aliphatic alkylene group having 1-15 carbon atoms as a structurant resin, a stable nitroxyl radical as an inhibitor, a substituted toluidine as an accelerator, and optionally a reactive diluent.

A more preferred reactive resin contains a compound of formula (IV) or (V)

as a structurant resin, a stable nitroxyl radical as an inhibitor, a substituted toluidine as an accelerator, and a reactive diluent.

A particularly preferred reactive resin contains a compound of formula (IV) or (V) as a structurant resin, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL) as an inhibitor, diisopropanol-p-toluidine as accelerator and a mixture of hydroxypropyl methacrylate and 1,4-butanediol dimethacrylate (BDDMA) as a reactive diluent.

The reactive resin according to the invention, due to the low-viscosity structure-forming resin, has a particularly low dynamic viscosity, so that it is possible to obtain a reactive resin component for a reactive resin system which, at application temperatures below 10° C., preferably at 0° C., exhibits significantly lower forces. extrusion than conventional systems without the need for the previously required high levels of reactive diluents.

Another aspect of the invention is a reactive resin component that contains a reactive resin. In addition to the reactive resin according to the invention, the reactive resin component may contain inorganic auxiliaries such as fillers and/or additives. It should be noted that some substances can be used both as a filler and, if necessary, in a modified form, as an additive. For example, pyrogenic silicic acid in its polar, untreated form serves more as a filler, and in its non-polar, post-treated form, rather as an additive. In cases where the same substance can be used as a filler or additive, its total amount should not exceed the upper limit for fillers set forth in this description.

In order to prepare a reactive resin component for building purposes, in particular for chemical anchoring, customary fillers and/or additives can be added to the reactive resin according to the invention. These fillers are usually inorganic fillers and additives, such as, for example, described below.

The reactive resin content of the reactive resin component is preferably from about 10 to about 70% by weight, more preferably from about 30 to about 50% by weight, based on the reactive resin component. Accordingly, the filler content is preferably from about 90 to about 30% by weight, more preferably from about 70 to about 50% by weight, based on the reactive resin component.

As fillers, conventional fillers are used, preferably mineral or similar mineral fillers, such as quartz, glass, sand, quartz sand, quartz flour, porcelain, corundum, ceramics, talc, silicic acid (for example, pyrogenic silicic acid, in particular polar non post-treated pyrogenic silicic acid), silicates, aluminum oxides (e.g. alumina), clay, titanium dioxide, chalk, barite, feldspar, basalt, aluminum hydroxide, granite or sandstone, polymeric fillers such as thermoset plastics, hydraulically settable fillers, such as gypsum, quicklime or cement (for example, aluminate cement (often referred to as aluminous cement) and Portland cement), metals such as aluminium, carbon black in addition, wood, mineral or organic fibers or the like, or mixtures of two or more of them. The fillers may be present in any form, for example, in the form of powder or flour, or in the form of molded articles, for example, in the form of cylinders, rings, balls, plates, columns, saddle-shaped articles or in the form of crystals, or, in addition, in the form of fibers (fibrous fillers), and the corresponding base particles preferably have a maximum diameter of 10 mm and a minimum diameter of 1 nm. This means that the diameter is about 10 mm, or any value less than about 10 mm but greater than about 1 nm. The preferred maximum diameter is about 5 mm, more preferably about 3 mm, even more preferably about 0.7 mm. Particularly preferred is a maximum diameter of about 0.5 mm. Preferred is a minimum diameter of about 10 nm, more preferably about 50 nm, even more preferably about 100 nm. Diameter ranges resulting from the combination of the indicated maximum diameters and the indicated minimum diameters are particularly preferred. However, globular inert substances (spherical shape) have a predominant and more pronounced reinforcing effect. Also, core-shell particles, preferably spherical in shape, can be used as fillers.

Preferred fillers are selected from the group consisting of cement, silicic acid, quartz, silica sand, silica flour, and mixtures of two or more of these. Particularly preferred for the reactive resin component (A) are fillers selected from the group consisting of cement, pyrogenic silicic acid, in particular untreated polar pyrogenic silicic acid, silica sand, silica flour, and mixtures of two or more of these. Most preferred for the reactive resin component (A) is a mixture of cement (particularly aluminate cement (often also referred to as aluminous cement) or Portland cement), pyrogenic silicic acid and quartz sand. For the hardener component (B), pyrogenic silicic acid is preferred as the sole filler or as one of several fillers; particularly preferably, in addition to pyrogenic silicic acid, one or more additional fillers are present.

As additives, the usual additives are used, in particular thixotropic agents, such as pyrogenic silicic acid, if necessary, post-treated with organic or inorganic substances (if it is not already used as a filler), bentonite, alkyl and methylcelluloses, castor oil derivatives or the like, plasticizers such as phthalic acid or sebacic acid esters, additional stabilizers besides the stabilizers and inhibitors used according to the invention, antistatic agents, thickeners, elasticizers, rheological aids, wetting agents, coloring additives, such as dyes, or in particular pigments, for example, for coloring components differently to better control their mixing, or the like, or mixtures of two or more of them. Non-reactive diluents (solvents) may also be present, preferably in amounts up to 30% by weight, based on the total amount of the reactive resin component, such as lower alkyl ketones, e.g. acetone, lower alkyl and lower alkanoyl dialkylalkanoyl amides, such as dimethylacetamide, lower alkyl alkylbenzenes such as xylenes or toluene, phthalic acid esters or paraffins, water or glycols. In addition, surface-modified pyrogenic silicic acid metal scavengers may be present in the reactive resin component. Preferably, at least one thixotropic agent is present as an additive, particularly preferably organo- or inorganic post-treated fumed silicic acid, most preferably non-polar post-treated fumed silicic acid.

In this regard, reference is made to international applications WO 02/079341 and WO 02/079293, as well as WO 2011/128061 A1.

The content of additives in the reactive resin component may be up to about 5% by weight, based on the reactive resin component.

The reactive resins prepared according to the invention can be used in many applications in which unsaturated polyester resins, vinyl ester resins or vinyl ester urethane resins are commonly used. They generally find use as a resin ingredient in a reactive resin component of a reactive resin system such as a multi-component system, typically a two-component system of a reactive resin component (A) and a curing agent component (B). This multi-component system can be in the form of a cassette system, a cartridge system or a foil tube system. In the intended application of the system, the components are extruded from foil cassettes, cartridges or tubes either by mechanical forces or gas pressure, mixed together, preferably by a static mixer through which the ingredients are passed, and applied.

Therefore, the subject of the present invention is also a reactive resin system containing the previously described reactive resin component (A) and a curing agent component (B) which contains an initiator for a urethane methacrylate compound.

The initiator is usually peroxide. All peroxides known to the person skilled in the art that are used to cure resins from unsaturated polyester resins and vinyl ester resins can be used. Peroxides of this type include organic and inorganic peroxides, either liquid or solid, and hydrogen peroxide may also be used. Examples of suitable peroxides are peroxycarbonates (formulas -OC(O)OO-), peroxyesters (formulas -C(O)OO-), diacyl peroxides (formulas -C(O)OOC(O)-), dialkyl peroxides (formulas -OO- ) and the like. These peroxides may be present as oligomers or polymers.

