BRANCHED URETHANE METHACRYLATE COMPOUNDS AND USE THEREOF

Abstract

Branched urethane methacrylate compounds are useful as backbone resins for increasing the performance of a fastening material. Furthermore, reactive resins and reactive resin components containing such compounds are useful for chemical fastening.

Claims

1: A compound of the general formula (I) ##STR00012## in which B is an aromatic hydrocarbon group, A is a linear or branched aliphatic C.sub.3-C.sub.10 alkylene group, each R.sub.1, respectively independently of one another, is a branched or linear aliphatic C.sub.1-C.sub.15 alkylene group, n is a whole number greater than or equal to 0, and m is a whole number greater than or equal to 3.

2: The compound according to claim 1, wherein B is an aromatic C.sub.6-C.sub.20 hydrocarbon group.

3: The compound according to claim 2, wherein B contains one or two benzene rings, which optionally are substituted.

4: The compound according to claim 1, wherein R.sub.1 is a C.sub.2-alkylene group or C.sub.3-alkylene group.

5: The compound according to claim 1, wherein the linear or branched aliphatic C.sub.3-C.sub.10 alkylene group A is a trivalent or polyvalent group, as is obtained by removal of the hydroxyl groups from a trifunctional or polyfunctional alcohol.

6: The compound according to claim 1, wherein n=0, 1 or 2 and m=3, 4 or 5.

7: The compound according to claim 6, wherein n=0 or 1 and m=3, 4 or 5, with n+m=4 or 5.

8: A method for production of a reactive resin or of a reactive-resin component for construction purposes, the method comprising: incorporating the compound according to claim 1 as a component of a reactive resin or of a reactive-resin component.

9: A method for increasing the bond strength of a cured fastening caulk, the method comprising: mixing the compound according to claim 1 as a component of a fastening caulk, curing said fastening caulk, to obtain a fastening caulk having increased bond strength compared to a fastening caulk without the compound according to claim 1.

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 (A) according to claim 11, and a hardener component (B), which contains an initiator.

13: The reactive-resin system according to claim 12, wherein at least one of the components (A) or (B) contains an inorganic aggregate.

14-15. (canceled)

16: The compound according to claim 5, wherein the linear or branched aliphatic C.sub.3-C.sub.10 alkylene group A is a trivalent or tetravalent group, as is obtained by removal of the hydroxyl groups from a trifunctional or tetrafunctional alcohol.

17: A method of filling drilled holes for construction purposes, the method comprising: mixing and applying a fastening caulk to said drilled hole, said fastening caulk comprising the reactive resin according to claim 10, and a hardener component.

18: A method of filling drilled holes for construction purposes, the method comprising: mixing and applying the reactive-resin system according to claim 12 to said drilled hole.

19: A method for chemically fastening anchors in drilled holes, comprising: mixing and applying a fastening caulk to said drilled hole, said fastening caulk comprising the reactive resin according to claim 10, and a hardener component.

20: A method for chemically fastening anchors in drilled holes, comprising: mixing and applying the reactive-resin system according to claim 12 to said drilled hole.

Description

EXAMPLES

[0225] First of all, reactive-resin master batches, reactive resins, reactive-resin components and two-component reactive-resin systems respectively containing the inventive compound (III) or (IV) as backbone resin were produced. The bond strengths of the cured fastening caulks were determined.

[0226] A1.1 Production of Reactive-Resin Master Batch A1.1 with Compound (IV)

[0227] 218 g Hydroxypropyl methacrylate and 669 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG) were first introduced into a 2-liter glass laboratory reactor with internal thermometer and stirrer shaft then 0.13 g phenothiazine (D Prills; Allessa Chemie), 0.37 g 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH), 0.23 g dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals) and 67 g trimethylol propane (TMP) were added. The batch was heated to 100° C. Then 380 g diphenylmethane diisocyanate (MDI; TC Deutschland GmbH) (3 equivalents per equivalent of TMP) was added dropwise with stirring (200 rpm) within 70 minutes. Thereafter stirring was continued for a further 300 minutes at 100° C. Finally, 666 g hydroxypropyl methacrylate was added.

