Reaction Resin Composition, Multi-Component System and Use Thereof

Abstract

Disclosed is a reaction resin composition comprising: a radically polymerizable compound; an initiator system having an a-halo carboxylic acid ester and a catalyst system containing a copper (II) salt, a reducing agent and at least one ligand containing nitrogen; a hydraulically curing compound; and water. Also disclosed is a two- or multi-component system containing said reaction resin composition and uses of said composition for construction applications.

Claims

1-20. (canceled)

21. Reaction resin composition having A radically polymerizable compound, An initiator system, which contains An -halocarboxylic acid ester and A catalyst system, which comprises A copper(II) salt A reducing agent and At least one nitrogen-containing ligand A hydraulically curing and/or polycondensable compound and Water.

22. Reaction resin composition according to claim 21, wherein the reducing agent is selected from the group consisting of ascorbic acid and its salts or derivatives, saccharides with a reducing effect, tin(II) carboxylates, hydroxylamines, phenolic reducing agents, catecholes, hydroxylamines [sic] and combinations thereof.

23. Reaction resin composition according to claim 21, wherein the -halocarboxylic acid ester is wholly or partially soluble or emulsifiable in water.

24. Reaction resin composition according to claim 21, wherein the -halocarboxylic acid ester is selected among compounds having the general formula (I): ##STR00002## in which X means chlorine, bromine or iodine, preferably chlorine or bromine, most preferably bromine; R.sup.1 stands for a straight-chained or branched, if applicable substituted C.sub.1-C.sub.20 alkyl group, a polyalkyleneoxide group or an aryl group; or preferably a C.sub.1-C.sub.10 alkyl group, a polyalkylene oxide chain or group or an aryl group; or for the residue of an acylated, branched, trivalent alcohol, the residue of a completely or partially acylated, linear penta- or hexavalent alcohol, the residue of a completely or partially acylated, linear or cyclic C.sub.4-C.sub.6 aldoses or C.sub.4-C.sub.6 ketoses or the remainder of a completely or partially acylated disaccharide, and isomers of these compounds; R.sup.2 and R.sup.3 stand, independently of each, for hydrogen, a C.sub.1-C.sub.20 alkyl group, a C.sub.3-C.sub.8 cyclo-alkyl group, a C.sub.2-C.sub.20 alkenyl or alkinyl group, oxiranyl group, glycidyl group, aryl group, heterocyclyl group, aralkyl group or aralkenyl group.

25. Reaction resin composition according to claim 24, wherein the copper(II) salt is selected from the group that consists of Cu(II)(PF.sub.6).sub.2, CuX.sub.2, where X=CI, Br, I, Cu(OTf).sub.2 and Cu(ll) carboxylates.

26. Reaction resin composition according to claim 21, wherein the nitrogen-containing ligand contains two or more nitrogen atoms and can form with copper(I) a chelate complex.

27. Reaction resin composition according to claim 26, wherein the nitrogen-containing ligand is selected among amino compounds with at least two primary, secondary and/or tertiary amino groups or amino compounds with at least two heterocyclic nitrogen atoms.

28. Reaction resin composition according to claim 21, wherein the radically polymerizable compound is an unsaturated polyester resin, a vinyl ester resin and/or a vinyl ester urethane resin.

29. Reaction resin composition according to claim 21, wherein the radically polymerizable compound is a (meth)acrylate-functionalized resin and the -halocarboxylic acid ester is an -halocarboxylic acid ester of isobutyric acid or propanoic acid.

30. Reaction resin composition according to claim 21, wherein the hydraulically curing compound is selected from cement and/or gypsum.

31. Reaction resin composition according to claim 21, wherein the polycondensable compound is selected from silicatic polycondensable compounds.

32. Reaction resin composition according to claim 21, wherein the composition also contains at least one other ingredient, which is selected from the group that consists of inhibitors, additives and fillers.

33. Reaction resin composition according to claim 21, wherein the copper(II) salt is separated in a reaction-inhibiting manner from the reducing agent and the water is separated in a reaction-inhibiting manner from the hydraulically curing and/or polycondensable compound.

34. Reaction resin composition according to claim 33, wherein the copper(II) salt is also separated in a reaction-inhibiting manner from the -halocarboxylic acid ester.

