MICHAEL-ADDITION-HARDENING HYBRID SYSTEM FOR CHEMICAL FIXING TECHNOLOGY

Abstract

A hybrid system for use as an adhesive, coating or paint, wherein the hybrid system includes a) a reaction resin based on α,β-unsaturated compounds, b) a reaction resin based on compounds that include CH-acidic methylene groups, and c) a primary amine, and to related subject matter.

Claims

1. A hybrid system for use as an adhesive, coating or paint, characterised in that the hybrid system includes a) a reaction resin based on α,β-unsaturated compounds, b) a reaction resin based on compounds that include CH-acidic methylene groups, and c) a primary amine.

2. The hybrid system according to claim 1 as an adhesive for chemical fixing technology, especially for fixing anchoring means in drilled holes, which system includes a reaction resin based on α,β-unsaturated compounds, a reaction resin based on compounds that include CH-acidic methylene groups, and a primary amine.

3. The hybrid system according to claim 1 in the form of a multi-component system, especially a two-component system.

4. The hybrid system according to claim 1 in the form of a two-component kit.

5. The hybrid system according to claim 1, further including a catalyst.

6. The hybrid system according to claim 1 in the form of a multi-component kit, wherein (i) constituents a) and b) are present in one component, while constituent c) is present together with a catalyst in a different component which is not capable of mixing in the stored state, it being optionally possible in each case for one or more further ingredients to be present; or (ii) constituents a), b) and the epoxy moiety of an epoxy/tert-amine catalyst are present in one component, and constituent c) is present together with the tert-amine moiety of an epoxy/tert-amine catalyst in a different component, it being optionally possible in each case for one or more further additional ingredients to be present.

7. The hybrid system according to claim 1, wherein the reaction resin based on α,β-unsaturated compounds is a reaction resin which comprises or consists of an α,β-unsaturated compound that carries at least one fumarate, maleate, itaconate or acrylate group or preferably two or more thereof, such as an acrylic acid ester or acrylamide, for example a mono- or especially di-, tri-, tetra- or higher polyacrylate, especially selected from hydroxy-C.sub.2-C.sub.10alkyl-acrylate, such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate, ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol acrylate, poly(butanediol) diacrylate, polybutadiene diacrylate, 3-methyl-1,5-pentanediol -diacrylate, 1,6-hexanediol diacrylate, diethyleneglycol diacrylate, tetraethyleneglycol diacrylate, tripropyleneglycol diacrylate, triethyleneglycol diacrylate, triisopropyleneglycol diacrylate, dipropyleneglycol diacrylate, neopentylglycol diacrylate, ethoxylated or propoxylated neopentylglycol diacrylate, tripropyleneglycol diacrylate, bisphenol-A-, bisphenol-F-, bisphenol-AF- or bisphenol-S-diglycidyl ether diacrylate, bisphenol-A-polyethoxydiacrylates, bisphenol-F-polyethoxydiacrylates, polyethyleneglycol diacrylates, polypropyleneglycol diacrylates, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, trimethylolpropane polyethoxy-triacrylate, ethoxylated or propoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxylated or propoxylated glycerol triacrylate, tris(2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol monohydroxytriacrylate, pentaerythritol triethoxytriacrylate, pentaerythritol tetraacrylate, ethoxylated or propoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol polyhexanolide hexaacrylate, dipentaerythritol hexaacrylate, tris(hydroxyethyl)isocyanuratopolyhexanolide triacrylate, tris(2-hydroxyethyl)isocyanuratotriacrylate, tricyclodecanedimethylol diacrylate, esterdiol diacrylate, 2-(2-acryloyloxy-1,1-dimethyl)-5-ethyl-5-acryloyloxymethyl-1,3-dioxane, tetrabromobisphenol-A-diethoxydiacrylate, 4,4-dimercaptodiphenylsulfide diacrylate, polytetraethyleneglycol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, dimethylolpropane tetraacrylate, cresol epoxyacrylates, novolak “poly”acrylate, acrylate-group-containing oligomers or polymers from the reaction of polyepoxides with acrylic acid or reactive derivatives thereof, such as acid halides or active esters or from the reaction of polyester polyols with acrylic acid or reactive derivatives thereof, especially as just mentioned, or urethane acrylates (obtainable, for example, by reaction of isocyanates with an OH-group-containing acrylate, such as hydroxyethyl-, hydroxypropyl-, hydroxybutyl- or pentaerythritol-tri-acrylate, and polyester acrylate resins, for example tetrafunctional polyester acrylates); an acrylic-functional alkoxysilane or organopolysiloxane, such as acrylatomethyl-trimethoxysilane, -methyldimethoxy-silane, -dimethylmethoxysilane, -triethoxysilane or -methyldiethoxysilane, acrylamido-methyl-trimethoxysilane, -methyldimethoxysilane, -dimethylmethoxysilane, -triethoxy-silane, or -methyldiethoxysilane, -methyl-dimethylethoxysilane; or a polyester resin based on maleic, fumaric or itaconic acid or a respective anhydride thereof; or a polyester, polyurethane, polyether and/or alkyd resin that carries activated, ethylenically unsaturated groups; or an α,β-unsaturated compound having biogenic content, especially an acrylate, preferably having biogenic acrylate content of hydroxy-group-containing vegetable oils, such as of castor oil or soybean oil, a wholly or at least partly biogenic (for example C.sub.1-C.sub.10)alkan(mono-, preferably di-, tri-, tetra-, penta- or hexa- or poly-)ol acrylate, a partly or preferably wholly biogenic polyglycerol acrylate, a wholly or partly biogenic acrylate of one or more sugar alcohols, such as mannitol, xylitol or sorbitol, a wholly or partly biogenic acrylated fusel oil, a wholly or partly biogenic 5- or 6-membered-ring heterocyclyl acrylate (especially having one or two hetero atoms selected from O, N and S in the ring), or a partly or preferably wholly biogenic glycerol or polyglycerol acrylate, or a wholly or partly biogenic saccharide acrylate; or the corresponding methacrylates; or a mixture of two or more of the mentioned α,β-unsaturated compounds.

