Use of salts as accelerators in an epoxy resin compound for chemical fastening

Abstract

A method includes using at least one salt (S) selected from the salts of nitric acid, salts of nitrous acid, salts of halogens or salts of trifluoromethanesulfonic acid as an accelerator in a multi-component epoxy resin compound for the chemical fastening of construction elements and/or anchoring means. Another method includes the chemical fastening of construction elements and anchoring elements, such as anchor rods, anchor bolts, rods, sleeves, reinforcing bars, screws and the like in boreholes in various substrates.

Claims

1: A method, comprising: accelerating an epoxy resin compound with 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.

2: The method according to claim 1, wherein the epoxy resin compound is a multi-component epoxy resin compound.

3: The method according to claim 2, wherein the multi-component epoxy resin compound comprises an epoxy resin component (A) which contains at least one curable epoxy resin, and a curing agent component (B) which contains at least one amine which is reactive to epoxy groups, and wherein the epoxy resin component (A) and the curing agent component (B) are separate from one another so as to prevent a reaction.

4: The method Use according to claim 3, wherein the multi-component epoxy resin compound is present in cartridges or film pouches which comprise two or more separate chambers in which the epoxy resin component (A) and the curing agent component (B) are separately arranged so as to prevent a reaction.

5: The method Use according to claim 1 further comprising: chemical fastening with the epoxy resin compound of construction element or anchoring means in a borehole.

6: The method 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.

7: The method according to claim 1, where 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.

8: The method according to claim 3, wherein the at least one amine reactive to epoxy groups is selected from 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), 4,4′-methylenebis(cyclohexyl-amine) (PACM), 4-methylcyclohexyl-1,3-diamine (mCDA), 1,2-diaminocyclohexane (1,2-BAC) and mixtures thereof.

9: The method according to claim 3, wherein the at least one salt (S) is present at least in the curing agent component (B).

10: The method according to claim 1, wherein the at least one salt (S) is present in the epoxy resin compound in a proportion of from 0.1 to 4 wt. % based on total weight of the epoxy resin compound.

11: The method according to claim 3, wherein the at least one curable epoxy resin is a diglycidyl ether of bisphenol A or bisphenol F or a mixture thereof.

12: A method for the chemical fastening of construction means and/or anchoring materials, the method comprising: chemical fastening of the construction means and/or anchoring materials with a multi-component epoxy resin compound which comprises an epoxy resin component (A) which contains at least one curable epoxy resin, and a curing agent component (B) which contains at least one amine which is reactive to epoxy groups, wherein the epoxy resin component (A) and the curing agent component (B) are separate from one another so as to prevent a reaction, and wherein the epoxy resin component (A) and/or the curing agent component (B) comprises at least one salt (S) as an accelerator, and wherein the 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.

13: The method according to claim 12, wherein the multi-component epoxy resin compound is present in cartridges or film pouches which comprise two or more separate chambers in which the epoxy resin component (A) and the curing agent component (B) are separately arranged so as to prevent a reaction.

14: The method according to claim 13, the method further comprising: discharging out of the separate chambers and mixing in a static mixer or dissolver the epoxy resin component (A) and the curing agent component (B).

15: The method according to claim 14, the method further comprising: introducing mixed multi-component epoxy resin compound into a borehole.

16: The method according to claim 1, the method further comprising: chemical fastening with the epoxy resin compound.

17: The method according to claim 1, the method further comprising: chemical fastening with the epoxy resin compound of an anchor rod, anchor bolt, rod, threaded rod, sleeve, threaded sleeve, reinforcing bar, and/or screw in a borehole.

