US20150307702A1 - Epoxy-based substance for fixing purposes, the use thereof and the use of specific components - Google Patents

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

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Publication number
US20150307702A1
US20150307702A1 US14/648,297 US201314648297A US2015307702A1 US 20150307702 A1 US20150307702 A1 US 20150307702A1 US 201314648297 A US201314648297 A US 201314648297A US 2015307702 A1 US2015307702 A1 US 2015307702A1
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Prior art keywords
component
amines
composition according
case
weight
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Abandoned
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US14/648,297
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English (en)
Inventor
Jürgen Grün
Martin Vogel
Christian Schlenk
Christian Weinelt
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Fisherwerke & Co KG GmbH
Fischerwerke GmbH and Co KG
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Fisherwerke & Co KG GmbH
Fischerwerke GmbH and Co KG
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Assigned to FISCHERWERKE GMBH & CO. KG reassignment FISCHERWERKE GMBH & CO. KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VOGEL, MARTIN, DR, GRUN, JURGEN, SCHLENK, CHRISTIAN, DR, WEINELT, CHRISTIAN
Publication of US20150307702A1 publication Critical patent/US20150307702A1/en
Priority to US15/241,201 priority Critical patent/US9796627B2/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/28Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/281Polyepoxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62Alcohols or phenols
    • C08G59/621Phenols
    • C08G59/623Aminophenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02Polycondensates containing more than one epoxy group per molecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/24Di-epoxy compounds carbocyclic
    • C08G59/245Di-epoxy compounds carbocyclic aromatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62Alcohols or phenols
    • C08G59/621Phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50Amines
    • C08G59/56Amines together with other curing agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/06Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the invention relates to 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.
  • an epoxy component (a) which contains curable epoxides
  • 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
  • Hardenable multi-component epoxy-based substances are known in principle. For example, they can be used in the production of lacquers, in the production of coatings and as moulding compounds and the like.
  • Synthetic mortar substances based on epoxy resins and amine hardeners are also known in the fixings sector, for example for the fixing of anchoring means, such as anchor rods.
  • the problem of the present invention is therefore to provide new epoxy resins for fixing purposes, especially in the building sector, which make it possible to achieve properties that are advantageous in comparison with the epoxy resins known hitherto, especially one or more of the properties improved, as above, in comparison with known substances, and more especially high pull-out values and high bond stresses, in particular also at elevated temperatures.
  • CYC is a monocyclic saturated ring having from 3 to 12 ring atoms or a condensed di- or (further) poly-cyclic saturated ring system having from 6 to 12 ring atoms, wherein in each case the ring atoms are selected from 0 to 3 nitrogen atoms, 0 to 3 oxygen atoms and 0 to 1 sulfur atoms and from carbon atoms;
  • X is CH 2 , wherein for each group —[X] n —NH 2 one X can be NH, O or S, with the proviso that in the case of X ⁇ O or S, n is at least 2 and the O or S is not bonded directly to a nitrogen atom present in the group —[X] n —NH 2 and in the case of one 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] n —NH 2 in question;
  • BAPP N,N′-bis(3-amino-n-propyl)piperazine
  • BAC 1,3-bis(aminomethyl)cyclohexane
  • AEP N-(2-aminoethyl)piperazine
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine
  • the Mannich bases to be used according to the invention are the reaction products of phenols, such as phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol, or bisphenols, such as bisphenol F or bisphenol A, especially phenol, or of styrenated phenols, as defined hereinbelow, with the “specific amines” defined hereinabove and aldehydes, or compounds yielding aldehydes by decomposition, especially aliphatic aldehydes, such as, in particular, formaldehyde (which term can also include compounds yielding formaldehyde by decomposition, such as trioxane or paraformaldehyde), the aldehydes advantageously being added and reacted in the form of an aqueous solution (especially at elevated temperature, such as at from 50 to 90° C.).
  • the preparation of the Mannich bases can be effected in accordance with methods known per se, using the above-defined “specific amines”.
  • Amine e.g. 2 mol
  • phenol or styrenated phenol e.g. 1 mol
  • Heating is carried out (e.g. at 80° C.).
  • formaldehyde is added dropwise (e.g. 0.7 mol in the form of 37% formaldehyde solution), especially with vigorous stirring.
  • further heating is carried out (for example at 105° C.) and the reaction conditions are maintained for a period of time (e.g.
  • the “low molecular weight amines” to be used in the mixture with styrenated phenols are the above-mentioned “specific amines”, especially those mentioned as being preferred, or other low molecular weight polyamines (“polyamines” also including diamines), especially oligomeric or monomeric aliphatic, cycloaliphatic, cycloheteroaliphatic, aromatic or araliphatic diamines, such as especially xylylenediamines, more especially m-xylylenediamine (1,3-bis(aminomethyl)benzene, MXDA); aliphatic polyamines, for example C 1 -C 10 alkane-di- or -poly-amines, e.g.
