REACTIVE DILUENTS FOR CHEMICAL FIXING

Abstract

Free-radical-hardenable synthetic resin fixing systems which include one or more reactive diluents selected from oligoalkylene glycol di(meth)acrylates having on average more than two alkylene glycol units per molecule and alkoxylated tri-, tetra- and penta-methacrylates, and the use and production thereof, and further related subject matter.

Claims

1. A free-radical-hardenable synthetic resin fixing system which includes one or more reactive diluents selected from oligoalkylene glycol di(meth)acrylates having on average more than two alkylene glycol units per molecule and alkoxylated tri-, tetra- and penta-methacrylates.

2. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein the free-radical-hardenable oligoalkylene glycol di(meth)acrylates are those of the formula I, ##STR00005## wherein the radicals R independently of one another denote C.sub.1-C.sub.7alkyl, especially methyl, and wherein n denotes on average from 2.5 to 13, preferably from 2.5 to 12, especially from 3.5 to 10, preferably from 4 to 8, especially preferably from 4.2 to 7, very especially from 4.5 to 6.

3. The free-radical-hardenable synthetic resin fixing system according to claim 2, wherein the free-radical-hardenable oligoalkylene glycol di(meth)acrylates are those of the formula I, wherein n denotes from 3 to 8 and R denotes methyl.

4. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein they are based on reactive synthetic resins selected from (meth)acrylate or (meth)acrylamide monomers, such as acrylic acid and/or methacrylic acid or preferably esters or amides thereof, especially (meth)acrylates such as mono-, di-, tri- or poly-(meth)acrylates, optionally in each case propoxylated or ethoxylated aromatic diol-, such as bisphenol-A-, bisphenol-F- or novolak-(especially di-)(meth)acrylate), epoxy(meth)acrylates (especially in the form of reaction products of di- or poly-epoxides, for example bisphenol-A-, bisphenol-F- or novolak-di- and/or -poly-glycidyl ethers, with unsaturated carboxylic acids, for example C.sub.2-C.sub.7alkenecarboxylic acids, such as especially (meth)acrylic acid), urethane- and/or urea-(meth)acrylates and unsaturated polyester resins; or a mixture of two or more of such hardenable unsaturated organic components, and also a hardener and no further ingredients or preferably one or more further ingredients.

5. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein they are based on reactive synthetic resins selected from those of the formula ##STR00006## wherein m denotes a number greater than or equal to 1, those of the formula ##STR00007## wherein a and b each independently of the other denote a number greater than or equal to 0, with the proviso that preferably at least one of the values is greater than 0, preferably both values being 1 or more; and urethane (meth)acrylates which result from the reaction of a prelengthened monomeric di- or poly-isocyanate and/or from the reaction of a polymeric di- or poly-isocyanate (for example: PMDI, MDI and/or MDI) with hydroxyethyl- or hydroxypropyl-(meth)acrylate.

6. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein it includes the reactive diluent(s) in a proportion by weight of from 0.1 to 90% by weight, especially from 0.5 to 75% by weight, especially from 1 to 40% by weight; and a/the reactive synthetic resin in a proportion by weight of from 1 to 99.5%, such as, for example, from 10 to 90%, for example from 15 to 80%; and preferably further ingredients in an amount of in total up to 80% by weight, preferably between 0.01 and 65% by weight.

7. The free-radical-hardenable synthetic resin fixing system according to claim 1 in the form of a multi-component system, especially two-component system, wherein the reactive diluent(s) are selected from triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, and furthermore polyethylene glycol 600 di(meth)acrylate.

8. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein as free-radical-hardening unsaturated reactive synthetic resin there are used urethane methacrylates which are obtainable by reacting, as starting material for the production of the vinyl ester urethane resin, especially a U(M)A resin, an isocyanate or an isocyanate mixture having a mean functionality of more than 2, which can also be achieved by mixing isocyanates having a functionality of less than two with isocyanates having a functionality of greater than 2, for example a functionality of 2.1, preferably 2.7, especially from 2.1 or 2.7 to 5, for example from 2.2 or 2.7 to 4, advantageously, for example, from 2.3 or 2.7 to 3.5, with an aliphatic alcohol having at least one CC double bond (non-conjugated -olefinic bond), especially a hydroxyalkyl (meth)acrylate, preferably hydroxy-lower alkyl (meth)acrylate, such as hydroxyethyl (meth)acrylate or especially hydroxypropyl (meth)acrylate, preferably 2-hydroxypropyl methacrylate (HPMA).

9. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein it includes one or more further reactive diluents, selected from mono-, di-, tri- or poly-(meth)acrylates, such as hydroxyalkyl (meth)acrylates, such as hydroxypropyl methacrylate, other (meth)acrylic acid esters selected from (meth)acrylic acid methyl ester, 1,4-butanediol di(meth)acrylate, 1,2-ethanediol di(meth)acrylate, diethyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate or polyethylene glycol di(meth)acrylate; and styrenes, such as styrene, -methylstyrene, vinyl toluene, tert.-butylstyrene and/or divinylbenzene, or mixtures of two or more thereof.

10. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein as free-radical-hardening unsaturated reactive synthetic resin it includes one without cyclic unsaturated groups.

11. The free-radical-hardenable synthetic resin fixing system according to claim 1, wherein it includes a hardener having a peroxide content of <1% by weight, based on the hardener, preferably having a peroxide content of <1% by weight, based on all components.

12. A method comprising using a synthetic resin fixing system according to claim 1 as an adhesive in fixing technology, especially for fixing anchoring means in drilled holes or crevices.

13. A process for the production of a synthetic resin fixing system according to claim 1, wherein reactive diluents, are mixed with the other constituents, especially a synthetic resin component in the case of a multi-component system, and especially, in the case of multi-component systems in separate compartments, are introduced into packagings.

14. A method for fixing, for example, anchoring means in drilled holes or crevices using the synthetic resin fixing systems according to claim 1, which include at least one of the free-radical-hardenable reactive diluents to be used according to the invention, including mixing the associated components, especially close to and/or directly in front of a hole or directly in front of and/or inside a hole or crevice, for example a drilled hole, and bonding an/the anchoring means in place.

Description

[0110] The Figures show:

[0111] FIG. 1: compressive strengths and compressive moduli of the resins from Example 1 in dependence upon the mean number n of ethylene oxide units of the reactive diluents from Example 1;

[0112] FIG. 2: bending tensile strengths and bending tensile moduli of the resins from Example 1 in dependence upon the mean number n of ethylene oxide units of the reactive diluents from Example 1;

[0113] FIG. 3: bond stresses of the resins from Example 1 in dependence upon the mean number n of ethylene oxide units of the reactive diluents from Example 1;

[0114] FIG. 4: comparison between bond stress in the case of poor intermixing (reduced-length static mixer) and normal intermixing for the resins from Example 1 in dependence upon the mean number n of ethylene oxide units of the reactive diluents from Example 1.

[0115] The inserted lines are to be understood only as showing the trend.

[0116] The Examples that follow serve as special forms of implementation which illustrate the invention but do not limit the scope thereof.

EXAMPLE 1: INJECTABLE MORTAR ACCORDING TO THE INVENTION AND COMPARISON INJECTABLE MORTAR WITH REACTIVE DILUENTS

[0117] Two-component synthetic resin fixing systems were

[0118] Formulations for fixing systems:

TABLE-US-00001 Raw material Content [%] Synthetic resin component Ethoxylated bisphenol-A-dimethacrylate 25 Reactive diluent* 15 Inhibitor mixture (selected from t-BBC, 0.06 hydroquinone and/or Tempol) Amine accelerator 0.5 Additives 0.94 Portland cement 25 Quartz powder 0.05-0.2 mm 31.5 Pyrogenic silicic acid 2 Total 100 Hardener Water, demineralised 30 Stabilised dibenzoyl peroxide (33%) 42 Quartz sand 26.5 Additives and thickeners 1.5 Total 100 *As reactive diluents the following were used:

TABLE-US-00002 Number (where applicable mean Comparison or number) of ethylene according to the Viscosity oxide units in Reactive diluent invention [mPa*s] formula I (n) Ethylene glycol comparison 3-9 1 dimethacrylate (EGDMA) Diethylene glycol comparison 10 2 dimethacrylate (DEGDMA) TIEGDMA according to the 5-16 3 invention TTEGDMA according to the 9-15 4 invention SR210 (Sartomer) according to the 13-16 4.5 invention, most preferred PEG400DMA according to the 20-70 9 invention PEG600DMA according to the 60-80 13 invention

[0119] The viscosity data are manufacturer's data and relate to 25 C.

[0120] In order to simulate poor mixing conditions, the synthetic resin component and the hardener were introduced in a ratio by volume of 5:1 into separate cartridge chambers of a commercially available fischer shuttle cartridge and introduced into drilled holes using a normal static mixer FIS V or a static mixer FIS V that had been reduced in length (from normally eight) to three windings (fischerwerke GmbH & CO KG, Waldachtal, Deutschland). This simulates poor mixing conditions, such as can be brought about, for example, by air bubbles formed during storage or by an increase in viscosity during storage.

[0121] FIGS. 1 and 2 show the compressive strengths and compressive moduli (FIG. 1) and the bending tensile strengths and the bending tensile modulus (FIG. 2) of the resins after curing in dependence upon the mean number n of ethylene oxide units.

[0122] The values decrease as the number n of ethylene oxide units increases, but values are still acceptable and usable even at n=13.

[0123] The corresponding measured values and further measured values can be found in the Tables below:

[0124] The tensile strength and the tensile modulus are determined using dumbbell test specimens of type 1 BA in accordance with DIN EN ISO 527; the compressive strength and the compressive modulus are measured in accordance with DIN EN ISO 604; the bending tensile strength and the bending tensile modulus are measured in accordance with DIN EN ISO 178, in each case using specimens after curing for 7 days at 23 C.

[0125] The bond stress is determined by 5 setting tests using M12 anchor rods in concrete (C20/C25) with a setting depth of 95 mm and a drilled hole diameter of 14 mm after a curing time of 60 min at 20 C. and a subsequent pull-out test.

TABLE-US-00003 Elongation Tensile strength after Tensile modulus at tensile n 24 h [MPa] [GPa] strength [%] 1 11.9 3.5 0.5 2 11.8 3.3 0.5 3 12.6 3.3 0.7 4 12.3 2.9 0.8 4.5 12.5 3.0 0.8 9 10.4 2.2 0.8 13 9.0 2.0 0.6

TABLE-US-00004 Compressive Compression at strength after 24 h Compressive compressive strength n [MPa] modulus [GPa] [%] 1 69.6 1.28 8.8 2 70.2 1.30 10.5 3 65.0 1.23 10.0 4 64.8 1.20 11.4 4.5 64.5 1.22 12.8 9 44.2 0.67 12.2 13 38.6 0.80 11.5

[0126] FIG. 3 shows the bond stress in dependence upon the mean number n of ethylene oxide units. Here too there is a decrease as n increases.