18: A composition, comprising: an epoxy resin compound and 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

Description

EXAMPLES

[0076] The chemicals listed in table 1 below have been used to illustrate the examples:

TABLE-US-00001 TABLE 1 List of chemicals used Substance Trade name CAS number Manufacturer Country 1,2,3-propanetriol Gycerol 56-81-5 Merck G 1,2-diaminocyclohexane Dytek DCH-99 694-83-7 Invista NL 1,3-cyclohexanedimethanamine 1,3-BAC 2579-20-5 Itochu G Deutschland 1,3-dihydroxybenzene Resorcinol 108-46-3 Sigma-Aldrich G 2,4,6- Ancamine K54 90-72-2, Air Products NL tris(dimethylaminomethyl)phenol, 71074-89-0 bis[(dimethylamino)methyl]phenol 2-methyl-1,5-pentamethylene Dytek A 15520-10-2 Invista NL diamine 4,4′-methylenebis(2-methyl- MACM 6864-37-5 Sigma-Aldrich G cyclohexylamine) Aluminum nitrate nonahydrate Aluminum nitrate 7784-27-2 Sidma-Aldrich G Ammonium nitrate Ammonium nitrate 6484-52-2 Sigma-Aldrich G Calcium Carbonate Calcium carbonate 471-34-1 Sigma-Aldrich G Calcium nitrate tetrahydrate Calcium nitrate 13477-34-4 Sigma-Aldrich G Calcium nitrite solution, 30% Calcium nitrate 13780-06-8 Sigma-Aldrich G solution, 30% in water Calcium oxide Calcium oxide 1305-78-8 Sigma-Aldrich G Calcium propionate Calcium propionate 4075-81-4 Sigma-Aldrich G Calcium sulfate dihydrate Calcium sulfate 10101-41-1 Hilliges G dihydrate 75 Gipswerk Calcium trifluoromethanesulfonate Calcium triflate 55120-75-7 Sigma-Aldrich G Isophorone diamine Vestamin IPD 2855-13-2 Evonik G Degussa Potassium nitrate Potassium nitrate 7757-79-1 Sigma-Aldrich G Potassium sulfate Potassium sulfate 7778-80-5 Sigma-Aldrich G Lithium hydroxide Lithium hydroxide 1310-65-2 Sigma-Aldrich G Lithium trifluoromethanesulfonate Lithium trifiate 33454-82-9 TCI Europe B Magnesium nitrate Magnesium nitrate 13446-18-9 Sigma-Aldrich G hexahydrate Magnesium trifluoromethanesulfonate Magnesium trifiate 60871-83-2 Alfa Aesar G m-Xylylenediamine mXDA 1477-55-0 ltochu G Deutschland Sodium bromide Sodium bromide 7647-15-6 Sigma-Aldrich G Sodium chloride Sodium chloride 7647-14-5 G Sodium iodide Sodium iodide 7681-82-5 Sigma-Aldrich G Sodium nitrate Chile-Salpeter 7631-99-4 Sigma-Aldrich G 4-hydroxyphenylacetic acid 4-hydroxyphenylacetic 156-38-7 TCI Europe B acid Phenol novolac resin Phenolite TD-2131 9003-35-4 DIC Europe G p-Toluenesulfonic acid p-Toluenesulfonic acid 6192-52-5 TCI Europe B monohydrate Salicylic acid Salicylic acid 69-72-7 Merck G Nitric acid 70% Nitric acid 7697-37-2 Sigma-Aldrich G Styrenated phenol Novares LS 500 61788-44-1 Rütgers G Novares GmbH Tetrabutylammonium nitrate Tetrabutylammonium 1941-27-1 Sigma-Aldrich G nitrate Trifluoroacetic acid Trifluoroacetic acid 76-05-1 TCI Europe B

1. Determination of the Reaction Kinetics by Temperature Measurement

Epoxy Resin Component (A)

[0077] 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.

[0078] The 1,4-butanediol-diglycidyl ether and trimethyolpropane-triglycidyl ether commercially available under the names Araldite DY-026 and Araldite™ DY-T (Huntsman), respectively, were used as the reactive diluents.

[0079] An epoxy resin component (A) composed as specified in table 2 below was prepared.

[0080] The components were mixed and stirred in the dissolver (PC laboratory system, volume 1 L) at a negative pressure of 80 mbar for 10 minutes at 3500 rpm.