Preferably the peroxides are selected from the group of organic peroxides. Suitable organic peroxides are: tertiary alkyl hydroperoxides such as tert-butyl hydroperoxide and other hydroperoxides such as cumene hydroperoxide, peroxyesters or peracids such as tert-butylperoxide, benzoyl peroxide, peracetates and perbenzoates, lauryl peroxide including (di)peroxyesters, ethers, such as peroxydiethyl ether, perketones such as methyl ethyl ketone peroxide. The organic peroxides used as curing agents are often tertiary peresters or tertiary hydroperoxides, that is, peroxide compounds having tertiary carbon atoms which are directly attached to the -O-O-acyl or -OOH group. However, mixtures of these peroxides with other peroxides can also be used according to the invention. These peroxides can also be mixed peroxides, that is, peroxides that contain two different peroxide-bearing structural units in the molecule. Preferably, dibenzoyl peroxide (BPO) is used for curing.

The reactive resin system can be in the form of a two- or multi-component system in which the respective components are spatially separated from each other so that the reaction (curing) of the components occurs only after they have been mixed.

The two-component reactive resin system preferably contains the A-component and the B-component separated without the reaction taking place in different containers, for example, in a multi-chamber design, such as a multi-chamber cassette and/or cartridge, from these containers both components are squeezed out under the action of a mechanical pressure efforts or under the influence of gas pressure and are mixed. Another possibility is to package the two-component reactive resin system in the form of two-component capsules, which are introduced into the drilled hole and destroyed by the impact-rotary setting of the fastener while simultaneously mixing both components of the fixing mass. Preferably, in this case, a cassette or injection system is used, in which both components are squeezed out of separated containers and passed through a static mixer, in which they are homogeneously mixed and then discharged through a nozzle, preferably directly into a drilled hole.

In a preferred embodiment of the reactive resin system according to the invention, the reactive resin system is a two-component system, and the reactive resin component (A), in addition to the structure-forming resin, additionally contains a hydraulically settable or polycondensable inorganic compound, in particular cement, and a hardener component (B) in addition to the initiator for the polymerization of the structure-forming resin, it also contains water. Hybrid mortar systems of this type are described in detail in German patent DE 4231161 A1. In this case, component (A) preferably contains cement, such as Portland cement or alumina cement, as a hydraulically settable or polycondensable inorganic compound, with cements containing no transition metal oxides or with a low content of transition metal oxides being particularly preferred. Gypsum can also be used as the hydraulically settable inorganic compound, either alone or mixed with cement. Component (A) as a polycondensable inorganic compound can also contain silicate, polycondensable compounds, in particular substances containing soluble, dissolved and/or amorphous silicon dioxide, such as polar non-post-treated pyrogenic silicic acid.

The volume ratio of component A to component B in a two-component system is preferably 3:1.5:1 or 7:1. Particularly preferably, the volume ratio is 3:1 or 5:1.

In one preferred embodiment, the reactive resin component (A) thus contains the following ingredients:

at least one urethane (meth)acrylate as described above, preferably one compound of formula (II) or (III);

at least one inhibitor, as described above, of the piperidinyl-N-oxy or tetrahydropyrrole-N-oxy type, preferably TEMPOL.

- at least one accelerator as described above, preferably a toluidine derivative, particularly preferably diisopropanol-p-toluidine;

at least one hydraulically settable or polycondensable inorganic compound, preferably cement; and

- at least one thixotropic agent, preferably pyrogenic silicic acid,

and the hardener component (B) contains:

- at least one initiator for initiating the polymerization of the urethane (meth)acrylate, preferably benzoyl peroxide (BPO) or tert-butylperoxybenzoate; and

- water.

In a more preferred embodiment, the reactive resin component (A) contains:

at least one urethane (meth)acrylate as described above, preferably one compound of formula (II) or (III);

- at least one inhibitor, as described above, piperidinyl-N-oxy or tetrahydropyrrole-N-oxy type, preferably TEMPOL;

at least one accelerator, preferably a toluidine derivative, particularly preferably diisopropanol-p-toluidine;

at least one hydraulically settable or polycondensable inorganic compound, preferably cement; and

- at least one thixotropic agent, preferably pyrogenic silicic acid,

and the hardener component (B) contains:

- at least one initiator for initiating the polymerization of the urethane (meth)acrylate, preferably benzoyl peroxide (BPO) or tert-butylperoxybenzoate;

- at least one filler, preferably quartz sand or quartz flour; and

- water.

In an even more preferred embodiment, the reactive resin component (A) contains:

at least one urethane (meth)acrylate as described above, preferably one compound of formula (II) or (III);

- at least one inhibitor, as described above, piperidinyl-N-oxy or tetrahydropyrrole-N-oxy type, preferably TEMPOL;

at least one accelerator, preferably a toluidine derivative, particularly preferably diisopropanol-p-toluidine;

- at least one additional inhibitor selected from the group consisting of catechins and phenothiazines;

at least one hydraulically settable or polycondensable inorganic compound, preferably cement; and

- at least one thixotropic agent, preferably pyrogenic silicic acid,

and the hardener component (B) contains:

- at least one initiator for initiating the polymerization of the urethane (meth)acrylate, preferably benzoyl peroxide (BPO) or tert-butylperoxybenzoate;

- at least one filler, preferably quartz sand or quartz flour;

- at least one thixotropic agent, preferably pyrogenic silicic acid, and

- water.

In an even more preferred embodiment, the reactive resin component (A) contains:

at least one urethane (meth)acrylate as described above, preferably one compound of formula (II) or (III);

at least one inhibitor, as described above, of the piperidinyl-N-oxy or tetrahydropyrrole-N-oxy type, preferably TEMPOL;

at least one accelerator, preferably a toluidine derivative, particularly preferably diisopropanol-p-toluidine;

- at least one additional inhibitor selected from the group consisting of catechins and phenothiazines;

at least one hydraulically settable or polycondensable inorganic compound, preferably cement;

- at least one thixotropic agent, preferably pyrogenic silicic acid, and

- at least one filler, preferably quartz sand,

and the hardener component (B) contains:

- benzoyl peroxide (BPO) or tert-butylperoxybenzoate as an initiator for initiating the polymerization of urethane (meth)acrylate;

- at least one filler, preferably quartz sand or quartz flour;

- at least one thixotropic agent, preferably pyrogenic silicic acid, and

- water.

In an even more preferred embodiment, the reactive resin component (A) contains:

- at least one urethane (meth)acrylate as described above, preferably one compound of formula (IV) or (V);

- TEMPOL;

- diisopropanol-p-toluidine;

- at least one additional inhibitor selected from the group consisting of catechins and phenothiazines;

- cement;

- pyrogenic silicic acid; and

- quartz sand,

and the hardener component (B) contains:

- at least one initiator for initiating the polymerization of urethane (meth)acrylate;

- pyrogenic silicic acid;

- quartz sand or quartz flour and

- water.

In each of these embodiments, a preferred embodiment is possible in which the reactive resin component (A) further comprises at least one reactive diluent. Preferably, said reactive diluent is a monomer or a mixture of several monomers of a structurant resin.

The reactive resin components (A) and hardener components (B) in each of these embodiments can be combined with each other as desired.

Such a reactive resin system is used primarily in the construction industry (construction purposes), for example for the production, maintenance or repair of structural parts and structures, for example made of concrete, as polymer concrete, as a polymer resin coating or as road markings. cold curing; for strengthening structural parts and structures such as walls, ceilings or floors, fastening structural components such as slabs or blocks, for example made of stone, glass or plastic, to structural parts and structures, for example by gluing (construction bonding). It is especially suitable for chemical fixing. They are particularly suitable for chemically fixing (with permanent or kinematic closure) anchoring means such as anchor rods, bolts, steel bars, screws and the like in recesses such as drilled holes, in particular in drilled holes in various substrates, in in particular mineral substrates such as substrates based on concrete, aerated concrete, brick, lime-sand brick, sandstone, natural stone, glass and the like, and metallic substrates such as steel. In one embodiment, the base of the drilled holes is concrete and the anchoring means are steel or iron. In one embodiment, the base of the drilled holes is steel and the anchors are steel or iron. To this end, the components are injected into the drill hole, after which the devices to be fastened, such as threaded anchor rods and the like, are inserted into the drill hole provided with a curable reactive resin coating, and appropriately positioned precisely.