35. Two- or multi-component system comprising a reaction resin composition according to claim 21.

36. Two- or multi-component system according to claim 35, wherein the copper(II) salt is separated in a reaction-inhibiting manner from the reducing agent and the water is separated in a reaction-inhibiting manner from the hydraulically curing and/or polycondensable compound.

37. Two- or multi-component system according to claim 36, wherein the copper(II) salt is also separated in a reaction-inhibiting manner from the -halocarboxylic acid ester.

38. Two- or multi-component system according to claim 36, wherein the radically polymerizable compound and the hydraulically curing and/or polycondensable compound are contained in a first component and the water is contained in a second component, and the copper(II) salt is contained in the first component and the reducing agent is contained in the second component, or the copper(II) salt is contained in the second component and the reducing agent is contained in the first component.

39. Two-component system according to claim 38, wherein the ligand the initiator are each contained independently of each other in a component or divided among both components.

40. A method of using the reaction resin composition according to claim 21 for construction purposes, comprising curing the composition by mixing the copper(II) salt with the reducing agent or the copper(II) salt with the reducing agent and the ligand.

41. A method of using the two- or multi-component system according to claim 35 for construction purposes, comprising containing the radically polymerizable compound along with the hydraulically curing and/or polycondensable compound in a first component and containing water in a second component, wherein the copper(II) salt is completely contained either in the first component or in the second component.

Description

EMBODIMENTS

[0124] To manufacture the following sample formulations, the following ingredients were used:

TABLE-US-00001 Abbreviation Description UMA-prepolymer I Prepolymer of MDI and HPMA (DE4111828) with 35% BDDMA by weight UMA-prepolymer II Prepolymer of MDI and HPMA (DE4111828) with 35% HPMA by weight Resin mixture I 33.3% UMA-prepolymer I by weight + 33.3% HPMA by weight + 33.3% BDDMA by weight MDI Diphenylmethane diisocyanate BDDMA 1,4-butanedioldimethacrylate HPMA Hydroxypropyl methacrylate THFMA Tetrahydrofurfuryl methacrylate BiBEE -bromoisobutyric acid ethyl ester or 2-bromisobutyric acid ethyl ester Bipy 2,2-bipyridine PMDETA N,N,N,N,N-pentamethyldiethylenetriamine Sn-octoate Sn(II)ethyl hexanoate Tempol 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl Tween 80 Polyoxyethylene sorbitan monooleate; Sigma- Aldrich Span 80 Sorbitan monooleate; Sigma-Aldrich Betolin V30 Polysaccharide-based anionic thickener; Wllner GmbH & Co. KG Aerosil 200 Pyrogenic silicic acid; Evonic Resource Efficiency GmbH Millisil W12 Quartz powder; Quarzwerke GmbH Quartz sand F12 Quartz sand; Quarzwerke sterreich GmbH Cab-O-Sil TS-720 Pyrogenic silicic acid; Cabot Corp. Secar 80 Calcium-aluminum cement; Kerneos Inc. HLB Hydrophilic-lipophilic balance

[0125] By means of the sample formulations, it is to be shown that the compositions according to the invention exhibit a sufficiently good curing behavior at least at room temperature (25 C.), which allows one to conclude that the compositions have the primary suitability to be used as cold-curing systems, for example in the field of chemical attachments.

Determining Gel Time and Exothermicity

[0126] The gel time of the compositions is determined using a commercially available device (GEL-NORM-Gel Timer) at a temperature of 25 C. To that end, all ingredients are mixed. This mixture is filled up to a height of 4 cm below the rim in a test tube, wherein the test tube is kept 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 time at which the test tube can be raised by the oscillating rod. Additional tests have shown that the degree of curing at the gel point (measured by dynamic scanning calorimetry (DSC)) is constant within the measurement accuracy.

[0127] The heat generation of the sample is recorded against time. The evaluation is performed according to DIN 16945. The gel time is the time at which a temperature increase of 10K is achieved, in this case from 25 C. to 35 C.

[0128] The reactivity measurement (exothermicity) occurs according to DIN 16945.

[0129] Furthermore, the peak time and the peak temperature were measured. Peak time is the time until the maximum temperature was reached. Peak temperature is the maximum temperature that is measured in the gel timer during curing. It is a measure of the quality of the curing. The higher the peak temperature given the same gel time, the better the sample cures.