TABLE-US-00002 TABLE 2 Composition of epoxy resin component (A) Substance Function Percent by weight Bisphenol A-based Epoxy resin 52 epoxy resin Bisphenol F-based Epoxy resin 28 epoxy resin 1,4-butanediol- Reactive diluent 10 diglycidyl ether Trimethylolpropane Reactive diluent 10 triglycidyl ether EEW [g/Eq] 158

[0081] Curing agent component (B) The amine isophorone diamine (IPDA, trade name Vestamin IPD) from Evonik Degussa, Germany was used as the curing agent component (B). To prepare the curing agent component (B), the amount of salt (S) specified in table 3 was added to IPDA and dissolved as far as possible. This mixture was used as the curing agent component. The mixing ratios were calculated based on the AHEW content of IPDA (42.6 g/EQ), the accelerator content and the EEW content of the epoxy resin component (A).

[0082] To determine the reaction kinetics by temperature measurement, the epoxy resin component (A) together with the curing agent component was poured into a 20-ml rolled-rim glass. A temperature sensor was placed in the center of the rolled-rim glass. The temperature change was recorded (device: Yokogawa, DAQ station, model: DX1006-3-4-2). With this method, the curing of the mortar could be followed over the course of the temperature development. If there was an acceleration during curing, the maximum temperature is shifted to shorter times, associated with a higher temperature. T.sub.max (maximum temperature reached) and t.sub.Tmax (time after which the maximum temperature was reached) were measured.

[0083] The results of the determination of the reaction kinetics by temperature measurement for different salts (S) as accelerators are shown in table 3 below.

TABLE-US-00003 TABLE 3 Results of the determination of the reaction kinetics Salt (S) Proportion [wt. %] T.sub.max [° C.] t.sub.max [hh:mm:ss] Calcium nitrate tetrahydrate 2 193 00:29:13 5 189 00:12:34 Calcium nitate tetrahydrate/Ancamin K54 2/2 85 00:12:05 Cacium nitrate tetrahydrate/Calcium triflate/ 2/2/2 111 00:07:34 Ancamin K54 Calcium nitrate/nitric acid solution 2 159 00:20:26 5 176 00:09:32 Potassium nitrate (25.0% in H.sub.2O) 8 153.2 00:43:50 20 145.8 00:19:25 Sodium nitrate (46.0% in H.sub.2O) 4.3 125.2 01:10:58 10.7 135.1 00:38:06 Magnesium nitrate hexahydrate 2 36 01:12:52 5 152 00:38:21 Aluminum nitrate nonahydrate 2 55 01:11:33 5 169 00:38:52 Ammonium nitrate 2 173.3 00:39:11 5 195.9 00:19:40 Calcium nitrite (33.0% in H.sub.2O) 6.7 207 00:12:53 16.7 164.7 00:06:41 Sodium chloride (26.4% in H.sub.2O) 7.6 130 00:43:56 18.9 157.7 00:27:29 Sodium bromide (47.56% in H.sub.2O) 4.2 157.2 00:47:22 10.5 145.8 00:29:37 Sodium iodide 2 135 01:13:03 5 152 00:24:46 Calcium triflate 2 212 00:21:49 5 230 00:07:05 Calcium triflate/Ancamine K54 2.2 141 00:16:53 Magnesium trifiate 2 46.2 02:34:25 5 100.5 01:35:59 Lithium triflate 2 183.5 00:34:48 5 222.6 00:14:56

[0084] For comparison, the reaction kinetics by temperature measurement were carried out for numerous accelerators which are known from the prior art. The results of this measurement are shown in table 4 below.

TABLE-US-00004 TABLE 4 Results of the determination of the reaction kinetics by temperature measurement for different accelerators (comparative examples) Concentration T.sub.max t.sub.max Accelerator [wt.%] [° C.] [hh:mm:ss] — 36.8 02:17:03 H.sub.2O 5 65.5 01:18:12 10 86.8 00:36:45 Resorcinol 10 81 01:18:20 20 172 00:27:48 Glycerol 5 24 04:55:38 10 32 02:15:26 Calcium oxide 2 23 05:04:05 5 27 00:51:02 Phenolacetic acid 5 28 00:23:14 10 23 00:16:37 Styrenated phenol 10 27 03:06:47 ′LS 500′ 20 29 02:28:30 p-Toluenesulfonic 2 26 03:02:25 acid 5 25 03:04:48 Ancamin K54 2 25 03:57:52 5 24 05:34:45 Salicylic acid 2 32 01:16:25 5 36 01:30:38 Phenolite TD-2131 15 165 00:54:23 25 147 00:38:37 Trifluoroacetic acid 2 31 01:47:13 5 73 01:22:20 Lithium hydroxide 2 23 00:17:00 5 23 05:21:27 Potassium sulfate 2 45.4 03:07:59 5 46.8 02:29:52 Calcium sulfate 2 25 05:14:48 5 24 04:41:34 Calcium propionate 2 36.5 03:26:25 5 41.5 03:22:06 Tetrabutylammonium 2 43 02:21:04 nitrate 5 38 02:27:56 Potassium sulfate 20.0 136.9 00:17:50 (10.02% in H.sub.2O) 49.9 98.2 00:12:12

