Curing agent composition for an epoxy resin compound, epoxy resin compound and multi-component epoxy resin system

Abstract

A curing agent composition for an epoxy resin compound for the chemical fastening of construction elements, an epoxy resin compound, and a multi-component epoxy resin system are described. Methods for the chemical fastening of construction elements in boreholes and methods of using a salt (S) as an accelerator in an epoxy resin compound for chemical fastening have the epoxy resin compound including 3-aminomethyl-3,5,5-trimethylcyclohexane and at least one further cycloaliphatic amine which is reactive to epoxy groups.

Claims

1: A curing agent composition, comprising: 3-aminomethyl-3,5,5-trimethylcyclohexane and at least one further cycloaliphatic amine which is reactive to epoxy groups and at least one salt (S), wherein the at least one salt (S) is selected from the group consisting of salts of nitric acid, salts of nitrous acid, salts of halogens, salts of trifluoromethanesulfonic acid and combinations thereof, and wherein the 3 aminomethyl-3,5,5-trimethylcyclohexane is contained in the curing agent composition in a proportion of at least 10 wt. % based on the total weight of all amines reactive to epoxy groups.

2: The curing agent composition according to claim 1, wherein the at least one further cycloaliphatic amine which is reactive to epoxy groups comprises at least one cyclohexyl group.

3: The curing agent composition according to claim 1, wherein the at least one further cycloaliphatic amine which is reactive to epoxy groups is selected from the group consisting of 4-methyl-cyclohexane-1,3-diamine, (bicyclo[2.2.1heptanebis(methyl-amine)), 1,2-diaminocyclohexane-1,3-cyclo-hexane-bis(methyl-amine), 4,4′-methylenebis(cyclohexylamine) and combinations thereof.

4: The curing agent composition according to claim 1, wherein the 3 aminomethyl-3,5-trimethylcyclohexane is contained in the curing agent composition in a proportion of at least 25 wt. % based on total weight of all amines reactive to epoxy groups.

5: The curing agent composition according to claim 1, wherein the at least one salt (S) is selected from the group consisting of nitrate (NO.sub.3.sup.−), iodide (I.sup.−), triflate (CF.sub.3SO.sub.3.sup.−) and mixtures thereof.

6: The curing agent composition according to claim 1, wherein the at least one salt (S) comprises a cation selected from the group consisting of alkali metals, alkaline earth metals, lanthanides, aluminum, ammonium and combinations thereof.

7: The curing agent composition according to claim 1, wherein the at least one salt (S) is contained in a proportion of from 0.1 to 15 wt. % based on total weight of the curing agent composition.

8: The curing agent composition according to claim 1, wherein the curing agent composition comprises 3-aminomethyl-3,5,5-trimethylcyclohexane and 1,3-cyclohexane-bis(methylamine).

9: The curing agent composition according to claim 1, wherein the curing agent composition comprises 3-aminomethyl-3,5,5-trimethylcyclohexane and 4,4′-methylenebis(cyclohexylamine).

10: An epoxy resin compound, comprising: at least one curable epoxy resin; and a curing agent composition according to claim 1.

11: The epoxy resin compound according to claim 10, wherein the epoxy resin compound is a multi-component epoxy resin compound.

12: A multi-component epoxy resin system, comprising: an epoxy resin component (A) and a curing agent component, wherein the epoxy resin component (A) contains a curable epoxy resin, and the curing agent component contains 3-aminomethyl-3,5,5-trimethylcyclohexane and at least one further cycloaliphatic amine which is reactive to epoxy groups, wherein 3-aminomethyl-3,5,5-trimethylcyclohexane is contained in the curing agent component in a proportion of at least 10 wt. % based on total weight of all amines reactive to epoxy groups, and further comprising a salt (S) selected from the group consisting of salts of nitric acid, salts of nitrous acid, salts of halogens, salts of trifluoromethanesulfonic acid and combinations thereof contained in the epoxy resin component (A) and/or in the curing agent component.

13: The multi-component epoxy resin system according to claim 12, wherein the salt (S) is contained in the curing agent component.

