Use of urethane methacrylate compounds in reactive resin compositions

Abstract

Low-viscosity urethane methacrylate compounds can be used in a reactive resin component to improve the thixotropic properties of the reactive resin component and/or the afterflow behavior of a reactive resin system containing the reactive resin component.

Claims

1: A reactive resin component for chemical fastening, comprising: a compound of the general formula (I) ##STR00014## wherein B is (i) a divalent aromatic hydrocarbon group, (ii) a divalent aromatic-aliphatic hydrocarbon group, or (iii) a divalent linear, branched or cyclic aliphatic hydrocarbon group, or an aliphatic hydrocarbon group comprising a cycloaliphatic moiety, and wherein each R.sub.1 is independently a branched or linear aliphatic C.sub.1-C.sub.15 alkylene group.

2: The reactive resin component according to claim 1, wherein B is an aromatic C.sub.6-C.sub.20 carbon group.

3: The reactive resin component according to claim 1, wherein B is (i) an optionally substituted benzene ring, two optionally substituted fused benzene rings or two optionally substituted benzene rings which are bridged via an alkylene group.

4: The reactive resin component according to claim 1, wherein B is (ii) a divalent aromatic-aliphatic hydrocarbon group of formula (Z) ##STR00015## in which R.sub.2 is a divalent branched or linear aliphatic C.sub.1-C.sub.6 alkylene group.

5: The reactive resin component according to claim 1, wherein B is (iii) a divalent linear or branched aliphatic C.sub.5-C.sub.8 hydrocarbon group.

6: The reactive resin component according to claim 1, wherein B is (iii) an aliphatic hydrocarbon group (Y) comprising a cycloaliphatic moiety, ##STR00016## in which R.sub.2 is a divalent branched or linear aliphatic C.sub.1-C.sub.6 alkylene group.

7: The reactive resin component according to claim 1, wherein the compound of general formula (I) is a compound of formula (II), (III) or (IV) ##STR00017## wherein each R.sub.1 is independently a branched or linear aliphatic C.sub.1-C.sub.15 alkylene group.

8: The reactive resin component according to claim 1, wherein R.sub.1 is a C.sub.2- or C.sub.3-alkylene group.

9: The reactive resin component according to claim 1, wherein the compound of general formula (I) is a compound of formula (V), (VI) or (VII) ##STR00018##

10: The reactive resin component according to claim 1, wherein the reactive resin component comprises at least one inhibitor, at least one accelerator, and optionally at least one reactive diluent.

11: The reactive resin component according to claim 10, wherein the reactive resin component further comprises an organic and/or inorganic filler and/or additive.

12: The reactive resin component according to claim 1, wherein a proportion of the compound of general formula (I) in the reactive resin component is about 2.5 wt. % to about 45 wt. %, based on the reactive resin component.

13: A two-component system, comprising the reactive resin component according to claim 1.

14: A multi-component system, comprising the reactive resin component according to claim 1.

15: A method, comprising: preparing the reactive resin component according to claim 1.

Description

EXAMPLES

[0231] First, reactive resin components and two-component reactive resin systems each containing the compound (V), (VI) or (VII) as a backbone resin were prepared. The dynamic viscosity of the reactive resin components and the rheological behavior of the reactive resin components during and after increased shear were investigated. Furthermore, on a two-component reactive resin system, the amounts of afterflowing material were determined.

[0232] Compound (V)

[0233] A1. Preparation of the Reactive Resin Masterbatch A1 with Compound (V)

[0234] 1419 g of hydroxypropyl methacrylate were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft and were mixed with 0.22 g of phenothiazine (D Prills; Allessa Chemie), 0.54 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.36 g of dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals). The batch was heated to 80° C. Subsequently, 490 g of m-xylene diisocyanate (TCI Europe) were added dropwise while stirring (200 rpm) over 45 minutes. The mixture was then stirred at 80° C. for a further 120 minutes. This produced the reactive resin master batch A1, containing 65 wt. % of the compound (V) as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch.

[0235] The compound (V) has the following structure:

##STR00010##

[0236] From the reactive resin masterbatch A1, a reactive resin A2 was prepared having a compound (V) as a backbone resin.

[0237] A2. Preparation of the Reactive Resin A2

[0238] 1.08 g of catechol (Catechol flakes; RHODIA), 0.36 g tert-butylpyrocatechol (TBC shed, RHODIA) and 9.2 g di-isopropanol-p-toluidine (BASF SE) were dissolved in a mixture of 160.0 g 1,4-butanediol dimethacrylate (Visiomer 1,4-BDDMA; Evonik Degussa GmbH) and 229.2 g of reactive resin masterbatch from A1.

[0239] From the reactive resin A2, a reactive resin component A3 was prepared having compound (V) as a backbone resin.