Examples 1 to 5 (Initiator in the B-Component)

[0130] General composition of examples 1 to 5 having a mixing ratio of 3:1:

TABLE-US-00002 A-component B-component Monomers Water Inhibitor Reducing agent Ligand Initiator Copper(II) salt Tenside Calcium-aluminate cement Silicic acid Silicic acid Fillers Fillers

[0131] For the examples 1 to 5, an A-component having the following composition was used:

TABLE-US-00003 % by weight Resin mixture I 40.29 Copperbis(2-ethylhexanoate) 0.15 Tempol 0.0243 Bipy 0.0334 CAB-O-SIL TS-720 2.5 Calcium-aluminate cement 18.5 Quartz sand 38.5

[0132] The A-component was produced by the copperbis(2-ethylhexanoate), Tempol, the resin mixture and the bipy being mixed in a Speedmixer container for 1 hour at 300 rpm. Subsequently, pyrogenic silicic acid, quartz powder and then quartz sand were sequentially added and prior to each addition, the ingredient was stirred by hand. Lastly, mixing was done using a dissolver for 8 min. at 2,500 rpm, the mixture was poured into cartridges, and stored at 25 C.

Example 1 (Ascorbic Acid as Reducing Agent)

[0133] The B-component had the following composition:

TABLE-US-00004 % by weight L-ascorbic acid 0.46 Deionized water 38.76 Tween 80 0.75 BiBEE 0.50 Aerosil 200 2.50 Millisil W12 18.51 Quartz sand F32 38.52

[0134] To manufacture the B-component, the L-ascorbic acid, deionized water, Tween 80 and BiEE were mixed in a Speedmixer container for 1 hour at 300 rpm. Subsequently, silicic acid, quartz powder, and then quartz sand were added, wherein after every addition, the mixture was stirred by hand. Lastly, the mixture was mixed using a dissolver for 8 min. at 2,500 rpm, poured into a cartridge, and stored at 25 C.

Example 2 (Sodium Ascorbate as Reducing Agent)

[0135] The B-component had the following composition:

TABLE-US-00005 % by weight Sodium ascorbate 0.51 Deionized water 38.76 Tween 80 0.75 BiBEE 0.507 Aerosil 200 2.5 Millisil W12 18.5 Quartz sand F32 38.5

[0136] To manufacture the B-component, the sodium ascorbate, the deionized water, TWEEN 80 and the BiBEE were mixed in a Speedmixer container for 1 hour at 300 rpm. Subsequently, pyrogenic silicic acid, quartz powder and then quartz sand were added, wherein after every addition, the mixture was stirred by hand. Lastly, the mixture was mixed using a dissolver for 8 min. at 3,500 rpm, poured into a cartridge, and stored at 25 C.

Example 3 (System with an Initiator Emulsion (HLB-13)

[0137] The B-component had the following composition:

TABLE-US-00006 % by weight Sodium ascorbate 0.52 Deionized water 39.00 Tween 80 0.62 Span 80 0.15 Betolin V30 0.20 BiBEE 0.52 Pyrogenic silicic acid 1.62 Millisil W12 18.62 Quartz sand F33 [sic] 38.75

[0138] To manufacture the B-component, the sodium ascorbate and the deionized water were mixed in a Speedmixer container for 1 hour at 300 rpm. Betolin V30 was added to this mixture and mixed for 4 to 5 hours at 300 rpm. The thusly obtained emulsifier mixture was mixed with BiBEE using a magnetic stirrer for 3 to 4 hours at 250-300 rpm. To this was added deionized water in a dropwise manner while stirring at 250-300 rpm until an O/W emulsion (22%/oil) was obtained. To this emulsion, a sodium ascorbate solution with xanthan was slowly added while stirring. The receiving emulsion was then stirred with a dissolver for 30 min. at 1,700 rpm. Subsequently, Aerosil 200, Millisil W12 and then quartz sand F32 were added sequentially, wherein after every addition, the mixture was stirred by hand. Lastly, the mixture was mixed using a dissolver for 8 min. at 3,500 rpm and poured into a cartridge.