14: A method for the chemical fastening of construction elements in boreholes, the method comprising: chemical fastening of the construction elements with an epoxy resin compound according to claim 10.

15: A method, comprising: employing as an accelerator at least one salt (S) selected from the group consisting of salts of nitric acid, salts of nitrous acid, salts of halogens, salts of trifluoromethanesulfonic acid and combinations thereof, in an epoxy resin compound comprising 3-aminomethyl-3,5,5-trimethylcyclohexane and at least one further cycloaliphatic amine which is reactive to epoxy groups.

16: A method for the chemical fastening of construction elements in boreholes, the method, comprising: chemical fastening with a multi-component epoxy resin system according to claim 12.

17: A cured compound formed by curing the epoxy resin compound according to claim 10.

Description

EXAMPLES

[0088] Epoxy Resin Component (A)

[0089] Starting Materials

[0090] In the examples, the bisphenol A-based and bisphenol F-based epoxy resins commercially available under the names Araldite GY 240 and Araldite GY 282 (Huntsman), respectively, were used as the epoxy resins.

[0091] The 1,4-butanediol-diglycidyl ether and trimethyolpropane-triglycidyl ether commercially available under the names Araldite DY-206 and Araldite™ DY-T (Huntsman), respectively, were used as the reactive diluents.

[0092] 3-glycidyloxypropyl-trimethoxysysilane available under the name Dynalsylan GLYMO™ (Evonik Industries) was used as the adhesion promoter.

[0093] The liquid components were premixed by hand. Subsequently, quartz (Millisil™ W12 from Quarzwerke Frechen) was added as a filler and fumed silica (CabOSil™ TS-720 from Cabot Rheinfelden) was added as a thickener and the mixture was stirred in the dissolver (PC laboratory system, volume 1 L) for 10 minutes at a negative pressure of 80 mbar at 3500 rpm.

[0094] The composition of the epoxy resin components A1 to A17 used in the examples is given in table 1 below.

TABLE-US-00001 TABLE 1 Composition of the epoxy resin components A1 to A17 in wt. % Bisphenol Bisphenol 1,4- A-based F-based butanediol- Trimethyolpropane- 3-glycidyl- epoxy epoxy diglycidyl triglycidyl oxypropyl- Silicic EEW resin resin ether ether trimethoxysilane Quartz acid [g/Eq] A1 25.2 13.6 4.9 4.9 2.8 45.9 2.7 314 A2 25.0 13.4 4.8 4.8 2.8 46.5 2.7 317 A3 26.0 14.0 5.0 5.0 2.8 44.5 2.7 305 A4 27.0 14.6 5.2 5.2 2.8 42.5 2.7 293 A5 29.2 15.7 5.6 5.6 3.4 37.8 2.7 271 A6 30.4 16.4 5.9 5.9 3.4 35.3 2.7 260 A7 27.0 14.6 5.2 5.2 2.8 42.5 2.7 293 A8 28.1 15.1 5.4 5.4 2.8 40.5 2.7 282 A9 28.9 15.6 5.6 5.6 2.8 38.8 2.7 275 A10 29.6 16.0 5.7 5.7 2.8 37.5 2.7 268 A11 31.2 16.8 6.0 6.0 3.4 33.9 2.7 254 A12 31.2 16.8 6.0 6.0 2.8 34.5 2.7 255 A13 28.2 15.2 5.4 5.4 2.8 40.3 2.7 282 A14 26.3 14.1 5.1 5.1 2.8 43.9 2.7 302 A15 32.0 17.2 6.2 6.2 2.8 32.9 2.7 249 A16 24.9 13.4 4.8 4.8 2.8 46.6 2.7 318 A17 31.3 16.9 6.0 6.0 2.8 34.3 2.7 255

[0095] The composition of the epoxy resin components VA1 to VA7 used in the comparative examples is given in table 2 below.

