Epoxy-based substance for fixing purposes, the use thereof and the use of specific components

Abstract

Compositions for a curable substance for fixing purposes, comprising an epoxy component (a), which contains curable epoxides, and a hardener component (b), which comprises a Mannich base formulation, obtainable by reaction of specific amines, and/or mixtures of styrenated phenols with low molecular weight amines, to novel Mannich base formulations or mixtures of styrenated phenols with low molecular weight amines, and to the use of such Mannich base formulations and/or of such mixtures of styrenated phenols with low molecular weight amines, and in each case especially further additional ingredients, especially in hardener components for epoxy resins.

Claims

1. A method for embedding an anchoring element in mortar in a hole or cavity in masonry or concrete, the method comprising: introducing into the hole or crevice a fixing mortar comprising a non-aqueous composition, the non-aqueous composition comprising an epoxy component (a), which contains curable epoxides, and a hardener component (b), which comprises (i) a Mannich base formulation obtainable by reaction of one or more specific amines with phenols and aldehydes, the specific amines being those of the formula ##STR00006## wherein “CYC” is a monocyclic saturated ring having from 3 to 12 ring atoms or a condensed dicyclic saturated ring system having from 6 to 12 ring atoms, wherein in each case the ring atoms are selected from 0 to 2 nitrogen atoms, 0 to 1 oxygen atoms and 0 to 1 sulfur atoms and from carbon atoms; X is CH.sub.2, NH, O or S, wherein for each group —[X].sub.n—NH.sub.2 one or zero X is NH, O or S, with the proviso that in the case of an X═O or S, in the group —[X].sub.n—NH.sub.2 in question n is at least 2, and the O or S is not bonded directly to a nitrogen atom, and in the case of an X═NH, n is at least 2 and the X═NH is bonded neither directly to a nitrogen ring atom nor to a nitrogen atom present in the group —[X].sub.n—NH.sub.2 in question; n is from 0 to 5, with the proviso that in at least one of the groups —[X].sub.n—NH.sub.2, n is from 1 to 5; and m is a whole positive number greater than or equal to 2; or salts thereof, or the specific amine is 4-(2-aminoethyl)piperazine; wherein the phenols are styrenated phenols; and/or (ii) mixtures of styrenated phenols with one or more low molecular weight amines, which are di- or poly-amines, or salts thereof; and introducing an anchoring element into the hole or crevice simultaneously with or subsequent to the introduction of the fixing mortar.

2. The method according to claim 1, wherein, in the case of (ii), the low molecular weight amine(s) are those of the formula shown under (i) in claim 1.

3. The method according to claim 1, wherein, in the case of (ii), the low molecular weight amine(s) are xylylenediamines, aliphatic polyamines, oligomeric diamines of the formula H.sub.2N—(CH.sub.2).sub.i—NH—[(CH.sub.2).sub.j—NH].sub.k—(CH.sub.2).sub.l—NH.sub.2, wherein i, j and l are each independently of the others from 2 to 4 and k is 0, 1 or 2; cycloaliphatic amines; or amine adducts; or mixtures of two or more thereof.

4. The method according to claim 1, wherein, in the case of (ii), the low molecular weight amine(s) are selected from m-xylylenediamine, 1,3-bis(aminomethyl)cyclohexane (BAC), triethylenetetraamine and isophoronediamine, or mixtures of two or more thereof.

5. The method according to claim 1, wherein, in the case of (i), the specific amines(s) are selected from 1,3-bis(aminomethyl)cyclohexane (BAC), 4-(2-aminoethyl)piperazine, N,N′-bis(3-amino-n-propyl)piperazine, and mixtures of two or more thereof.

6. The method according to claim 1, wherein, in the case of (i), for the Mannich base preparation there are used the styrenated phenols and as aldehydes formaldehyde or a precursor thereof.

7. The method according to claim 6, wherein the content of free phenol is less than 1% by weight of the Mannich base formulation.