The following examples serve to explain the present invention in more detail.

EXAMPLES

First, reactive resins, reactive resin components, and two-component reactive resin systems were prepared, each containing the compound (IV) according to the invention as a structurant resin. The dynamic viscosity of the reactive resins and components of the reactive resins, the extrusion forces of two-component systems based on reactive resins, and the adhesive stress of the cured fixing masses were determined.

Compound (IV) according to the invention

A1. Preparation of a Masterbatch of Reactive Resin A1 with Compound (IV)

In a 2 liter laboratory glass reactor with an internal thermometer and stirrer, 1542 g of hydroxypropyl methacrylate was placed and mixed with 0.24 g of phenothiazine (D Prills, Allessa Chemie), 0.60 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl -1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.40 g of dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals). The resulting mixture was heated to 80°C. Then 500 g of toluene-2,4-diisocyanate (TDI, TCI Deutschland GmbH) was added with stirring at 200 rpm for 45 minutes. After that, additionally stirred for 180 minutes at 80°C.

As a result, a master batch of reactive resin A1 containing 65% wt. compounds (IV) as structure-forming resin and 35% wt. hydroxypropyl methacrylate, based on the total weight of the reactive resin masterbatch.

Compound (IV) has the following structure:

From the master batch of reactive resin A1 was obtained reactive resin (A2.1) with 33% wt. and reactive resin (A2.2) with 41% wt. compound (IV) as a structure-forming resin.

A2.1 Getting reactive resin A2.1 with 33% wt. compounds (IV)

301 g of the reactive resin A1 masterbatch was mixed with 90 g of hydroxypropyl methacrylate and 196 g of 1,4-butanediol dimethacrylate (BDDMA, Evonik AG). To this mixture were added 2.75 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL, Evonik Degussa GmbH) and 10.5 g of diisopropanol-p-toluidine (BASF SE).

The result was a reactive resin (A2.1) with 33% wt. compound (IV) as a structure-forming resin.

A2.2 Getting reactive resin A2.2 with 41% wt. compounds (IV)

376 g of a master batch of reactive resin A1 was mixed with 39 g of hydroxypropyl methacrylate and 171 g of 1,4-butanediol dimethacrylate (BDDMA, Evonik AG). To this mixture were added 2.75 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL, Evonik Degussa GmbH) and 10.5 g of diisopropanol-p-toluidine (BASF SE).

The result was a reactive resin (A2.2) with 41% wt. compound (IV) as a structure-forming resin.

A3. Obtaining components of reactive resins A3.1 and A3.2

354 g of A2.1 or A2.2 reactive resin were mixed with 185 g of Secar® 80 (Kerneos Inc.), 27 g of Cab-O-Sil® TS-720 (Cabot Corporation) and 335 g of F32 quartz sand (Quarzwerke GmbH) using a PC LaboratorSystem dissolver - type LDV 0.3-1 for 8 minutes at 3500 rpm in vacuum (pressure ≤100 mbar) with a 55 mm dissolver disc and a scraper that cleans the edges.

As a result, components of reactive resins A3.1 and A3.2 were obtained.

From them, systems based on reactive resins were obtained in the form of a two-component system

A4. Obtaining two-component systems based on reactive resins A4.1 and A4.2

To obtain two-component systems based on reactive resins A4.1 and A4.2, the components of reactive resins A3.1 and A3.2 (component (A)) and in each case the hardener component (component (B)) of the commercially available product HIT-HY 110 (Hilti Aktiengesellschaft, batch number 1610264) were filled in plastic cartridges (Ritter GmbH, volume ratio A:B=3:1) with an internal diameter of 47 mm (component (A)) or 28 mm (component (B)), respectively.

As a result, two-component systems were obtained based on reactive resins A4.1 (containing 33 wt. % compound (IV) in reactive resin) and A4.2 (containing 41 wt. % compound (IV) in reactive resin).

To introduce a higher content of compound (IV) into the reactive resin, another master batch of reactive resin (B1) was obtained with a high content of 80% wt. compounds (IV).

IN 1. Preparation of the Masterbatch of Reactive B1 Resin with Compound (IV)

1396 g of hydroxypropyl methacrylate were placed in a 2-liter laboratory glass reactor with an internal thermometer and a stirrer and mixed with 0.29 g of phenothiazine (D Prills, Allessa Chemie), 0.70 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl- 1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.49 g of dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals). The resulting mixture was heated to 80°C. Then 602 g of toluene-2,4-diisocyanate (TCI Deutschland GmbH) was added with stirring at 200 rpm for 45 minutes. After that, additionally stirred for 180 minutes at 80°C.

As a result, a master batch of reactive resin B1 containing 80% wt. compounds (IV) as structure-forming resin and 20% wt. hydroxypropyl methacrylate, based on the total weight of the reactive resin masterbatch.

From the master batch of reactive resin B1, a reactive resin with a different content of compound (IV) as a structure-forming resin was also obtained.

B2.1 Getting reactive resin B2.1 with 37% wt. compounds (IV)

186 g of the B1 reactive resin masterbatch was mixed with 43 g of hydroxypropyl methacrylate and 160 g of 1,4-butanediol dimethacrylate (BDDMA, Evonik AG). To this mixture were added 1.08 g of pyrocatechol (manufactured by Solvay Catechol Flakes) and 0.36 g of 4-tert-butyl pyrocatechol and 9.2 g of diisopropanol-p-toluidine (BASF SE).

The result was a reactive resin (B2.1) with 37% wt. compound (IV) as a structure-forming resin.

B2.2 Getting reactive resin B2.2 with 40% wt. compounds (IV)

200 g of the B1 reactive resin masterbatch was mixed with 37 g of hydroxypropyl methacrylate and 153 g of 1,4-butanediol dimethacrylate (BDDMA, Evonik AG). To this mixture were added 1.08 g of pyrocatechol (Solvay Catechol Flakes) and 0.36 g of 4-tert-butylpyrocatechol and 9.2 g of diisopropanol-p-toluidine (manufactured by BASF SE).

The result was a reactive resin (B2.2) with 40% wt. compound (IV) as a structure-forming resin.

B2.3 Getting reactive resin B2.3 with 45% wt. compounds (IV)

225 g of the B1 reactive resin masterbatch was mixed with 26 g of hydroxypropyl methacrylate and 140 g of 1,4-butanediol dimethacrylate (BDDMA, Evonik AG). To this mixture were added 1.08 g pyrocatechol (Solvay Catechol Flakes) and 0.36 g 4-tert-butyl pyrocatechol and 9.2 g diisopropanol-p-toluidine (BASF SE).

The result was a reactive resin (B2.3) with 45% wt. compound (IV) as a structure-forming resin.

B2.4 Getting reactive resin B2.4 with 50% wt. compounds (IV)

250 g of the B1 reactive resin masterbatch was mixed with 13 g of hydroxypropyl methacrylate and 127 g of 1,4-butanediol dimethacrylate (BDDMA, Evonik AG). To this mixture were added 1.08 g pyrocatechol (Solvay Catechol Flakes) and 0.36 g 4-tert-butyl pyrocatechol and 9.2 g diisopropanol-p-toluidine (BASF SE).