8. The hybrid system according to claim 1, wherein the reaction resin that carries one or more CH-acidic methylene groups is one comprising malonic acid or a malonic acid ester, such as malonic acid dimethyl ester, malonic acid diethyl ester, malonic acid di-n-propyl ester, malonic acid diisopropyl ester, malonic acid dibutyl ester, malonic acid di-(2-ethylhexyl) ester or malonic acid dilauryl ester, cyanoacetic acid esters, such as 2-ethylhexyl cyanoacetate, butyl cyanoacetate, octyl cyanoacetate, 2-methoxyethyl cyanoacetate, a dione, such as pentane-2,4-dione, hexane-2,4-dione, heptane-2,4-dione, 1-methoxy-2,4-pentanedione, 1-phenyl-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, 4,6-dioxoheptanoic acid methyl ester, 5,7-dioxooctanoic acid methyl ester, an acetoacetate, such as benzoylacetoacetic acid methyl, ethyl or butyl ester, propionylacetic acid methyl, ethyl or butyl ester, butyroylacetic acid methyl ester, acetoacetic acid methyl, ethyl, isopropyl, n-butyl, isobutyl or tert-butyl ester, acetoacetic acid (2-methoxyethyl) ester, acetoacetic acid (2-ethylhexyl) ester, acetoacetic acid lauryl ester, 2-acetoacetatoethyl acrylate, acetoacetic acid benzyl ester, 1,4-butanediol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentyl glycol diacetoacetate, 2-ethyl-2-butyl-1, 3-propanediol diacetoacetate, cyclohexanedimethanol diacetoacetate, free or ethoxylated bisphenol-A-, -F-, -AF- or -S-diacetoacetate, trimethylolpropane triacetoacetate, pentaerythritol tri- or tetra-acetoacetate, ditrimethylolpropane tetraacetoacetate, di pentaerythritol hexaacetoacetate, an acetoacetate-group-carrying oligomer or polymer which is obtainable, for example, by transesterification of acetoacetic acid (for example ethyl) esters, an acetoacetate-group-carrying oligomer or polymer which is obtainable by copolymerisation of acetoacetoxyethyl methacrylate, an oligomer or polymer which is obtainable from dialkyl malonates and diols, or an acetoacetylated novolak, or a mixture of two or more thereof.