8. The method according to claim 1, wherein the ratio by weight of components (a) to (b) is 10 to 1 or less.

9. The method according to claim 1, wherein the ratio by weight of components (a) to (b) is 5 to 1 or less.

10. The method according to claim 1, wherein in the case of (i), the proportion of Mannich base, based on the total weight of the component (b), has a proportion of from 10 to 100% by weight.

11. The method according to claim 1, wherein in the case of (i), the proportion of Mannich base, based on the total weight of the component (b), has a proportion of from 30 to 75% by weight.

12. The method according to claim 1, wherein in the case of (ii), the proportion of the mixture of styrenated phenols and low molecular weight amines, based on the total weight of the component (b), has a proportion of from 10 to 100% by weight.

13. The method according to claim 1, wherein in the case of (ii), the proportion of the mixture of styrenated phenols and low molecular weight amines, based on the total weight of the component (b), has a proportion of from 30 to 75% by weight.

Description

EXAMPLES

(1) The following Examples serve to illustrate the invention but do not limit the scope thereof:

(2) Abbreviations used:

(3) AEP N-(2-aminoethyl)piperazine

(4) BAC 1,3-bis(aminomethyl)cyclohexane

(5) BAPP N,N′-bis(3-amino-n-propyl)piperazine

(6) DCH (comparison) 1,2-diaminocyclohexane

(7) IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine

(8) MXDA m-xylylenediamine

(9) TETA triethylenetetramine

(10) T.sub.g glass transition temperature

Example 1

Mortars Obtained with Mannich Base Formulations? for use According to the Invention and, as Comparison Tests, with Mannich Bases that have been Obtained Using Amines Already Known in the Fixings Sector

(11) Using the amines AEP, BAC, BAPP, IPDA and, as comparison, DCH, the corresponding Mannich base formulations were produced as described at the beginning. The formulations were mixed together with epoxy resin component and Portland cement in stoichiometric amounts in accordance with the following Table.

(12) An epoxy resin based on bisphenol A/F having a viscosity of 6000-8000 mPas/25° C. and an epoxy equivalent of 175 is mixed, in the amount indicated in the Table, with a further epoxy resin based on trimethylolpropane having a viscosity of 120-180 mPas/25° C. and an epoxy equivalent of 140, likewise in the amount indicated in the Table. The mixture, consisting of the two epoxy resins and the filler dispersed therein, is hardened at RT for 24 h with the amount of the respective Mannich base corresponding to the hydrogen equivalent, as listed in the following Tables (e.g. stoichiometrically in this case, but greater or lesser crosslinking can also be chosen).

(13) Mortar component A (corresponding to (a) in the general part) is produced in accordance with the following formulation:

(14) TABLE-US-00001 Weight Percent EP Hydrogen introduced by weight Ingredient equivalent equivalent [g] [%] EP resin based 175 — 20.00 40.00 on bisphenol A/F EP resin based 140 — 7.50 15.00 on trimethylol- propane Cement — — 22.50 45.00 Total 50.00 100.00 (1) Analogously, the following amounts of component B, based on 50 g of component A, are weighed out and introduced (Mannich bases based on phenol and corresponding amine in brackets):

(15) TABLE-US-00002 Weight Hydrogen introduced Ingredient equivalent [g] MB 1 (BAC) 53 8.90 MB 2 (BAPP) 69 11.58 MB 3 (AEP) 68 11.41 MB 4 (IPDA) 61 10.24 MB 5 (DCH 45 7.55 comparison example not according to the invention) (2) Alternatively, the following amounts of component B, based on 50 g of component A, are weighed out and introduced (Mannich bases based on styrenated phenol and corresponding amine in brackets):

(16) TABLE-US-00003 Weight Hydrogen introduced Ingredient equivalent [g] MB 6 (BAC) 77 12.93 MB 7 (BAPP) 92 15.44 MB 8 (AEP) 101 16.95 MB 9 (IPDA) 84 14.10 MB 10 (DCH 69 11.58 comparison example not according to the invention)

