REACTIVE RESIN COMPOSITION AND USE OF THE SAME

Abstract

A reactive resin composition is described, with a resin component, which contains a radical-polymerizable compound, and an initiator system, which contains an α-halocarboxylic acid and a catalyst system, which comprises a nitrogen-containing ligand and Cu(0) or an inorganic Cu(I) compound, as is the use of the same for construction purposes.

Claims

1. A reactive resin composition, comprising: a resin component, which comprises a radical-polymerizable compound, and an initiator system, which comprises an α-halocarboxylic acid ester and a catalyst system, wherein the catalyst system comprises at least one nitrogen-containing ligand and Cu(0) or an inorganic Cu(I) compound.

2. The reactive resin composition according to claim 1, wherein the α-halocarboxylic acid ester is selected from the group consisting of compounds of the general formula (I) ##STR00002## in which X denotes chlorine, bromine or iodine; R.sup.1 stands for a straight-chain or branched C.sub.1-C.sub.20 alkyl group, optionally substituted, or an aryl group; or for the radical of an acylated, branched, trihydric alcohol, the radical of a completely or partly acylated, linear or branched tetrahydric alcohol, the radical of a completely or partly acylated, linear pentahydric or hexahydric alcohol, the radical of a completely or partly acylated, linear or cyclic C.sub.4-C.sub.6 aldose or C.sub.4-C.sub.6 ketose or the radical of a completely or partly acylated disaccharide, and isomers of these compounds; R.sup.2 and R.sup.3, independently of one another, stand for hydrogen, a C.sub.1-C.sub.20 alkyl group, a C.sub.3-C.sub.8 cycloalkyl group, C.sub.2-C.sub.20 alkenyl or alkynyl group, oxiranyl group, glycidyl group, aryl group, heterocyclyl group, aralkyl group or aralkenyl group.

3. The reactive resin composition according to claim 2, wherein the α-halocarboxylic acid ester is a C.sub.1-C.sub.6 alkyl ester of an α-halo-C.sub.1-C.sub.6 carboxylic acid.

4. The reactive resin composition according to claim 3, wherein the α-halo-C.sub.1-C.sub.6 carboxylic acid is an α-bromo-C.sub.1-C.sub.6 carboxylic acid.

5. The reactive resin composition according to claim 1, wherein the nitrogen-containing ligand contains two or more nitrogen atoms and is able to form a chelate complex with copper(I).

6. The reactive resin composition according to claim 5, wherein the nitrogen-containing ligand is selected from the group consisting of i) amino compounds with at least two primary, secondary and/or tertiary amino groups and ii) amino compounds with at least one heterocyclic nitrogen atom.

7. The reactive resin composition according to claim 5, wherein the nitrogen-containing ligand is present in excess compared to the Cu(0) or an inorganic Cu(I) compound.

8. The reactive resin composition according to claim 1, wherein the inorganic Cu(I) compound is a Cu(I) compound with elements of Group VI.

9. The reactive resin composition according to claim 8, wherein the inorganic Cu(I) compound is at least one selected from the group consisting of Cu.sub.2O, Cu.sub.2S, Cu.sub.2Se and Cu.sub.2Te.

10. The reactive resin composition according to claim 1, wherein the initiator system further comprises an accelerator.

11. The reactive resin composition according to claim 10, wherein the accelerator is a phenol or a phenol derivative.

12. The reactive resin composition according to claim 1, wherein the radical-polymerizable compound is an unsaturated polyester resin, a vinyl ester resin and/or a vinyl ester-urethane resin.

13. The reactive resin composition according to claim 1, wherein the radical-polymerizable compound is a (meth)acrylate-functionalized resin and the α-halocarboxylic acid ester is an α-halocarboxylic acid ester of isobutanoic acid or propanoic acid.

14. The reactive resin composition according to claim 1, wherein the composition further contains comprising a non-phenolic inhibitor.

15. The reactive resin composition according to claim 14, wherein the non-phenolic inhibitor is a stable N-oxyl radical.

16. The reactive resin composition according to claim 1, wherein the resin component further comprises at least one reactive diluent.

17. The reactive resin composition according to claim 1, wherein the composition further contains comprising an inorganic aggregate.

18. The reactive resin composition according to claim 17, wherein the inorganic aggregate is an additive and/or a filler.

19. A two-component or multicomponent system, comprising: the reactive resin composition according to claim 1, wherein the nitrogen-containing ligand and the Cu(0) or the inorganic Cu(I) compound are stored separately from one another in a way that inhibits reaction.