The result was a reactive resin (B2.4) with 50% wt. compound (IV) as a structure-forming resin.

AT 3. Preparation of Reactive Resin Components B3.1, B3.2, B3.3 and B3.4

In each case, 311 g of reactive resin B2.1, B2.2, B2.3 and B2.4 were mixed with 167 g of Secar® 80 (Kerneos Inc.), 9 g of Cab-O-Sil® TS-720 (Cabot Corporation) , 16 g Aerosil® R812 (Evonik Industries AG) and 398 g quartz sand F32 (Quarzwerke GmbH) in a dissolver under vacuum. Mixing was carried out using a PC Laborsystem type LDV 0.3-1 dissolver as described in paragraph A3.

As a result, reactive resin components B3.1, B3.2, B3.3 and B3.4 were obtained, which contained the compound (IV) as a structure-forming resin.

From them, systems based on reactive resins were obtained in the form of a two-component system.

AT 4. Obtaining two-component systems based on reactive resins B4.1 - B4.4

To obtain two-component systems based on reactive resins B4.1, B4.2, B4.3 and B4.4, the components of reactive resins B3.1, B3.2, B3.3 and B3.4 (component (A)) and in each In the case of the hardener component (component (B)) of the commercially available product HIT HY-200 (Hilti Aktiengesellschaft, batch number 8104965) was filled into plastic cartridges (manufactured by Ritter GmbH, volume ratio A:B=5:1) with an inner diameter of 32.5 mm (component (A)) or respectively 14 mm (component (B)).

As a result, two-component systems based on reactive resins B4.1 (with a content of 37% wt. Compound (IV) in a reactive resin), B4.2 (with a content of 40% wt. Compound (IV) in a reactive resin), B4.3 (containing 45 wt. % compound (IV) in the reactive resin), and B4.4 (containing 50 wt. % compound (IV).

Comparative Examples C and D

For comparison, reactive resin master batches, reactive resins and reactive resin components with Comparative Compounds 1 and 2 were prepared as follows.

C1. Preparation of Comparative Masterbatch of Reactive Resin C1 with Comparative Compound 1

Comparative master batch of reactive resin C1 with 65% wt. comparative compound 1 as structure-forming resin and 35% wt. hydroxypropyl methacrylate was obtained in accordance with the method described in European patent application EP 0 713 015 A1, which is incorporated here by reference and the full disclosure of which is hereby reference.

The product (comparative compound 1) has an oligomeric distribution, with the repeating unit oligomer having the following structure:

C2.1 Obtaining a comparative reactive resin C2.1 with 33% wt. reference compound 1

9.2 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL) and 35.0 g of diisopropanol-p-toluidine (BASF SE) were added to a mixture of 1004 g of C1 reactive resin masterbatch, 300 g of hydroxypropyl methacrylate; and 652 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

The result was a comparative reactive resin C2.1 with 33% wt. Comparative Compound 1 as a structure-forming resin.

C2.2 Obtaining a comparative reactive resin 1 with 37% wt. reference compound 1

229 g of the C1 reactive resin reference masterbatch were mixed with 160 g of 1,4-butanediol dimethacrylate (BDDMA, Evonik AG). To this mixture were added 1.08 g pyrocatechol (Solvay Catechol Flakes) and 0.36 g 4-tert-butyl pyrocatechol (tBBK, CFS EUROPE S.p.A. (Borregaard Italia S.p.A.)) and 9.2 g diisopropanol-p-toluidine (BASF SE) .

The result was a comparative reactive resin C2.2 with 37% wt. Comparative Compound 1 as a structure-forming resin.

C2.3 Obtaining a comparative reactive resin C2.3 with 41% wt. reference compound 1

2.8 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL, Evonik Degussa GmbH) and 10.5 g of diisopropanol-p-toluidine (BASF SE) were added to a mixture of 377 g of a reactive reference masterbatch resin C1, 39 g of hydroxypropyl methacrylate and 174 g of 1,4-butanediol dimethacrylate.

The result was a comparative reactive resin C2.3 with 41% wt. Comparative Compound 1 as a structure-forming resin.

C3. Preparation of Comparative Components of Reactive Resin C3.1 - C3.3

In each case, 354 g of comparative reactive resin C2.1 or C2.3 respectively were mixed with 185 g of Secar® 80 (Kerneos Inc.), 27 g of Cab-O-Sil® TS-720 (Cabot Corporation) and 335 g of F32 quartz sand (Quarzwerke GmbH) in a dissolver under vacuum. Mixing was carried out using a PC Laborsystem type LDV 0.3-1 dissolver as described in paragraph A3.

The result was comparative components of reactive resins C3.1 with 33% wt. comparative compound 1 in a reactive resin (from C2.1) and C3.2 with 41% wt. comparative compound 1 in reactive resin (from C2.3).

311 g of C2.2 comparative reactive resin was mixed with 167 g of Secar® 80 (Kerneos Inc.), 9 g of Cab-O-Sil® TS-720 (Cabot Corporation), 16 g of Aerosil® R812 (Evonik Industries AG) and 398 g quartz sand F32 (Quarzwerke GmbH) in a dissolver under vacuum. Mixing was carried out using a PC Laborsystem type LDV 0.3-1 dissolver as described in paragraph A3.

The result was a comparative component of the reactive resin C3.3 with 37% wt. comparative compound 1 in a reactive resin.

C4. Preparation of comparative two-component systems based on reactive resins C4.1 - C4.3

To obtain comparative two-component systems based on C4.1 and C4.2 reactive resins, components of C3.1 and C3.2 reactive resins (component (A)) and in each case the hardener component (component (B)) of the commercially available product HIT-HY 110 (Hilti Aktiengesellschaft, batch number 1610264) were filled in plastic cartridges (Ritter GmbH, volume ratio A:B=3:1) with an internal diameter of 47 mm (component (A)) or 28 mm respectively (component (B)).

The result was a comparative two-component system based on reactive resins C4.1 with 33% wt. Comparative Compound 1 in reactive resin (from C3.1) and C4.2 with 41% wt. comparative compound 1 in reactive resin (from C3.2).

To obtain a comparative two-component system based on C4.3 reactive resin, the C3.3 reactive resin components (component (A)) and in each case the hardener component (component (B)) of the commercially available product HIT-HY 200 (Hilti Aktiengesellschaft, batch number 8104965 ) were filled in plastic cartridges (Ritter GmbH, volume ratio A:B=5:1) with an inner diameter of 32.5 mm (component (A)) or 14 mm (component (B)), respectively.

The result was a comparative two-component system based on reactive resin C4.3 with 37% wt. comparative compound 1 in reactive resin (from C3b).

D1. Preparation of Comparative Masterbatch of Reactive Resin D1 with Comparative Compound 2

Comparative master batch of reactive resin D1 in each case with 65% wt. comparative compound 2 as structure-forming resin and 35% wt. hydroxypropyl methacrylate, in each case based on the total weight of the reactive resin masterbatch, was prepared according to the method described in European patent application EP 0 713 015 A1, which is incorporated herein by reference and the full disclosure of which is hereby incorporated by reference.

Comparative compound 2 has the following structure:

From it, a comparative reactive resin was obtained with different high content of comparative compound 2.

D2. Preparation of Comparative Reactive Resin D2

4.6 g 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL, Evonik Degussa GmbH) and 17.5 g diisopropanol-p-toluidine (BASF SE) were added to a mixture of 502 g comparative masterbatch reactive resin D1, 150 g of hydroxypropyl methacrylate and 326 g of 1,4-butanediol dimethacrylate (1,4-BDDMA; Evonik Degussa GmbH).