Example 4 (System with an Initiator Nano-Emulsion (HLB=15))

[0139] The B-component had the following composition

TABLE-US-00007 % by weight Sodium ascorbate 0.515 Deionized, demineralized water 38.76 Tween 80 0.760 2-bromobutyric acid ethyl ester 0.507 Aerosil A200 2.5 Millisil W12 18.49 Quartz sand F32 38.47

[0140] To manufacture the B-component, the sodium ascorbate and the deionized water were mixed in a Speedmixer container for 10 minutes at 300 rpm. The thusly obtained emulsifier mixture was mixed with BiBEE using a magnetic stirrer for 3 to 4 hours at 250-300 rpm. To this was added the sodium ascorbate solution in a dropwise manner at a rate of 1 drop/30 sec until reaching 20% by weight, then 1 drop/1 min 30 sec until the emulsion became liquid, while stirring at 250-300 rpm. To this emulsion, a sodium ascorbate solution with xanthan was slowly added while stirring. The receiving emulsion was then stirred with a dissolver for 30 min. at 1,700 rpm. Subsequently, Aerosil 200, Millisil W12 and then quartz sand F32 were added, wherein after every addition, the mixture was stirred by hand. Lastly, the mixture was mixed using a dissolver for 8 min. at 3,500 rpm and poured into a cartridge.

Example 5 (System with an Initiator Nano-Emulsion (HLB=15))

[0141] The B-component had the following composition:

TABLE-US-00008 % by weight L-ascorbic acid 0.46 Deionized water 38.78 Tween 80 0.76 BiBEE 0.50 Aerosil 200 2.50 Millisil W12 18.50 Quartz sand F32 38.50

[0142] To manufacture the B-component, the ascorbic acid and the deionized water were mixed in a Speedmixer container for 10 minutes at 300 rpm. The thusly obtained emulsifier mixture was mixed with BiBEE using a magnetic stirrer for 3 to 4 hours at 250-300 rpm. To this, the ascorbic acid solution was added in a dropwise manner while stirring at 250-300 rpm at a rate of 1 drop/30 s until reaching 20% by weight, then 1 drop/1 min 30 s until the emulsion became liquid. To this emulsion, an ascorbic acid solution was slowly added while stirring. Subsequently, Aerosil 200, Millisil W12 and then quartz sand F32 were sequentially added, wherein after every addition, the mixture was stirred by hand. Lastly, the mixture was mixed using a dissolver for 8 min. at 3,500 rpm and poured into a cartridge.

TABLE-US-00009 TABLE 1 Results of the gel time measurements of the freshly produced compositions and the composition after storage over the indicated period Example 1 2 3 4 5 fresh 14 days fresh 2 days fresh 2 days fresh 2 days 3 days Gel time 5 C. 29.92 [min] Peak time 28.93 [min] Peak 35.44 temperature [ C.] Gel time 25 C. 4.05 4.03 5.22 5.07 18.97 19.53 8.35 8.43 10.62 [min] Peak time 4.98 5.47 6.45 7.25 23.05 24.44 9.50 10.22 12.23 [min] Peak 82.20 76.97 77.59 75.13 58.86 57.96 77 72.93 71.60 temperature [ C.] Gel time 40 C. 0.03 [min] Peak time 1.60 [min] Peak 101.85 temperature [ C.]

[0143] These results show that the system with the emulsified initiator have good curing and that the reactivity also does not change after storage.

Examples 6 to 10 (Initiator in the A-Component)

[0144] General composition of examples 6 to 11 with a mixing ratio of 3:1:

TABLE-US-00010 A-component B-component Monomers Water Initiator Reducing agent Inhibitor Silicic acid Ligand Fillers Copper(II) salt Calcium-aluminate cement Silicic acid Fillers

[0145] For examples 6 to 11, an A-component having the following composition was used:

TABLE-US-00011 % by weight Resin mixture I 40.21 Copperbis(2-ethyl hexanoate) 0.15 BiBEE 0.17 Tempol 0.02 Bipy 0.04 Cab-O-Sil TS-720 2.50 Secar 80 18.47 Quartz sand F32 38.44

[0146] The A-component was produced by mixing the copperbis(2-ethylhexanoate), Tempol, the resin mixture, BiBEE and the bipy in a Speedmixer container for 1 hour at 300 rpm. Subsequently, Cab-O-Sil TS-720, Millisil W12 and then quartz sand F32 were sequentially added and before every addition, the ingredient was mixed by hand. Lastly, mixing was done using a dissolver for 8 min. at 2500-3000 rpm, the mixture was poured into cartridges, and stored at 25 C.