20. The two-component system according to claim 19, wherein the Cu(0) or the inorganic Cu(I) compound and optionally an accelerator are contained in a first component, and the nitrogen-containing ligand and the initiator are contained in a second component, the radical-polymerizable compound and optionally the inhibitor are distributed among the two components, wherein the two components are kept separate from one another in a way that inhibits reaction.

21. The two-component system according to claim 20, wherein the reactive resin composition further comprises at least one reactive diluent and/or inorganic aggregates, which are contained in one or in both components.

22. A method for anchoring of an anchoring elements in a drilled hole, said method comprising: applying in said drilled hole the reactive resin composition according to claim 1.

Description

EXEMPLARY EMBODIMENTS

[0100] The following ingredients were used for manufacture of the following exemplary formulations.

TABLE-US-00001 Abbreviation Designation UMA-1 Urethane methacrylate prepolymer, MW approx. 1000 g/mol, dissolved to 33 wt % in a 1:1 (w/w) mixture of HPMA and 1,4-BDDMA (hydroxypropyl methacrylate and 1,4-butanediol dimethacrylate) Cu powder Copper powder, particle size <75 μm Cu.sub.2O Copper(I) oxide, particle size <5 μm MeHQ Methylhydroquinone Tempol 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl TS-720 Pyrogenic silica Cab-O-Sil TS-720 F32 Silica sand F31 W12 Silica flour Millisil W12 bipy 2,2′-Bipyridyl TMEDA N,N,N′,N′-Tetramethylethylenediamine HMTETA 1,1,4,7,10,10-Hexamethyltriethylenetetramine TDMAEA Tris-(Dimethylaminoethyl)amine PMDETA N,N,N′,N″,N″-Pentamethyldiethylenetriamine BiBEE α-Bromo-iso-butyric acid ethyl ester

[0101] Preparation of the Compositions

[0102] Inorganically filled two-component systems with the compositions shown in Tables 1 to 5 were prepared and various properties of the masses obtained were investigated.

[0103] Firstly the two components A and B are prepared separately, by first preparing homogeneous mixtures from the respective ingredients of the A and B components shown in Tables 1 to 5, wherein pasty, readily flowing components are obtained. Curing is started by thorough mixing of the two components A and B, wherein the components were mixed in the volume ratio A:B=3:1.

EXAMPLES 1 AND 2

[0104] In order to appraise the applicability of the initiator system to cold-curing methacrylate esters for chemical reactive resin mortars, the reactive resin compositions listed in Table 1 were prepared, wherein Cu(0) was used as catalyst in Example 1 and Cu.sub.2O was used in Example 2, and the reactivity of the reactive resin composition was determined on the basis of the gel time at +25° C. and of the exothermicity.

[0105] Determination of the Gel Time and of the Exothermicity

[0106] The gel time of the compositions is determined with a commercial apparatus (GELNORM®-Gel Timer) at a temperature of 25° C. All ingredients are mixed for this purpose. This mixture is filled into a test tube up to a height of 4 cm below the rim, while the test tube was maintained at a temperature of 25° C. (DIN 16945, DIN EN ISO 9396). A glass rod or a spindle is moved up and down in the resin at 10 strokes per minute. The gel time corresponds to the moment at which the test tube is lifted by the oscillating rod. Additional tests have shown that the degree of curing at the gel point (measured by differential scanning calorimetry (DSC)) is constant within the measurement accuracy.

[0107] The heat generation of the sample is plotted against time. The evaluation is based on DIN 16945. The gel time is the time at which a temperature rise of 10 K is attained, in the present case from 25° C. to 35° C.

[0108] The reactivity measurement (exothermicity) is based on DIN 16945.

TABLE-US-00002 TABLE 1 Example.sup.a) 1 2 A component Methacrylate resin UMA-1 39.8% UMA-1 39.8% Catalyst Cu 0.49% Cu.sub.2O 0.49% Thickener TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% W12 18.5% W12 18.5% B component Methacrylate resin UMA-1 38.6% UMA-1 38.6% Ligand PMDETA 0.93% PMDETA 0.93% Initiator BiBEE 0.94% BiBEE 0.94% Thickener TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% W12 18.5% W12 18.5% Reactivity Gel time 25° C. 26 min no curing.sup.b) Exothermicity 64° C. — .sup.a)All values in wt % .sup.b)Measurement stopped after 2.5 h

EXAMPLES 3 TO 12

[0109] In order to appraise the influence of an accelerator, the reactive resin compositions listed in Table 2 were prepared, wherein Cu(0) was used as catalyst in Examples 3 to 7 and Cu.sub.2O as catalyst in Examples 8 to 12, methylhydroquinone was used respectively as accelerator in different concentrations and the reactivity of the reactive resin composition was determined on the basis of the gel time at +25° C. and of the exothermicity in accordance with the above description.

