MICHAEL-ADDITION-HARDENING SYNTHETIC RESIN FOR CHEMICAL FIXING TECHNOLOGY

Abstract

Use of a synthetic resin system as an adhesive for chemical fixing technology, especially for fixing anchoring means in drilled holes, which synthetic resin 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 catalyst, and to related subject matter.

Claims

1. A method of using a synthetic resin system as an adhesive for chemical fixing technology, wherein the synthetic resin 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 catalyst.

2. The method according to claim 1, wherein the reaction resin based on α,β-unsaturated compounds has an average functionality 2 and the reaction resin based on compounds that include CH-acidic methylene groups has an average functionality ≥4.

3. The method according to claim 1 wherein it has a crosslinking index ≥3.

4. The method according to claim 1, wherein the synthetic resin system is a multi-component system.

5. The method according to claim 1, wherein the synthetic resin system is in the form of a two-component kit.

6. The method according to claim 1, wherein it has a crosslinking index ≥3.5.

7. The method according to claim 1 in the form of a multi-component kit, wherein (i) the reaction resin based on α,β-unsaturated compounds and the reaction resin based on compounds that include CH-acidic methylene groups are present in one component (K1), while the catalyst is present on its own or together with a non-reactive solvent/diluent/plasticiser and/or adhesion promoter in a different component (K2) (which component is not capable of mixing, that is to say is kept separate, in the stored state); 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.

8. The method according to any 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-C2-C1oalkyl-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, neopentyl-glycol 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-trimethylol-propane tetraacrylate, trimethylolpropane polyethoxytriacrylate, ethoxylated or propoxylated trimethylolpropane triacrylate, glycerol triacrylate, ethoxylated or propoxylated glycerol triacrylate, tris(2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol monohydroxytriacrylate, pentaerythritol triethoxy-triacrylate, 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-acryloyloxym ethyl-1,3-dioxane, tetrabromo-bisphenol-A-diethoxydiacrylate, 4,4-dimercaptodiphenylsulfide diacrylate, polytetra-ethyleneglycol 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, -methyldimethoxysilane, -dimethylmethoxysilane, -triethoxysilane or -methyldiethoxysilane, acrylam idomethyl-trimethoxysilane, -methyl-dimethoxysilane, -dimethylmethoxysilane, -triethoxysilane, or -methyldiethoxy-silane, -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 a,I3-unsaturated compounds.

9. The method 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-m ethoxyethyl 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, trim ethylolpropane triacetoacetate, pentaerythritol tri- or tetra-acetoacetate, ditrimethylolpropane tetraacetoacetate, dipentaerythritol hexaaceto-acetate, 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.

10. The method according to claim 9, wherein the reaction resin based on compounds that include CH-acidic methylene groups is an acetoacetate.

11. The method according to claim 10 wherein the reaction resin based on compounds that include CH-acidic methylene groups is a mixture of a diacetoacetate and a trisacetoacetate.

12. The method 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; 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.

13. The method 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.

14. A method of using a multi-component synthetic resin system, composed as defined in claim 1, as an adhesive, for fixing anchoring means in substrates, such as masonry or concrete, or for fixing fibres, laid fabrics, woven fabrics or composites for reinforcement of built structures.

15. A method for mortar-bonded fixing of anchoring elements in holes or crevices, wherein a multi-component synthetic resin system according claim 1 is used for mortar-bonded fixing of anchoring means, the synthetic resin system and an anchoring means being introduced one after the other, or—at least substantially—simultaneously into a hole or crevice in a substrate.

16. A synthetic resin system as an adhesive for chemical fixing technology, wherein the synthetic resin system is as defined in claim 1.

