EPOXY METHACRYLATE COMPOUNDS AND USE THEREOF

Abstract

Low-viscosity epoxy methacrylate compounds are useful for lowering the viscosity of reactive resins and for reducing the forces for extruding a reactive-resin component containing these compounds. Furthermore, the low-viscosity epoxy methacrylate compounds are useful for chemical fastening.

Claims

1. A compound of the general formula (1) ##STR00011## in which m is a whole number greater than or equal to 2, and B is a linear, branched or cyclic aliphatic hydrocarbon group.

2. The compound according to claim 1, wherein the aliphatic hydrocarbon group B is substituted.

3. The compound according to claim 2, wherein the aliphatic hydrocarbon group B is hydroxy-substituted.

4. The compound according to claim 1, wherein the aliphatic hydrocarbon group is a linear or branched C.sub.2-C.sub.12 alkylene group.

5. The compound according to claim 4, wherein the aliphatic hydrocarbon group is a linear or branched C.sub.2-C.sub.8 alkylene group.

6. The compound according to claim 1, wherein m is 2 or 3 and the aliphatic hydrocarbon group is a linear or branched C.sub.2-C.sub.8 alkylene group.

7. A method of construction, comprising: incorporating the compound according to claim 1 in a reactive resin or a reactive-resin component.

8. A method of lowering a viscosity in a reactive-resin component for construction purposes, the method comprising: incorporating the compound of claim 1 in a reactive-resin component for construction purposes in need thereof.

9. A method of reducing a force for extruding a reactive-resin component or a reactive-resin system, the method comprising: incorporating the compound according to claim 1 in a reactive-resin component or a reactive-resin system in need thereof.

10. A reactive resin, comprising: the compound according to claim 1, an inhibitor, an accelerator, and optionally a reactive diluent.

11. A reactive-resin component, comprising: the reactive resin according to claim 10.

12. A reactive-resin system, comprising: the reactive-resin component according to claim 11 and a hardener component.

13. The reactive-resin system according to claim 12, wherein the reactive-resin component and/or the hardener component contains at least one inorganic filler and/or an inorganic additive.

14. (canceled)

15. (canceled)

16. A method of construction with the reactive resin according to claim 10, the method comprising: combining at least the compound, the inhibitor, and the accelerator, thereby obtaining the reactive resin, and applying the reactive resin for construction.

17. A method of construction with the reactive-resin system according to claim 12, the method comprising: combining the reactive-resin component and the hardener component, thereby obtaining the reactive-resin system, and applying the reactive-resin system for construction.

18. A method for chemically fastening an anchor in a drilled hole with the reactive resin according to claim 10, the method comprising: combining at least the compound, the inhibitor, and the accelerator, thereby obtaining the reactive resin, and chemically fastening the anchor in the drilled hole with the reactive resin.

19. A method for chemically fastening an anchor in a drilled hole with the reactive-resin system according to claim 12, the method comprising: combining the reactive-resin component and the hardener component, thereby obtaining the reactive-resin system, and chemically fastening the anchor in the drilled hole with the reactive-resin system.

Description

EXAMPLES

[0198] Reactive-resin master batches, reactive resins, reactive-resin components and two-component reactive-resin systems were produced as backbone resin using compounds (II) and (VI). The dynamic viscosity of the reactive resins and of the reactive-resin components were determined, as were the forces for extruding the two-component reactive-resin systems.

A1. Production of Reactive-Resin Master Batch A1 with Compound (II)

[0199] 645 g 1,4-Butanediol diglycidyl ether (Araldite DY 026 SP; Huntsmann Advanced Materials), 518 g methacrylic acid (BASF SE), 6.0 g tetraethylammonium bromide (Merck KGaA Germany), 0.23 g phenothiazine (D Prills; Allessa Chemie) and 0.25 g 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-l-oxyl (TEMPOL; Evonik Industries AG) were introduced into a 2-liter glass laboratory reactor with internal thermometer and stirrer shaft. The batch was heated for 240 minutes at 100 C.

[0200] Hereby reactive-resin master batch A1 and containing the compound (II) as backbone resin was obtained. Compound (II) has the following structure:

##STR00008##

A2. Production of Reactive Resin A2

[0201] 6.5 g 4-Hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 26.25 g di-iso-propanol-p-toluidine (BASF SE) were added to a mixture of 489 g reactive-resin master batch A1, 489 g hydroxypropyl methacrylate and 489 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

[0202] Hereby reactive resin A2 containing compound (II) as backbone resin was obtained.