[0110] These examples show that the proportion of methylhydroquinone has a substantial influence on the reactivity and that polymerization without MeHQ takes place more slowly and more poorly (exothermicity much lower). Furthermore, it is apparent that Cu(0) is activated much better than Cu.sub.2O.

TABLE-US-00003 TABLE 2 Example.sup.a) Example 1, 3-7 2, 8-12 A component Methacrylate resin UMA-1 39.8% UMA-1 39.8% Co-initiator Cu 0.49% Cu.sub.2O 0.49% Accelerator MeHQ Variable MeHQ Variable Thickener TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% W12 18.5% W12 18.5% B component Methacrylate resin UMA-1 38.6% UMA-1 38.6% Ligand PMDETA 0.93% PMDETA 0.93% Initiator BiBEE 0.94% BiBEE 0.94% Thickener TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% W12 18.5% W12 18.5% Reactivity Example Example 1 MeHQ/g UMA 0 mmol 2 0 mmol Gel time 25° C. 48 min no curing.sup.b) Exothermicity 55° C. 3 MeHQ/g UMA 0.01 mmol 8 0.01 mmol Gel time 25° C. 16 min 18.5 min Exothermicity 65° C. 85° C. 4 MeHQ/g UMA 0.015 mmol 9 0.015 mmol Gel time 25° C. 12.6 min 15.7 min Exothermicity 77° C. 90° C. 5 MeHQ/g UMA 0.02 mmol 10 0.02 mmol Gel time 25° C. 9 min 13.9 min Exothermicity 88° C. 88° C. 6 MeHQ/g UMA 0.04 mmol 11 0.04 mmol Gel time 25° C. 4.6 min 13.1 min Exothermicity 88° C. 87° C. 7 MeHQ/g UMA 0.06 mmol 12 0.06 mmol Gel time 25° C. 3.8 min 11.0 min Exothermicity 86° C. 87° C. .sup.a)All values in wt %; .sup.b)Measurement stopped after 2.5 h

EXAMPLES 13 TO 16

[0111] In order to appraise the different reactivity of the Cu(I) chalcogens, the reactive resin compositions listed in Table 3 were prepared and the reactivity of the reactive resin composition was determined on the basis of the gel time at +25° C. and of the exothermicity in accordance with the above description.

[0112] The examples show that all Cu(I) compounds used act as catalysts, with the following order of reactivity (with respect to the gel time): Cu.sub.2Te>Cu.sub.2Se>Cu.sub.2O>Cu.sub.2S.

TABLE-US-00004 TABLE 3 Example.sup.a) 13 14 15 16 A component Methacrylate resin UMA-1 38.3% UMA-1 38.8% UMA-1 38.9% UMA-1 38.8% Catalyst Cu.sub.2Te 1.98% Cu.sub.2Se 0.81% Cu.sub.2S 0.57% Cu.sub.2O 0.56% Accelerator MeHQ 0.20% MeHQ 0.20% MeHQ 0.20% MeHQ 0.20% Thickener TS-720 2.50% TS-720 2.53% TS-720 2.54% TS-720 2.54% Filler F32 38.5% F32 39.0% F32 39.1% F32 39.1% W12 18.5% W12 18.7% W12 18.8% W12 18.8% B component Methacrylate resin UMA-1 38.6% UMA-1 38.6% UMA-1 38.6% UMA-1 38.6% Ligand PMDETA 0.93% PMDETA 0.93% PMDETA 0.93% PMDETA 0.93% Initiator BiBEE 0.94% BiBEE 0.94% BiBEE 0.94% BiBEE 0.94% Thickener TS-720  2.5% TS-720  2.5% TS-720  2.5% TS-720  2.5% Filler F32 38.5% F32 38.5% F32 38.5% F32 38.5% W12 18.5% W12 18.5% W12 18.5% W12 18.5% Reactivity Gel time 25° C. 0.8 min 4.7 min 18.0 min 6.0 min Exothermicity 100° C.   90° C.   55° C.  95° C.   .sup.a)All data in wt %

EXAMPLES 17 TO 19

[0113] In order to appraise the different reactivity of copper powder with different specific surface areas, the reactive resin compositions listed in Table 4 were prepared and the reactivity of the reactive resin composition was determined on the basis of the gel time at +25° C. and of the exothermicity in accordance with the above description.