Description

EXAMPLES

The Examples that follow serve to Illustrate the Invention but do not Limit the Scope thereof

[0090]

TABLE-US-00001 TABLE 1 Constituents and abbreviations used Abbreviation Item RMA Real Michael addition/C-Michael addition M Molecular weight in g/mol F Functionality TMPTAcAc Trimethylolpropane triacetoacetate GTAcAc Glycerol triacetoacetate; equivalent weight 123.5 g/mol acetoacetate TCDDAcAc Tricyclodecanedimethanol diacetoacetate; equivalent weight 199.7 g/mol ISDAcAc Isosorbide diacetoacetate; equivalent weight 176.6 g/mol acetoacetate EGDAcAc ethyleneglycol diacetoacetate; equivalent weight 122 g/mol acetoacetate TMPTA Trimethylolpropane triacrylate CN104 Epoxyacrylate; M = 1000, F = 2; (Sartomer) CN110 Modified epoxyacrylate; M = 1000, F = 2; (Sartomer) CN2303 Hyperbranched polyester acrylate; M = 1400, F = 6; (Sartomer) CN9210 Aliphatic urethane acrylate; M = 1500, F = 6; (Sartomer) CN925 Modified aliphatic urethane acrylate; M = 2500, F = 4; (Sartomer) CN9165A Aromatic urethane acrylate; M = 900, F = 4; (Sartomer) SR238 1,6-Hexanediol diacrylate TMG N,N,N′,N′-Tetramethylguanidine DBU Diazabicycloundecene NaOH Saturated NaOH solution RD20 ipox RD20; Trimethylolpropane triglycidyl ether (ipox chemicals) TETA Triethylenetetraamine (Huntsman Corporation) 10P Palatinol 10 P; bis(2-propylheptyl)phthalate; (BASF) Minex-10 Micronized functional filler produced from nepheline syenite, a natural silica deficient sodium-potassium alumina silicate (The Cary Company, Illinois, USA)

EXAMPLE 1

Compositions and Pull-Out Tests from Concrete of Synthetic Resin Systems According to the Invention

[0091] 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.

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] 4.59 GTAcAc [g] 4.77 TCDDAcAc [g] 6.21 ISDAcAc [g] 5.85 EGDAcAc [g] 4.74 TMPTA [g] 7.82 7.65 6.21 6.57 7.67 TMG [g] 0.09 0.09 0.09 0.09 0.09 Minex-10 [g] 12.50 12.50 12.50 12.50 12.50 Bond stress 31.0 30.2 31.2 30.8 29.3 [N/mm.sup.2]

[0092] The bond stresses listed in Table 2 demonstrate that the known real Michael addition (in short: RMA or C-Michael addition) known from the field of (floor) coatings is also entirely suitable for use as a synthetic resin system for chemical fixing technology. Table 2 also shows that an extremely wide range of compounds carrying CH-acidic methylene groups can be used without suffering any significant loss of performance. Of special interest in this connection is ISDAcAc, which is an acetoacetate based on renewable raw materials, that is to say has a BioC content.

EXAMPLE 2

Compositions and Pull-Out Tests from Concrete with different TMPTA Ratios

[0093] In order to demonstrate the robustness of the synthetic resin system according to the invention, setting tests, in accordance with the afore-mentioned methods for determination of parameters, are carried out with different TMPTA ratios (±from the optimum mixing ratio).

TABLE-US-00003 TABLE 3 Formulations of the B148 screening and bond stresses determined Item B2.1 B2.2 B2.3 B2.4 B2.5 B2.6 B2.7 TMPTAcAc [g] 4.64 4.62 4.60 4.59 4.58 4.57 4.55 TMPTA [g] 7.65 7.73 7.78 7.82 7.86 7.91 7.99 TMG [g] 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Minex-10 [g] 12.63 12.56 12.53 12.50 12.47 12.44 12.38 Bond stress [N/mm.sup.2] 31.6 31.1 31.2 30.4 28.4 28.2 29.5 Crosslinking index 3.9 3.9 3.9 3.9 3.9 3.9 3.9

[0094] It will be apparent from Table 3 that despite departing from the optimum mixing ratio (B2.4—determined with DSC in accordance with ISO 11357-2 (2013)) the bond stress remains relatively constant.