(17) The components listed here are weighed out and introduced in succession and carefully mixed together. The resulting mixture is then introduced into the corresponding moulds and hardened at RT for 24 h and then tested. The following measured values are obtained: In the case of mixtures containing component B according to (1) with Mannich base from phenol itself and the amine indicated in each case:

(18) TABLE-US-00004 Compressive Tensile Bond strength strength T.sub.g Viscosity Pull-out stress Amine [MPa] [MPa] [° C.] [mPas] [kN] [n/mm.sup.2] BAC 81 39 52 314 87 32 (MB1) BAPP 75 39 48 774 53 20 (MB2) AEP 69 29 50 497 70 26 (MB3) IPDA 66 11 44 1990 81 29 (MB4) DCH 66 6 43 203 58 22 (MB5)

(19) Compared with the comparison using DCH, which is not according to the invention, increased pull-out and bond stress values and increased T.sub.g values (being an indirect measure of increased thermal dimensional stability) as well as increased tensile strength in all cases and increased compressive strength in almost all cases are observed, with comparable viscosities.

(20) In the case of mixtures containing component B according to (2) with Mannich base from styrenated phenol and the amine indicated in each case:

(21) TABLE-US-00005 Compressive Tensile Bond strength strength T.sub.g Viscosity Pull-out stress Amine [MPa] [MPa] [° C.] [mPas] [kN] [n/mm.sup.2] BAC 73 20 50 1259 83 28 (MB6) BAPP 68 30 50 2108 77 28 (MB7) AEP 59 5 47 2200 76 27 (MB8) IPDA 40 6 37 9427 52 19 (MB9) DCH 54 5 32 1720 34 12 (MB10)

(22) Compared with the comparison using DCH, which is not according to the invention, increased pull-out and bond stress values and increased T.sub.g values (being an indirect measure of increased thermal dimensional stability) as well as increased or identical tensile strength in all cases and increased compressive strength in almost all cases are observed, with comparable viscosities.

Example 2

Mortars Obtained with Mixtures of Styrenated Phenol and Low Molecular Weight Amine According to the Invention and for Use According to the Invention

(23) (3) Alternatively, the following amounts of component B, based on 50 g of component A as described above, are weighed out and introduced: (hardener without Mannich bases)

(24) TABLE-US-00006 Weight Hydrogen introduced Ingredient equivalent [g] Mixture 1 47 7.89 (MXDA/BAC) Mixture 2 47 7.89 (BAC) Mixture 3 45 7.55 (MXDA) Mixture 4 57 9.57 (IPDA) Mixture 5 32 5.37 (TETA)

(25) Using the amines BAC in admixture with MXDA (14 parts by weight BAC to 1 part MXDA); BAC; MXDA; IPDA; and TETA, in each case there was produced a mixture consisting of the amine in question (without the presence of Mannich base), styrenated phenol (Novares LS 500) and salicylic acid in a mixing ratio of 75:20:5 (w/w). The mixtures were mixed in stoichiometric amounts (in respect of the functionalities amino and epoxy) with component A (see Table in Example 1) and used as a “curable substance” as described above for the parameter determination.

(26) Using the methods of parameter determination described at the beginning, the following results were obtained:

(27) TABLE-US-00007 Compressive Tensile Bond strength strength T.sub.g Viscosity Pull-out stress Amine [MPa] [MPa] [° C.] [mPas] [kN] [n/mm.sup.2] BAC + 83 30 51 72 96 34 MXDA BAC 83 38 50 72 82 30 MXDA 84 39 50 58 90 33 IPDA 66 12 44 311 76 28 TETA 70 36 45 140 46 17

(28) The mentioned mixtures exhibit very good values which, for the most part, are even higher than when Mannich bases are used in Example 1.