TABLE-US-00002 TABLE 2 Composition of the epoxy resin components VA1 to VA7 in wt. % Bisphenol Bisphenol 1,4- A-based F-based butanediol- Trimethyolpropane- 3-glycidyl- epoxy epoxy diglycidyl triglycidyl oxypropyl- Silicic EEW resin resin ether ether trimethoxysilane Quartz acid [g/Eq] VA1 28.3 15.3 5.5 5.5 2.8 39.9 2.7 280 VA2 26.5 14.3 5.1 5.1 2.8 43.5 2.7 299 VA3 32.8 17.6 6.3 6.3 2.8 31.5 2.7 244 VA4 31.5 16.9 6.1 6.1 2.8 33.9 2.7 253 VA5 31.2 16.8 6.0 6.0 3.4 33.9 2.7 254 VA6 31.3 16.9 6.0 6.0 2.8 34.3 2.7 255 VA7 31.3 16.9 6.0 6.0 2.8 34.3 2.7 254

[0096] Curing Agent Composition (B)

[0097] Starting Materials

[0098] 3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA) from Evonik Degussa, Germany, 1,3-cyclohexanedimethanamine (1,3-BAC) and m-xylylenediamine (mXDA) from MGC, Japan. 1,2-diaminocyclohexane (Dytek DCH-99) from Invista, 2-piperazino-ethylamine (N-AEP) and 4,4′-methylenebis(cyclohexylamine) (PALM) from Sigma Aldrich Germany, methylcyclohexanediamine (Baxxodur EC 210) from BASF SE, Germany, bicyclo[2.2.1]heptanebis(methyl-amine) (PRO-NKDA) from Mitsui Chemicals, Japan and 2-methypentamethylenediamine (Dytek A) from Invista, the Netherlands, were used as amines for the preparation of the curing agent composition (B).

[0099] 3-aminopropyl-triethoxysilane, which is available under the trade name Dynasylan AMEO from Evonik Degussa, was used as an adhesion promoter.

[0100] Quartz (Millisil™ W12 from Quarzwerke Frechen) and calcium aluminate cement (Secar 80 from Kerneos SA) were used as a filler and fumed silica (Cab-O-Sit™ TS-720 from Cabot Rheinfelden) was used as a thickener.

[0101] The constituents given in table 3 below were used to prepare the salts (S) used in the curing agent composition B.

TABLE-US-00003 TABLE 3 List of salts and accelerator components used (examples and comparative examples) Set (S) or accelerator Trade name Manufacturer Calcium nitrate Calcium nitrate tetrahydrate Sigma-Aldrich Calcium carbonate Calcium carbonate Sigma-Aldrich Nitric acid 70% Nitric acid Sigma-Aldrich Calcium triflate Calcium trifluoromethanesulfonate Sigma-Aldrich 2,4,6-tris(dimethylaminomethyl)phenol, Ancamine K54 Evonik bis[(dimethylamino)methyl]phenol Styrenated phenol Novares LS 500 Rütgers Novares GmbH Phenol novolac Supraplast 3616 Süd-West Chemie

[0102] The salt calcium nitrate was used as a solution in glycerol (1,2,3-propanetriol, CAS No. 56-81-5, Merck, G). For this purpose, 400.0 g calcium nitrate tetrahydrate was added to 100 g glycerol and stirred at 56° C. until completely dissolved (approx. 3 hours). The solution prepared in this way contained 80.0% calcium nitrate tetrahydrate.

[0103] Calcium triflate was dissolved as a solid in the amine of the particular curing agent.

[0104] A calcium nitrate/nitric acid solution (calcium nitrate/nitric acid) was also used as an accelerator. To prepare this solution, 52.6 g calcium carbonate was slowly added to 135.2 g nitric acid and then stirred for 5 minutes.

[0105] The liquid components were mixed to prepare the curing agent compositions (B). The salt was added and quartz powder and silicic acid were then added and stirred in the dissolver (PC laboratory system, volume 1 L) for 10 minutes at a negative pressure of 80 mbar at 2500 rpm.

[0106] The composition of the curing agent compositions (B) prepared in this way is specified in tables 4 to 8 (according to the invention) and 9 (comparative examples) below.

[0107] In the curing agent compositions B2 to B10 (table 4), a combination of IPDA and 1,3-BAC was used as the curing agent and combined with different salts (S).