9. The hybrid system according to claim 1, wherein the primary amine is a primary di- or poly-amine which contains aliphatic, heteroaliphatic, alicyclic, heterocyclic, aromatic, aliphatic-aromatic and silane/siloxane molecular structures or two or more selected independently therefrom, especially selected from the group of aminoamides, polyaminoamides, Mannich bases and amine adducts, isocyanate-amine adducts, Bucherer adducts and Michael addition adducts, especially selected from the group of alkylamines, such as 1,2-diaminoethane, 2-methylpentanediamine, 2,2-dimethyl-1,3-propanediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, heteroalkylamines, such as 1,13-diamino-4,7,10-trioxatridecane, commercially available amine-functionalised polyoxyalkylenes, triethylenetetramine and/or higher homologues, cycloalkylamines, such as isophoronediamine, 1,3- and/or 1,4-bisaminomethylcyclohexane, TCD-diamine, 1,2- or 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornanediamine, diaminodicyclohexylmethane or 2,2-bis(4-aminocyclohexyl)propane, hetero-cycloalkylamines, such as: aminoethylpiperazine, and aliphatic-aromatic amines, such as 1,3- or 1,4-benzenedimethanamine; or a mixture of two or more of those compounds; especially selected from 2-methylpentanediamine, 1,2-diamino-cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-benzene-dimethanamine, 1,4-benzenedimethanamine, 1,6-diamino-2,2,4-trimethylhexane, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, 1,3-bis(aminomethyl)cyclohexane, TCD-diamine, Jeffamines, dipropylenetriamine, N, N′-dicyclohexyl-1,6-hexanediamine, N, N′-dimethyl-1,3-diaminopropane, N, N′-diethyl-1,3-diaminopropane, N, N-dimethyl-1, 3-diaminopropane, secondary polyoxypropylene-di- and -tri-amines, 2,5-diamino-2,5-dimethylhexane, bis(aminomethyl)tricyclopentadiene, 1,8-diamino-p-menthane and bis(4-amino-3,5-dimethylcyclohexyl)methane, or an aminoalkylsilane that includes at least one hydrolysable group, such as alkoxy, for example methoxy or ethoxy—bonded to the silicon —, especially selected from the group comprising one or more of the following compounds: aminoalkyl-tri- or -di-alkoxysilanes, such as 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-amino-propylphenyldiethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylethyldiethoxy-silane, and N-(aminoalkyl)-amino-alkyl-tri- or -di-alkoxysilanes, such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropyl-methyldimethoxysilane; or a copolymer of one of the above-mentioned silanes or a different silane; or a mixture of two or more of the mentioned (poly)amines.

10. The hybrid system according to claim 1, which includes a catalyst or two or more thereof, selected from strongly basic catalysts, such as alkali metal hydroxides, alkali metal alkoxides, quaternary ammonium compounds, tertiary amines, guanidines, amidines; silicates; metal oxides; phosphine catalysts, for example tricyclohexylphosphine (especially preferred), tricyclopentylphosphine, tri-n-hexylphosphine, tris(2,4,4-trimethylpentyl)phosphine, tris(2-ethylhexyl)phosphine, tri-n-octylphosphine (especially preferred), tri-n-decylphosphine, tri-n-dodecylphosphine (especially preferred), tristearylphosphine and triphenylphosphine; and catalysts in the form of mixtures of an epoxide with one or more tertiary amines, it being possible for salts of strong bases or small amounts of the strong bases themselves additionally to be added; or a mixture of two or more of the mentioned catalysts.

11. The hybrid system according to claim 1, including one or more further additives, especially selected from fillers, rheology aids, thixotropic agents, plasticisers, colouring additives, adhesion promoters, solvents and reactive diluents.