[0240] A3. Preparation of the Reactive Resin Component A3

[0241] 310.5 g of reactive resin A2 are mixed under vacuum with 166.5 g of Secar® 80 (Kemeos Inc.), 9.0 g of Cab-OSil® TS-720 (Cabot Corporation), 16.2 g of Aerosil® R 812 (Evonik Industries AG), and 397.8 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver with a PC laboratory system dissolver type LDV 0.3-1. The mixture was stirred for 2 minutes at 2500 rpm.Math.min.sup.−1, and then for 10 minutes at 4500 rpm.Math.min.sup.−1 under vacuum (pressure 5100 mbar) with a 55 mm dissolver disc and an edge scraper. As a result, the reactive resin component A3 was obtained.

[0242] A4. Preparation of the Two-Component Reactive Resin System A4

[0243] For the preparation of the two-component reactive resin system A4, the reactive resin component A3 (component (A)) and the hardener component (component (B)) of the commercially available product HIT HY 200 (Hilti Aktiengesellschaft, lot number: 8107090) were filled in a plastic cartridge (Ritter GmbH Volume ratio A:B=5:1) having the inner diameters of 32.5 mm (component (A)) and 14 mm (component (B)). As a result, the two-component reactive resin system A4 (for the measurement of the afterflow behavior) was obtained.

[0244] Compound (VI)

[0245] B1. Preparation of Reactive Resin Masterbatch B1 with Compound (VI)

[0246] 1179 g of hydroxypropyl methacrylate were provided in a 2 liter laboratory glass reactor with an internal thermometer and stirrer shaft and were mixed with 0.17 g of phenothiazine (D Prills; Allessa Chemie), 0.43 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 0.29 g of dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals). The batch was heated to 80° C. Subsequently, 500 g of 1,3-bis(2-isocyanato-2-propyl)benzene (TCI Europe) were added dropwise with stirring (200 rpm) over 45 minutes. The mixture was then stirred at 80° C. for a further 120 minutes. This produced the reactive resin master batch B1, containing 65 wt. % of the compound (VI) as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch.

[0247] The compound (VI) has the following structure:

##STR00011##

[0248] From the reactive resin masterbatch B1, a reactive resin B2 was prepared having a compound (VI) as a backbone resin.

[0249] B2. Preparation of the Reactive Resin 12

[0250] 1.08 g of catechol (Catechol flakes; RHODIA), 0.36 g tert-butylpyrocatechol (TBC shed, RHODIA) and 9.2 g di-isopropanol-p-toluidine (BASF SE) were dissolved in a mixture of 160.0 g 1,4-butanediol dimethacrylate (Visiomer 1,4-BDDMA; Evonik Degussa GmbH) and 229.2 g of reactive resin masterbatch from B1.

[0251] From the reactive resin B2, a reactive resin component B3 was prepared having compound (VI) as a backbone resin.

[0252] B3. Preparation of the Reactive Resin Component B3

[0253] 310.5 g of reactive resin B2 are mixed under vacuum with 166.5 g of Secar®80 (Kemeos Inc.), 9.0 g of Cab-OSil® TS-720 (Cabot Corporation), 16.2 g of Aerosil® R 812 (Evonik Industries AG), and 397.8 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver with a PC laboratory system dissolver type LDV 0.3-1. The mixture was stirred for 2 minutes at 2500 rpm.Math.min.sup.−1, and then for 10 minutes at 4500 rpm.Math.min.sup.−1 under vacuum (pressure 5100 mbar) with a 55 mm dissolver disc and an edge scraper. As a result, the reactive resin component B3 was obtained.

[0254] B4. Preparation of the Two-Component Reactive Resin System B4

[0255] For the preparation of the two-component reactive resin system B4, the reactive resin component B3 (component (A)) and the hardener component (component (B)) of the commercially available product HIT HY 200 (Hilti Aktiengesellschaft, lot number: 8107090) were filled in a plastic cartridge (Ritter GmbH Volume ratio A:B=5:1) having the inner diameters of 32.5 mm (component (A)) and 14 mm (component (B)). As a result, the two-component reactive resin system B4 (for the measurement of the afterflow behavior) was obtained.

[0256] Compound (VII)

[0257] C1. Preparation of the Reactive Resin Masterbatch C1 with Compound (VII)

[0258] 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. This produced the reactive resin master batch C1, containing 65 wt. % of the compound (VII) as a backbone resin and 35 wt. % of hydroxypropyl methacrylate based on the total weight of the reactive resin master batch.

