Hardener component for multi-component epoxy resin material, and multi-component epoxy resin material

Abstract

A hardener component is useful for a multi-component epoxy resin material, and includes a benzoxazine amine adduct as an accelerator and an amine as a hardener. The benzoxazine amine adduct is present in the hardener component in a proportion of from 8.5 wt. % to 75 wt. %. The multi-component material including the benzoxazine amine adduct in the hardener component already has a quick curing time at room temperature and can therefore be used advantageously for the chemical fastening of construction elements.

Claims

1. A hardener component for a multi-component epoxy resin material for chemical fastening of construction elements, the hardener component comprising: a benzoxazine amine adduct, selected from the group consisting of a substance according to formula Ia: ##STR00004## a substance according to formula Ib: ##STR00005## a mixture thereof, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each independently selected from the group consisting of H, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylalkyl, heteroalkyl, alkoxy, hydroxyl, hydroxyalkyl, carboxyl, halo, haloalkyl, amino, aminoalkyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonylamino, aminosulfonyl, sulfonic acid, alkylsulfonyl groups, and a combination thereof, wherein each of the groups is unsubstituted or optionally substituted; wherein R.sup.6 and R.sup.7 each independently represent H or an amino, diamino or polyamino group selected from the group consisting of aliphatic, alicyclic, aromatic, araliphatic amine groups, and a combination thereof, wherein each of the groups is unsubstituted or optionally substituted; wherein Z is selected from the group consisting of a direct bond, —C(O)—, —S—, —O—, —S(O)—, —S(O).sub.2—, —C(R.sup.8)(R.sup.9)—, —[C(R.sup.8)(R.sup.9)].sub.m—C(R.sup.8)(R.sup.9)—[C(R.sup.10)(R.sup.11)].sub.n—, —[C(R.sup.8)(R.sup.9)].sub.m—C(R.sup.8)(aryl)-[C(R.sup.10)(R.sup.11)].sub.n—, —[C(R.sup.8)(R.sup.9)].sub.m—C(O)—[C(R.sup.10)(R.sup.11)].sub.n—, —[C(R.sup.8)(R.sup.9)].sub.m—S—[C(R.sup.10)(R.sup.11)].sub.n—, —[C(R.sup.8)(R.sup.9)].sub.m—O—[C(R.sup.10)(R.sup.11)].sub.n—, —[C(R.sup.8)(R.sup.9)].sub.m—S(O)—[C(R.sup.10)(R.sup.11)].sub.n—, —[C(R.sup.8)(R.sup.9)].sub.m—S(O).sub.2—[C(R.sup.10)(R.sup.11)].sub.n—, a divalent heterocycle, —[C(R.sup.8)(R.sup.9)].sub.m-arylene-[C(R.sup.10)(R.sup.11)].sub.n—, where m and n are each independently from 0 to 10, wherein R.sup.8, R.sup.9, R.sup.10, and R.sup.11 each independently have the same meaning as the groups R.sup.1 to R.sup.5, or R.sup.8 and R.sup.9 together form a lactone group; and an amine which is selected from the group consisting of aliphatic, alicyclic, aromatic, araliphatic amines, and a combination thereof, and which has on average per molecule at least two reactive hydrogen atoms bonded to a nitrogen atom; wherein the benzoxazine amine adduct is present in the hardener component in a proportion of from 8.5 wt. % to 75 wt. %, and wherein the hardener component, when present with an epoxy resin component comprising at least one hardenable epoxy resin, is capable of curing at a temperature of at most 40° C.

2. The hardener component according to claim 1, wherein R.sup.3 and R.sup.5 each represent H.

3. The hardener component according to claim 1, wherein the benzoxazine amine adduct is obtained by the process comprising: reacting a benzoxazine with an amine, which is at least one amine selected from the group consisting of an aliphatic amine, an araliphatic amine, a diamine, a polyamine, and a combination thereof, wherein the benzoxazine is at least one selected from following structures: ##STR00006##

4. The hardener component according to claim 3, wherein the amine reacted with the benzoxazine and the amine present in the hardener component are each selected from the group consisting of 2,2,4- or 2,4,4-trimethyl-1,6-diaminohexane and mixtures thereof, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1,3-bis(aminomethyl)-cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)-cyclohexane (1,4-BAC), 2-methyl-1,5-pentanediamine (DYTEK A), (3(4),8(9)bis(aminomethyl)dicyclo[5.2.1.02,6]decane and isomer mixtures thereof (TCD-diamine), aminomethyltricyclo[5.2.1.02.6]decane and isomer mixtures thereof (TCD amine), 1,6-hexamethylene diamine, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), 1,3-benzenedimethanamine (mXDA), 1,4-benzenedimethanamine (pXDA), N,N′-dimethyl-1,3-benzenedimethanamine, and mixtures of two or more thereof.