[0228] Hereby reactive-resin master batch A.1 containing the compound (IV) as backbone resin was obtained. The product exists as an oligomer distribution, wherein the oligomer containing a repeat unit has the following structure:

##STR00009##

[0229] A1.2 Production of Reactive-Resin Master Batch A1.2 with Compound (IV)

[0230] 300 g hydroxypropyl methacrylate and 660 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG) were first introduced into a 2-liter glass laboratory reactor with internal thermometer and stirrer shaft then 0.12 g phenothiazine (D Prills; Allessa Chemie), 0.29 g 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH), 0.21 g dioctyltin dilaurate (TIB KAT*216; TIB Chemicals) and 31 g trimethylol propane were added. The batch was heated to 100° C. Then 348 g diphenylmethane diisocyanate MDI (6 equivalents per equivalent of TMP) was added dropwise with stirring (200 rpm) within 70 minutes. Thereafter stirring was continued for a further 300 minutes at 100° C. Finally, 660 g hydroxypropyl methacrylate was added.

[0231] Hereby reactive-resin master batch A.2 containing the compound (IV) as backbone resin was obtained. The product also exists as an oligomer distribution, but it is different from the product produced under A1.1.

[0232] A2.1 Production of Reactive Resin A2.1

[0233] 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 1271 g reactive-resin master batch A1.1.

[0234] Hereby reactive-resin A2.1 containing the compound (IV) as backbone resin was obtained.

[0235] A2.2 Production of Reactive Resin A2.2

[0236] 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 1271 g reactive-resin master batch A1.2.

[0237] Hereby reactive-resin A2.2 containing the compound (IV) as backbone resin was obtained.

[0238] The production of reactive resins A2.1 and A2.2 was carried out without addition of further reactive diluents.

[0239] A3.1 Production of Reactive-Resin Component A3.1

[0240] 354 g Reactive resin A2.1 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 mixture was stirred for 8 minutes at 3500 rpm under vacuum (pressure s 100 mbar) with a 55 mm dissolver disk and an edge scraper.

[0241] Hereby reactive-resin component A3.1 was obtained.

[0242] A3.2 Production of Reactive-Resin Component A3.2

[0243] 354 g Reactive resin A2.2 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, by analogy with A3.1.

[0244] Hereby reactive-resin component A3.2 was obtained.

[0245] B1.1 Production of Reactive-Resin Master Batch B1.1 with Compound (III)

[0246] 271 g Hydroxypropyl methacrylate and 657 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG) were first introduced into a 2-liter glass laboratory reactor with internal thermometer and stirrer shaft then 0.16 g phenothiazine (D Prills; Allessa Chemie), 0.39 g 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH), 0.28 g dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals) and 83 g trimethylol propane were added. The batch was heated to 100° C. Then 328 g toluene diisocyanate (TDI; TC Deutschland AG) (3 equivalents per equivalent of TMP) was added dropwise with stirring (200 rpm) within 45 minutes. Thereafter stirring was continued for a further 300 minutes at 100° C. Finally, 659 g hydroxypropyl methacrylate was added.

[0247] Hereby reactive-resin master batch B.1.1 containing the following compound (III) as backbone resin was obtained. The product exists as an oligomer distribution, wherein the oligomer containing a repeat unit has the following structure:

##STR00010##

[0248] B1.2 Production of Reactive-Resin Master Batch B1.2 with Compound (III)

[0249] 354 g Hydroxypropyl methacrylate and 660 g 1,4-butanediol dimethacrylate (BDDMA; Evonik AG) were first introduced into a 2-liter glass laboratory reactor with internal thermometer and stirrer shaft then 0.14 g phenothiazine (D Prills; Allessa Chemie), 0.34 g 4-hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH), 0.24 g dioctyltin dilaurate (TIB KAT® 216; TIB Chemicals) and 37 g trimethylol propane were added. The batch was heated to 100° C. Then 286 g toluene diisocyanate (TDI; TC Deutschland AG) (6 equivalents per equivalent of TMP) was added dropwise with stirring (200 rpm) within 45 minutes. Thereafter stirring was continued for a further 300 minutes at 100° C. Finally, 662 g hydroxypropyl methacrylate was added.

[0250] Hereby the reactive-resin master batch B1.2 containing the compound (III) as backbone resin was obtained. The product also exists as an oligomer distribution, but it is different from the product produced under B1.1.

[0251] B2.1 Production of Reactive Resin B2.1

[0252] 2.1 g 4-Hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 7.9 g di-iso-propanol-p-toluidine (BASF SE) were added to 440 g reactive-resin master batch B1.1.

[0253] Hereby reactive-resin B2.1 containing the compound (II) as backbone resin was obtained.

[0254] B2.2 Production of Reactive Resin B2.2

[0255] 2.1 g 4-Hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) and 7.9 g di-iso-propanol-p-toluidine (BASF SE) were added to 440 g reactive-resin master batch B1.2.

[0256] Hereby reactive-resin B2.2 containing the compound (II) as backbone resin was obtained.