As a result, Comparative Reactive Resin D2 was obtained with Comparative Compound 2 as a structurant resin.

D3. Obtaining Comparative Component Reactive Resin D3

354 g of D2 Comparative Reactive Resin was mixed with 185 g of Secar® 80 (Kerneos Inc.), 27 g of Cab-O-Sil® TS-720 (Cabot Corporation) and 335 g of F32 silica sand (Quarzwerke GmbH) in a dissolver under vacuum. Mixing was carried out using a PC Laborsystem type LDV 0.3-1 dissolver as described in paragraph A3.

As a result, a comparative component of reactive resin D3 was obtained with comparative compound 2 as a structurant resin.

D4. Preparation of Comparative Two-Component System Based on D4 Reactive Resin

To obtain a comparative two-component system based on D4 reactive resin, a comparative component of D3 reactive resin (component (A)) and a hardener component (component (B)) of the commercially available product HIT-HY 110 (Hilti Aktiengesellschaft, lot number 1610264) were charged into a plastic cartridge ( company Ritter GmbH, volume ratio A:B=3:1) with an internal diameter of 47 mm (component (A)) or 28 mm (component (B)).

As a result, a comparative component of reactive resin D4 was obtained.

In order to show the effect of the compound (IV) according to the invention on the viscosity of the reactive resin masterbatch, the reactive resin and the reactive resin component containing said compound, and the effect on the adhesive stress of the cured fixing mass, the viscosities of the reactive resin masterbatch, the reactive resins, the reactive resin components were measured. , the extrusion forces of two-component systems based on reactive resins and the adhesive stress of the cured fixing masses and compared in each case with comparative compositions.

Dynamic Viscosity Measurement of A1 Reactive Resin Masterbatch and Comparative C1 and D1 Reactive Resin Masterbatches

Measurement of the dynamic viscosity of the A1 reactive resin masterbatch and the comparative C1 and D1 reactive resin masterbatches (Table 1) was carried out using a cone-plate measuring system according to DIN 53019. The cone diameter was 20 mm and the opening angle was 1°. The measurement was carried out at a constant shear rate of 100/s and at the appropriate temperature (0, 5, 10, 15, 20, 30 and 40°C). The duration of the measurement was 120 s, and one measurement point was created every second. To achieve the shear rate at the appropriate temperature, an acceleration from 0 to 100/s for 30 s was preliminarily turned on. Since we are talking about Newtonian fluids, a linear evaluation of the measuring segment was carried out along the measuring segment with a constant shear rate of 100/s and the viscosity was determined. In each case, three measurements were made, and in table 1 for each case, the average values are given.

Measurement of dynamic viscosity of components of reactive resins A3.1. B3.1, B3.2, B3.3 and B3.4. as well as comparative components of reactive resins C3.1. C3.3 and D3

Measurement of the dynamic viscosity of A3 reactive resin components and comparative C3 and D3 reactive resin components (Table 2), as well as components of B3.1, B3.2, B3.3 and B3.4 reactive resins and comparative components of C3.3 reactive resins (Table 2). 3) was carried out using a plate-to-plate measuring system according to DIN 53019. The plate diameter was 20 mm and the slot distance was 3 mm. To prevent the sample from leaking out of the slot, a Teflon restrictive ring was used, located at a distance of 1 mm from the top plate. The measurement temperature was 25°C. The method consisted of three segments: 1. Minor shift, 2. Major shift, 3. Minor shift. On the first segment for 3 minutes, the shear rate was 0.5/s. In the second segment in 8 stages of 15 seconds each, the shear rate was logarithmically increased from 0.8/s to 100/s. The individual stages were: 0.8/s; 1.724/s; 3.713/s; 8/s; 17.24/s; 37.13/s; 80/s; 100/s. The 3rd segment was a repetition of the 1st segment. At the end of each segment, the viscosity was calculated. Table 2 shows the values from the second segment at 100/s. Three measurements were taken in each case, the values given in Table 2 being the average of the three measurements.

Then, the dynamic viscosities of the A1 reactive resin masterbatch and the comparative C1 and D1 reactive resin masterbatches were compared at different temperatures (Table 1). The master batches of reactive resins contained in each case 65% wt. structure-forming resin and 35% wt. hydroxypropyl methacrylate.

The measurement results in Table 1 show that the compounds according to the invention are characterized by a decrease in dynamic viscosity, especially at low temperatures. In particular, at temperatures below 20°C, the dynamic viscosity of the inventive reactive resin masterbatch containing the compound (IV) of the invention is lower than the dynamic viscosity of the C1 and D1 reactive resin masterbatches that contain comparative compounds 1 and 2.

Next, the dynamic viscosity of the A3.1 reactive resin component prepared from the A1 reactive resin masterbatch according to the invention was compared with the dynamic viscosity of the C3.1 and D3 reactive resin components prepared from the comparative C1 and D1 reactive resin masterbatches (Table 2). All components of the reactive resins from table 2 contained 33% of the mass. structure-forming resin in a reactive resin.

The measurement results in Table 2 show that the compounds of the invention also lead to a reduction in the dynamic viscosity of the reactive resin components containing these compounds. The dynamic viscosity of the reactive resin component of the invention containing the compound (IV) of the invention is lower than the dynamic viscosity of the reactive resin components C3.1 and D3 that contain comparative compounds 1 and 2.

In order to show that with the compounds according to the invention, for example compound (IV), it is possible to increase the content of the structurant resin in the reactive resin and therefore in the reactive resin component without too much increase in viscosity and extrusion forces as a result, the dynamic viscosity of the components of the reactive resin was measured. resins with different content of structure-forming resin (table 3).

The results in Table 3 show that the dynamic viscosity of the reactive resin components remains relatively low despite the increase in the content of the structurant resin. Even an increase in the content of structure-forming resin up to 45% wt. results in a reactive resin component having a lower viscosity than a comparative reactive resin component having a structurant resin content of 37% wt.

Even when the content of structure-forming resin 50% wt. the viscosity of the reactive resin component is only slightly higher than the viscosity of the comparative component of the reactive resin with a structure-forming resin content of 37% wt. With the same content of structurant resin in the reactive resin, the dynamic viscosity of the reactive resin component of the invention is significantly lower than that of the comparative reactive resin component.

Determination of extrusion forces

To determine the extrusion forces of reactive resin systems, the cartridges with the respective reactive resin components (component (A)) and hardener components (component (B)) were brought to 0°C or 25°C respectively. The cartridges were extruded on a Zwick material testing machine with a force sensor (test range up to 10 kN) through a static mixer (HIT-RE-M mixer, Hilti Aktiengesellschaft) at a constant speed of 100 mm/min over a distance of 45 mm and the average force generated was measured. wherein.

The extrusion forces of a two-component system based on reactive resin A4.1, as well as comparative two-component systems based on reactive resins C4.1 and D4, each of which contained 33% wt. structurant resin in the reactive resin were measured at 0°C and 25°C (Table 4).

The extrusion forces of a two-component system based on reactive resin B4.1, as well as a comparative two-component system based on reactive resin C4.3, each of which contained 37% wt. structure-forming resin in the reactive resin were measured at 0°C and 25°C (Table 5).

The results in Tables 4 and 5 show that the extrusion forces of the two-component reactive resin systems according to the invention at both 0°C and 25°C are lower than the extrusion forces of comparative two-component reactive resin systems.