5. The hardener component according to claim 3, wherein the amine reacted with the benzoxazine and the amine present in the hardener component are each selected from the group consisting of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 2-methyl-1,5-pentanediamine (DYTEK A), m-xylylenediamine (mXDA), 1,3-bis(aminomethyl)-cyclohexane (1,3-BAC), and mixtures thereof.

6. The hardener component according to claim 1, wherein the benzoxazine amine adduct is present in the hardener component in a proportion of from 9 wt. % to 65 wt. %.

7. The hardener component according to claim 6, wherein the benzoxazine amine adduct is present in the hardener component in a proportion of from 10 wt. % to 35 wt. %.

8. The hardener component according to claim 1, wherein the hardener component further comprises: at least one additive selected from the group consisting of accelerators, adhesion promoters, thickeners, and fillers.

9. A multi-component epoxy resin material, comprising: an epoxy resin component comprising at least one hardenable epoxy resin, and the hardener component according to claim 1.

10. The multi-component epoxy resin material according to claim 9, wherein the multi-component epoxy resin material further comprises: at least one additive selected from the group consisting of accelerators, adhesion promoters, reactive diluents, thickeners, inorganic fillers, and organic fillers.

11. The multi-component epoxy resin material according to claim 9, wherein the multi-component epoxy resin material cures at a temperature of at most 40° C.

12. The multi-component epoxy resin material according to claim 9, wherein the multi-component epoxy resin material cures at an ambient temperature of 21° C. within 48 hours or less.

13. A method for chemical fastening, comprising: applying the multi-component epoxy resin material according to claim 9 to a fastening element in a borehole.

14. The method according to claim 13, wherein application of the multi-component epoxy resin material anchors the fastening element in the borehole.

15. A method of accelerating curing of an epoxy resin material, comprising: producing an epoxy resin material comprising the hardener component according to claim 1, comprising the benzoxazine amine adduct as an accelerator.

16. The method according to claim 15, further comprising applying the epoxy resin material to construction elements to chemically fasten the construction elements.

17. The hardener component according to claim 1, wherein m and n are each independently from 0 to 5.

18. The hardener component according to claim 1, wherein Z is selected from the group consisting of a direct bond, —C(R.sup.8)(R.sup.9)—, —C(R.sup.8)(aryl)-, —C(O)—, —S—, —O—, —S(O)—, —S(O).sub.2—, a divalent heterocycle, —[C(R.sup.8)(R.sup.9)].sub.m-arylene-[C(R.sup.10)R.sup.11)].sub.n—, where m and n are each independently from 0 to 5.

19. The hardener component according to claim 1, wherein R.sup.3 and R.sup.5 each represent H, and wherein Z is selected from the group consisting of a direct bond and —C(R.sup.8)(R.sup.9)—, where R.sup.8 and R.sup.9 are: (a) each independently selected from the group consisting of H, C.sub.1-C.sub.4 alkyl groups, and a combination thereof, or (b) together form a lactone group.

20. The hardener component according to claim 19, where R.sup.8 and R.sup.9 are both selected from the group consisting of H and a methyl group.

Description

EXAMPLES

(1) Epoxy Resin Component (A)

(2) In the examples, the bisphenol A-based and bisphenol F-based epoxy resins commercially available under the names DER 330 and DER 354 (Dow Europe), respectively, were used as the epoxy resins.

(3) 3-glycidyloxypropyl-trimethoxysysilane available under the name Dynalsylan GLYMO™ (Evonik Industries) was used as the adhesion promoter.

(4) The 1,4-butanediol-diglycidyl ether and trimethyolpropane-triglycidyl ether commercially available under the names Polypox™ R3 (Dow Europe) and Araldite™ DY-T (Huntsman), respectively, were used as reactive diluents.

(5) The liquid components were premixed by hand. Subsequently, quartz (Millisil™ W12 from Quarzwerke Frechen) was added as a filler and silicic acid (Cab-O-Sil™ TS-720 from Cabot Rheinfelden) was added as a thickener and the mixture was stirred in a dissolver (PC laboratory system, volume 1 L) for 10 minutes under a vacuum at 3500 rpm.

(6) The composition of the epoxy resin component (A) used in the examples is given in table 1 below.