  • 1,2-diaminoethane, trimethylhexane-1,6-diamine, diethylenetriamine or triethylenetetraamine; oligomeric diamines of the formula H 2 N—(CH 2 ) i —NH—[(CH 2 ) j —NH] k —(CH 2 ) l —NH 2 , wherein i, j and l are each independently of the others from 2 to 4 and k is 0, 1 or 2, especially “triethylenetetramine” (TETA N,N′-bis(2-aminoethyl)ethylenediamine) or tetraethylenepentamine (TEPA); cycloaliphatic amines, such as 1,2-diaminocyclohexane or bis(aminomethyl)tricyclodecane (TCD) or bis(4-aminocyclohexyl)methane (PACM), or amine adducts; or mixtures of two or more thereof; especially mixtures of one or
  • Styrenated phenols are to be understood as being the reaction products (electrophilic substitution products) of phenols (such as phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol or p-cresol, especially phenol) with styrene or styrene analogues, such as vinyltoluene, divinylbenzene or 4-vinylpyridine, especially with styrene, especially “styrenated phenol” itself (reaction product of styrene and phenol; CAS Reg. No. 61788-44-1), which, by way of example, can contain mixtures of compounds or individual compounds of the following formulae:
  • oligo- and poly-styrene portions or compounds oligomeric or polymeric products obtained from cationic polymerisation of styrenes in phenols, for example of the formula
  • the epoxy resin component (example of a component (a) to be used according to the invention) is mixed with the corresponding Mannich base or mixture of styrenated phenol and low molecular weight amine (example of a component (b) to be used according to the invention) in stoichiometric amounts (the mixture stoichiometry is determined by the epoxy equivalent values and the H equivalents by calculation (e.g. from manufacturer's data)) and cured for 24 h at room temperature (about 23° C.).
  • the epoxy resin component in the Examples is a mixture of 40% by weight bisphenol A/F diglycidyl ether, 15% by weight trimethylolpropane triglycidyl ether and 45% by weight Portland cement. Further additional ingredients are possible.
  • the test specimen has the following dimensions: diameter 12 mm, length 40 mm.
  • the test specimen is axially compressed parallel to its main axis at a constant rate of 1 mm/min until it breaks or until the stress or decrease in length has reached a pre-set value.
  • the compressive strength is the maximum compressive stress borne by a test specimen during a compression test.
  • tensile strength in accordance with DIN EN ISO 527
  • a dumbbell test specimen in accordance with DIN EN ISO 527-2 Type 1BA is produced.
  • the test specimen is clamped in a jig and stretched along its main axis at a constant rate of 5 mm/min until it breaks.
  • the tensile strength is the maximum stress borne by the test specimen during a tensile test.
  • a hammer drill and a hammer drill bit are used to drill holes (diameter 14 mm; depth 72 mm) in a concrete test specimen (concrete type C20/25) lying in a horizontal position.
  • the drilled holes are cleaned using a hand blower and a hand brush.
  • the drilled holes are then filled two-thirds full with the particular curable substance for fixing purposes to be tested (Mannich base and/or mixture of styrenated phenols with the specific amines, in the form of an epoxy resin component a mixture of 40% by weight bisphenol A/F diglycidyl ether, 15% by weight trimethylolpropane triglycidyl ether and 45% by weight Portland cement).
  • a threaded rod is pushed into each drilled hole by hand.
  • the excess mortar is removed using a trowel. After 24 hours (minimum curing time) at room temperature, the threaded rod is subject to pulling until it fails, the failure load being measured.
  • the measurement of the viscosities is carried out with a Brookfield rotational viscometer using spindle 3 at 23° C. at from 10 to 50 rev/min, preferably 10 rev/min.
  • the measurement of the glass transition temperature is effected by means of dynamic differential calorimetry (DSC) in accordance with ISO 11357-2 on samples cured for 24 h.
  • the permissible temperature range for the cured product can likewise be determined by pull-out tests after treatment with different temperatures (for example 24 h curing at room temperature, at 50° C. and/or at 80° C.).
  • a multi-component kit is to be understood as being especially a two-component kit (preferably a two-component kit containing components (a) and (b)), preferably a two-chamber or, further, multi-chamber device, in which the components (a) and (b) that are capable of reacting with one another are contained in such a way that they are unable to react with one another during storage, the components preferably being contained in such a way that they do not come into contact with one another prior to use.