Coupling stress measurement

To determine the bond stress (load value) of the cured fixing mass, M12 anchor threaded rods were inserted into a drilled hole in C20/25 concrete with a diameter of 14 mm and a drilled hole depth of 72 mm, which was filled with reactive resin mortar compositions. Coupling stresses were determined by centered pulling of threaded anchor studs. In each case, five anchor threaded studs were fixed and their bond stress was determined after 24 hours of curing. The fixing masses were extruded from the cartridges through a static mixer (HIT-RE-M mixer; Hilti Aktiengesellschaft) and introduced into the drilled holes.

Determination of the adhesive stress was carried out under the following conditions of the drilled hole:

A1: This is a clean, dust-free, dry, percussion drilled hole. Introduction, curing and stretching is carried out at room temperature. The temperature of the two-component systems based on reactive resins or fixing masses is 20°C when injected.

F1b*: This is a semi-cleaned (approximately 50% dust-free), damp, drilled hole with an impact drill. Introduction, curing and stretching is carried out at room temperature. The temperature of the two-component systems based on reactive resins or fixing masses is 20°C when injected.

A21 (80°C): This is a clean, dust-free, dry, drilled hole with an impact drill. The introduction and curing is carried out at room temperature. After that, the concrete and the dowel are kept at 80°C for 24 hours. The stretching is carried out at 80°C. The temperature of the two-component systems based on reactive resins or fixing masses is 20°C when injected.

A23 (-5°C): This is a clean, dust-free, dry, drilled hole with an impact drill. Introduction, curing and stretching is carried out at -5°C. The temperature of two-component systems based on reactive resins or fixing masses is 0°C when injected.

The adhesive stresses thus determined (N/mm ² ) are given in the following tables 6 and 7 as the average of five measurements.

The results in Table 6 show that the adhesive stresses of the fixing mass from A4.1, which has a structure-forming resin content of 33% by weight, under conditions A1, F1b* and A23 are approximately at the same level as the adhesive stresses of the comparative fixing mass from C4 .one. Under conditions A21, the adhesive stresses of the fixing mass from A4.1 are slightly higher than the adhesive stresses of the comparative fixing mass from C4.1. It can also be seen that an increase in the structurant resin content, as in the case of the fixing mass from A4.2, also leads to an increase in bond stresses.

This is also evidenced by the results shown in Table 7, in which, with increasing content of structurant resin (B4.1 → B4.4), an increase in bond stresses is observed compared to the adhesive stress of the comparative fixing mass from C4.3 (37% wt. structurant resin in reactive resin).

In addition, reactive resins, reactive resin components, and two-component reactive resin systems were obtained, each containing the compound (IV) according to the invention as a structurant resin. The dynamic viscosity of the reactive resins and reactive resin components, as well as the extrusion forces of two-component systems based on reactive resins, were determined.

Compound (V) according to the invention

In addition, a reactive resin masterbatch, reactive resins, reactive resin components, and two-component reactive resin systems were prepared, each containing the compound (V) of the invention as a structure-forming resin. The dynamic viscosity of the reactive resin masterbatch and the reactive resin components, as well as the extrusion forces of the two-component reactive resin systems, were determined and compared with the corresponding values for comparative compositions.

E1.1 Obtaining a master batch of reactive resin E1.1 with 65% wt. compounds (V) and 35% of the mass. 1,4-butanediol dimethacrylate

80400 g of hydroxypropyl methacrylate (Visiomer® HPMA; Evonik Degussa GmbH) was placed in a 300 liter steel reactor with an internal thermometer and stirrer and mixed with 36 g of phenothiazine (D Prills, Allessa Chemie), 70 g of 4-hydroxy-2,2,6 ,6-tetramethylpiperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 56 g of dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals). The resulting mixture was heated to 60°C. Then, 69440 g of methylene di(phenylisocyanate) (MDI, Lupranat® MIS, BASF SE) was added dropwise over 1.5 hours with stirring. After that, additionally stirred for 45 minutes at 80°C. Then 50,000 g of 1,4-butanediol dimethacrylate (Visiomer 1,4-BDDMA, Evonik Degussa GmbH) was added.

A master batch of reactive E1.1 resin containing 75 wt. % was obtained. compounds (V) as structure-forming resin and 25% wt. 1,4-butanediol dimethacrylate, based on the total weight of the reactive resin masterbatch.

By diluting with 1,4-butanediol dimethacrylate, the E1.1 reactive resin masterbatch could be diluted to such an extent that the masterbatch contained 65% wt. compounds (V) and 35% wt. 1,4-butanediol dimethacrylate.

Compound (V) has the following structure:

E1.2 Obtaining a master batch of reactive resin E1.2 according to the invention with 65% wt. compounds (V) and 35% of the mass. hydroxypropyl methacrylate

1396 g of hydroxypropyl methacrylate (Visiomer® HPMA 98; Evonik Degussa GmbH) was placed in a 2 L laboratory glass reactor with an internal thermometer and stirrer and mixed with 0.3 g of phenothiazine (D Prills, Allessa Chemie), 0.6 g of 4-hydroxy- 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.48 g of dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals). The resulting mixture was heated to 60°C. Then, 602.6 g of methylene di(phenylisocyanate) (MDI, Lupranat® MIS, BASF SE) was added dropwise over 1.5 hours with stirring (600 rpm). After that, additionally stirred for 30 minutes at 80°C.

The result was a master batch of reactive resin E1.2 containing 65% wt. compound (V) as structure-forming resin and 35% wt. hydroxypropyl methacrylate, based on the total weight of the reactive resin masterbatch.

E2. Getting reactive resin E2 with 45% wt. connections (V)

2520 g of the E1.1 reactive resin masterbatch was mixed with 439.74 g of hydroxypropyl methacrylate and 1128.54 g of 1,4-butanediol dimethacrylate (1,4-BDDMA, Evonik Degussa GmbH). To this mixture were added 96.6 g of diisopropanol-p-toluidine (BASF SE), 13.44 g of catechol (Catechol Flakes, RHODIA) and 5.88 g of tert-butyl pyrocatechol (tBBK, CFS EUROPE SpA (Borregaard Italia SpA) and stirred until complete homogenization.

The result was a reactive resin E2 with 45% wt. compound (V) as a structure-forming resin.

E3.1 Preparation of the reactive resin component E3.1

(for measuring viscosity and extrusion forces at 23°C)

2106 g E2 reactive resin was mixed with 930.42 g Secar® 80 (Kerneos Inc.), 64.8 g Cab-O-Sil® TS-720 (Cabot Corporation), 16 g Aerosil® R812 (Evonik Industries AG) and 2222 64 g of quartz sand F32 (Quarzwerke GmbH) in a PC Laborsystem type LDV 0.3-1 dissolver under vacuum. The mixture was agitated for 2 minutes at 2500 rpm and then for 10 minutes at 4500 rpm under vacuum (pressure ≤100 mbar) with a 55 mm dissolver disc and edge scraper.

As a result, the reactive resin component E3.1 was obtained.

E3.2 Preparation of the reactive resin component E3.2

(for measuring viscosity at 0°C and 25°C and extrusion forces at 0°C)

1053 g E2 reactive resin was mixed with 465.21 g Secar® 80 (Kerneos Inc.), 27 g Cab-O-Sil® TS-720 (Cabot Corporation), 48.6 g Aerosil® R812 (Evonik Industries AG) and 1111 .32 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver under vacuum. Mixing was carried out using a PC Laborsystem type LDV 0.3-1 dissolver as described in paragraph E3.1.

As a result, the reactive resin component E3.2 was obtained.