(7) TABLE-US-00001 TABLE 1 Composition of epoxy resin component (A) Percent by weight Substance Function [wt. %] 3-glycidyloxypropyl- Adhesion promoter 2.6 trimethoxysysilane Bisphenol A-based Epoxy resin 31.3 epoxy resin Bisphenol F-based Epoxy resin 16.7 epoxy resin 1,4-butanediol- Reactive diluent 6.0 diglycidyl ether Trimethyolpropane- Reactive diluent 6.0 triglycidyl ether Quartz Filler 34.7 Silicic acid Thickener 2.7 EEW [g/Eq] 256
Hardener Component (B)
Starting Materials

(8) The benzoxazines used to prepare the hardener component (B) are available under the trade names Araldite MT 35600 CH (benzoxazine A; CAS number; 154505-70-1), Araldite MT 35700 CH (benzoxazine F; CAS number: 214476-06-9) and Araldite MT 35710 FST (benzoxazine FST: mixture of benzoxazine F and 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine) from Huntsman Advanced Materials, Basel, Switzerland. 1,3-cyclohexanedimethanamine (1,3-BAC) and m-xylylenediamine (mXDA) from Itochu Deutschland and 2-methlypentamethylenediamine (Dytek A) from Invista, the Netherlands, were used as amines for preparing the hardener component (B).

(9) In addition, a mixture of 2,4,6-tris(dimethylaminomethyl)phenol and bis[(dimethylamino)-methyl]phenol, which is available under the trade name Ancamine™ K45 from Air Products, was added to the hardener components as an accelerator.

(10) 3-aminopropyl-triethoxysilane, which is available under the trade name Dynasylan AMEO from Evonik Degussa, was used as an adhesion promoter.

(11) Quartz (Millisil™ W12 from Quarzwerke Frechen) was used as a filler and silicic acid (Cab-O-Sil™ TS-720 from Cabot Rheinfelden) was used as a thickener.

(12) Preparation of the Benzoxazine Amine Adduct

(13) Variant A

(14) Benzoxazine (1 eq) was dissolved in chloroform. The amine (2.4 eq) was added in drops at room temperature (RT) under nitrogen. The solution was then heated for 24 hours to 55° C. After this time, the chloroform was removed by distillation under reduced pressure. A yellow substance which was solid at room temperature was obtained.

(15) The following benzoxazine amine adduct was prepared according to variant A: A1: Benzoxazine F/Dytek A
Variant B

(16) Benzoxazine was dissolved in excess amine and the solution was heated, with stirring, for 24 hours to 55° C. A yellow to yellow-brown viscous solution was obtained (benzoxazine/amine adduct approx. 60% in amine).

(17) The following benzoxazine amine adducts were prepared according to variant B: B1: Benzoxazine A/Dytek A, 60% in Dytek A B2: Benzoxazine F/1,3-BAC, 60% in 1,3-BAC B3: Benzoxazine F/mXDA, 60% in mXDA B4: Benzoxazine FST/1,3-BAC, 60% in 1,3-BAC B5: Benzoxazine F/IPDA, 55% in IPDA
Variant C

(18) Benzoxazine was dissolved in amine according to a formulation for the preparation of a hardener component (B). The remaining components of the hardener component (B) were then added to this solution according to the relevant formulation and stirred in a dissolver (PC laboratory system, volume 1 L) for 10 minutes under a vacuum at 3500 rpm. The hardener component (B) prepared in this way was stored for at least one week before being mixed with the epoxy resin component (A), in order to ensure the reaction of the benzoxazine with the amine for forming the benzoxazine amine adduct.

(19) According to variant C, a hardener component (B) comprising a benzoxazine/amine adduct was prepared using the following benzoxazine: C1: Benzoxazine F C2: Benzoxazine FST

Examples 1 to 12

(20) To prepare the hardener component (B) from examples 1 to 12 below, the relevant benzoxazine amine adduct or the benzoxazine was dissolved in the liquid constituents or introduced as a solution in amine (variant B). Quartz powder and silicic acid were then added and stirred in a dissolver (PC laboratory system, volume 1 L) for 10 minutes under a vacuum at 3500 rpm.

(21) The hardener component (B) prepared according to variant C above was stored at room temperature for at least one week to ensure the formation of a sufficient amount of the benzoxazine/amine adduct.

(22) The composition of the hardener components (B) prepared in this way is given in table 2 below.