12. A method comprising using the hybrid system, composed as recited in claim 1, as an adhesive, for fixing anchoring means in substrates, or, for fixing fibres, laid fabrics, woven fabrics or composites for reinforcement of built structures.

13. A method for mortar-bonded fixing of anchoring elements in holes or crevices, comprising using the hybrid system, according to claim 1 for mortar-bonded fixing of anchoring means, the hybrid system and an anchoring means being introduced one after the other, first the hybrid system and then the anchoring means, or—at least substantially—simultaneously into a hole or crevice in a substrate.

Description

EXAMPLES: THE EXAMPLES THAT FOLLOW SERVE TO ILLUSTRATE THE INVENTION BUT DO NOT LIMIT THE SCOPE THEREOF

[0078]

TABLE-US-00001 TABLE 1 Constituents and abbreviations used Abbreviation Item RMA Real Michael addition/C-Michael addition AMA Aza-Michael addition/N-Michael addition En Enamine reaction TMPTAcAc Trimethylolpropane triacetoacetate ISDAcAc Isosorbide diacetoacetate TMPTA Trimethylolpropane triacrylate CN9165A aromatic urethane acrylate oligomer (Sartomer) TMG N,N,N′,N′-Tetramethylguanidine MXDA Meta-xylylenediamine 1146 Dynasylan 1146; oligomeric diaminosilane (Evonik Industries) Dytek A Dytek A; 2-methylpentamethylenediamine (INVISTA Specialty Intermediates) EDR148 Jeffamine EDR-148 (amine-functionalised polyoxyalkylene from Huntsman Corporation) TETA Triethylenetetraamine (Huntsman Corporation) BAC 1,3-Bis(aminomethyl)cyclohexane (Mitsubishi Gas Chemical Company, Inc.) AEP Aminoethylpiperazine (Huntsman Corporation) IPDA Isophoronediamine (BASF) DCH-99 1,2-Diaminocyclohexane (INVISTA Specialty Intermediates) AMMO Dynasylan AMMO; 3-aminopropyltrimethoxysilane (Evonik Industries) RD20 ipox RD20; Trimethylolpropane triglycidyl ether (ipox chemicals) Minex-10 Micronized functional filler produced from nepheline syenite, a natural silica deficient sodium-potassium alumina silicate (The Cary Company, Illinois, USA)

Example 1: Composition and Pull-Out Tests from Concrete of Hybrid Systems According to the Invention (RMA+AMA Preferred)

[0079] Setting tests are carried out in accordance with the afore-mentioned methods for determining parameters for “pull-out tests from concrete”. Table 2 shows the constituents used and the bond stresses determined. The amount of primary amines used and the primary amino (—NH.sub.2) groups present in the system as a result are balanced by additional acrylate groups, so that reactions i. and ii. can take place preferentially.

TABLE-US-00002 TABLE 2 Formulations of the setting tests and bond stresses determined Item B1.1 B1.2 B1.3 B1.4 B1.5 TMPTAcAc [g] 5.51 5.51 3.67 5.51 3.67 TMPTA [g] 9.82 10.25 8.43 11.12 10.60 TMG [g] 0.10 0.10 0.07 0.10 0.07 MXDA [g] 0.10 0.20 0.50 0.20 0.50 Minex-10 [g] 15.53 16.07 12.67 16.94 14.85 Bond stress 33.0 33.8 35.7 33.3 32.0 [N/mm.sup.2]

[0080] In Examples B1.1 to B1.3 the molar ratio of the primary amino groups to acrylate groups is 1:1 (NH.sub.2:C═C=1:1), whereas in Examples B1.4 and B1.5 a 1:2 ratio (NH:C═C=1:1) between primary amino groups and acrylate groups was chosen.

[0081] The bond stresses listed in Table 2 demonstrate the tremendous performance of the hybrid system according to the invention. Furthermore, Table 2 demonstrates the robustness of the hybrid system, since both the content of primary amine and the molar ratios between amino groups and acrylate groups can be varied within a wide range without suffering loss of performance.