Variation of the Amine in the Curing Agent Component

[0085] The curing agent component (B) was modified in that the amine IPDA was replaced by the amines listed in table 5 below and combined with the salts (S) specified in each case. The results of the determination of the reaction kinetics by temperature measurement are given in tables 5 (according to the invention) and 6 (comparative examples) below.

TABLE-US-00005 TABLE 5 Results of the determination of the reaction kinetics by temperature measurement with variation of the amine in the curing agent component T.sub.max t.sub.max Amine Salt (S) Proportion [° C.] [hh:mm:ss] 1,3-BAC Calcium nitrate 2 165 00:11:45 tetrahydrate 1,3-BAC Calcium nitrate 2.5 257.5 00:13:20 tetrahydrate in glycerol (80% solution) MACM Calcium nitrate 2 61 00:55:29 tetrahydrate Dytek A Calcium nitrate 2.5 226.5 00:15:32 tetrahydrate in glycerol (80% solution) 1,2-BAC Calcium triflate 2 146.5 01:14:13 mXDA Sodium iodide 5.5 239.0 00:40:52 in glycerol (36.4% solution)

TABLE-US-00006 TABLE 6 Results of the determination of the reaction kinetics by temperature measurement with variation of the amine in the curing agent component using a novolac accelerator Amines Accelerator Concentration [%] Tmax [°C,] tnnax [hh:mm:ss] 1,3-BAC — 33 03:03:35 MACM — 22 03:12:37 mAcm Phenolite TD-2131 15 50 01:20:40 Dytek A Phenolite TD-2131 15 222.7 00:33:17 1,2-BAC Phenolite TD-2131 15 57.1 01:25:53 1,3-BAC Phenolite TD-2131 15 209.5 00:25:07 mXDA Phenolite TD-2131 15 224.9 00:38:46

2. Mortar Compounds and Pull-Out Tests

Epoxy Resin Component (A)

[0086] 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.

[0087] The 1,4-butanediol-diglycidyl ether and trimethyolpropane-triglycidyl ether commercially available under the names Araldite DY-026 and Araldite™ DY-T (Huntsman), respectively, were used as the reactive diluents.

[0088] 3-glycidyloxypropyl-trimethoxysysilane available under the name Dynalsylan GLYMO™ (Evonik Industries) was used as the adhesion promoter.

[0089] The liquid components were premixed by hand. Subsequently, quartz (Millisil™ W12 from Quarzwerke Frechen) was added as a filler and fumed silica (Cab-O-Sil™ S-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.

[0090] The composition of the epoxy resin component (A) used in the examples is given in table 7 below.

TABLE-US-00007 TABLE 7 Composition of the epoxy resin umponent (A) in wt,% Percent by weight Substance Function [wt,%] 3-glycidyloxypropyl- Adhesion promoter 2.8 trimethoxysysilane Bisphenol A-based Epoxy resin 31.3 epoxy resin Bisphenol F-based Epoxy resin 16.9 epoxy resin 1,4-butanediol- Reactive diluent 6.0 diglycidyl ether Trimethyolpropane- Reactive diluent 6.0 trigiycidyl ether Quartz Filler 34.4 Silicic acid Thickener 2.7 EEW [g/Eq] 255

Curing Agent Component (B)

Starting Materials

[0091] Isophorone diamine (IPDA) from Evonik Degussa, Germany, 1,3-cyclohexanedimethanamine (1,3-BAC) and m-xylylenediamine (mXDA) from MGC, Japan and 2-methlypentamethylenediamine (Dytek A) from Invista, the Netherlands, were used as amines for preparing the curing agent component (B).