[0114] These examples show that the copper powder must have a sufficiently large specific surface area in order to achieve good reactivity—the “Cu 400μ” copper powder, which exists in relatively coarse, sand-like form, leads to rather weak exothermicity after a very long time, thus suggesting only inadequate initiation.

TABLE-US-00005 TABLE 4 Example.sup.a) 17 18 19 A component Methacrylate resin UMA-1 39.9% UMA-1 39.9% UMA-1 39.9% Catalyst Cu <10μ 0.49% CU <75μ 0.49% Cu 400μ 0.49% Accelerator MeHQ 0.20% MeHQ 0.20% MeHQ 0.20% Thickener TS-720 2.50% TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% F32 38.5% W12 18.5% W12 18.5% W12 18.5% B component Methacrylate resin UMA-1 38.6% UMA-1 38.6% UMA-1 38.6% Ligand PMDETA 0.93% PMDETA 0.93% PMDETA 0.93% Initiator BiBEE 0.94% BiBEE 0.94% BiBEE 0.94% Thickener TS-720 2.51% TS-720 2.51% TS-720 2.51% Filler F32 38.5% F32 38.5% F32 38.5% W12 18.5% W12 18.5% W12 18.5% Reactivity Gel time 25° C. 6.3 min 3.5 min 45 min Exothermicity 76° C. 88° C. 27° C. .sup.a)All data in wt %

EXAMPLES 20 TO 24

[0115] In order to appraise the different reactivity of various nitrogen-containing ligands, the reactive resin compositions listed in Table 5 were prepared and the reactivity of the reactive resin composition was determined on the basis of the gel time at +25° C. and of the exothermicity in accordance with the above description.

[0116] The examples show that, in principle, various nitrogen-containing ligands are suitable. For equal molar proportions, the following order of reactivity is obtained: TDMAEA>HMTETA>PMDETA>bipy>TMEDA.

TABLE-US-00006 TABLE 5 Example.sup.a) 20 21 22 23 24 A component Methacrylate resin UMA-1 38.8% UMA-1 39.8% UMA-1 39.8% UMA-1 39.8% UMA-1 39.8% Co-initiator Cu.sub.2O 0.56% Cu.sub.2O 0.49% Cu.sub.2O 0.49% Cu.sub.2O 0.49% Cu.sub.2O 0.49% Accelerator MeHQ 0.20% MeHQ 0.20% MeHQ 0.20% MeHQ 0.20% MeHQ 0.20% Thickener TS-720 2.54% TS-720 2.50% TS-720 2.50% TS-720 2.50% TS-720 2.50% Filler F32 39.1% F32 38.5% F32 38.5% F32 38.5% F32 38.5% W12 18.8% W12 18.5% W12 18.5% W12 18.5% W12 18.5% B component Methacrylate resin UMA-1 38.6% UMA-1 38.7% UMA-1 38.8% UMA-1 38.5% UMA-1 38.5% Ligand PMDETA 0.93% Bipy 0.84% TMEDA 0.62% HMTETA 1.23% TDMAEA 1.23% Initiator BiBEE 0.94% BiBEE 0.94% BiBEE 0.94% BiBEE 0.93% BiBEE 0.93% Thickener TS-720  2.5% TS-720 2.51% TS-720 2.52% TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% F32 38.6% F32 38.4% F32 38.4% W12 18.5% W12 18.5% W12 18.5% W12 18.4% W12 18.5% Reactivity Gel time 25° C. 6.0 min 15.5 min 15.1 min 4.2 min 3.4 min Exothermicity 95° C.   45° C.  32° C.  88° C.   93° C.   .sup.a)All data in wt %

EXAMPLES 25 AND 26

[0117] In order to appraise the influence of the nitrogen-containing ligand, the reactive resin compositions listed in Table 6 were prepared and the reactivity of the reactive resin composition was determined on the basis of the gel time at +25° C. and of the exothermicity in accordance with the above description. From Table 6 it is apparent that a nitrogen-containing ligand is absolutely necessary for the composition to cure.