E4. Obtaining two-component systems based on reactive resins E4.1 and E4.2

To obtain two-component systems based on reactive resins E4.1 and E4.2 in each case, the component of the reactive resin E3.1 or E3.2 respectively (component (A)) and the hardener component (component (B)) of the commercially available product HIT-HY 200 (Hilti Aktiengesellschaft, batch number 8104965) was filled in a plastic cartridge (manufactured by Ritter GmbH, volume ratio A:B=5:1) with an internal diameter of 32.5 mm (component (A)) or 14 mm respectively (component (B) ).

As a result, two-component systems were obtained based on reactive resins E4.1 (for measuring extrusion forces at 23°C) and E4.2 (for measuring extrusion forces at 0°C).

Comparative Examples F and G

For comparison, reactive resin master batches, reactive resins and reactive resin components with Comparative Compounds 1 and 2 were prepared as follows.

F1. Preparation of comparative components of reactive resins F1.1 and F1.2

Comparative master batch of reactive resin with 65% wt. comparative compound 1 as structure-forming resin and 35% wt. 1,4-Butanediol dimethacrylate (F1.1) or respectively hydroxypropyl methacrylate (F1.2), in each case based on the total weight of the reactive resin masterbatch, was synthesized according to the method described in European Patent Application EP 0 713 015 A1 , which is incorporated here by reference and the full disclosure of which is hereby referenced.

The product (comparative compound 1) has an oligomeric distribution, with the repeating unit oligomer having the following structure:

F2. Obtaining a comparative reactive resin F2 with 45% wt. reference compound 1

830.76 g of F1.1 reactive resin reference masterbatch was mixed with 125.64 g of hydroxypropyl methacrylate and 211.68 g of 1,4-butanediol dimethacrylate (1,4-BDDMA, Evonik Degussa GmbH). To this mixture were added 27.6 g diisopropanol-p-toluidine (BASF SE), 3.24 g pyrocatechol (Catechol Flakes, RHODIA) and 1.08 g tert-butylpyrocatechol (tBBK, CFS EUROPE SpA (Borregaard Italia SpA) and stirred until complete homogenization.

The result was a comparative reactive resin F2 with a content of 45% wt. Comparative Compound 1 as a structure-forming resin.

F3.1. Preparation of Comparative Reactive Resin F3.1 Component

(for measuring viscosity and extrusion forces at 23°C)

1053 g F2 Comparative Reactive Resin was mixed with 465.21 g Secar® 80 (Kerneos Inc.), 32.4 g Cab-O-Sil® TS-720 (Cabot Corporation), 45.36 g Aerosil® R812 (Evonik Industries AG ) and 1111.33 g of F32 quartz sand (Quarzwerke GmbH) in a dissolver under vacuum.

As a result, a comparative component of reactive resin F3.1 was obtained with comparative compound 1 as a structurant resin.

F3.2. Preparation of Comparative Component of F3.2 Reactive Resin

(for measuring viscosity at 0°C and 25°C and extrusion forces at 0°C)

1053 g F2 Comparative Reactive Resin was mixed with 465.21 g Secar® 80 (Kerneos Inc.), 27 g Cab-O-Sil® TS-720 (Cabot Corporation), 48.6 g Aerosil® R812 (Evonik Industries AG) and 1111.32 g of F32 quartz sand (Quarzwerke GmbH) in a dissolver under vacuum.

As a result, a comparative component of reactive resin F3.2 was obtained with comparative compound 1 as a structurant resin.

F4. Preparation of comparative two-component systems based on reactive resins F4.1 and F4.2

For the production of two-component systems based on reactive resins F4.1 and F4.2 in each case, the reactive resin component F3.1 or F3.2 respectively (component (A)) and the hardener component (component (B)) of the commercially available product HIT-HY 200 (Hilti Aktiengesellschaft, batch number 8104965) was filled in a plastic cartridge (manufactured by Ritter GmbH, volume ratio A:B=5:1) with an internal diameter of 32.5 mm (component (A)) or 14 mm respectively (component (B) ).

As a result, comparative two-component systems based on reactive resins F4.1 (for measuring extrusion forces at 23°C) and F4.2 (for measuring extrusion forces at 0°C) were obtained.

G1. Preparation of Comparative Components of Reactive G1.1 and G1.2 Resins

Comparative master batches of reactive resins G1.1 and G1.2 in each case with 65% wt. comparative compound 2 as structure-forming resin and 35% wt. 1,4-butanediol dimethacrylate (G1.1) or respectively hydroxypropyl methacrylate (G1.2), in each case based on the total weight of the reactive resin masterbatch, were synthesized according to the method described in European patent application EP 0 713 015 A1 , which is incorporated here by reference and the full disclosure of which is hereby referenced.

Comparative compound 2 has the following structure:

G2. Obtaining a comparative reactive resin G2 with 45% wt. comparative compound 2

830.76 g of a G1.1 reactive resin reference masterbatch was mixed with 125.64 g of hydroxypropyl methacrylate and 211.68 g of 1,4-butanediol dimethacrylate (1,4-BDDMA, Evonik Degussa GmbH). To this mixture were added 27.6 g diisopropanol-p-toluidine (BASF SE), 3.24 g pyrocatechol (Catechol Flakes, RHODIA) and 1.08 g tert-butylpyrocatechol (tBBK, CFS EUROPE SpA (Borregaard Italia SpA) and stirred until complete homogenization.

The result was a comparative reactive resin G2 with a content of 45% wt. comparative compound 2 as a structurant resin in hydroxypropyl methacrylate and 1,4-butanediol dimethacrylate.

G3.1. Preparation of Comparative Reactive Resin Component G3.1

(for measuring viscosity and extrusion forces at 23°C)

1053 g Comparative Reactive G2 Resin was mixed with 465.21 g Secar® 80, 32.4 g Cab-O-Sil® TS-720 (Cabot Corporation), 45.36 g Aerosil® R812 (Evonik Industries AG) and 1111.32 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver under vacuum.

As a result, a comparative component of reactive resin G3.1 was obtained with comparative compound 2 as a structurant resin.

G3.2. Preparation of Comparative Reactive Resin Component G3.2

(for measuring viscosity at 0°C and 25°C and extrusion forces at 0°C)

1053 g of G2 Comparative Reactive Resin was mixed with 465.21 g of Secar® 80 (Kerneos Inc.), 27 g of Cab-O-Sil® TS-720 (Cabot Corporation), 48.6 g of Aerosil® R812 (Evonik Industries AG) and 1111.32 g of F32 quartz sand (Quarzwerke GmbH) in a dissolver under vacuum.

As a result, a comparative component of reactive resin G3.2 was obtained with comparative compound 2 as a structurant resin.

G4. Preparation of comparative two-component systems based on reactive resins G4.1 and G4.2

To obtain comparative two-component systems based on G4.1 and G4.2 reactive resins, in each case the G3.1 or G3.2 reactive resin component (component (A)) and the hardener component (component (B)) of the commercially available HIT- HY 200 (Hilti Aktiengesellschaft, batch number 8104965) was filled into a plastic cartridge (Ritter GmbH, volume ratio A:B=5:1) with an internal diameter of 32.5 mm (component (A)) or 14 mm respectively (component (B )).

As a result, comparative two-component systems based on reactive resins G4.1 (for measuring extrusion forces at 23°C) and G4.2 (for measuring extrusion forces at 0°C) were obtained.

In order to show the effect of the compound (V) according to the invention on the viscosity of the reactive resin masterbatch, the reactive resin and the reactive resin component containing said compound, the viscosity of the reactive resin masterbatch, the reactive resins, the reactive resin components, and the extrusion force of the reactive resin systems were measured. and compared in each case with comparative formulations.