[0147] The respective B-component was produced by deionized water and the reducing agent being stirred in a container by a magnetic stirrer at 300 rpm until a homogeneous solution was obtained. Then, for sample formulations 9 to 11, Betolin V30 was added. Subsequently, Aerosil 200, Millisil W12 and then quartz sand F32 were sequentially added and before every addition, the ingredient was stirred by hand. Lastly, mixing was done using a dissolver for 8 min. at 2500 rpm, the mixture was poured into cartridges, and stored at 25 C.

Example 6

[0148] For example 6, a B-component having the following composition was used:

TABLE-US-00012 pH = 4 % by weight 40% sodium bisulfate solution 2.76 Deionized water 35.90 Aerosil A200 3.72 Millisil W12 18.70 Quartz sand F32 38.92

Example 7

[0149] For example 7, a B-component having the following composition was used:

TABLE-US-00013 % by weight 40% sodium bisulfate solution 5.33 Deionized water 34.72 Aerosil A200 4.22 Millisil W12 18.09 Quartz sand F32 37.64

Example 8

[0150] For example 8, a B-component having the following composition was used, wherein the pH value was adjusted using an NaOH solution:

TABLE-US-00014 pH = 7 % by weight 40% sodium bisulfate solution 5.37 Deionized water 34.99 Aerosil A200 3.47 Millisil W12 18.23 Quartz sand F32 37.94

Example 9

[0151] For example 9, a B-component having the following composition was used, wherein the pH value was adjusted using an NaOH solution:

TABLE-US-00015 pH = 7 % by weight 40% sodium bisulfate solution + 5.41 1% xanthan gum Deionized water 35.20 Betolin V30 0.35 Aerosil A200 2.54 Millisil W12 18.34 Quartz sand F32 38.16

Example 10 (Ascorbic Acid/Sodium Ascorbate (pH=2; 3; 5; 7))

[0152] For example 10, a B-component having the following composition was used, wherein pH values of 2, 3 and 5 were adjusted with an NaOH solution and a pH value of 7 was produced directly with sodium ascorbate.

TABLE-US-00016 % by weight deionized water 38.85 Ascorbic acid 0.46 Betolin V30 0.39 Aerosil A200 3.21 Millisil W12 18.54 Quartz sand F32 38.55

[0153] The B-component was produced, by deionized water (retain 20 mL) and Betolin V30 being stirred in a container by a magnetic stirrer for approximately 1.5 hours at 300-500 rpm. Subsequently, a solution of 20 mL deionized water and 2.86 g ascorbic acid were added and their pH value was adjusted with a sodium solution. This solution was added to a xanthan gum solution and mixed for 5 minutes at 300 rpm. Subsequently, Aerosil 200, Millisil W12 and then quartz sand F32 were sequentially added and before every addition, the ingredient was stirred by hand. Lastly, mixing was done using a dissolver for 8 min. at 2500 rpm, the mixture was poured into cartridges, and stored at 25 C.

TABLE-US-00017 TABLE 2 Results of the gel time measurement of the freshly produced compositions and the composition from example 10, in which the composition was adjusted to various pH values. Example 10 6 7 8 9 pH = 2 pH = 3 pH = 5 pH = 7 Gel time 25 C. [min] 1.43 0.95 1.82 2.2 3.77 3.5 3.42 3.48 Peak time [min] 3.10 2.42 3.87 4.57 5.03 4.70 4.35 4.62 Peak temperature 74.47 78.47 73.05 67.47 77.43 76.67 79.84 77.95 [ C.]

[0154] These results show that the systems with the initiator in the A-component also cure well and quickly (short gel time, high exothermicity), and that the pH value (system 10) has no appreciable influence on the curing.

Examples 11 to 15 (Reducing Agent in A-Component, Cu(11) Salt in B-Component)

[0155] General composition of examples 12 to 16 at a mixing ratio of 3:1:

TABLE-US-00018 A-component B-component Monomers Water Initiator Copper(II) salt reducing agent Silicic acid Inhibitor Fillers Ligand Calcium-aluminate cement Silicic acid Fillers

[0156] For examples 11 to 15, an A-component having the following composition was used:

[0157] The A-component was produced by mixing the reducing agent, the ligand, the resin mixture and the Tempol in a container for 1 to 3 hours at 300 rpm. Subsequently, Cab-O-Sil TS-720, Secar 80 and then quartz sand F32 were sequentially added and before every addition, the ingredient was stirred by hand. Lastly, mixing was done using a dissolver for 8 min. at 3,500 rpm, the mixture was poured into cartridges, and stored at 25 C.