TABLE-US-00007 TABLE 6 Example.sup.a) 25 26 A component Methacrylate resin UMA-1 39.8% UMA-1 39.8% Co-initiator Cu 0.49% Cu.sub.2O 0.49% Accelerator MeHQ 0.06 mmol MeHQ 0.06 mmol Inhibitor Thickener TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% W12 18.5% W12 18.5% B component Methacrylate resin UMA-1 38.6% UMA-1 38.6% Ligand PMDETA Variable PMDETA Variable Initiator BiBEE 0.94% BiBEE 0.94% Thickener TS-720 2.50% TS-720 2.50% Filler F32 38.5% F32 38.5% W12 18.5% W12 18.5% Reactivity 0% PMDETA 0 mmol 0 mmol Gel time 25° C. no curing.sup.b) no curing.sup.b) Exothermicity — — 0.93% PMDETA 0.01 mmol 0.01 mmol Gel time 25° C. 10.2 min 10.0 min Exothermicity 83° C. 85° C. .sup.a)All values in wt % .sup.b)Measurement stopped after 3 h

EXAMPLES 27 TO 31

[0118] In order to appraise the different reactivity of various nitrogen-containing ligands, the reactive resin compositions listed in Table 7 were prepared and the reactivity of the reactive resin composition was determined on the basis of the gel time at +25° C. and of the exothermicity in accordance with the above description.

[0119] These examples show that the reactivity can be adjusted by variation of the concentration of the initiator system. Furthermore, the examples show that the gel time can be adjusted by means of a polymerization inhibitor.

[0120] Furthermore, it was shown on the basis of these examples that the inventive reactive resin compositions are suitable as binding agents for reactive resin mortars for chemical fastening.

[0121] Determination of the Pull-Out Resistance

[0122] Respectively 3 M12×72 anchor rods were inserted into dry and cleaned drilled holes of 14 mm diameter in C20/25 concrete and after 24 hours of curing were pulled out to failure (central tension), and the following failure loads were determined at the test temperatures indicated in Table 7 (mean values of 3 measurements).

[0123] On the basis of Examples 27 to 31, it is apparent that, with the inorganically filled reactive resin compositions, polymerization of methacrylates, which can be delayed with an inhibitor, is achieved at room temperature and, even after a long open time (gel time approx. 20 minutes), still yields good polymerization (peak temperature approx. 90° C.) as well as leads to good mechanical properties at room temperature and at elevated temperatures. This suggests that it is possible, with the inventive reactive resin compositions, to adjust the gel time selectively and to adapt it to the respective needs of application.

TABLE-US-00008 TABLE 7 Example.sup.a) 27 28 29 30 31 A component Methacrylate UMA-1 39.8% UMA-1 39.8% UMA-1 39.8% UMA-1 39.8% UMA-1 39.8% resin Co-initiator Cu-pulver 0.49% Cu- 0.49% Cu- 0.49% Cu.sub.2O 0.49% Cu.sub.2O 0.49% pulver pulver Accelerator MeHQ 0.20% MeHQ 0.30% MeHQ 0.30% MeHQ 0.30% MeHQ 0.30% Inhibitor Tempol 0.042%  Tempol 0.010%  Tempol 0.01% Thickener TS-720 2.50% TS-720  2.5% TS-720  2.5% TS-720  2.5% TS-720 2.50% Filler F32 38.5% F32 38.5% F32 38.5% F32 38.4% F32 38.4% W12 18.5% W12 18.5% W12 18.5% W12 18.5% W12 18.5% B component Methacrylate UMA-1 38.6% UMA-1 38.6% UMA-1 38.6% UMA-1 38.6% UMA-1 38.6% resin Ligand PMDETA 0.93% PMDETA 0.93% PMDETA 0.93% PMDETA 0.93% PMDETA 0.93% Initiator BiBEE 0.94% BiBEE 0.94% BiBEE 0.94% BiBEE 0.94% BiBEE 0.94% Thickener TS-720  2.5% TS-720  2.5% TS-720  2.5% TS-720  2.5% TS-720  2.5% Filler F32 38.5% F32 38.5% F32 38.5% F32 38.5% F32 38.5% W12 18.5% W12 18.5% W12 18.5% W12 18.5% W12 18.5% Reactivity Gel time 25° C. 1.5 min 12.4 min 8.4 min 10.1 min 19.5 min Exothermicity 90° C. 90° C. 90° C. 86° C. 89° C. Failure loads  −5° C. 1.7 N/mm.sup.2 11.6 N/mm.sup.2 7.0 N/mm.sup.2 No curing Not cured  +5° C. 3.4 N/mm.sup.2 13.0 N/mm.sup.2 8.1 N/mm.sup.2 5.9 N/mm.sup.2 6.0 N/mm.sup.2 +20° C. 7.0 N/mm.sup.2 14.2 N/mm.sup.2 10.1 N/mm.sup.2 9.4 N/mm.sup.2 8.0 N/mm.sup.2 +40° C. 12.8 N/mm.sup.2 16.8 N/mm.sup.2 14.5 N/mm.sup.2 15.4 N/mm.sup.2 15.5 N/mm.sup.2 .sup.a)All data in wt %