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 method of fixing anchoring means in a drilled hole or crevice in masonry or concrete, comprising (i) mixing in front of said hole or crevice and then introducing the mixture and/or (ii) introducing and mixing inside said drilled hole or crevice the components of a free-radical-hardenable synthetic resin system for the fixing of the anchoring means 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 and wherein the synthetic resin fixing system comprises reactive resins selected from (a) those of the formula ##STR00005## wherein a and b each independently of the other denote a number greater than or equal to 0, with the proviso that at least one of the values is greater than 0; and from (b) 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 with hydroxyethyl- or hydroxypropyl-(meth)acrylate and fixing the anchoring means in said drilled hole or crevice.

2. The method according to claim 1, wherein the free-radical-hardenable oligoalkylene glycol di(meth)acrylates are those of the formula I, ##STR00006## wherein the radicals R independently of one another denote C.sub.1-C.sub.7alkyl and wherein n denotes on average from 3.5 to 10.

3. The method according to claim 1, 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 method according to claim 1, wherein the free-radical-hardenable synthetic resin system includes the reactive diluent(s) in a proportion by weight of from 0.1 to 90% by weight; and the reactive resin in a proportion by weight of from 10 to 90% by weight; with or without further ingredients in an amount of in total up to 80% by weight.

5. The method according to claim 1, wherein the free-radical-hardenable synthetic resin system is in the form of a 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 polyethylene glycol 600 di(meth)acrylate.

6. The method according to claim 1, wherein as the free-radical-hardening synthetic resin there is used a urethane (meth)acrylate which is obtainable by reacting, as starting material for the production of the vinyl ester urethane 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 2.1, with hydroxyethyl- or hydroxypropyl-(meth)acrylate.

7. The method according to claim 1, wherein the free-radical-hardenable synthetic resin system includes one or more further reactive diluents, selected from mono-, di-, tri- or poly-(meth)acrylates and styrenes, or mixtures of two or more of these further reactive diluents.

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

9. The method according to claim 1, wherein the free-radical-hardenable synthetic resin system includes a hardener having a peroxide content of <1% by weight, based on the hardener.

10. The method according to claim 1, wherein the free-radical-hardenable synthetic resin system comprises urethane (meth)acrylates which result from the reaction of MDI with hydroxyethyl- or hydroxypropyl-(meth)acrylate.

11. The method according to claim 1, wherein the free-radical-hardenable synthetic resin system comprises urethane (meth)acrylates which result from the reaction of PMDI with hydroxyethyl- or hydroxypropyl-(meth)acrylate.

12. The method according to claim 1, wherein the free-radical-hardenable synthetic resin system includes the reactive diluent(s) in a proportion by weight of from 0.5 to 75% by weight; and the reactive synthetic resin in a proportion by weight of from 15 to 80% by weight; with or without further ingredients in an amount in total between 0.01 and 65% by weight.

13. The method according to claim 1, wherein as free-radical-hardening radical synthetic resin there are used urethane methacrylates which are obtainable by reacting, as starting material for the vinyl ester urethane resin, an isocyanate or isocyanate mixture having a mean functionality of from 2.1 or 2.7 to 5.

14. The method according to claim 1, wherein as free-radical-hardenable radical synthetic resin there are used urethane methacrylates which are obtainable by reacting, as starting material for the production of the vinyl ester urethane resin, an isocyanate or isocyanate mixture having a mean functionality of from 2.3 or 2.7 to 3.5 and wherein the hydroxypropyl-(meth)acrylate is 2-hydroxypropyl methacrylate.

15. The method according to claim 1, wherein the one or more further reactive diluents are selected from hydroxyalkyl (meth)acrylates, other (meth)acrylic acid esters selected from (meth)acrylic acid methyl ester, 1,4-butandediol di(meth)acrylate, 1,2-ethandiol (meth)acrylate, diethyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate or polyethylene glycol di(meth)acrylate; and styrenes selected from styrene, a-methylstyrene, vinyl toluene, tert-butylstyrene and divinylbenzene, or mixtures of two or more of these further reactive diluents.

Description

[0106] The Figures show:

[0107] 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;

[0108] 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;

[0109] 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;

[0110] FIGS. 4A and 4B: 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.

[0111] The inserted lines are to be understood only as showing the trend.

[0112] 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

[0113] Two-component synthetic resin fixing systems were

[0114] 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- 0.06 BBC, hydro-quinone 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

[0115] )*As reactive diluents the following were used:

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

[0116] The viscosity data are manufacturer's data and relate to 25 C.

[0117] 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.

[0118] 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.

[0119] The values decrease as the number n of ethylene oxide units increases, but values are still acceptable and usable even at n=13.

[0120] The corresponding measured values and further measured values can be found in the Tables below:

[0121] 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.

[0122] The bond stress is determined by 5 setting tests using M12 anchor rods in concrete (C20/025) 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 Tensile Elongation strength after Tensile at tensile n 24 h [MPa] modulus [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 strength after Compressive at compressive n 24 h [MPa] modulus [GPa] strength [%] 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

[0123] 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.

[0124] The corresponding measured values and further measured values can be found in the following Table:

TABLE-US-00005 Bending Bending Bending Bending at tensile strength tensile tensile bending tensile after 24 h modulus modulus strength n [MPa] [MPa] [GPa] [%] 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

[0125] 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 =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).

[0126] The corresponding measured values can be found in the following Table:

TABLE-US-00006 Bond stress Bond stress [N/mm.sup.2] [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

[0127] 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

[0128]

TABLE-US-00007 Raw material Content [%] Synthetic resin component UM resin Example 2 25 SR210 15 Inhibitor mixture (selected from t- 0.06 BBC, 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

[0129] 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

[0130] 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- 0.001 BBC, 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

[0131] 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.