Mixture of radically curable compounds and use thereof

Abstract

A mixture includes at least two radically curable compounds as a backbone resin, and is useful in reactive resins. In particular, the mixture reduces the viscosity of such reactive resin-containing mixtures and thus the dispensing forces required for ejecting the reactive resin components produced therefrom. The mixture also increases the performance of the reactive resins containing such mixtures and of the reactive resin components produced therefrom. Further, said reactive resins and the reactive resin components thereof are useful for construction purposes, in particular for chemical fastening.

Claims

1-25. (canceled)

26. A reactive resin system, comprising: a reactive resin component (A), comprising at least two radically curable compounds having a structure of at least one of compounds of the general formula (I), compounds of the general formula (V) and compounds of the general formula (VII) ##STR00027## in which each R.sub.1 is independently a branched or linear aliphatic C.sub.1-C.sub.15 alkylene group, A is a linear or branched aliphatic C.sub.3-C.sub.10 alkylene group, B is a linear, branched or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group, X is a divalent linear, branched or cyclic aliphatic or aromatic hydrocarbon group, or a group Z of the formula ##STR00028## in which R.sub.2 is a divalent branched or linear aliphatic C.sub.1-C.sub.6 alkylene group, Y is an aromatic hydrocarbon group, n is a whole number greater than or equal to 0, m is a whole number greater than or equal to 3, and p is a whole number greater than or equal to 2, an inhibitor, an accelerator, and optionally a reactive diluent, and a hardener component (B) comprising an initiator, wherein at least one of the components (A) or (B) contains an inorganic aggregate having a particle size minimum diameter of about 50 nm and an amount of 30-90% wt. %.

27. The reactive resin system according to claim 26, wherein X is a divalent aromatic C.sub.6-C.sub.20 hydrocarbon group or a divalent linear, branched or cyclic aliphatic hydrocarbon group.

28. The reactive resin system according to claim 26, wherein X is a divalent C.sub.6-C.sub.20 aromatic hydrocarbon group containing one or two benzene rings which are optionally alkyl substituted.

29. The reactive resin system according to claim 26, wherein B is an aliphatic hydrocarbon group which is optionally hydroxy and/or alkyl substituted.

30. The reactive resin system according to claim 29, wherein the aliphatic hydrocarbon group B is a linear or branched C.sub.2-C.sub.12 alkylene group.

31. The reactive resin system according to claim 26, wherein B is an aromatic hydrocarbon group.

32. The reactive resin system according to claim 26, wherein p is 2 or 3.

33. The reactive resin system according to claim 26, wherein Y is a C.sub.6-C.sub.20 aromatic hydrocarbon group.

34. The reactive resin system according to claim 26, wherein Y contains one or two benzene rings, which are optionally alkyl substituted.

35. The reactive resin system according to claim 26, wherein A is a trivalent or higher-valency-group, as obtained by removing the hydroxyl groups from a trifunctional or higher-function alcohol.

36. The reactive resin system according to claim 26, wherein n=0, 1, or 2 and m=3, 4, or 5.

37. The reactive resin system according to claim 26, wherein n=0 or 1 and m=3, 4, or 5, where n+m=4 or 5.

38. The reactive resin system according to claim 26, wherein R.sub.1 is a divalent linear or branched C.sub.1-C.sub.6 alkylene group.

39. A method of preparing the reactive resin system according to claim 26 for construction purposes, the method comprising: combining the reactive resin component (A) and the hardener component (B).

40. A method for chemical fastening of an anchor in a borehole for construction purposes, the method comprising: chemically fastening an anchor in a borehole with the reactive resin system according to claim 26.

Description

EXAMPLES

[0330] In order to determine the influence of mixtures of radically curable compounds as a backbone resin on the viscosity of reactive resins and reactive resin components produced using these mixtures and the influence on the performance of fastening compositions containing these mixtures, mixtures of two or three reactive resins with different structural elements (aromatic, aliphatic) and/or different types of bonds (urethane methacrylate, glycidyl methacrylate) are produced in order to obtain the mixture of radically curable compounds. Reactive resins were obtained by mixing the reactive resins, which then contained the mixture of radically curable compounds as the backbone resin, from which reactive resin components, reactive resin systems and fastening compositions were then prepared and their properties (viscosity, dispensing forces, load values) were examined.

[0331] Reactive resin master batches, reactive resins, reactive resin components and two-component reactive resin systems containing the compounds (IId), (IIc), (VId), (VIIIe), (IIId), (VIIIa) and (IIIe) as the backbone resins were initially used for this purpose. These served as a basis for producing the mixtures according to the invention as the backbone resin. These compounds and the reactive resins, reactive resin components and two-component reactive resin systems produced therewith are also used for comparison, as explained in more detail below.

Compounds (IId), (IIc), (VId), (VIIIe), (IIId), (VIIIa) and (IIIe)

[0332] 1. Production of Reactive Resin Master Batch 1 with Compound (IId)

[0333] 1396 g of hydroxypropyl methacrylate were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft and were mixed with 0.2 g of phenothiazine (D Prills; Allessa Chemie), 0.5 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.4 g of dioctyltin dilaurate (TIB KAT 216; TIB Chemicals). The batch was heated to 70 C. Subsequently, 603 g of methylene di(phenyl isocyanate) (Lupranat MIS; BASF SE) were added dropwise with stirring at 200 rpm for 45 minutes. The mixture was then stirred at 80 C. for a further 45 minutes.