[0092] Quartz (Millisil™ W12 from Quarzwerke Frechen) and calcium aluminate cement (Secar 80 from Kemeos SA) were used as a filler and fumed silica (Cab-O-Sil™ TS-720 from Cabot Rheinfelden) was used as a thickener.

[0093] The salts calcium nitrate and sodium iodide were used as solutions in glycerol (1,2,3-propanetriol, CAS No. 56-81-5, Merck, G). To prepare the calcium nitrate solution, 400.0 g calcium nitrate tetrahydrate was added to 100.0 g glycerol and stirred at 50° C. until completely dissolved (approx. 3 hours). The solution prepared in this way contained 80.0% calcium nitrate tetrahydrate. To prepare the sodium iodide solution, 36.4 g sodium iodide was added to 63.6 glycerol and stirred at 50° C. until completely dissolved. The solution prepared in this way contained 36.4% sodium iodide.

[0094] Calcium triflate was dissolved as a solid in the amine of the particular curing agent.

[0095] A calcium nitrate/nitric acid solution was also used as the salt (S). To prepare this solution, 52.6 g calcium carbonate was slowly added to 135.2 g nitric acid and then stirred for 5 minutes.

[0096] The liquid components were mixed to prepare the curing agent components (B). The accelerator 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.

[0097] The composition of the curing agent components (B) prepared in this way is specified in tables 8 (according to the invention) and 9 (comparative examples) below:

TABLE-US-00008 TABLE 8 Composition of the curing agent component (B) in wt,% Example 1 2 3 4 Amine 1,3-BAC 36.75 — — — mXDA — 41.2 — — IPDA — — 42.0 — DYTEK A — — — 42.0 Accelerator Sodium iodide 8.25 — — — Calcium nitrate — 3.3 — — Calcium nitrate/nitric acid — — 3.0 — Calcium inflate — — — 3.0 Quailz 25.0 25.0 25.0 25.0 Calcium aluminate cement 25.0 25.0 25.0 25.0 Thickener 5.0 5.0 5.0 5.0 AHEW [g/Eq] 97 83 101 69

TABLE-US-00009 TABLE 9 Composition of the curing agent component (B) of comparative examples 1 to 5 in wt. % Example 1 2 3 4 5 Amine 1,3-BAC 36.6 — — — — mXDA — 36.6 — — — IPDA — — 27.6 36.6 — DYTEK A — — — — 36.6 Accelerator Phenolite TD-2131 6.0 6.0 — 6.0 6.0 Ancamine K54 2.4 2.4 2.4 2.4 2.4 Novares LS 500 — — 15.0 — — Quartz 25.0 25.0 25.0 25.0 25.0 Calcium aluminate cement 25.0 25.0 25.0 25.0 25.0 Thickener 5.0 5.0 5.0 5.0 5.0 AHEW [g/Eq] 97 93 154 116 79

Mortar Compounds and Pull-Out Tests

[0098] The epoxy resin component (A) and the curing agent 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.

[0099] The pull-out strength of the mortar compounds obtained by mixing the epoxy resin component (A) and the curing agent component (B) according to the above 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 by means of compressed air (2×6 bar), a wire brush (2×) and again by compressed air (2×6 bar).

[0100] The boreholes were filled up, by two thirds from the bottom of the borehole, 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.

[0101] The curing time in test 1 was 4 hours at 25° C. In test 2, the curing time was 24 hours at 25° C.

[0102] 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 component (B) according to examples 1 to 4 and comparative examples 1 to 5 are shown in table 10 below.

TABLE-US-00010 TABLE 10 Determination of the load values Examples Comparative examples Test 1 2 3 4 1 2 3 4 5 Pull-out tests number Load value [N/mm.sup.2]  4 h curing 1 31.1 29.1 7.4 24.6 25.8 18.9 1.7 0.4 17.9 24 h curing 2 34.4 38.8 35.5 35.0 37.3 38.2 36.5 36.8 36.1