HARDENER COMPOSITION FOR ADDITION-POLYMERISATION-BASED SYNTHETIC FIXING MORTAR SYSTEMS, AND THE USE AND PRODUCTION THEREOF

Abstract

Hardener composition for an addition-polymerisation-curable synthetic fixing mortar system for embedding anchoring means in mortar in holes or crevices, wherein the hardener composition includes oligomeric siloxanes having on average per molecule at least one or preferably two or more organic radicals that carry one or more (secondary or primary) amino and/or thiol groups that react with isocyanate or epoxy groups in the addition reaction and having on average per molecule at least one or more hydrolysable groups, and, in addition, can include one or more further customary additives, to synthetic fixing mortar systems including such a hardener composition, to the use of such synthetic fixing mortar systems for embedding anchoring means in mortar in holes or crevices and to methods of producing and using the synthetic fixing mortar systems and the hardener composition.

Claims

1. A hardener composition for an addition-polymerisation-curable synthetic fixing mortar system for embedding anchoring means in mortar in holes or crevices, wherein the hardener composition includes oligomeric siloxanes having on average per molecule at least one organic radical that carries one or more secondary and/or primary amino and/or thiol groups that react with isocyanate or epoxy groups in the addition reaction and having on average per molecule one or more hydrolysable groups, and, in addition, can include one or more further customary additives.

2. The hardener composition according to claim 1, wherein the oligomeric siloxanes are siloxane oligomers which are functionalised with amino and/or thiol groups and which have per molecule of oligomer at least two or more amino and/or thiol groups and at least one hydrolysable groups bonded to silicon and have Si—O-crosslinked structural elements which form at least one structure selected from chain-like, cyclic, crosslinked and optionally three-dimensionally crosslinked structures.

3. The hardener composition according to claim 1, wherein the oligomeric siloxanes include at least one structure in idealised form of the general formula (I),
(R.sup.1O)[(R.sup.1O).sub.{2−(a+e)}(R.sup.2).sub.aSi(A).sub.eO].sub.b—[Si(Y).sub.2O].sub.c—[Si(B).sub.e(R.sup.4).sub.d(OR.sup.3).sub.{2-(d+e(}O].sub.fR.sup.3   (I) wherein the structural elements are derived from alkoxysilanes and A and B each independently of the other are alkyl that includes at least one (primary or secondary) amino and/or thiol group; Y denotes OR.sup.5 and/or R.sup.5 or, in crosslinked and optionally three-dimensionally crosslinked structures, independently of any other denotes OR.sup.5, R.sup.5 or O.sub.0.5; the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5, each on its own and independently of one another, denote an unsubstituted or substituted—optionally hetero-atom-containing—linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms; and a, b, c, d, e and f, based on a structural unit, independently of one another denote whole numbers, wherein a independently of any other is 0 or 1 or 2; b is 1 or more; c is 0 or more; d independently of any other is 0 or 1 or 2; e independently of any other is 1 or 2; and f is 0 or more, preferably 1 or more; with the proviso that b+c+f is 2 or more, for example 2.001 or more.

4. The hardener composition according to claim 3, wherein the oligomeric siloxanes include structural elements of the formula (I), wherein A and B are 3-aminopropyl, 3-am inopropyl-methyl, N-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl-methyl, N-cyclohexyl-3-aminopropyl, N-cyclohexylaminomethyl, N-phenylaminomethyl, N-cyclohexylaminomethyl, N-cyclohexylaminomethyl-methyl, 3-[2-(2-aminoethylamino)ethylamino]propyl and/or 3-mercaptopropyl and the other symbols are as defined in claim 3.

5. A synthetic fixing mortar system hardenable by addition polymerisation, including the hardener composition according to claim 1 and a hardenable epoxy- and/or isocyanate-based reactive synthetic resin.

6. The synthetic fixing mortar system according to claim 5, wherein the proportion of hardener composition is from 10 to 80% by weight.

7. The synthetic fixing mortar system according to claim 5, wherein a hardenable epoxy-based reactive synthetic resin is included.

8. The synthetic fixing mortar system according to claim 5, wherein the hardenable epoxy-based reactive synthetic resin is selected from those based on glycidyl compounds, which can optionally include further glycidyl ether(s) as reactive diluent.

9. The synthetic fixing mortar system according to claim 5, wherein a hardenable isocyanate-based reactive synthetic resin is included.