[0334] This produced the reactive resin master batch 1, containing 65 wt. % of the compound (IId) as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch.

[0335] The compound (IId) has the following structure:

##STR00017##

2. Production of Reactive Resin Master Batch 2 with Compound (IIc)

[0336] 1542 g of hydroxypropyl methacrylate were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft and were mixed with 0.24 g of phenothiazine (D Prills; Allessa Chemie), 0.60 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.40 g of dioctyltin dilaurate (TIB KAT 216; TIB Chemicals). The batch was heated to 80 C. Subsequently, 500 g of toluene-2,4-diisocyanate (TCI Deutschland GmbH) were added with stirring at 200 rpm for 45 minutes. The mixture was then stirred at 80 C. for a further 180 minutes.

[0337] This produced the reactive resin master batch 2, containing 65 wt. % of the compound (IIc) as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch.

[0338] The compound (IIc) has the following structure:

##STR00018##

3. Production of Reactive Resin Master Batch 3 with Compound (VId)

[0339] 218 g of hydroxypropyl methacrylate and 669 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG) were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft and were mixed with 0.13 g of phenothiazine (D Prills; Allessa Chemie), 0.37 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH), 0.23 g of dioctyltin dilaurate (TIB KAT 216; TIB Chemicals) and 67 g of trimethylolpropane. The batch was heated to 100 C. Subsequently, 380 g of MDI were added dropwise with stirring at 200 rpm for 70 minutes. The mixture was then stirred at 100 C. for a further 300 minutes. Finally, 666 g of hydroxypropyl methacrylate were added.

[0340] This produced the reactive resin master batch 3, containing the compound (VId) as a backbone resin, hydroxypropyl methacrylate and 1,4-butanediol dimethacrylate in a ratio of 1:1:1.

[0341] The product (compound (VId)) has an oligomer distribution, the oligomer with a repeating unit having the following structure:

##STR00019##

4. Reactive Resin Master Batch 4 with Compound (VIIIe)

[0342] A reactive resin master batch containing 80 wt. % of compound (VIIIe) and 20 wt. % of 1,4-butanediol dimethacrylate, based on the total weight of the reactive resin master batch, is commercially available under the trade name Ecocryl 05345 (bisphenol A diglycidyl ether dimethacrylate; Hexion Inc.).

[0343] The compound (VIIIe) has the following structure:

##STR00020##

5. Production of Reactive Resin Master Batch 5 with Compound (IIIa)

[0344] 1444 g of hydroxypropyl methacrylate were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft and were mixed with 0.23 g of phenothiazine (D Prills; Allessa Chemie), 0.56 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.38 g of dioctyltin dilaurate (TIB KAT 216; TIB Chemicals). The batch was heated to 80 C. Subsequently, 455 g of hexamethylene-1,6-diisocyanate (Sigma Aldrich) were added dropwise with stirring (200 rpm) for 45 minutes. The mixture was then stirred at 80 C. for a further 60 minutes.

[0345] This produced the reactive resin master batch 5, containing 65 wt. % of the compound (IIIa) as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch.

[0346] The compound (IIIa) has the following structure:

##STR00021##

6. Production of Reactive Resin Master Batch 6 with Compound (VIIIa)

[0347] 645 g of 1,4-butanediol diglycidylether (Araldite DY 026 SP; Huntsmann Advanced Materials), 518 g of methacrylic acid (BASF SE), 6.0 g of tetraethylammonium bromide (Merck KGaA Deutschland), 0.23 g of phenothiazine (D Prills; Allessa Chemie) and 0.25 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft. The batch was heated to 100 C. for 240 minutes.

[0348] This produced the reactive resin master batch 6, containing the compound (VIIIa) as a backbone resin. The compound has the following structure:

##STR00022##

7. Production of Reactive Resin Master Batch 7 with Compound (IIIe)

[0349] 1433 g of hydroxypropyl methacrylate were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft and were mixed with 0.21 g of phenothiazine (D Prills; Allessa Chemie), 0.53 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.36 g of dioctytin dilaurate (TIB KAT 216; TIB Chemicals). The batch was heated to 80 C. Subsequently, 566 g of isophorone diisocyanate (Sigma Aldrich) were added dropwise with stirring (200 rpm) for 45 minutes. The mixture was then stirred at 80 C. for a further 120 minutes.

[0350] This produced the reactive resin master batch 7, containing 65 wt. % of the compound (IIIe) as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch.

[0351] The compound (IIIe) has the following structure:

##STR00023##

[0352] From the above reactive resin master batches 1 to 7, reactive resins were produced as follows:

Production of Reactive Resins

8. Reactive Resin 1

[0353] 10.1 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL: Evonik Industries AG) and 38.5 g of di-isopropanol-p-toluidine (BASF SE) were added to a mixture of 1103 g of reactive resin master batch 1, 330 g of hydroxypropyl methacrylate and 717 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

9. Reactive Resin 2

[0354] 301 g of reactive resin master batch 2 were mixed with 91 g of hydroxypropyl methacrylate and 196 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG). 2.75 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 10.5 g of di-iso-propanol-p-toluidine (BASF SE) were added to this mixture.