Example 2: Compositions and Pull-Out Tests from Concrete with Different Primary Amines (RMA+AMA Preferred)

[0082] In order to demonstrate that all primary amines can be used in the hybrid systems according to the invention, one example is selected from each of the afore-mentioned groups of primary amines and setting tests are carried out in accordance with the afore-mentioned parameters.

TABLE-US-00003 TABLE 3 Formulations of the amine screening and bond stresses determined Item B2.1 B2.2 B2.3 B2.4 B2.5 B2.6 B2.7 B2.8 TMPTAcAc 5.51 5.51 5.51 5.51 5.51 5.51 5.51 5.51 [g] TMPTA [g] 9.69 10.23 10.05 10.06 10.08 10.15 9.96 10.25 TMG [g] 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 1146 [g] 0.50 Dytek A [g] 0.50 EDR148 [g] 0.50 TETA [g] 0.50 BAC [g] 0.50 AEP [g] 0.50 IPDA [g] 0.50 DCH-99 [g] 0.50 Minex-10 [g] 15.81 16.35 16.17 16.17 16.19 16.26 16.08 16.36 Bond stress 34.7 30.9 31.5 30.2 31.7 30.7 30.0 32.3 [N/mm.sup.2] Gel time 02:28 02:38 02:36 02:20 [mm:ss]

[0083] It will be apparent from Table 3 that all primary amines can be used in the hybrid systems according to the invention. Table 3 also demonstrates that using the hybrid systems according to the invention it is possible to combine the advantages of the systems previously used—in chemical fixing technology: rapid curing as in the case of free-radical-hardening systems and the high bond stresses of epoxy systems. This is demonstrated by the gel times and bond stresses determined. Example B2.1 is mixed again with half the amount of TMG. The resulting gel time is 07:20 [mm:ss]. This test shows that the gel time can be controlled and adjusted to a desired gel time by means of the amount of catalyst used.

Example 3: Compositions and Pull-Out Tests from Concrete of Hybrid Systems According to the Invention (RMA+En Preferred)

[0084] Table 4 below shows the constituents used and the bond stresses determined of hybrid systems according to the invention in which the amount of primary amines used and the primary amine groups (—NH.sub.2) present in the system as a result are balanced by CH-acidic methylene groups (—CH.sub.2—), so that reactions i. and iii. can take place preferentially.

TABLE-US-00004 TABLE 4 Formulations of the setting tests and bond stresses determined Item B3.1 B3.2 B3.3 B3.4 B3.5 B3.6 B3.7 TMPTAcAc [g] 5.80 6.09 5.57 5.62 4.85 5.29 4.66 TMPTA [g] 9.38 9.38 7.51 9.38 7.51 7.51 7.51 TMG [g] 0.10 0.10 0.08 0.10 0.08 0.08 0.08 MXDA [g] 0.15 0.30 0.60 AMMO [g] 0.15 0.60 1.20 1146 [g] 0.60 Minex-10 [g] 15.44 15.88 13.76 15.26 13.04 14.08 12.85 Bond stress 30.3 32.9 33.4 32.5 35.0 38.0 30.9 [N/mm.sup.2]

[0085] Table 4 also illustrates the tremendous performance of the hybrid systems according to the invention already indicated in Table 2, as well as the robustness thereof.

Example 4: Pull-Out Tests from Concrete with Mixtures of Constituents a, b and c

[0086] In order to show that it is also possible to use different mixtures of ingredients of constituents a, b and c in the hybrid systems according to the invention, setting tests are carried out in accordance with ETAG 001 PART 5. Table 5 lists the constituents used and the bond stressed determined.

TABLE-US-00005 TABLE 5 Formulations with mixtures a, b, c and bond stresses determined Item B4.1 B4.2 B4.3 TMPTAcAc [g] 3.00 4.60 5.43 ISDAcAc [g] 3.00 TMPTA [g] 9.20 5.25 7.51 CN9165A [g] 1.75 TMG [g] 0.10 0.08 0.08 MXDA [g] 0.50 0.30 0.30 AMMO [g] 0.60 Minex-10 [g] 15.80 11.98 13.92 Bond stress 29.6 31.5 35.7 [N/mm.sup.2]

[0087] In Example B4.1 the additional primary amino groups are saturated by acrylate groups (RMA+AMA preferred), whereas in Examples B4.2 and B4.3 the amino groups are saturated by CH-acidic methylene groups (—CH.sub.2-) (RMA+En preferred). The high bond stresses demonstrate that it is also possible to use varying mixtures of ingredients of constituents a, b and c for formulating hybrid systems according to the invention.