[0158] The B-component was produced by stirring deionized water and the copper(II) salt in a container using a magnetic stirrer for approximately 5 minutes at 300 rpm. Then optionally, the Betolin V30 was added over 3 to 5 hours at 300 rpm. Subsequently, Aerosil 200, Millisil W12 and then quartz sand F32 were sequentially added, and before every addition, the ingredient was stirred by hand.

[0159] Lastly, mixing was done using a dissolver for 8 min. at a maximum speed of 800 rpm, the mixture was poured into cartridges, and stored at 25 C.

Example 11

[0160] For example 11, an A-component and a B-component having the following composition were used:

TABLE-US-00019 % by weight A-component Resin mixture I 40.11 Tempol 0.01 Bipy 0.03 BiBEE 0.17 Sn-octoate 0.35 Cab-O-SilTS-720 2.49 Secar 80 18.45 Quartz sand F32 38.39 B-component: Deionized water 39.22 Copper(II) sulfate, 0.21 Betolin V80 0.39 Aerosil 200 2.53 Millisil W12 18.71 Quartz sand F32 38.94

Example 12

[0161] For example 12, an A-component and a B-component having the following composition were used:

TABLE-US-00020 % by weight A-component: Resin mixture I 40.10 PMEDTA 0.04 BiBEE 0.17 Sn-octoate 0.35 Cab-O-Sil TS-720 2.49 Secar 80 18.46 Quartz sand F32 38.39 B-component: Deionized water 38.45 Copper(II) sulfate, 0.20 Betolin V80 0.38 Aerosil 200 4.45 Millisil W12 18.35 Quartz sand F32 38.17

Example 13

[0162] For example 13, an A-component and a B-component having the following composition were used:

TABLE-US-00021 % by weight A-component: Resin mixture I 40.10 Bipy 0.04 BiBEE 0.17 Sn-octoate 0.36 Cab-O-Sil TS-720 2.49 Secar 80 18.45 Quartz sand F32 38.39 B-component: Deionized water 39.19 Copper(II) bromide 0.29 Betolin V80 0.39 Aerosil 200 2.53 Millisil W12 18.70 Quartz sand F32 38.90

Example 14

[0163] For example 14, an A-component and a B-component having the following composition were used:

TABLE-US-00022 % by weight A-component: Resin mixture I 40.10 Bipy 0.04 BiBEE 0.17 Sn-octoate 0.36 Cab-O-Sil TS-720 2.49 Secar 80 18.45 Quartz sand F32 38.39 B-component: Deionized water 39.31 Copper(II) bromide 0.28 Aerosil 200 3.53 Millisil W12 18.57 Quartz sand F32 38.65

Example 15

[0164] For example 15, an A-component and a B-component having the following composition were used:

TABLE-US-00023 % by weight A-component: Resin mixture I 40.18 Bipy 0.04 BiBEE 0.02 5,6-lsopropylidene-L-ascorbic acid 0.19 Cab-O-Sil TS-720 2.51 Secar 80 18.49 Quartz sand F32 38.57 B-component: Deionized water 39.19 Copper(II) bromide 0.29 Betolin V80 0.39 Aerosil 200 2.53 Millisil W12 18.70 Quartz sand F32 38.90

TABLE-US-00024 TABLE 3 Results of the gel time measurements for freshly produced compositions and the composition from example 11 after 3 days storage over the indicated period Example 11 12 13 14 15 fresh 3 days fresh fresh fresh fresh Gel time 25 C. [min] 8.82 10.40 9.87 3.53 9.72 3.65 Peak time [min] 10.18 11.63 13.30 4.72 12.2 5.93 Peak temperature [ C.] 78.05 76.27 68.93 76.36 71.86 73.92

[0165] These results show that these systems, which use water-soluble Cu(II) salts in the B-component and resin-soluble reducing agents in the A-component, also have good curing (short gel time, strong exothermicity).