10. Reactive Resin 3

[0355] 6.0 g of 4-hydroxy-2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 22.8 g of di-isopropanol-p-toluidine (BASF SE) were added to 1271 g of reactive resin master batch 3.

11. Reactive Resin 4

[0356] 9.0 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 40.3 g of di-isopropanol-p-toluidine (BASF SE) were added to a mixture of 937 g of reactive resin master batch 4, 751 g of hydroxypropyl methacrylate and 563 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

12. Reactive Resin 5

[0357] 6.4 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 24.5 g of di-isopropanol-p-toluidine (BASF SE) were added to a mixture of 702 g of reactive resin master batch 5, 210 g of hydroxypropyl methacrylate and 456 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

13. Reactive Resin 6

[0358] 6.5 g of 4-hydroxy-2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 26.25 g of di-isopropanol-p-toluidine (BASF SE) were added to a mixture of 489 g of reactive resin master batch 6, 489 g of hydroxypropyl methacrylate and 489 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

14. Reactive Resin 7

[0359] 3.3 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 14.0 g of di-isopropanol-p-toluidine (BASF SE) were added to a mixture of 401 g of reactive resin master batch 7, 120 g of hydroxypropyl methacrylate and 261 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

[0360] As a result, the reactive resins 1 to 7 were obtained.

Comparative Compounds 1, 2 and 3

[0361] As a further comparison, in particular with the reactive resin master batches, reactive resins, reactive resin components and reactive resin systems containing the mixtures according to the invention as the backbone resin, comparative reactive resin master batches, comparative reactive resins, comparative reactive resin components and comparative two-component reactive resin systems containing comparative compounds 1, 2 and 3 were produced.

15. Production of Comparative Reactive Resin Master Batch 1 with Comparative Compound 1

[0362] 30.9 g of hydroxypropyl methacrylate were provided in a 250 ml laboratory glass flask with an internal thermometer and stirrer shaft and were mixed with 0.018 g of phenothiazine (D Prills; Allessa Chemie), 0.044 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Industries GmbH), 0.032 g of dioctytin dilaurate (TIB KAT216; TIB Chemicals) and 12.69 g of 1,6-hexanediol (TCI Deutschland GmbH). The batch was heated to 80 C. Subsequently, 53.7 g Lupranat MIS (mixture of 2,4- and 4,4-diphenylmethylene diisocyanat (MDI; BASF Polyurethanes GmbH)) were added dropwise with stirring (200 rpm) for 45 minutes. The mixture was then stirred at 80 C. for a further 45 minutes. Subsequently, 52.6 g of hydroxypropyl methacrylate were added.

[0363] This produced the comparative reactive resin master batch 1, containing 65 wt. % of the comparative compound 1 as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch was obtained.

[0364] The comparative compound 1 has the following structure and thus contains structural elements of the compounds (IId) and (IIId):

##STR00024##

16. Production of Comparative Reactive Resin 1

[0365] 2.3 g of 4-hydroxy-2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 8.75 g of di-isopropanol-p-toluidine (BASF SE) were added to 489 g of reactive resin master batch 1.

[0366] As a result, comparative reactive resin 1 was obtained.

17. Production of Comparative Reactive Resin Master Batch 2 with Comparative Compound

[0367] 31 g of hydroxypropyl methacrylate were provided in a 250 ml laboratory glass flask with an internal thermometer and stirrer shaft and were mixed with 0.02 g of phenothiazine, 0.05 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Industries GmbH), 0.04 g of dioctytin dilaurate (TIB KAT 216; TIB Chemicals) and 11.9 g of resorcinol. The batch was heated to 120 C. Subsequently, 54 g Lupranat MIS (mixture of 2,4- and 4,4-diphenylmethylene diisocyanat (MDI; BASF Polyurethanes GmbH)) were added dropwise with stirring (200 rpm) for 45 minutes. The mixture was then stirred at 120 C. for a further 480 minutes. Subsequently, 53 g of hydroxypropyl methacrylate were added.

[0368] This produced the comparative reactive resin master batch 2, containing 65 wt. % of the comparative compound 2 as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch was obtained.

[0369] The comparative compound 2 has the following structure and contains structural elements of the compounds (IId) and (IIc):

##STR00025##

18. Production of Comparative Reactive Resin 2

[0370] 1.2 g of 4-hydroxy-2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 4.6 g of di-isopropanol-p-toluidine (BASF SE) were added to a mixture of 133 g of comparative reactive resin master batch 2, 40 g of hydroxypropyl methacrylate and 86 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

[0371] As a result, comparative reactive resin 2 was obtained.

19. Production of Comparative Reactive Resin Master Batch 3 with Comparative Compound 3

[0372] 191 g of bisphenol A diglycidyl having an average viscosity (Epilox A 19-03; viscosity at 25 C. (DIN 53 015) of 10,000-14,000 mPa.Math.s; LEUNA-Harze GmbH), 49 g of methacrylic acid (BASF SE), 70 g of 1,4-butanediol dimethacrylate (BDDMA; Evonik AG), 38 g of adipic acid, 2.2 g of tetraethylammonium bromide (Merck KGaA Deutschland), 0.05 g of phenothiazine (D Prills; Allessa Chemie) and 0.05 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Industries GmbH) were provided in a 500 ml laboratory glass flask with an internal thermometer and stirrer shaft. The batch was heated to 100 C. for 240 minutes.