Measurement of dynamic viscosity of E1.1 and E1.2 reactive resin masterbatches and comparative F1.1, F1.2, G1.1 and G1.2 reactive resin masterbatches

Measurement of the dynamic viscosity of masterbatches of reactive resins E1.1 and E1.2 and comparative masterbatches of reactive resins F1.1, F1.2, G1.1 and G1.2 (table 8) was carried out using a measuring system "cone-plate" in according to DIN 53019. The cone diameter was 20 mm and the opening angle was 1°. The measurement was carried out at a constant shear rate of 100/s and at the appropriate temperature (0, 5, 10, 15, 20, 30 and 40°C). The duration of the measurement was 120 s, and one measurement point was created every second. To achieve the shear rate at the appropriate temperature, an acceleration from 0 to 100/s for 30 s was preliminarily turned on. Since we are talking about Newtonian fluids, a linear evaluation of the measuring segment was carried out along the measuring segment with a constant shear rate of 100/s and the viscosity was determined. In each case, three measurements were made, with the corresponding average values given in Table 8 below.

Measurement of the dynamic viscosity of the reactive resin component E3.1. as well as comparative components of reactive resins F3.1 and G3.1

The measurement of the dynamic viscosity of the E3.1 reactive resin component, as well as the comparative components of the F3.1 and G3.1 reactive resins (Table 9), was carried out using a plate-to-plate measuring system in accordance with DIN 53019. The plate diameter was 35 mm, and the slot distance was 3 mm. To prevent the sample from leaking out of the slot, a Teflon restrictive ring was used, located at a distance of 1 mm from the top plate. The measurement temperature was 23°C. The method consisted of two segments: 1. Acceleration from 0/s to 10/s with a duration of 120 s with 100 measurement points. 2. Constant shear rate of 10/s for 180 s with 180 measurement points. On the second segment, a linear evaluation was carried out, and this value was indicated as the viscosity. Three measurements were taken in each case, with Table 9 listing the respective averages.

Measurement of dynamic viscosity of E3.2 reactive resin component as well as comparative components of F3.2 and G3.2 reactive resins

The measurement of the dynamic viscosity of the E3.2 reactive resin component, as well as the comparative components of the F3.2 and G3.2 reactive resins (Table 10), was carried out using a plate-to-plate measurement system in accordance with DIN 53019. The plate diameter was 20 mm, and the slot distance was 3 mm. To prevent the sample from leaking out of the slot, a Teflon restrictive ring was used, located at a distance of 1 mm from the top plate. The measurement temperature was 0°C or 25°C respectively. The method consisted of three segments: 1. Minor shift, 2. Major shift, 3. Minor shift. On the first segment for 3 minutes, the shear rate was 0.5/s. In the second segment in 8 stages of 15 seconds each, the shear rate was logarithmically increased from 0.8/s to 100/s. The individual stages were: 0.8/s; 1.724/s; 3.713/s; 8/s; 17.24/s; 37.13/s; 80/s; 100/s. The 3rd segment was a repetition of the 1st segment. At the end of each segment, the viscosity was calculated. Table 10 shows the values from the second segment at 8/s and 100/s. Three measurements were taken in each case, with Table 10 listing the respective averages.

Then, the dynamic viscosities of the E1.1 and E1.2 reactive resin masterbatch and the comparative F1.1, F1.2, G1.1, and G1.2 reactive resin masterbatches were compared at different temperatures (Table 8). The master batches of reactive resins contained 65% of the mass. structure-forming resin and 35% of the mass. hydroxypropyl methacrylate (E1.1, F1.1, G1.1) or 1,4-butanediol dimethacrylate (E1.2, F1.2, G1.2) respectively.

The measurement results show that the reactive resin masterbatches according to the invention are characterized by a decrease in dynamic viscosity, especially at low temperatures. In particular, at temperatures below 20° C., the dynamic viscosity of the inventive reactive resin masterbatch containing the compound (V) of the invention as a structurant resin is significantly lower than the viscosities of the comparative reactive resin masterbatches containing comparative compounds 1 and 2.

Next, the dynamic viscosity of the E3.1 reactive resin component prepared from the E1.1 reactive resin masterbatch according to the invention was compared with the dynamic viscosity of the comparative F3.1 and G3.1 reactive resin components prepared from the comparative F1.1 and G1 reactive resin masterbatches. .1 (table 9). All listed in table 9 components of reactive resins contained 45% of the mass. structure-forming resin in a reactive resin.

The results in Table 9 show that the dynamic viscosity of the reactive resin component containing the compound (V) according to the invention is relatively low compared to the dynamic viscosity of the comparative reactive resin components that contain comparative compounds 1 or 2, respectively.

To rule out that differences in the dynamic viscosity of the reactive resin components were due to the silicic acid composition used, the measurements were repeated with the content of silicic acid changed in each case (reactive resin component E3.2 and comparative reactive resin components F3.2 and G3.2) and at two different shear rates (8 s ^-1 and 100 s ^-1 ) and two temperatures (0°C and 25°C). The results are presented in table 10.

The results in Table 10 show that despite the changed composition of silicic acid, the dynamic viscosity of the E3.2 reactive resin component containing the compound (V) according to the invention, both at 0°C and at 25°C, is relatively low compared to the dynamic the viscosity of the comparative components of the reactive resins F3.2 and G3.2, which contain comparative compounds 1 or 2, respectively.

Determination of extrusion forces

To determine the extrusion forces at 0 and 23°C, systems based on reactive resins E4.1, as well as comparative systems based on reactive resins F4.1 and G4.1, were brought to a temperature of 0°C or 23°C, respectively. The cartridges were extruded on a Zwick material testing machine with a force sensor (test range up to 10 kN) through a static mixer (HIT-RE-M mixer, Hilti Aktiengesellschaft) at a constant speed of 100 mm/min over a distance of 45 mm and the average force generated was measured. wherein.

The extrusion forces of a two-component system based on reactive resin E4.1, which contains the compound (V) according to the invention, were compared with the extrusion force of comparative two-component systems based on reactive resins F4.1 and G4.1, which contain comparative compounds 1 or 2, respectively. , at 0°С and 23°С. The measurement results are presented in table 11.

The results in Table 11 show that the two-component reactive resin system containing the compound (V) of the invention both at 0°C and 23°C has a lower extrusion force than the comparative two-component reactive resin system containing reference compounds 1 or 2, respectively, the differences being particularly noticeable at 0°C.

This demonstrates that the compounds according to the invention lead to a reduction in the viscosity of the reactive resin masterbatches and hence the corresponding reactive resins. The reactive resin components obtained from them also have a reduced viscosity, which is reflected in a decrease in extrusion forces.

In addition to reducing the viscosity, the use of the compounds according to the invention leads to an increase in the load values of the cured fixing masses.

Claims (8)

1. Use of a compound of general formula (I)

wherein B means an aromatic hydrocarbon group, which is a divalent group, which is obtained by removing isocyanate groups from an aromatic diisocyanate selected from the group consisting of 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene , 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and 1,5-diisocyanatonaphthalene, and each R ₁ is independently a branched or linear aliphatic alkylene group having 1-15 carbon atoms, to increase the adhesive tension of the cured fixing mass. 2. Use according to claim 1, wherein R ₁ is an alkylene group having 2 or 3 carbon atoms. 3. Use according to claim 1 or 2, wherein the fixing mass contains a reactive resin for construction purposes containing a compound as defined in one of paragraphs. 1 or 2, inhibitor, accelerator and reactive diluent.