Examples 16 to 19 (Ligand in B-Component)

[0166] General composition of examples 17 to 19 having a mixing ratio of 3:1:

TABLE-US-00025 A-component B-component Monomers Water Initiator Copper(II) salt reducing agent Ligand Inhibitor Silicic acid Calcium-aluminate cement Fillers Silicic acid Fillers

Example 16

[0167] For example 16, an A-component and a B-component having the following composition were used:

TABLE-US-00026 % by weight A-component: Resin mixture I 40.11 Tempol 0.02 BiBEE 0.17 Sn-octoate 0.35 Cab-O-Sil TS-720 2.49 Secar 80 18.45 Quartz sand F32 38.40 B-component: deionized water 38.73 Copper(II) sulfate, anhydrous 0.20 Bipy 0.16 Betolin 0.58 Aerosil A200 2.63 Millisil W12 18.98 Quartz sand F32 38.72

Example 17

[0168] For example 17, an A-component and a B-component having the following composition were used:

TABLE-US-00027 % by weight A-component: Resin mixture I 40.11 BiBEE 0.17 Sn-octoate 0.31 Cab-O-Sil TS-720 2.49 Secar 80 18.46 Quartz sand F32 38.41 B-component: deionized water 39.58 Copper(II) sulfate, anhydrous 0.21 PMEDTA 0.12 Aerosil A200 2.22 Millisil W12 18.78 Quartz sand F32 38.99

Example 18

[0169] For example 18 an A-component and a B-component having the following composition were used:

TABLE-US-00028 % by weight A-component: Resin mixture I 40.12 BiBEE 0.17 Sn-octoate 0.35 Cab-O-Sil TS-720 2.49 Secar 80 18.46 Quartz sand F32 38.41 B-component: deionized water 39.02 Copper(II) sulfate, anhydrous 0.27 PMEDTA 0.13 Aerosil A200 3.22 Millisil W12 18.63 Quartz sand F32 38.74

Example 19 (Water-Soluble Monomer in B Substitutes Part of the Water)

[0170] For example 20 [sic], an A-component and a B-component having the following composition were used:

TABLE-US-00029 % by weight A-component: UMA Prepolymer II 20.62 HPMA 6.19 1,4-BDDMA 13.40 Copper(II)-2-ethylhexanoate 0.15 BiBEE 0.17 Bipy 0.04 TEMPOL 0.04 Cab-O-Sil TS-720 2.50 Secar 80 18.45 Quartz sand F32 38.44 B-component: Deionized water 19.40 L-ascorbic acid 0.47 MPEG-35Q-methacrylate 19.41 Ultragel 300 0.40 Aerosil 200 3.00 Millisil W12 19.10 Quartz sand F32 38.22

TABLE-US-00030 TABLE 4 Results of the get time measurements after the composition was stored for 2 days Example 16 17 18 19 Gel time 25 C. [min] 18.17 10 10.57 4.5 Peak time [min] 19.60 12.80 13.08 5.5 Peak temperature [ C.] 77.18 75.64 70.29 87

[0171] These results show that the ligand can definitely also be stored in the B-component, and that if necessary some of the water can be exchanged for water-soluble monomers (which could simultaneously act as a tenside if necessary).

Determining the Extraction Resistance

[0172] Each of 3 M1272 anchor rods are set in C20/25 concrete into dry and cleaned boreholes having a diameter of 14 mm and are pulled out until failure after 24 hours of curing (central tension) and the following load values are determined for the test temperatures indicated in Table 5 (mean values of 3 measurements).

Determining the Internal Strength

[0173] The extraction test is conducted as for determining the extraction strength, however one uses steel sleeves with a profiled hole, which the borehole simulates. One sets 5 sleeves with M8100 anchor rods and conducts a tensile test using a Zwick tensile test machine until the anchor fails. By this experiment, one can exclude the influence of the concrete borehole wall on the mortar.

TABLE-US-00031 TABLE 5 Results of determining the extraction strength Load values Examples [N/mm.sup.2] 1 2 3 4 5 Ref. 8.1 4.1 1.5 3.4 3.6 5 C. 8.9 +5 C. 5.2 +40 C. 9.9 Examples Load values 10 10 10 10 [N/mm.sup.2] (pH = 2) (pH = 3) (pH = 5) (pH = 7) 11 19 Ref. 6 7.0 6.6 6.8 3.1 9 5 C. 0.3 +5 C. +40 C. 3.3 12.5

TABLE-US-00032 TABLE 6 Results of the internal strength assessments Example 1 Example 2 Internal strength [N/mm.sup.2] 10.65 6.11

[0174] The results show that appreciable failure load values can be achieved with the compositions, so that the compositions have a primary suitability as chemical anchors.