[0373] This produced the comparative reactive resin master batch 3, containing 80 wt. % of the comparative compound 3 as a backbone resin and 20 wt. % of 1,4-butanediol dimethacrylate.

[0374] The comparative compound 3 has the following structure and contains structural elements of the compounds (VIIIe) and (VIIIa):

##STR00026##

20. Production of Comparative Reactive Resin 3

[0375] 2.0 g of 4-hydroxy-2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 8.8 g of di-isopropanol-p-toluidine (BASF SE) were added to a mixture of 204 g of comparative reactive resin master batch 3, 163 g of hydroxypropyl methacrylate and 122 g of 1,4-butanediol methacrylate.

[0376] As a result, comparative reactive resin 3 was obtained.

21. Mixtures of Reactive Resins 1 to 7 (Backbone Resins 8-19)

[0377] From the above reactive resins 1 to 7, mixtures were produced to obtain reactive resins each containing a mixture of the radically curable compounds as a backbone resin.

[0378] For mixing the reactive resins, more precisely for the mixing ratio, the following was applied:

[0379] In order to produce a reactive resin mixture which is to be compared with a comparative reactive resin containing a specific comparative compound, the molar ratios of the structural elements of the difunctional starting materials present in the particular comparative compound used to produce the comparative compound were applied. For example, comparative compound 1 (structural elements of compound (IId) and compound (IIId)) contains two methylene di(phenylene) groups and one hexylene group as structural elements. In order to produce a corresponding reactive resin mixture for which a reactive resin is intended to be used as comparison with comparative compound 1, a reactive resin with a compound having a methylene di(phenylene) group as a structural element (reactive resin 1 with compound (IId)) and another reactive resin with a compound having a hexylene group as a structural element (reactive resin 5 with compound (IIId)) were selected. Accordingly, for the mixture of reactive resins 1 and 5 corresponding to the molar ratio of structural elements present in the comparative compound (methylene di(phenylene) group:hexylene group=2:1), a molar ratio of compound (IId) to compound (IIId) (IId:IIId=2:1) for the reactive resin mixture to be compared was also selected. Analogously, comparative mixtures were produced for the other comparative compounds.

[0380] In order to measure the viscosity of reactive resin mixtures, reactive resin components produced therefrom and the dispensing forces of two-component reactive resin systems produced from the reactive resin components, mixtures of reactive resins 1, 2, 4, 5 and 6 were produced at room temperature according to the compositions shown schematically in Table 1. Production was carried out by mixing at least two of the above-mentioned reactive resins in a boiler having a mixer.

TABLE-US-00001 TABLE 1 Schematic composition of the reactive resin mixtures for measuring the viscosity of the reactive resin mixtures, reactive resin components produced therefrom and the dispensing forces of two-component reactive resin systems produced from the reactive resin components Mixture 1 2 3 4 5 6 7 Resulting reactive resin 8 9 10 11 12 13 14 Reactive 1 + 5 1 + 2 4 + 6 1 + 6 4 + 5 1 + 4 + 5 1 + 4 + 6 resins used Compounds IId + IId + VIIIe + IId + VIIIe + IId + IId + IIId IIc VIIIa VIIIa IIId VIIIe + VIIIe + IIId VIIIa Corresponding 1 2 3 1 and 3 1 and 3 1 and 3 1 and 3 comparative compound(s)

[0381] In order to measure the bond strengths of fastening compositions that contain the mixtures according to the invention, mixtures of reactive resins 1, 2, 3, 4, 5, 6 and 7 were produced at room temperature according to the compositions shown schematically in Table 2. Production was carried out by mixing at least two of the above-mentioned reactive resins in a boiler having a mixer.

TABLE-US-00002 TABLE 2 Schematic composition of the reactive resin mixtures for measuring the load values of the mortar compositions of two-component reactive resin systems with the reactive resin mixtures according to the invention Mixture 8 9 10 11 12 Resulting reactive resin 15 16 17 18 19 Reactive resins used 1 + 2 4 + 3 5 + 7 4 + 6 7 + 4 + 6 Compounds IId + VIIIe + IIId + VIIIe + IIIe + IIc VId IIIe VIIIa VIIIe + VIIIa

[0382] These reactive resin mixtures 1 to 12 (also referred to as reactive resins 8 to 19) resulted in the backbone resins 8 to 19, which are present as a mixture of two or three compounds.

22. Production of Reactive Resin Components 1 to 19

[0383] In order to produce the reactive resin components 1 to 7, 354 g in each case of the reactive resins 1 to 7 produced above, and in order to produce the reactive resin components 8 to 19, 354 g in each case of the reactive resin mixtures 1 to 12 produced above, were mixed with 185 g of Secar 80 (Kemeos Inc.), 27 g of Cab-O-Sil TS-720 (Cabot Corporation) and 335 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver under vacuum using a PC laboratory system dissolver of the LDV 0.3-1 type. The mixtures were stirred for 8 minutes at 3500 rpm under vacuum (pressure s 100 mbar) with a 55 mm dissolver disk and an edge scraper.

23. Production of Comparative Reactive Resin Components 1 to 3

[0384] 354 g in each case of comparative reactive resin 1, 2 and 3 were mixed with 185 g of Secar 80 (Kemeos Inc.), 27 g of Cab-O-Sil TS-720 (Cabot Corporation) and 335 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver under vacuum mixed using a PC laboratory dissolver of the LDV 0.3-1 type. The mixtures were stirred for 8 minutes at 3500 rpm under vacuum (pressure 100 mbar) with a 55 mm dissolver disk and an edge scraper.