EXAMPLE 3

Compositions and Pull-Out Tests using Different Catalysts and Screening Catalyst Content

[0095] Table 4 below shows the constituents used and the bond stresses determined of synthetic resin systems according to the invention in which the nature and the amount of catalysts used are varied.

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 TMPTAcAc [g] 4.59 4.59 4.59 4.60 4.61 4.58 TMPTA [g] 7.82 7.82 7.82 7.84 7.85 7.80 DBU [g] 0.09 NaOH [g] 0.09 TMG [g] 0.09 0.06 0.04 0.12 Minex-10 [g] 12.50 12.50 12.50 12.50 12.50 12.50 Bond stress [N/mm.sup.2] 30.4 30.6 31.0 29.7 26.8 32.2 Gel time [mm:ss] 03:20 12:40 17:20 01:35

[0096] Table 4 makes it clear that all strongly basic compounds can be used as catalysts for the synthetic resin systems according to the invention. Table 4 also shows that the gel time can be varied or adjusted to a desired gel time by means of the amount of catalyst used. Moreover, Table 4 makes it clear that using the synthetic resin 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 4

Compositions and Pull-Out Tests at Low Temperatures and Reference Tests

[0097] In order once again to underline the tremendous performance of the synthetic resin systems according to the invention, pull-out tests at −5° C. and reference tests are carried out and the following bond stresses determined.

TABLE-US-00005 TABLE 5 Bond stress of synthetic resin systems according to the invention at −5° C./48 h and reference tests B3.6 B4.2 FIS EM Ref1 Ref2 Item (RT) (−5° C./48 h) (−5° C./48 h) (RT) (RT) TMPTAcAc [g] 4.58 4.58 TMPTA [g] 7.80 7.80 9.96 RD20 [g] 10.57 TETA [g] 2.46 1.84 TMG [g] 0.12 0.12 0.10 0.10 Minex-10 [g] 12.50 12.50 12.50 12.50 Bond stress 32.2 33.8 7.0 21.0 16.2 [N/mm.sup.2]

[0098] It will be apparent from Table 5 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 synthetic resin systems according to the invention, despite a similar chemical structure of the starting materials and functionalities. The tremendous performance of synthetic resins according to the invention is again illustrated in Example 4.2. After only 48 h curing at −5° C., the performance achieved is already the same as that after 24 h curing at room temperature (B3.6), whereas FIS EM 390 S® (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 [fischerwerke GmbH & Co. KG, Waldachtal, Germany]) has still not fully cured.

EXAMPLE 5

Compositions and Pull-Out Tests after Different Curing Times

[0099] As mentioned at the beginning, the inventors have ascertained that using the synthetic resin systems according to the invention it is possible to combine the advantages of the commercially available chemical fixing systems. This is again illustrated in Table 6 below.

TABLE-US-00006 TABLE 6 Bond stress after different curing times Bond stress [N/mm.sup.2] 1 h 31.0 24 h 32.3 7 d 33.0

[0100] The constituents and amounts used here can be found in formulation B3.3. Table 6 shows that the synthetic resin systems according to the invention—as free-radical-hardening systems—are already virtually fully cured after 1 h, but the bond stresses tend to be in the region of the epoxy systems.

EXAMPLE 6

Acrylate Mixtures and Bond Stresses Determined

[0101] Table 7 below shows mixtures of different acrylates and the bond stresses thereof determined in a pull-out test, and the onset/glass transition temperatures thereof.