10. The synthetic fixing mortar system according to claim 5, wherein the hardenable isocyanate-based reactive synthetic resin is selected from monomeric and/or oligomeric and/or polymeric, for example polynuclear, mono-, di- or poly-isocyanates and isocyanate prepolymers customary in polyurethane and/or polyurea.

11. The synthetic fixing mortar system according to claim 5, wherein, in addition to the hardener composition, further hardeners are included therein, selected from di- or poly-amines; di- or poly-thiols.

12. The synthetic fixing mortar system according to claim 5, wherein it is a multi-component system.

13. A method of using the synthetic fixing mortar system according to any one of claims 5 to 12, comprising embedding anchoring means in mortar in a hole or crevice with the synthetic mortar system.

14. A method for fixing anchoring elements in a hole or crevice, in which a synthetic fixing mortar system according to claim 5 and an anchoring means are introduced successively or substantially simultaneously into the hole or crevice in a substrate.

15. A method of using the hardener composition according to claim 1 for producing a synthetic fixing mortar system hardenable by addition polymerisation, including the hardener composition and a hardenable epoxy- and/or isocyanate-based reactive synthetic resin, wherein the hardener composition and a reactive synthetic resin, hardenable by addition hardening are provided as constituent of components of a multi-component system.

16. The hardener composition according to claim 2, comprising at least two of the hydrolysable groups.

17. The hardener composition according to claim 3, wherein Y is OR.sup.5.

18. The synthetic fixing mortar system according to claim 8, wherein the glycidyl compounds have an average glycidyl group functionality of 1.5 or greater.

19. The synthetic fixing mortar system according to claim 8, including as reactive diluent poly(including di)-glycidyl ethers of at least one polyvalent alcohol or phenol.

20. The synthetic fixing mortar system according to claim 11, wherein the di- or poly-amines are selected from among aliphatic, heteroaliphatic, cycloaliphatic, araliphatic and aromatic di- or poly-amines, amido-amines, amine adducts, polyether diamines or polyphenyl/polymethylene-polyamines, Mannich bases, alone or in admixture with one or more further di- or poly-amines, polyamides; and the di- or poly-thiols are selected from among ethoxylated and/or propoxylated alcohols of mono-, di-, tri-, tetra-, penta-ols and/or other polyols with thiol end groups and/or thiols that include ester groups.

Description

EXAMPLE 1

Synthesis of a 3-aminopropylsiloxane Oligomer with 45% Saturation of the Alkoxy Groups

[0113] 150 g of 3-aminopropyltrimethoxysilane (Dynasilan® AMMO; Evonik Industries GmbH, Essen, Germany) were placed in a reaction flask. 75 g of methanol (solvent) were mixed with 10.00 g of water and 0.20 g of HCl 37% (catalyst) and transferred to a dropping funnel. At room temperature and normal pressure, slow dropwise addition, with stirring, from the dropping funnel to the 3-aminopropyltrimethoxysilane was carried out. When the addition was complete, the oil bath was heated at 80-100° C. so that the methanol boiled under reflux. After 4-6 hours, the methanol was distilled off as far as possible. The residues of methanol and HCl were then removed with application of a vacuum at a slowly falling pressure to 100 mbar. When 100 mbar was reached, that pressure was maintained for a further 15 minutes. The resulting residue was a 3-aminopropylsiloxane oligomer still having at least 55% hydrolysable residual methoxy groups.

[0114] Total formulation:

TABLE-US-00001 Ingredient Weight introduced [g] AMMO 150.00 Water 10.00 HCl 37% 0.20 Methanol* 75.00 *Water content: 0.05%

[0115] The siloxane oligomer prepared according to Example 1 has a mean degree of polymerisation of 3.0 (simplified calculation; for the purposes of illustration only):

n(AMMO)/[n(AMMO)−n(water)]=0.837 mol/[0.837 mol−0.565 mol]=3.07 where n(water):n(AMMO)×3×desired saturation in %/100×0.5.