TABLE-US-00004 TABLE 4 Composition of the curing agent compositions B1 to B10 in wt. %: Calcium 1.3- Calcium nitrate/ Calcium Adhesion AHEW IPDA BAC nitrate Nitric acid triflate promoter Quartz Filler Thickener [g/Eq] B1 44.7 — 7.5 — — 1.5 20.5 20.8 5.0  94 B2 18.4 18.3 7.5 — — 1.5 23.5 25.8 5.0 104 B3 19.0 19.0 6.25 — — 1.5 23.5 25.75 5.0 101 B4 19.6 19.6 5.0 — — 1.5 23.5 25.8 5.0  98 B5 21.0 21.0 3.75 — — — 23.5 25.75 5.0  92 B6 21.7 21.6 2.5 — — — 23.5 25.7 5.0  90 B7 20.1 20.1 — 4.0 — 1.5 23.5 25.8 5.0  95 B8 20.6 20.6 — 3.0 — 1.5 23.5 25.8 5.0  93 B9 20.6 20.6 — — 3.0 1.5 23.5 25.8 5.0  93 B10 21.1 21.1 — — 2.0 1.5 23.5 25.8 5.0  91

[0108] Calcium nitrate was used as the salt (S) in the curing agent compositions B11 to B15 and the ratio of PDA to 1,3-BAC was varied.

TABLE-US-00005 TABLE 5 Composition of the curing agent cornpositions B11 to B15 [wt. %]: Variation of the ratio of IPDA and 1,3-BAC Calcium AHEW IPDA 1,3-BAC nitrate Quartz Filler Thickener [g/Eq] B11 42.0 — 3.7 23.5 25.8 5.0 101 B12 33.6  8.4 3.7 23.5 25.8 5.0  93 B13 25.2 16.8 3.7 23.5 25.8 5.0  94 B14 16.8 25.2 3.7 23.5 25.8 5.0  91 B15  8.4 33.6 3.7 23.5 25.8 5.0  88

[0109] In the curing agent compositions B16 to B20, PDA was combined with different cycloaliphatic amines.

TABLE-US-00006 TABLE 6 Composition of the curing agent compositions B11 to B20 [wt. %] 1,3- Baxxodur PRO- Dytek Calcium Ancamin Adhesion AHEW IPDA BAC EC210 NBDA DCH-99 nitrate K54 promoter Quartz Filler Thickener [g/Eq] B16 27.9 27.8 — — —  7.50 — 1.5 16.0 13.0 4.3  69 B17 25.4 25.3 — — —  7.50 5.0 1.5 18.0 13.0 4.3  76 B18 19.0 — 19.0 — —  8.8 — 1.5 22.5 24.2 5.0  95 B19 20.0 — — 20.0 —  6.25 — 1.5 22.5 24.75 5.0 100 B20 19.3 — — — 19.2 11.25 — 1.5 21.5 22.25 5.0  88

[0110] Calcium nitrate was used as the salt (S) in the curing agent compositions B21 to B24 and the ratio of IPDA to PACM was varied.

TABLE-US-00007 TABLE 7 Composition of the curing agent compositions B21 to B24 [wt. %]: Variation of the IPDA/PACM ratio Calcium AHEW IPDA PACM nitrate Quartz Filler Thickener [g/Eq] B21 46.6 11.6 5.0 19.5 13.0 4.3 76 B22 34.9 23.3 5.0 19.5 13.0 4.3 79 B23 23.3 34.9 5.0 19.5 13.0 4.3 83 B24 11.6 46.6 5.0 19.5 13.0 4.3 86

TABLE-US-00008 TABLE 8 Composition of the curing agent compositions B25 to B26 [wt. %] Calcium nitrate/ Calcium Nitric acid Adhesion AHEW IPDA PACM nitrate solution promoter Quartz Filler Thickener [g/Eq] B25 26.9 26.0 8.8 — 1.5 19.0 13.5 4.3  88 B26 42.0 — — 3.0 — 25.0 25.0 5.0 101

[0111] The composition of the curing agent compositions VB1 to VB10 used in the comparative examples is given in table 9 below.