(23) TABLE-US-00002 TABLE 2 Composition of the hardener component (B) Example 1 2 3 4 5 6 7 8 9 10 11 12 Component Wt. % A1 29.9 29.9 B1 50.0 B2 50.0 B3 50.0 50.0 27.3 B4 50.0 27.3 B5 29.2 C1 19.5 C2 18.1 mXDA 24.1 4.0 4.0 26.7 Dytek A 4.0 34.5 1,3-BAC 4.0 24.1 4.0 35.9 26.7 29.2 Adhesion promoter 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 Accelerator 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 2.4 Filler 39 39 39 39 39 39 39 39 39 39 39 32.5 Thickener 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 4.3 AHEW [g/Eq] 100 83 97 85 103 97 83 97 79 94 76 83

Comparative Examples 1 to 9

(24) To prepare the hardener component (B) according to comparative examples 1 to 4 and 7 to 9 below, the amine was added to a benzoxazine component and stirred at room temperature for less than 24 hours. The remaining liquid constituents were then added. The quartz powder and silicic acid were then added and stirred in a dissolver (PC laboratory system, volume 1 L) for 10 minutes under a vacuum at 3500 rpm. In order to prevent the benzoxazine from reacting with the amine to form the benzoxazine amine adduct, the hardener component (B) prepared in this way was mixed with the epoxy resin component (A) no later than 48 hours after the amine was added to the benzoxazine, and the curing as an anchor began.

(25) The hardener component (B) for comparative examples 5 and 6 was prepared using a benzoxazine/amine adduct prepared according to variant B described above.

(26) Table 3 shows the composition of the hardener components (B) from comparative examples 1 to 9.

(27) TABLE-US-00003 TABLE 3 Composition of the hardener component (B) Comparative example 1 2 3 4 5 6 7 8 9 Component Wt. % B4 13.5 4.9 Benzoxazine F 19.5 18.6 10.0 Benzoxazine FST 18.1 10.0 mXDA 35.4 44.0 54.0 Dytek A 34.5 54.0 1,3-BAC 35.9 44.1 40.5 49.1 Adhesion promoter 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 Accelerator 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 Filler 39 39 39 39 39 39 39 39 39 Thickener 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 AHEW [g/Eq] 83 53 97 79 71 67 94 76 62
Mortar Compositions and Pull-Out Tests

(28) The epoxy resin component (A) and the hardener component (B) were mixed in a speed mixer in a ratio resulting in a balanced stoichiometry according to the EEW and AHEW values. The mixture was poured into a one-component cartridge as far as possible without bubbles, and was immediately injected into the borehole made for the pull-out tests.

(29) The pull-out strength of the mortar compositions obtained by mixing the epoxy resin component (A) and hardener component (B) according to the above examples was determined using a high-strength anchor threaded rod M12 according to ETAG 001 Part 5, which was doweled into a hammer- or diamond-drilled borehole having a diameter of 14 mm and a borehole depth of 72 mm by means of the relevant mortar composition in C20/25 concrete.

(30) For this purpose, the boreholes were filled up, by two thirds from the bottom of the borehole, with the mortar composition to be tested in each case. The threaded rod was pushed in by hand. The excess mortar was removed using a spatula.

(31) The tested boreholes were made using a hammer drill in tests 1 to 6, 8 and 9, and using a diamond drill in test 7.

(32) In tests 1 to 6 and 8 and 9, the borehole was cleaned twice with compressed air (6 bar), brushed twice and then blown out again twice with compressed air (6 bar). In test 7, the borehole was rinsed once, brushed once, rinsed again, blown out for 10 seconds, brushed again and blown out again for 10 seconds.

(33) The curing time in test 1 was 24 hours at 23° C. In tests 2 to 6, the curing time was 6 hours at 23° C., and the curing time in test 7 was 48 hours at 23° C.

(34) In test 8, the borehole was filled with water after being drilled and cleaned. The mortar was injected into the water-filled borehole via a mixer extension comprising a piston plug. The curing time of the mortar was 48 hours at 23° C.

(35) In test 9, the curing time in the wet borehole was 24 hours at 23° C., followed by storage for 48 hours at 80° C. and the anchor being pulled at a concrete temperature of 80° C. +/−2° C.

(36) The failure load was determined by centrally pulling out the anchor threaded rod with a narrow support. The load values obtained with the mortar compositions using a hardener component (B) according to examples 1 to 11 and comparative examples 1 to 9 are shown in table 4 below.