[0116] VOC calculation+reduction−with reference to Example 1:

[0117] Case a: Use of monomeric AMMO

[0118] In Example 1, 150 g of AMMO are used:

TABLE-US-00002 Ingredient m [g] M [g/mol] n [mol] AMMO 150.00 179.29 0.837 Methoxy 2.510 MeOH.sub.Ammo 80.42 32.00 2.510

[0119] Accordingly, the VOC content is calculated as follows:

m(MeOHAmmo)/m(AMMO)×100=% VOC

[0120] When monomeric AMMO is used, the VOC content (monomer) is: 53.61%˜54% (rounded)

[0121] Case b: Use of oligomerised AMMO according to Example 1

[0122] In Example 1, 150 g of AMMO are oligomerised with 10.17 g of water:

TABLE-US-00003 Ingredient m [g] M [g/mol] n [mol] AMMO 150.00 179.29 0.837 Water 10.17 18.00 0.565 Hydrolysed 1.129 methoxy MeOH.sub.OUT* 36.19 32.00 1.129 * MeOH.sub.OUT: methanol removed by hydrolysis

[0123] This gives:

[0124] Methanol bound in oligomer (m(MeOH.sub.oligomer)):

m(MeOH.sub.oligomer)=m(MeOH.sub.AMMO)−m(MeOH.sub.OUT) =44.23 g Mass m(oligomer)=m(AMMO)−m(MeOH.sub.OUT)+m(water)=123.98 g

[0125] Accordingly, the VOC content (oligomer) is calculated as follows:

m(MeOH.sub.oligomer)/m(oligomer)×100=35.68% 36% (rounded)

[0126] This corresponds to a VOC reduction of:

[0127] [VOC content (monomer)−VOC content (oligomer)]/VOC content (monomer)×100 =33.46%

EXAMPLE 2

Synthesis of a 3-Aminopropyl/Mercaptopropylsiloxane Co-Oligomer with 40% Saturation of the Alkoxy Groups

[0128] 60 g of Dynasilan® AMMO and 60 g of 3-mercaptopropyltrimethoxysilane (Dynasilan® MTMO; Evonik Industries GmbH, Essen, Germany) were placed in a reaction flask. 60 g of methanol (solvent) were mixed with 6.79 g of water and 0.16 g of HCl 37% (catalyst) and transferred to a dropping funnel. At room temperature and normal pressure, the resulting mixture was slowly added dropwise from a dropping funnel, with stirring, to the 3-aminopropyltrimethoxysilane/mercaptopropyltrimethoxysilane mixture. When the addition was complete, the oil bath was heated at 80-100° C. so that the methanol boiled under reflux. After 4-6 hours, the methanol was distilled off as far as possible. The residues of methanol and HCl were then removed with application of a vacuum at a slowly falling pressure to 100 mbar. When 100 mbar was reached, that pressure was maintained for a further 15 minutes. The resulting residue was a 3-aminopropyl/mercaptopropylsiloxane co-oligomer still having at least 60% hydrolysable residual methoxy groups.

[0129] Total formulation:

TABLE-US-00004 Ingredient Weight introduced [g] AMMO 60.00 MTMO 60.00 Water 6.79 HCl 37% 0.16 Methanol* 60.00 *Water content: 0.05%

[0130] The siloxane co-oligomer prepared according to Example 2 has a mean degree of polymerisation of 2.5 (simplified calculation; for the purposes of illustration only):

(n(AMMO)+n(MTMO))/[(n(AMMO)+n(MTMO))−n(water)]=0.640 mol/[0.640 mol−0.384 mol]=2.50

[0131] where n (water):(n (AMMO)+n (MTMO))×3×desired saturation in %/100×0.5.

EXAMPLE 3

Synthetic Fixing Mortar System Based on Oligomeric Hardener

[0132] Component A:

TABLE-US-00005 Raw material Content [%] Bisphenol A/F epichlorohydrin resin 45 Trimethylolpropane triglycidyl ether 15 White Portland cement 35 Various additives, pigments and rheology aids 5

[0133] Component A has a viscosity of 75,000 mPa*s (Brookfield Sp. 7 at 23° C.)

[0134] Component B:

TABLE-US-00006 Raw material Content [%] Mannich base formulation 61 3-Aminopropylsiloxane olidomer from Example 1 26 White Portland cement 7 Various additives, pigments and rheology aids 6

[0135] Component B has a viscosity of 55,000 mPa*s (Brookfield Sp. 7 at 23° C.)

[0136] The components are subjected to an adhesion failure test, using a commercially available two-chamber cartridge with a static mixer, analogously to the conditions described in the guideline of the “European Organisation for Technical Approvals” (EOTA) (2001): ETAG No. 001 November 2006 edition, Guideline for European Technical Approval of Metal Anchors for Use in Concrete, Part 5: Bonded Anchors,

[0137] February 2008, under 5.1.2.1 (b). The mean value of the adhesion failure load from five tests for M12 bolts at an anchoring depth of 72 mm is 90.5 kN.