TABLE-US-00009 TABLE 9 Composition of the curing agent compositions VB1 to VB10 [wt. %] 1,3- Calcium Ancamin Styrenated Adhesion AHEW IPDA mXDA N-AEP DytekA BAC nitrate 54 phenol Novolac promoter Quartz Filler Thickener [g/Eq] VB1 19.0 19.0 — — — 6.25 — — — 1.5 23.5 25.7 5.0 98 VB2 22.3 — 22.2 — — 3.75 — — — 1.5 21.5 23.7 5.0 95 VB3 20.3 — — 20.2 — 3.75 — — — 1.5 23.5 25.7 5.0 84 VB4 22.1 22.1 — — — — — — — 1.5 23.5 25.8 5.0 87 VB5 — — — — 42.0 3.7 — — — — 23.5 25.8 5.0 85 VB8 — 41.2 — — — 3.8 — — — — 25.0 25.0 5.0 83 VB7 41.8 — — — — — 2.4 — — 1.5 29.7 20.3 4.3 68 VB8 34.2 — — — — — 2.4 7.6 — 1.5 29.7 20.3 4.3 83 VB9 34.2 — — — — — 2.4 7.6  3.0 1.5 26.7 20.3 4.3 83 VB10 31.8 — — — — — 2.4 — 10.0 1.5 29.7 20.3 4.3 89

[0112] Mortar Compounds and Pull-Out Tests

[0113] The epoxy resin component (A) and the curing agent composition (B) were each used from a 3:1 hard cartridge. For this purpose, the epoxy resin component (A) and the curing agent composition (B) were poured into a 3:1 hard cartridge after mixing in a static quadro mixer (18 mixing levels, length of the mixing element: 11.5 cm, manufacturer Sulzer AG, Switzerland) and applied into the borehole.

[0114] In examples 11-15, 16, 17, 21-24 and 26 and in comparative examples 5 to 10, the epoxy resin component (A) and the curing agent composition (B) were mixed in a speed mixer in a ratio resulting in a balanced stoichiometry according to the FEW 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.

[0115] The pull-out strength of the mortar compounds obtained by mixing the epoxy resin component (A) and curing agent composition (B) according to the below examples was determined using a high-strength threaded anchor rod M12 according to ETAG 001 Part 5, which was doweled into a hammer-drilled borehole having a diameter of 14 mm and a borehole depth of 69 mm with the relevant mortar compound in C20/25 concrete. The boreholes were cleaned; the number and type of the respective cleaning steps depended on the type of pull-out test.

[0116] For this purpose, the boreholes were filled up, by two thirds from the bottom of the borehole (A1, A22 and A21, 80° C.) or completely (F1c), with the mortar compound to be tested in each case. The threaded rod was pushed in by hand. The excess mortar was removed using a spatula.

[0117] The following types of pull-out tests were carried out.

[0118] A1: Dry concrete; [0119] Hammer drilled; [0120] Cleaning: blowing out with compressed air (6 bar) twice, brushing twice and then again blowing out with compressed air (6 bar) twice; [0121] Embedding depth: 68 mm: [0122] Curing for 24 hours at 25° C.;

[0123] A22: Dry concrete; [0124] Hammer drilled; [0125] Cleaning: blowing out with compressed air (6 bar) twice, brushing twice and then again blowing out with compressed air (6 bar) twice; [0126] Embedding depth: 68 mm; [0127] Curing for 6 hours at 25° C.;

[0128] A21, 80° C.: Dry concrete; [0129] Hammer drilled; [0130] Cleaning: blowing out with compressed air (6 bar) twice, brushing twice and then again blowing out with compressed air (6 bar) twice; [0131] Embedding depth: 68 mm; [0132] Curing for 6 hours at 25° C.:

[0133] F1c: Water-saturated concrete; [0134] Hammer drilled; [0135] Cleaning: blowing out with compressed air (6 bar) once, brushing once and then again blowing out with compressed air (6 bar) once; [0136] Injection: mixer extension with a piston plug into the water-filled borehole; [0137] Embedding depth 68 mm [0138] Curing for 48 hours at 25° C.