TABLE-US-00007 TABLE 7 Acrylate mixtures Item B6.1 B6.2 B6.3 B6.4 B6.5 B6.6 FIS EM TMPTAcAc [g] 4.35 4.32 4.52 4.49 4.29 4.53 TMPTA [g] 6.05 6.07 5.92 5.94 6.09 5.91 CN104 [g] 2.02 CN110 [g] 2.02 CN2303 [g] 1.97 CN9210 [g] 1.98 CN925 [g] 2.03 CN9165A [g] 1.97 TMG [g] 0.08 0.08 0.09 0.09 0.08 0.09 Minex-10 [g] 12.50 12.50 12.50 12.50 12.50 12.50 Bond stress [N/mm.sup.2] 33.9 33.7 28.7 30.5 27.6 34.1 Crosslinking index 3.9 3.9 4.2 4.2 4.0 4.1 1st run: onset 24 h [° C.] 50.1 48.4 53.4 54.0 53.5 55.8 51.6 2nd run: Tg 24 h [° C.] 99.2 101.2 96.4 115.6 106.7 114.4 82.9

[0102] Table 7 demonstrates that all acrylates can be used in the synthetic resin systems according to the invention. The onset/glass transition temperature listed, which is a measure of the thermal dimensional stability of the particular system, shows that the synthetic resin systems according to the invention are suitable for use under building site conditions (where high temperatures may occur, depending upon the weather conditions) and even surpass the injection mortar FIS EM 390 S® in the second run.

EXAMPLE 7

Compositions and Pull-Out Tests with Different Crosslinking Indices

[0103] The inventors have also discovered that to achieve the present objective (to combine the advantages of the commercially available fixing systems) the synthetic resin systems according to the invention should have a certain crosslinking index. This differs markedly from the crosslinking indices used for (floor) coatings from the prior art. Table 8 below will illustrate this.

TABLE-US-00008 TABLE 8 Bond stresses of different crosslinking indices Item B7.1 B7.2 B7.3 B7.4 B7.5 B7.6 B7.7 B7.8 B7.9 SR238 [g] 7.00 7.00 5.98 3.50 7.00 3.50 TMPTA [g] 3.50 7.00 3.50 5.22 7.00 ISDAcAc [g] 5.47 2.00 5.87 6.26 2.00 TCDDAcAc [g] 6.19 TMPTAcAc [g] 2.00 4.09 4.39 2.00 4.68 TMG [g] 0.09 0.09 0.07 0.09 0.08 0.09 0.08 0.06 0.08 Minex-10 [g] 12.56 13.28 10.05 12.96 11.17 13.36 11.46 9.29 11.76 Bond stress [N/mm.sup.2] 7.0 15.2 19.0 22.8 23.2 25.7 31.2 31.3 31.5 Crosslinking index 2.7 2.7 2.9 3.0 3.0 3.4 3.5 3.7 4.0 1st run: Tg 24 h [° C.] 27.2 14.5 24.5 43.2 29.2 41.3 51.8 54.9 53.3 2nd run: Tg 24 h [° C.] 34.1 20.3 30.4 58.2 35.4 83.9 72.1 100.5 110.0

[0104] It will be evident from Table 8 that the bond stress increases as the crosslinking index of the synthetic resins according to the invention increases. Table 8 also shows that the glass transition temperature (a characteristic value important for a fixing system, because it is an indirect measure of the thermal dimensional stability) likewise increases as the crosslinking index increases. For this reason the synthetic resins according to the invention should have a crosslinking index ≥3.

EXAMPLE 8

Cartridge Formulation for Pull-Out Tests

[0105] The constituents listed in Table 9 are introduced into a 150 ml cartridge with a volume ratio of 7:1 and subjected to a setting test in accordance with the afore-mentioned methods for determining parameters for “pull-out tests from concrete”. Component A is introduced into the larger part by volume.

TABLE-US-00009 TABLE 9 Cartridge formulation Component A TMPTAcAc [% by weight] 18.27 TMPTA [% by weight] 31.11 Filler [% by weight] 49.38 Additive [% by weight] 1.23 Component B 10P [% by weight] 23.95 TMG [% by weight] 3.19 Minex-10 [% by weight] 70.86 Additive [% by weight] 2.00

[0106] The bond stress determined is 28 N/mm2.