(37) TABLE-US-00004 TABLE 4 Determination of the load values Example Test 1 2 3 4 5 6 7 8 9 10 11 12 Pull-out tests number Load value [N/m] Dry concrete (hammer drilled) 24 h curing 1 40.1 36.4 38.1 37.5 38.0 37.3 38.6 37.4 35.4 6 h curing 2 16.2 6 h curing 3 22.6 6 h curing 4 15.6 6 h curing 5 17.7 6 h curing 6 10.6 Wet concrete 48 h curing 7 35.9 32.2 35.9 36.2 36.2 34.7 33.4 (diamond drilled) 48 h curing 8 23.9 23.8 24.7 27.3 21.0 24.6 (hammer drilled) 24 h curing 9 21.9 19.5 24.5 22.0 24.2 25.3 20.2 26.4 25.6 (storage at 80° C.) Comparative example Test 1 2 3 4 5 6 7 8 9 Pull-out tests number Load value [N/m] Dry concrete (hammer drilled) 24 h curing 1 38.3 38.4 6 h curing 2 7.5 2.3 6 h curing 3 15.7 6 h curing 4 10.3 7.4 7.6 6 h curing 5 15.1 6 h curing 6 Wet concrete 48 h curing 7 33.9 (diamond drilled) 48 h curing 8 24.8 (hammer drilled) 24 h curing 9 23.8 (storage at 80° C.)

(38) The mortar compositions from comparative examples 1, 3, 4, 7 and 8 each contain the same amount of benzoxazine as the compositions from examples 2, 6, 9, 10 and 11. The examples according to the invention and the corresponding comparative example (e.g. comparative example 7 and example 10) thus have comparable compositions, but the benzoxazine and amine have already reacted to form the adduct in the examples according to the invention, whereas both species are still in free form in the comparative examples.

(39) The pull-out tests after 6 hours show that the mortar compositions of the examples according to the invention each have higher load values than the compositions of the comparative examples in which benzoxazine and amine are still in free form.

(40) The compositions which contain very little or no benzoxazine have the lowest load values after six hours (comparative examples 2, 5, 6 and 9). In the pull-out tests, the benzoxazine amine adduct already exhibits a significant accelerating effect after six hours, by comparison with the compositions not involving benzoxazine and also by comparison with the compositions in which benzoxazine and amine are in free form. The free benzoxazine also already has an accelerating effect, which, however, is not as pronounced as the accelerating effect of the benzoxazine amine adduct.

(41) From test 9 it can be seen that, by contrast with the amine, the type of benzoxazine has no influence on the curing time. If a benzoxazine amine adduct is present in a sufficiently high concentration, this accelerates the curing of the mortar composition.

(42) Determination of the Curing Time

(43) An epoxy resin component (A) having the composition given in table 5 below was prepared. The liquid components were mixed and stirred in a dissolver (PC laboratory system, volume 1 L) for 10 minutes under a vacuum at 3500 rpm.

(44) TABLE-US-00005 TABLE 5 Epoxy resin component (A) Percent by weight Substance Function [wt. %] Bisphenol A-based Epoxy resin 31.3 epoxy resin Bisphenol F-based Epoxy resin 16.7 epoxy resin 1,4-butanediol- Reactive diluent 6.0 diglycidyl ether Trimethyol-propane- Reactive diluent 6.0 triglycidyl ether EEW [g/Eq] 256

(45) The following mixtures or compounds were used as hardener component (B):

Example 13

(46) Benzoxazine amine adduct of benzoxazine FST and 1,3-BAC (60% in 1,3-BAC; AHEW=56 g/EQ), prepared according to variant B above.

Comparative Example 10

(47) Solution consisting of benzoxazine FST (Araldite MT 35710 FST) in 1,3-BAC (36.2% benzoxazine FST in 1,3-BAC; AHEW=56 g/EQ). The solution was prepared 24 hours before the measurement and stored at room temperature.

Comparative Example 11

(48) Only the amine 1,3-BAC (AHEW=35.6 g/EQ) was used.

(49) The epoxy resin component (A) was weighed out and heated to 5° C. After approximately 30 minutes, the 5° C. hardener component (B) was added. The batch was mixed in a speed mixer for one minute at 1500 rpm, then transferred to a pot and immediately placed in the oven once the sample size had been noted down.

(50) The curing time of the mixture was determined by means of DSC measurements. The curing was monitored in the DSC apparatus as an isothermal measurement at 21° C. for 24 hours. The results of the DSC measurements are given in table 6 below.

(51) TABLE-US-00006 TABLE 6 DSC measurements Example End of curing [min] Example 13 358 Comparative example 10 538 Comparative example 11 601

(52) As with the determination of the load values after six hours, the DSC measurement also shows that curing is quickest when the benzoxazine amine adduct is used as the hardener component (B). If the benzoxazine and the amine are unreacted in free form, the reaction is only accelerated by approximately 60 minutes by comparison with the comparative example not involving benzoxazine.