[0385] The reactive resin components 1 to 19 and comparative reactive resin components 1 to 3 thus produced served as the A component in the production of two-component reactive resin systems.

24. Production of the Two-Component Reactive Resin Systems 1 to 19

[0386] In order to produce the two-component reactive resin systems 1 to 7 containing the reactive resins 1 to 7 and the two-component reactive resin systems 8 to 19 containing the reactive resins 8 to 19 (reactive resin mixtures 1 to 12), the respective reactive resin components (component (A)) and in each case the hardener component (component (B)) of the commercially available product HIT-HY 110 (Hilti Aktiengesellschaft; batch number: 1610264) were filled into plastic cartridges (Ritter GmbH; volume ratio A:B=3:1) with the inner diameters 47 mm (component (A)) or 28 mm (component (B)).

[0387] In order to determine the influence of the backbone resins according to the invention (mixtures of radically curable compounds) on the properties of reactive resins, reactive resin components, two-component reactive resin systems and the cured fastening compositions, in particular the viscosity and the dispensing forces of reactive resin components and two-component reactive resin systems and the bond strengths of cured fastening compositions, the viscosity of reactive resins and reactive resin components, each containing the backbone resins according to the invention, and the dispensing forces of two-component reactive resin systems produced therefrom, and the bond strengths of the cured fastening materials, were measured and compared with the measured values of the formulations containing only a radically curable compound as a backbone resin and of the comparative formulations containing the comparative backbone resins.

Measurement of the Dynamic Viscosity of Reactive Resins 1, 2, 4, 5, 6, 8, 9 and 10 and Comparative Reactive Resins 1, 2 and 3

[0388] The dynamic viscosity of reactive resins 1, 5 and 8 and comparative reactive resin 1 (Table 3), of reactive resins 1, 2 and 9 and comparative reactive resin 2 (Table 4), of reactive resins 4, 6 and 10 and comparative reactive resin 3 (Table 5) was measured using a cone-plate measuring system according to DIN 53019. The diameter of the cone was 60 mm and the opening angle was 1. Measurement was carried out at a constant shear rate of 150/s and a temperature of 23 C. (unless indicated otherwise in the measurement data). The measuring time was 180 s and a measuring point was generated every second. In order to reach the shear rate, a ramp of 0-150/s with a duration of 120 s was connected upstream. Since these are Newtonian liquids, a linear evaluation over the measuring stage was made at a constant shear rate of 150/s over the measuring stage and the viscosity was determined. In each case three measurements were made; the corresponding mean values are indicated in Table 3.

Measurement of the Dynamic Viscosity of Reactive Resin Components 1, 2, 4, 5, 6, 8, 9 and 10 and Comparative Reactive Resin Components 1, 2 and 3

[0389] The dynamic viscosity of reactive resin components 1, 5 and 8 and comparative reactive resin component 1 (Table 3), of reactive resin components 1, 2 and 9 and comparative reactive resin component 2 (Table 4), of reactive resin components 4, 6 and 10 and of comparative reactive resin component 3 (Table 5) was measured using a plate-plate measuring system according to DIN 53019. The diameter of the plate was 20 mm and the gap distance was 3 mm. In order to prevent the sample from leaking out of the gap, a limiting ring made of Teflon and placed at a distance of 1 mm from the top plate was used. The measuring temperature was 25 C. The method consisted of three stages: 1. Low shear, 2. High shear, 3. Low shear. In the first stage, shearing took place for 3 minutes at 0.5/s. In the second stage, the shear rate was increased logarithmically from 0.8/s to 100/s in 8 steps of 15 seconds each. The individual stages in this case were: 0.8/s; 1.724/s; 3.713/s; 8/s; 17.24/s; 37.13/s; 80/s; 100/s. The third stage was a repetition of the first stage. At the end of each stage, the viscosities were read. Tables 3 to 5 show the value of the second stage at 100/s. In each case three measurements were made; the corresponding mean values are indicated in Tables 3 to 5.

Measurement of Dispensing Forces:

[0390] In order to measure the dispensing forces at 25 C., the reactive resin systems were heated to 25 C. The cartridges were ejected on a material testing machine from Zwick with a force transducer (test range up to 10 kN) via a static mixer (mixer HIT-RE-M; Hilti Aktiengesellschaft) at a constant speed of 100 mm/min over a distance of 45 mm and the average force occurring in the process was measured.

[0391] In one example, compositions having urethane methacrylate-based backbone resins were compared with one another. For this purpose, the dynamic viscosity of reactive resin 1 having an aromatic urethane methacrylate as the backbone resin, of reactive resin 5 having an aliphatic urethane methacrylate as the backbone resin and of comparative reactive resin 1 having the comparative compound 1, which contains the structural elements of the two urethane methacrylates, as the backbone resin is compared with the dynamic viscosity of reactive resin 8 (mixture 1 of aromatic and aliphatic urethane methacrylate). Furthermore, the dynamic viscosity of the reactive resin components produced from the above-mentioned reactive resins and the dispensing forces of the corresponding reactive resin systems were compared with one another. The results are shown in Table 3.