[0088] The very high bond stresses of Examples B3.5, B3.6 and B4.3, in which the silane AMMO is used, are remarkable. Without wishing to be bound to this theory, a possible reason for the very high performance may be that water is formed by the enamine reaction of the primary amine with the compound carrying CH-acidic methylene groups (—CH.sub.2—). This in turn brings about a hydrolysis and condensation reaction of the silane AMMO. Together with the Michael addition (real Michael addition/C-Michael addition) between the α,β-unsaturated compound and the compound carrying CH-acidic methylene groups there is thus formed a strongly crosslinked and close-knit network, which would explain the very high bond stresses.

Example 5: Reference Tests

[0089] In order once again to underline the tremendous performance of the hybrid systems according to the invention, reference tests were carried out and the following bond stresses determined.

TABLE-US-00006 TABLE 6 Reference tests in comparison with hybrid systems according to the invention Item Ref1 Ref2 B2.4 TMPTAcAc 5.51 TMPTA [g] 9.96 10.06 RD20 [g] 10.57 TETA [g] 2.46 1.84 0.50 TMG [g] 0.10 0.10 0.10 Minex-10 [g] 12.50 12.50 16.17 Bond stress 21.0 16.2 30.2 [N/mm.sup.2]

[0090] It will be apparent from Table 6 that neither reference test Ref1 (acrylate—amine/N-Michael addition) nor reference test Ref2 (classic epoxide—amine reaction) achieves the high bond stresses of the hybrid systems according to the invention, despite a similar chemical structure of the starting materials.

Example 6: Composition and Determination of the Onset and Glass Transition Temperatures of Hybrid Systems According to the Invention

[0091] On exceeding the glass transition temperature, a solid polymer enters into a rubber-like to viscous state. In other words, the glass transition temperature is a measure of strength under the effect of heat. Since high temperatures can occur on building sites, depending upon the weather conditions, it is desirable to develop systems having correspondingly high glass transition temperatures. Table 7 below shows the onset and glass transition temperatures of hybrid systems according to the invention in comparison with a standard epoxy/amine system.

TABLE-US-00007 TABLE 7 Onset and glass transition temperatures of hybrid systems according to the invention FIS Item B6.1 B6.2 B6.3 B6.4 B6.5 B6.6 B6.7 B6.8 EM TMPTAcAc [g] 3.67 5.51 5.51 5.51 5.51 5.51 5.51 5.51 TMPTA [g] 6.98 10.23 10.05 10.06 10.08 10.15 9.96 10.25 TMG [g] 0.07 0.10 0.10 0.10 0.10 0.10 0.10 0.10 MXDA [g] 0.50 Dytek A [g] 0.50 EDR148 [g] 0.50 TETA [g] 0.50 BAC [g] 0.50 AEP [g] 0.50 IPDA [g] 0.50 DCH-99 [g] 0.50 1st run: onset 54.9 52.2 48.7 51.4 53.0 54.6 51.9 54.0 51.6 24 h [° C.] 2nd run: Tg 104.0 107.9 97.9 108.6 107.0 102.6 112.4 112.3 82.9 24 h [° C.]

[0092] FIS EM 390 S® (fischerwerke GmbH & Co. KG, Waldachtal, Germany) is a successful, commercially well-established example of a two-component injection mortar system for mortar-bonded fixing of anchoring elements, based on an epoxy/amine reaction. Table 7 shows that the onset temperatures of the hybrid systems according to the invention are comparable with those of a well-established injection mortar system and even surpass that system in respect of the glass transition temperature in the second run. The hybrid systems according to the invention accordingly also have the necessary thermal dimensional stability required under building site conditions.