[0139] The failure load was determined by centrally pulling out the threaded anchor rod with close support. The load values obtained with the mortar compounds using a curing agent composition (B) according to examples 1 to 26 and comparative examples 1 to 10 are shown in tables 10 and 11 below.

[0140] In order to be able to evaluate the mortar compounds under difficult conditions such as failure load at an elevated temperature and after application in the water-filled borehole, the quotient of failure load under difficult conditions (A21, F1c) and failure load in the reference borehole (dry, cleaned borehole, at room temperature) is generally formed. The result is the percentage of the reference load that remains under difficult conditions. The corresponding results are shown in the table below.

TABLE-US-00010 TABLE 10 Failure loads of the mortar compounds according to the invention according to examples 1 to 26 Pull-out tests load values [N/mm.sup.2] Ratio (A) (B) A1 A22 A21 80° C. F1c A21:A1 F1c:A1 Example 1  1  1 31.7 17.5 18.6 27.5 0.59 0.87 Example 2  2  2 32.3 28.2 26.6 19 0.82 0.59 Example 3  3  3 34.3 27.9 26.9 20.5 0.78 0.60 Example 4  4  4 31.1 22.7 26 20.7 0.84 0.67 Example 5  5  5 31.3 26.2 24.5 21.2 0.78 0.68 Example 6  6  6 32.1 24.6 25.7 25.8 0.80 0.80 Example 7  7  7 33.1 23.3 22 23.8 0.66 0.72 Example 8  8  8 34.1 27.6 24.3 22.7 0.71 0.67 Example 9  9  9 31.5 19.8 26.6 25.5 0.84 0.81 Example 10 10 10 34 23.3 27.6 26.6 0.81 0.78 Example 11 11 11 34.9 21.9 28.6 19.3 0.82 0.55 Example 12 11 12 37.2 28 28.8 20.6 0.77 0.55 Example 13 11 13 37.8 31.6 27.9 19.5 0.74 0.52 Example 14 11 14 36.8 34.5 28.8 19.6 0.78 0.53 Example 15 11 15 37.6 35.9 26.6 18.9 0.71 0.50 Example 16 12 16 33.2 30.2 — — — — Example 17 12 17 34.3 29.5 — — — — Example 18 13 18 33.7 25.4 29.2 19.2 0.87 0.57 Example 19 14 19 30.4 22.2 24.6 23.6 0.81 0.78 Example 20 15 20 31.2 14.6 23.7 26.5 0.76 0.85 Example 21 11 21 34.3 21.2 25.2 30.2 0.73 0.88 Example 22 11 22 30.3 21.9 29 29.8 0.96 0.98 Example 23 11 23 31.9 21.2 24.8 29.1 0.78 0.91 Example 24 11 24 34.3 26.5 21.6 27.5 0.63 0.80 Example 25 16 25 32.4 21.8 28.3 19.5 0.87 0.60 Example 26 17 26 35.5 31.3 25.9 0.88 0.73

TABLE-US-00011 TABLE 11 Failure loads of the mortar compounds according to comparative examples 1 to 10 Put-out tests load values [N/mm.sup.2] Ratio VA VB A1 A22 A21 80° C. F1c A21:A1 F1c:A1 Comparative example 1 1  1 35.4 24.0 20.7 19.2 0.58 0.54 Comparative example 2 2  2 29.4 22.5 17.6 16.3 0.60 0.55 Comparative example 3 3  3 33.6 28.8 19 17.6 0.57 0.52 Comparative example 4 4  4 29.6 10.9 20.2 19.8 0.68 0.67 Comparative example 5 5  5 33.2 37.4 26.9 18.5 0.70 0.43 Comparative example 6 6  6 38.8 — 23.9 20.6 0.62 0.53 Comparative example 7 7  7 25.4 — — — — — Comparative example 8 7  8 15.4 — — — — — Comparative example 9 7  9 19.1 — — — — — Comparative example 10 7 10 24.5 — — — — —