TABLE-US-00003 TABLE 3 Results of the measurement of the dynamic viscosity of reactive resins 1, 5 and 8, of comparative reactive resin 1, of the reactive resin components 1, 5 and 8 and comparative reactive resin component 1 produced therefrom and of the dispensing forces of reactive resin systems 1, 5 and 8 and of comparative reactive resin system 1 Dynamic viscosity reactive Dynamic viscosity Dispensing forces resin reactive resin two-component [mPa .Math. s] component [Pa .Math. s] reactive resin Reactive resin used (23 C.) (25 C.) system [N] Reactive resin 1 43 13.6 972 Reactive resin 5 25 11.2 937 Reactive resin 8 35 14.2 910 (Reactive resin mixture 1) Comparative 287 31.4 1748 reactive resin 1

[0392] In another example, compositions having other urethane methacrylate-based backbone resins were compared with one another. For this purpose, the dynamic viscosity of reactive resin 1 having an aromatic urethane methacrylate as the backbone resin, of reactive resin 2 also having an aromatic urethane methacrylate as the backbone resin and of comparative reactive resin 2 having the comparative compound 2, which contains the structural elements of the two urethane methacrylates, as the backbone resin is compared with the dynamic viscosity of reactive resin 9 (mixture 2 of two aromatic urethane methacrylates). Furthermore, the dynamic viscosity of the reactive resin components produced from the above-mentioned reactive resins and the dispensing forces of the corresponding reactive resin systems were compared with one another.

[0393] The results are shown in Table 4.

TABLE-US-00004 TABLE 4 Results of the measurement of the dynamic viscosity of reactive resins 1, 2 and 9, of comparative reactive resin 2, of the reactive resin components 1, 2 and 9 and comparative reactive resin component 2 produced therefrom and of the dispensing forces of reactive resin systems 1, 2 and 9 and of comparative reactive resin system 2 Dynamic viscosity Dispensing force Dynamic viscosity reactive resin two-component Reactive reactive resin component [Pa .Math. s] reactive resin resin used [mPa .Math. s] (23 C.) (25 C.) system [N] Reactive 43 13.6 972 resin 1 Reactive 39 10.8 1036 resin 2 Reactive 40 11.2 855 resin 9 (Reactive resin mixture 2) Comparative 173 18.6 912 reactive resin 2

[0394] In another example, compositions having glycidyl methacrylate-based backbone resins were compared with one another. For this purpose, the dynamic viscosity of reactive resin 4 having an aromatic glycidyl methacrylate as the backbone resin, of reactive resin 6 having an aliphatic glycidyl methacrylate as the backbone resin and of comparative reactive resin 3 having the comparative compound 3, which contains the structural elements of the two glycidyl methacrylates, as the backbone resin is compared with the dynamic viscosity of reactive resin 10 (mixture 3 of aromatic and aliphatic glycidyl methacrylate). Furthermore, the dynamic viscosity of the reactive resin components produced from the above-mentioned reactive resins and the dispensing forces of the corresponding reactive resin systems were compared with one another. The results are shown in Table 5.

TABLE-US-00005 TABLE 5 Results of the measurement of the dynamic viscosity of reactive resins 4, 6 and 10, of comparative reactive resin 3, of the reactive resin components 4, 6 and 10 and comparative reactive resin component 3 produced therefrom and of the dispensing forces of reactive resin systems 4, 6, 10 and of comparative reactive resin system 3 Dynamic viscosity Dispensing force Dynamic viscosity reactive resin two-component Reactive resin reactive resin component [Pa .Math. s] reactive resin used [mPa .Math. s] (23 C.) (25 C.) system [N] Reactive resin 4 45 12.1 1035 Reactive resin 6 22 9.3 785 Reactive resin 10 33 12.6 844 (Reactive resin mixture 3) Comparative 151 20.1 1240 reactive resin 3

[0395] In another example, reactive resin components having a glycidyl methacrylate-based backbone resin and a urethane methacrylate-based backbone resin were compared with one another. For this purpose, the dispensing forces of reactive resin system 1 having an aromatic urethane methacrylate as the backbone resin, of reactive resin system 6 having an aliphatic glycidyl methacrylate as the backbone resin and of comparative reactive resin systems 1 and 3 having comparative compounds 1 and 3, respectively, as the backbone resin were compared with the dispensing force of reactive resin system 11 (mixture 4 of aromatic and aliphatic glycidyl methacrylate as the backbone resin). Furthermore, the dispensing forces of reactive resin system 4 having an aromatic glycidyl methacrylate as the backbone resin, of reactive resin system 5 having a urethane methacrylate as the backbone resin and of comparative reactive resin systems 1 and 3 having comparative compounds 1 and 3, respectively, as the backbone resin were compared with the dispensing force of reactive resin system 12 (mixture 5 of aromatic glycidyl methacrylate and an aliphatic urethane methacrylate). The results are shown in Table 6.