A3. Production of Reactive-Resin Component A3

[0203] 354 g Reactive resin A2 was mixed with 185 g Secar 80 (Kerneos Inc.), 27 g CAB-O-SIL TS-720 (Cabot Corporation) and 335 g quartz sand F32 (Quarzwerke GmbH) in the dissolver under vacuum, using a PC Labor System Dissolver of LDV 0.3-1 type. The caulk was stirred decentrally for 8 minutes at 3500 rpm under vacuum (p5. 100 mbar) with a 55 mm dissolver disk and an edge scraper.

[0204] Hereby reactive-resin component A3 was obtained.

B1. Production of Reactive-Resin Master Batch B1 with Compound (VI)

[0205] 840 g Trimethylolpropane triglycidyl ether, 742 g methacrylic acid, 17.5 g tetraethylammonium bromide, 0.33 g phenothiazine (D Prills; Allessa Chemie) and 0.36 g 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) were introduced into a 2-liter glass laboratory reactor with internal thermometer and stirrer shaft. The batch was heated for 300 minutes at 100 C. Then 400 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG) was added.

[0206] Hereby reactive-resin master batch B1 containing compound (VI) as backbone resin was obtained. Compound (VI) has the following structure:

##STR00009##

B2. Production of Reactive Resin B2

[0207] 6.0 g 4-Hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 22.8 g di-iso-propanol-p-toluidine (BASF SE) were added to a mixture of 530 g reactive-resin master batch B1, 424 g hydroxypropyl methacrylate and 318 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

[0208] Hereby reactive-resin B2 containing compound (VI) as backbone resin was obtained.

B3. Production of Reactive-Resin Component B3

[0209] 354 g Reactive resin B2 was mixed with 185 g Secar 80 (Kerneos Inc.), 27 g CAB-O-SIL TS-720 (Cabot Corporation) and 335 g quartz sand F32 (Quarzwerke GmbH) in the dissolver under vacuum, using a PC Labor System Dissolver of LDV 0.3-1 type, as indicated under heading A3.

[0210] Hereby reactive-resin component B3 was obtained.

C1. Production of Comparison Reactive-Resin Master Batch with Comparison Compound 1

[0211] Comparison reactive-resin master batch C1 containing comparison compound 1 as backbone resin was synthesized according to the method in EP 0 713 015 A1, which is included herewith as reference and to the entire disclosure of which reference is made.

[0212] Hereby comparison reactive-resin master batch C1 containing 65 wt % comparison compound 1 as backbone resin and 35 wt % hydroxypropyl methacrylate, relative to the total weight of the comparison reactive-resin master batch, was obtained.

[0213] The product (comparison compound 1) has an oligomer distribution, wherein the oligomer containing a repeat unit has the following structure:

##STR00010##

C2. Production of Comparison Reactive Resin C2

[0214] 9.2 g 4-Hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Industries AG) and 35.0 g di-iso-propanol-p-toluidine (BASF SE) were added to a mixture of 1004 g comparison reactive-resin master batch C1, 300 g hydroxypropyl methacrylate and 652 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG).

[0215] Hereby comparison reactive-resin C2 containing the comparison compound 1 as backbone resin was obtained.

C3. Production of Comparison Reactive-Resin Component C3

[0216] 354 g Comparison reactive resin C2 was mixed with 185 g Secar 80 (Kerneos Inc.), 27 g CAB-O-SIL TS-720 (Cabot Corporation) and 335 g quartz sand F32 (Quarzwerke GmbH) in the dissolver under vacuum, using a PC Labor System Dissolver of LDV 0.3-1 type, as indicated under heading A3.

[0217] Hereby comparison reactive-resin component C3 was obtained.

[0218] In order to demonstrate the influence of compounds (II) and (VI) on the viscosity of a reactive-resin master batch containing these compounds, of a reactive resin and of a reactive-resin component, the viscosity of the inventive reactive-resin component as well as the forces for extruding two-component reactive-resin systems were measured and respectively compared with the comparison reactive-resin component and the comparison two-component reactive-resin system.

Measurement of the Dynamic Viscosity of the Reactive Resins

[0219] The dynamic viscosity of reactive resins A2 and B2 and of comparison reactive resin C2 was measured with a cone-and-plate measuring system according to DIN 53019. The diameter of the cone was 60 mm and the opening angle was 1. The measurement was performed at a constant shear velocity of 150/s and a temperature of 23 C. (unless otherwise specified for the measured data). The measurement duration was 180 s and one measured point was generated every second. The shear velocity was attained by a preceding ramp from 0 to 150/s over a duration of 120 s. Since Newtonian fluids are involved, a linear evaluation over the measurement portion was undertaken and the viscosity was determined with constant shear velocity of 150/s over the measurement portion. Respectively three measurements were made, wherein the values indicated in Table 1 are the mean values of the three measurements.