[0257] The production of reactive resins B2.1 and B2.2 was carried out without the addition of further reactive diluents.

[0258] B3.1 Production of Reactive-Resin Component B3.1

[0259] 354 g Reactive resin B2.1 was mixed with 185 g Secar® 80 (Kemeos Inc.), 27 g Cab-O-Sil® TS-720 (Cabot Corporation) and 335 g quartz sand F32 (Quarzwerke) in the dissolver under vacuum, by analogy with A3.1.

[0260] Hereby reactive-resin component B3.1 was obtained.

[0261] 3.2 Production of Reactive-Resin Component B3.2

[0262] 354 g Reactive resin B2.2 was mixed with 185 g Secar® 80 (Kemeos Inc.), 27 g Cab-O-Sil® TS-720 (Cabot Corporation) and 335 g quartz sand F32 (Quarzwerke GmbH) in the dissolver under vacuum, by analogy with A3.1.

[0263] Hereby reactive-resin component B3.2 was obtained.

[0264] C1. Production of Comparison Reactive-Resin Master Batch C1 with Comparison Compound 1

[0265] The comparison reactive-resin master batch 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 produced 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.

[0266] The product (comparison compound 1) exists as an oligomer distribution, wherein the oligomer containing a repeat unit has the following structure:

##STR00011##

[0267] C2. Production of Comparison Reactive Resin C2

[0268] 9.2 g 4-Hydroxy-2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPOL; Evonik Degussa GmbH) 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).

[0269] Hereby comparison reactive-resin C2 containing the comparison compound 1 as backbone resin was obtained.

[0270] C3. Production of Comparison Reactive-Resin Component C3

[0271] 354 g Comparison reactive resin C2 was mixed with 185 g Secar® 80 (Kemeos Inc.), 27 g Cab-O-Sil TS-720 (Cabot Corporation) and 335 g quartz sand F32 (Quarzwerke GmbH) in the dissolver under vacuum, by analogy with A3.1.

[0272] Production of the Two-Component Reactive-Resin Systems

[0273] For production of the two-component reactive-resin systems A4.1, A4.2, B4.1 and B4.2 and of the comparison two-component reactive-resin system C4, the reactive-resin components A3.1, A3.2, B3.1 and B3.2 and respectively the comparison reactive-resin component C3 (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 canisters (Ritter GmbH; volume ratio A:B=3:1) with inside diameters of 32.5 mm (component (A)) and respectively 14 mm (component (B)).

[0274] Hereby the two-component reactive-resin systems A4.1, A4.2, B4.1 and B4.2 as well as the comparison reactive-resin system C4 were obtained.

[0275] In order to demonstrate the influence of the inventive compounds (II) and (IV) on the bond strengths of a hardened fastening caulk, the bond strengths of the cured fastening caulks containing the reactive-resin components A3.1, A3.2, B3.1 and B3.2 were measured and compared with the bond strength of the cured fastening caulk containing the comparison reactive-resin components.

[0276] To measure the bond strengths (load ratings) of the cured fastening caulks, M12 threaded anchor rods were inserted into drilled holes in C20/25 concrete, which had a diameter of 14 mm and a drilled-hole depth of 72 mm and were filled with the fastening caulks. These drilled holes were cleaned, dust-free, dry and hammer-drilled; curing took place at 20° C. The temperature of the two-component reactive-resin system or of the fastening caulk during setting was 20° C. The bond strengths were determined by pulling out the threaded anchor bars centrally. Respectively five threaded anchor bars were set and the bond strength was determined after 24 hours of curing. The fastening caulks were extruded from the canisters and injected into the drilled holes via a static mixer (HIT-RE-M Mixer; Hilti Aktiengesellschaft).

[0277] The bond strengths (N/mm.sup.2) determined in this way are listed as the mean value of five measurements in the following Table 1.

TABLE-US-00001 TABLE 1 Results of measurement of the bond strength of the cured fastening caulks containing the reactive-resin components A3.1, A3.2, B3.1 and B3.2 as well as of the cured fastening caulk containing the comparison reactive-resin component C3 Bond strength [N/mm.sup.2] Fastening caulk with reactive-resin component A3.1 21.3 Fastening caulk with reactive-resin component A3.2 19.4 Fastening caulk with reactive-resin component B3.1 20.0 Fastening caulk with reactive-resin component B3.2 18.2 Comparison fastening caulk with comparison 18.0 reactive-resin component C3

[0278] The results show that the fastening caulks produced with the inventive branched urethane methacrylate compounds, compound (II) and compound (IV), have higher bond strengths (load ratings) than the comparison fastening caulk produced with comparison compound 1.