TABLE-US-00006 TABLE 6 Results of the measurement of the dispensing forces of the reactive resin systems 1, 4, 5, 6, 11 and 12 and of the comparative reactive resin systems 1 and 3 Dispensing Dispensing force two- force two- component component Reactive resin reactive resin Reactive resin reactive resin used system [N] used system [N] Reactive resin 1 972 Reactive resin 4 1035 Reactive resin 6 785 Reactive resin 5 937 Reactive resin 11 945 Reactive resin 12 920 (Reactive resin (Reactive resin mixture 4) mixture 5) Comparative 1748 Comparative 1748 reactive resin 1 reactive resin 1 Comparative 1240 Comparative 1240 reactive resin 3 reactive resin 3

[0396] In another example, the dispensing forces of compositions having a glycidyl methacrylate-based backbone resin and a urethane methacrylate-based backbone resin were compared with one another. For this purpose, on the one hand the dispensing force of reactive resin system 1 with an aromatic urethane methacrylate as the backbone resin, of reactive resin system 4 with an aromatic gycidyl methacrylate as the backbone resin, of reactive resin system 5 with an aliphatic urethane methacrylate as the backbone resin and of comparative reactive resin systems 1 and 3 are compared with comparative compounds 1 and 3, respectively, as the backbone resin is compared with the dispensing force of reactive resin system 13 (mixture 6 of aromatic and aliphatic urethane methacrylate and aromatic glycidyl methacrylate). Furthermore, the dispensing force of reactive resin system 1 having an aromatic urethane methacrylate as the backbone resin, of reactive resin system 4 having an aromatic glycidyl methacrylate as the backbone resin, of reactive resin system 6 having an aliphatic glycidyl methacrylate as the backbone resin and of comparative reactive resin systems 1 and 3 having comparative compounds 1 and 3, respectively, as the backbone resin is compared with the dispensing force of reactive resin system 14 (mixture 7 of aromatic and aliphatic glycidyl methacrylate and aromatic urethane methacrylate). The results are shown in Table 7.

TABLE-US-00007 TABLE 7 Results of the measurement of the dispensing forces of the reactive resin systems 1, 4, 5, 6, 13 and 14 and of the comparative reactive resin systems 1 and 3 Dispensing Dispensing force two- force two- component component Reactive resin reactive resin Reactive resin reactive resin used system [N] used system [N] Reactive resin 1 972 Reactive resin 1 972 Reactive resin 4 1035 Reactive resin 4 1035 Reactive resin 5 937 Reactive resin 6 785 Reactive resin 13 897 Reactive resin 14 828 (Reactive resin (Reactive resin mixture 6) mixture 7) Comparative 1748 Comparative 1748 reactive resin 1 reactive resin 1 Comparative 1240 Comparative 1240 reactive resin 3 reactive resin 3

[0397] The results show a significant reduction in the viscosity of the reactive resin components and a reduction in the dispensing forces of the two-component reactive resin systems, which each contain a mixture of low-viscosity compounds according to the invention as the backbone resin, compared with the viscosity of the reactive resin components and the dispensing forces of the two-component reactive resin systems, which contain the comparative compounds and only one compound as the backbone resin. In particular, a mixture of an aromatic urethane methacrylate compound and an aliphatic urethane methacrylate compound results in a significant reduction in the dispensing force of the two-component reactive resin system containing this mixture as the backbone resin, compared with the dispensing force of the two-component reactive resin system containing the corresponding comparative compound as the backbone resin.

Measurement of Bond Strength

[0398] In order to measure the bond strength (load values) of the cured fastening compositions, M12 anchor threaded rods were inserted into boreholes in C20/25 concrete having a diameter of 14 mm and a borehole depth of 72 mm, which boreholes were filled with the reaction resin mortar compositions. The bond strength was determined by centric extension of the anchor threaded rods. In each case, five anchor threaded rods were placed and after 24 hours of curing, the bond strength was determined. In this case the commercially available product Hilti HIT-HY 110 (Hilti Aktiengesellschaft) served as a comparison. The fastening compositions were ejected out of the cartridges via a static mixer (HIT-RE-M mixer Hilti Aktiengesellschaft) and injected into the boreholes.

[0399] The bond strength was measured under the following borehole conditions:

A1: It is a cleaned, dust-free, dry, hammer-drilled borehole. Placing, curing and extending take place at room temperature. The temperature of the two-component reactive resin system or the fastening composition is 20 C. when setting.

[0400] In the following, the bond strengths of fastening compositions containing the backbone resins according to the invention (mixture of two or three radically curable compounds) are compared with the bond strengths of fastening compositions containing the corresponding radically curable compound as a single compound as the backbone resin, and with the bond strengths of the commercially available product Hilti HIT-HY 110. In order to show that the influence of the backbone resins according to the invention on the bond strengths of a fastening composition containing said resins is not additively composed of the backbone resins, which in each case comprise only one radically curable compound, theoretical bond strengths were calculated for the mixtures of the bond strengths of the fastening compositions having the backbone resins, each comprising only a radically curable compound.

[0401] In one example, fastening compositions having two urethane methacrylate-based backbone resins were compared with one another. For this purpose, the bond strength of fastening composition 1 having an aromatic urethane methacrylate as the backbone resin, of fastening composition 2 having another aromatic urethane methacrylate as the backbone resin and of Hilti HIT-HY 110 was compared with the bond strength of fastening composition 15 (mixture 8 of aromatic urethane methacrylates). The results are shown in Table 8. Table 8 also shows the mean bond strength calculated from the bond strengths of fastening compositions 1 and 2 (theoretical bond strength 1+2=mean value of bond strength 1 and bond strength 2).