[0259] The compound (VII) has the following structure:

##STR00012##

[0260] C2. Preparation of the Reactive Resin C2

[0261] 1.08 g of catechol (Catechol flakes; RHODIA), 0.36 g tert-butylpyrocatechol (TBC shed, RHODIA) and 9.2 g di-isopropanol-p-toluidine (BASF SE) were dissolved in a mixture of 160.0 g 1,4-butanediol dimethacrylate (Visiomer 1,4-BDDMA; Evonik Degussa GmbH) and 229.2 g of reactive resin masterbatch from C1. The reactive resin C2 was thereby obtained.

[0262] From the reactive resin B2, a reactive resin component B3 was prepared having compound (VI) as a backbone resin.

[0263] C3. Preparation of the Reactive Resin Component C3

[0264] 310.5 g of reactive resin C2 are mixed under vacuum with 166.5 g of Secar®80 (Kemeos Inc.), 9.0 g of Cab-OSil® TS-720 (Cabot Corporation), 16.2 g of Aerosil® R 812 (Evonik Industries AG), and 397.8 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver with a PC laboratory system dissolver type LDV 0.3-1. The mixture was stirred for 2 minutes at 2500 rpm.Math.min.sup.−1, and then for 10 minutes at 4500 rpm.Math.min.sup.−1 under vacuum (pressure≤100 mbar) with a 55 mm dissolver disc and an edge scraper. As a result, the reactive resin component C3 was obtained.

[0265] C4. Preparation of the Two-Component Reactive Resin System C4

[0266] For the preparation of the two-component reactive resin system C4, the reactive resin component C3 (component (A)) and the hardener component (component (B)) of the commercially available product HIT HY 200 (Hilti Aktiengesellschaft, lot number: 8107090) were filled in a plastic cartridge (Ritter GmbH Volume ratio A:B=5:1) having the inner diameters of 32.5 mm (component (A)) and 14 mm (component (B)). As a result, the two-component reactive resin system C4 (for the measurement of the afterflow behavior) was obtained.

Comparison Example D

[0267] For comparison, a reactive resin masterbatch, a reactive resin and a reactive resin component were prepared as follows with the comparative compound 1.

[0268] D1. Preparation of Comparative Reactive Resin Masterbatch D1 with Comparative Compound (I)

[0269] The comparative reactive resin masterbatch D1 was prepared with 65 wt. % of comparative compound (I) as the backbone resin and 35 wt. % of hydroxypropyl methacrylate according to the method in EP 0 713 015 A1, which is hereby introduced as a reference and reference is made to the entire disclosure thereof.

[0270] The product (comparative compound (I)) has an oligomer distribution, and the oligomer having a repeating unit has the following structure:

##STR00013##

[0271] From the comparative reactive resin masterbatch D1, a comparative reactive resin D2 with comparative compound (I) as a backbone resin was prepared.

[0272] D2. Preparation of the Comparative Reactive Resin D2

[0273] 1.08 g of catechol (Catechol flakes; RHODIA), 0.36 g tert-butylpyrocatechol (TBC shed, RHODIA) and 9.2 g di-isopropanol-p-toluidine (BASF SE) were dissolved in a mixture of 160.0 g 1,4-butanediol dimethacrylate (Visiomer 1,4-BDDMA; Evonik Degussa GmbH) and 229.2 g of the comparative reactive resin masterbatch from D1.

[0274] From the comparative reactive resin D2, a comparative reactive resin component D3 with comparative compound (I) as a backbone resin was prepared.

[0275] D3. Preparation of the Comparative Reactive Resin Components D3

[0276] 310.5 g of comparative reactive resin D2 are mixed under vacuum with 166.5 g of Secar® 80 (Kemeos Inc.), 9.0 g of Cab-OSil® TS-720 (Cabot Corporation), 16.2 g of Aerosil® R 812 (Evonik Industries AG), and 397.8 g of quartz sand F32 (Quarzwerke GmbH) in a dissolver with a PC laboratory system dissolver type LDV 0.3-1. The mixture was stirred for 2 minutes at 2500 rpm.Math.min.sup.−1, and then for 10 minutes at 4500 rpm.Math.min.sup.−1 under vacuum (pressure≤100 mbar) with a 55 mm dissolver disc and an edge scraper. As a result, the comparative reactive resin component D3 was obtained.

[0277] D4. Preparation of the Comparative Two Component Reactive Resin System D4 For the preparation of the comparative two-component reactive resin system D4, the comparative reactive resin component D3 (component (A)) and the hardener component (component (B)) of the commercially available product HIT HY 200 (Hilti Aktiengesellschaft, lot number: 8107090) were filled in a plastic cartridge (Ritter GmbH Volume ratio A:B=5:1) having the inner diameters of 32.5 mm (component (A)) and 14 mm (component (B)). As a result, the two-component comparative reactive resin system D4 (for the measurement of the afterflow behavior) was obtained.