Measurement of the Dynamic Viscosity of the Reactive-Resin Components

[0220] The dynamic viscosity of reactive-resin components A3 and B3 and of comparison reactive-resin component C3 was measured with a cone-and-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 escape of the sample from the gap, a limiting ring of Teflon having a distance of 1 mm from the upper plate was used. The measurement temperature was 25 C. The method consisted of three portions: 1st Low shear, 2nd High shear, 3rd Low shear. During the 1st portion, shear was applied for 3 minutes at 0.5/s. In the 2nd portion, the shear velocity was increased logarithmically from 0.8/s to 100/s in 8 stages of 15 seconds each. These individual stages were: 0.8/s; 1.724/s; 3.713/s; 8/s; 17.24/s; 37.13/s; 80/s; 100/s. The 3rd portion was a repetition of the 1st portion. The viscosities were read at the end of each portion. The values summarized in Table 2 correspond to the value of the second portion at 100/s. Respectively three measurements were made, wherein the values indicated in Table 2 are the mean values of the three measurements.

Measurement of the Forces for Extruding the Two-Component Reactive-Resin Systems

[0221] For determination of the extrusion forces at 0 C. and 25 C., the reactive-resin components (component (A)) and the hardener component (component (B)), produced as in the foregoing, of the commercially available product HIT-HY 110 (Hilti Aktiengesellschaft; batch number: 1610264) were filled into plastic canisters (Ritter GmbH; volume ratio A:B=3:1) with inside diameters of approximately 47 mm (component (A)) and respectively approximately 28 mm (component (B)) and adjusted to temperatures of 0 C. and 25 C. respectively. Using a material-testing machine of the Zwick Co. with a load cell (test range up to 10 kN), the canisters were extruded via a static mixer (HIT-RE-M mixer; Hilti Aktiengesellschaft) by with a constant speed of 100 mm/min over a path of 45 mm and in the process the mean force developed was measured.

[0222] The dynamic viscosity of reactive resins A2 and B2 was compared with the dynamic viscosity of comparison reactive resin C2. The results are compiled in Table 1.

TABLE-US-00001 TABLE 1 Results of measurement of the dynamic viscosity of reactive resins A2 and B2 and of comparison reactive resin C2 Comparison Reactive Reactive reactive resin A2 resin B2 resin C2 Viscosity 22 28 70 [mPa .Math. s]

[0223] From the values in Table 1, it is evident that reactive resins A2 and B2, which contain the inventive compounds (II) and (IV) as backbone resin, have a much lower dynamic viscosity compared with the dynamic viscosity of the comparison resin C2, which contains comparison compound 1 as backbone resin.

[0224] The dynamic viscosity of reactive-resin components A3 and B3 was compared with the dynamic viscosity of comparison reactive-resin component C3. The measured values are summarized in Table 2.

TABLE-US-00002 TABLE 2 Results of the measurement of the dynamic viscosity of reactive-resin components A3 and B3 and of comparison reactive-resin component C3 Comparison Reactive resin Reactive resin reactive resin component A3 component B3 component C3 Viscosity 11.3 12.2 13.9 [mPa .Math. s]

[0225] The values in Table 2 show that reactive-resin components A3 and B3 produced from reactive resins A2 and B2 also have a low dynamic viscosity compared with the dynamic viscosity of comparison component C3 from comparison reactive resin C2.

[0226] The forces for extruding two-component reactive-resin systems containing the inventive reactive-resin components A3 and B4 were compared with the force for extruding the comparison two-component reactive-resin system, which contains comparison reactive-resin component C3. The values measured at 0 C. and at 25 C. are summarized in Table 3.

TABLE-US-00003 TABLE 3 Forces at 0 C. and at 25 C. for extruding two-component reactive-resin systems containing reactive-resin components A3 and B3 and the comparison two-component reactive-resin system, which contains comparison reactive-resin component C3 Comparison reactive resin Reactive resin Reactive resin system with system with system with comparison reactive-resin reactive-resin reactive-resin component A3 component B3 component C3 Force at 0 C. [N] 1203 1270 1631 Force at 25 C. [N] 843 959 1151

[0227] The results in Table 3 show that the two-component reactive-resin systems, which contain the inventive compounds (II) and (VI) as backbone resins, exhibit much lower extrusion forces at 25 C. and also at 0 C. than does the comparison two-component reactive-resin system, which contains comparison compound 1 as backbone resin.