TABLE-US-00008 TABLE 8 Results of the measurement of the bond strength of fastening compositions 1, 2, 15 and of Hilti HIT-HY 110 as well as the theoretical bond strength 1 + 2 Bond strength [N/mm.sup.2] Fastening composition 1 20.1 Fastening composition 2 20.1 Fastening composition 15 21.4 Theoretical bond strength 1 + 2 20.1 Hilti HIT-HY 110 20.7

[0402] In another example, fastening compositions having two urethane methacrylate-based backbone resins were compared with one another. For this purpose, the bond strength of fastening composition 4 having an aromatic urethane methacrylate as the backbone resin, of fastening composition 3 having a branched aromatic urethane methacrylate as the backbone resin and of Hilti HIT-HY 110 was compared with the bond strength of fastening composition 16 (mixture 9 of two aromatic urethane methacrylates). The results are shown in Table 9. Table 9 also shows the mean bond strength calculated from the bond strengths of fastening compositions 3 and 4 (theoretical bond strength 3+4=mean value of bond strength 3 and bond strength 4).

TABLE-US-00009 TABLE 9 Results of the measurement of the bond strength of fastening compositions 4, 3, 16 and of Hilti HIT-HY 110 as well as the theoretical bond strength 3 + 4 Bond strength [N/mm.sup.2] Fastening composition 4 17.5 Fastening composition 3 22.0 Fastening composition 16 22.8 Theoretical bond strength 3 + 4 19.8 HIT-HY 110 20.7

[0403] In another example, fastening compositions having two urethane methacrylate-based backbone resins were compared with one another. For this purpose, the bond strength of fastening composition 7 having a cycloaliphatic urethane methacrylate as the backbone resin, of fastening composition 5 having a linear aliphatic urethane methacrylate as the backbone resin and of Hiti HIT-HY 110 was compared with the bond strength of fastening composition 17 (mixture 10 of a cycloaliphatic and a linear aliphatic urethane methacrlate). The results are shown in Table 10. Table 10 also shows the mean bond strength calculated from the bond strengths of fastening compositions 5 and 7 (theoretical bond strength 5+7=mean value of bond strength 5 and bond strength 7).

TABLE-US-00010 TABLE 10 Results of the measurement of the bond strength of fastening compositions 7, 5, 17 and of Hilti HIT-HY 110 as well as the theoretical bond strength 5 + 7 Bond strength [N/mm.sup.2] Fastening composition 7 14.9 Fastening composition 5 14.2 Fastening composition 17 16.9 Theoretical bond strength 5 + 7 14.6 HIT-HY 110 20.7

[0404] In another example, fastening compositions having two glycidyl methacrylate-based backbone resins were compared with one another. For this purpose, the bond strength of fastening composition 4 having an aromatic glycidyl methacrylate as the backbone resin, of fastening composition 6 having a linear aliphatic glycidyl methacrylate as the backbone resin and of Hilti HIT-HY 110 was compared with the bond strength of fastening composition 18 (mixture 11 of anaromatic and a linear aliphatic glycidyl methacrylate). The results are shown in Table 11. Table 11 also shows the mean bond strength calculated from the bond strengths of fastening compositions 4 and 6 (theoretical bond strength 4+6=mean value of bond strength 4 and bond strength 6).

TABLE-US-00011 TABLE 11 Results of the measurement of the bond strengths of fastening compositions 4, 6, 18 and of Hilti HIT-HY 110 as well as the theoretical bond strength 4 + 6 Bond strength [N/mm.sup.2] Fastening composition 4 15.5 Fastening composition 6 9.7 Fastening composition 18 17.4 Theoretical bond strength 4 + 6 12.6 Hilti HIT-HY 110 20.7

[0405] In another example, fastening compositions having two gycidyl methacrylate-based backbone resins and one urethane methacrylate-based backbone resin were compared with one another. For this purpose, the bond strength of fastening composition 4 having an aromatic gycidyl methacrylate as the backbone resin, of fastening composition 6 having a linear aliphatic gycidyl methacrylate as the backbone resin, of fastening composition 6 having a cycloaliphatic urethane methacrylate as the backbone resin and of Hilti HIT-HY 110 was compared with the bond strength of fastening composition 19 (mixture 19 of an aromatic and a linear aliphatic glycidyl methacrylate and a cycloaliphatic urethane methacrylate). The results are shown in Table 12. Table 12 also shows the mean bond strength calculated from the bond strengths of fastening compositions 4, 6 and 7 (theoretical bond strength 4+6+7=mean value of bond strength 4, bond strength 6 and bond strength 7).

TABLE-US-00012 TABLE 12 Results of the measurement of the bond strengths of fastening compositions 7, 4, 6, 19 and of Hilti HIT-HY 110 as well as the theoretical bond strength 4 + 6 + 7 Bond strength [N/mm.sup.2] Fastening composition 7 14.9 Fastening composition 4 17.1 Fastening composition 6 10.4 Fastening composition 19 15.9 Theoretical bond strength 4 + 6 + 7 14.1 Hilti HIT-HY 110 20.7

[0406] The results show that the bond strengths of cured fastening compositions which each contain a mixture of two radically curable compounds as the backbone resin are higher than the bond strength of the cured comparative fastening composition from Hilti HIT-HY 110.

[0407] Furthermore, it can be seen from the tables that the theoretical bond strengths are lower than the bond strengths of cured fastening compositions which each contain a mixture of two radically curable compounds as the backbone resin. This demonstrates the synergistic effect of the backbone resins according to the invention, i.e. the mixtures according to the invention of at least two radically curable compounds.