[0127] The corresponding measured values and further measured values can be found in the following Table:

TABLE-US-00005 Bending Bending Bending tensile tensile tensile Bending at strength after 24 h modulus modulus bending tensile n [MPa] [MPa] [GPa] strength [%] 1 19.7 4228 4.2 0.6 2 21.1 4013 4.0 0.7 3 21.6 3433 3.4 0.9 4 20.1 3405 3.4 0.9 4.5 20.7 3335 3.3 0.9 9 16.5 2258 2.3 1.2 13 15.5 2158 2.2 1.2

[0128] FIG. 4 shows the measurement of the bond stress in the case of poor intermixing (FIG. 4 Breduced-length static mixer) in comparison with good intermixing (FIG. 4 Astatic mixer not reduced in length). In this case there is a plateau in the range from n=2.5 to approximately n=9. This shows that under conditions of poor intermixing, synthetic resin fixing systems according to the invention surprisingly have advantages over those having 1 or 2 ethylene oxide units (EGDMA or DEGDMA).

[0129] The corresponding measured values can be found in the following Table:

TABLE-US-00006 Bond stress [N/mm.sup.2] Bond stress [N/mm.sup.2] n Normal intermixing Poor intermixing 1 26.5 12.6 2 26.3 12.5 3 26.7 16.0 4 25 14.0 4.5 24.6 17.1 9 20.6 13.0 13 18.6 10.0

EXAMPLE 2: PREPARATION OF A NON-HAZARD-CLASSIFIED URETHANE METHACRYLATE REACTIVE RESIN

[0130] In a 1000 ml glass flask equipped with a reflux condenser having a drying tube, stirrer, dropping funnel and thermometer, 170.94 g of HPMA, 268.86 g of SR210, 1.07 g of KAT 20% in SR210, 0.3 g of STAB1 5% in SR210, 1.2 g of STAB2 10% in HPMA are used as initial charge and heated in an oil bath at 60 C. The PMDI (Desmodur VKS 20, Bayer AG; average functionality about 2.7) was slowly added dropwise to the reaction mixture so that the temperature did not exceed 90 C. When the addition of the PMDI was complete, stirring was continued at 80 C. in order to complete the reaction. Full reaction (freedom from isocyanate groups detectable by IR spectroscopy) was checked by means of FT-IR. The content of free HPMA was <0.3% (calculated and confirmed by GC analysis).

EXAMPLE 3: PREPARATION OF A NON-HAZARD-CLASSIFIED FIXING SYSTEM

[0131]

TABLE-US-00007 Raw material Content [%] Synthetic resin component UM resin Example 2 25 SR210 15 Inhibitor mixture (selected from t-BBC, 0.06 hydroquinone and/or Tempol) Amine accelerator 0.5 Additives 0.94 Quartz powder 0.05-0.2 mm 56.5 Pyrogenic silicic acid 2 Total 100 Hardener Water, demineralised 30 Stabilised dibenzoyl peroxide (33%) 17 Filler 51 Additives and thickeners 2 Total 100

[0132] 445 g of the mortar and 85 g of the hardener are introduced into a commercially available fischer Multibond cartridge (ratio by volume about 5:1). Using the injection system, 5 setting tests are carried out using M12 anchor rods in concrete (C20/C25) with a setting depth of 95 mm and a drilled hole diameter of 14 mm and, after a curing time of 60 min at 20 C., subjected to a pull-out test. Very good bond stresses of 22 N/mm.sup.2 are obtained.

EXAMPLE 4

[0133] Preparation of a Non-Hazard-Classified Fixing System which Contains an Epoxyacrylate as Reactive Resin.

TABLE-US-00008 Raw material Content [%] Synthetic resin component Epoxyacrylate CN159 (Sartomer) 20 SR210 20 Inhibitor mixture (selected from t-BBC, 0.001 hydroquinone and/or Tempol) Amine accelerator 3 Additives 0.999 Quartz powder 0.05-0.2 mm 54 Pyrogenic silicic acid 2 Total 100 Hardener Water, demineralised 35 Stabilised dibenzoyl peroxide (33%) 2.95 Filler 60 Additives and thickeners 2.05 Total 100

[0134] Mortar and hardener are introduced into a commercially available fischer shuttle cartridge (ratio by volume about 3:1). Good bond stresses of 18 N/mm.sup.2 are obtained.