[0278] Determination of Rheological Properties

[0279] The influence of the compounds (V), (VI) and (VII) on the viscosity and on the thixotropy of reactive resin components containing these compounds was determined from the dynamic viscosities of the reactive resin components. For this purpose, the dynamic viscosities of the reactive resin components A3, B3 and C3 were measured after different shearing and compared in each case with those of the comparative formulation.

[0280] Measurement of the Dynamic Viscosity of the Reactive Resin Components A3. B3 and C3 and of the Comparative Reactive Resin Component D3

[0281] The measurement of the dynamic viscosity of the reactive resin components A3, B3 and C3 and the comparative reactive resin component D3 was carried out 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 measurement method consisted of three sections: 1. Low shear, 2. High shear, 3. Low shear. In the 1st section, the shear process took place for 3 minutes at 0.5/s. In the 2nd section, the shear rate was logarithmically increased in 8 steps of 15 seconds from 0.8/s to 100/s. The 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 section was a repetition of the 1st section.

[0282] At the end of each section, the viscosities were read. Table 1 shows the value of the second section at 100/s. Three measurements each were made, with the values given in Table 1 being the average of the three measurements.

[0283] The thus determined dynamic viscosities of the reactive resin components A3, B3 and C3 were compared with the dynamic viscosities of the comparative reactive resin component D3. The results are summarized in Table 1.

[0284] They show that the use according to the invention of the compounds (V), (VI) and (VII) as backbone resin also leads to a lowering of the dynamic viscosity of the reactive resin components prepared therewith at room temperature (23° C.).

[0285] Furthermore, the results in table 1 show that after completion of the 2nd measuring section, in which a shear rate of 100 s.sup.−1 was used, the reactive resin components reached again a high dynamic viscosity, and the reactive resin components accordingly show a thixotropic behavior. The dynamic viscosity at the end of the 2nd section was so high again that the composition no longer began to flow, such that with these compositions overhead applications are possible without the risk of the compositions flowing out of the borehole. This could be demonstrated in manual experiments in which the two-component reactive resin systems were injected from below into a downwardly open cylinder. All compositions remained in the cylinder. None of the compositions flowed out of the cylinder.

TABLE-US-00001 TABLE 1 Results of the measurement of the dynamic viscosities at different shear rates of the reactive resin components A3, B3 and C3 and the comparative reactive resin component D3 Reactive resin Reactive resin Reactive resin Comparative reactive component component component resin component A3 B3 C3 D3 Dynamic viscosity [Pa .Math. s] 156.1 84.1 122.7 297.0 at a shear of 0.5 s.sup.−1 (1. section) Dynamic viscosity [Pa .Math. s] 5.0 4.6 4.7 12.4 at a shear of 100 s.sup.−1 (2. section) Dynamic viscosity [Pa .Math. s] 61.9 48.0 64.2 143.6 at a shear of 0.5 s.sup.−1 (3. section)

[0286] Determination of the Afterflow Behavior

[0287] To determine the afterflow behavior at 0° C. 25° C. and 40° C., the reactive resin systems A4, B4 and C4 and the comparative reactive resin system F4 were tempered to 0° C. or 25° C. and 40° C. The cartridges were manually dispensed with a 5:1 two-component analyzer over a static mixer (HIT RE-M mixer; Hilti Aktiengesellschaft). A preflow of five strokes was discarded. Subsequently, a stroke was dispensed and after the end of the stroke, the dispenser was not unlocked. The composition of material flowing out (afterflowing) after the end of the stroke was determined after curing.

[0288] The compositions of afterflowing material of the two-component reactive resin systems A4, B4 and C4, which contain the compounds according to the invention, were mixed with the composition of afterflowing material of the comparative two-component reactive resin system D4, which contains the comparative compound 1, compared at 0° C., at 25° C. and at 40° C.

[0289] Five measurements were carried out respectively. The measurement results are summarized in Table 2.

TABLE-US-00002 TABLE 2 Results of the measurement of the amounts of afterflowing material in the reactive resin systems A4, B4 and C4 and the comparative reactive resin system D4 Two-component reactive resin Composition of afterflowing material in g system 0° C. 25° C. 40° C. A4 0.63 0.03 0.91 B4 0.76 0.86 0.61 C4 0.29 0.25 0.45 D4 1.95 1.11 1.26

[0290] The results in Table 2 clearly show that, despite the lower viscosity of the reactive resin components A3. B3 and C3 over the comparative reactive resin component D3 and the lower high shear viscosity (100 s.sup.−1) (see data from Table 1), the systems containing the compounds (V), (VI) and (VII) as a backbone resin are much less prone to afterflowing over the entire temperature range than the systems containing the comparative compound (I) as a backbone resin.