  • Capsules are a possibility.
  • cartridges or foil sachets having two or more chambers, or containers, such as buckets or tubs, having a plurality of chambers, or sets e.g.
  • a single-component or multi-component kit is a possible embodiment preferred for use, wherein, based on the total weight of the mortar component (b) introduced, the Mannich base formulation has a proportion of from 10 to 100% by weight, preferably from 30 to 75% by weight.
  • a single-component or multi-component kit especially a two-component kit, in which the mixture of styrenated phenols and low molecular weight amines, based on the total weight of the mortar component (b) introduced, has a proportion of from 10 to 100% by weight, preferably from 30 to 75% by weight, is likewise a preferred embodiment, as is also the use thereof.
  • a multi-component kit as described hereinabove and hereinbelow and especially to the use thereof according to the invention, characterised in that the Mannich base formulation or the mixture of styrenated phenols and low molecular weight amines has H equivalents in the range of from 30 to 105 and a viscosity in the range of from 50 to 10,000 mPa ⁇ s, and preferably a content of free phenol of 20% by weight or less, for example of less than 1% by weight, e.g. of 0.1% by weight or less, based on the Mannich base formulation or the mixture of styrenated phenols and low molecular weight amines.
  • the determination of the H equivalents is effected in a manner known to the person skilled in the art, with reference to the formulation of the reaction mixture, from the known H equivalents of the starting materials and raw materials used, from which they are calculated.
  • the epoxy equivalent values are generally indicated on the starting materials by the manufacturers or they are determined or calculated in accordance with known methods. They indicate the amount in g of resin that contains 1 mol of epoxy groups.
  • the ratio by volume of components (a) to (b) is 10 to “1 or less”, especially 5 to “1 or less”, preferably 3 to “1 or less”, the lower limit advantageously being 1 in each case.
  • Curable epoxy resins are preferably polyglycidyl ethers of at least one polyvalent alcohol or phenol, such as novolak, or especially bisphenol F or bisphenol A, or mixtures of two or more of those compounds, or other aromatic or heteroaromatic glycidyl ethers having an epoxy functionality of at least 2 or especially tri- or higher glycidyl ethers, or likewise mixtures of two or more of all the mentioned alternatives.
  • the epoxy resins have, for example, an epoxy equivalent of from 100 to 2000, preferably from 120 to 400.
  • the proportion in the epoxy component (a) is >0 to 100%, preferably from 10 to 60%.
  • the mortars according to the invention or for use according to the invention may contain further customary additional ingredients in one or more of their components (especially component (a), (b) or (a) and (b)) (the person skilled in the art will know to what extent such constituents should not come into contact with the components of a multi-component kit according to the invention or in accordance with the invention, such as especially a two-component kit with the components (a) and (b), prior to mixing for use).
  • reactive diluents which should not be present in a hardener component, that is to say are preferably contained (in the case of a two-component system solely) in component (a)
  • reactive diluents there can be used glycidyl ethers of aliphatic, cycloaliphatic, araliphatic or aromatic mono- or especially poly-alcohols, such as monoglycidyl ethers, e.g.
  • o-cresyl glycidyl ether and/or especially glycidyl ethers having an epoxy functionality of at least 2, such as 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, hexanediol diglycidyl ether and/or especially tri- or higher glycidyl ethers, e.g. glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether or trimethylolpropane triglycidyl ether, or, further, mixtures of two or more of those reactive diluents.
  • 1,4-butanediol diglycidyl ether such as 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, hexanediol diglycid
  • the reactive diluents are preferably present in amounts of from 0 to 60% by weight, especially from 1 to 30% by weight, based on the total weight of the epoxy component (a).
  • Fillers can be present in one or more components, for example of a multi-component kit according to the invention, for example in one or both components of a corresponding two-component kit; the proportion of fillers is preferably from 0 to 90% by weight, for example from 10 to 90% by weight.
  • fillers there are used customary fillers, such as hydraulically curable fillers, such as gypsum, quicklime, water glass or active aluminium hydroxides, or especially cements, such as Portland cement or high-alumina cements, chalks, quartz powder, corundum or the like, which can be added in the form of powder, in granular form or in the form of shaped bodies, or other fillers, such as mentioned, for example, in WO 02/079341 and WO 02/079293 (which in this regard are incorporated herein by reference), or mixtures thereof; it being further or especially possible for the fillers also to be silanised, for example in the form of amino- or epoxy-silane-treated quartz powder, such as Silbond AST or EST® from Quarzwerke GmbH, in the form of amino- or glycidyl-silane-treated silica, such as Aktisil AM or EM® from Hoffmann Mineral, or amino- or glycidyl-silane-treated pyrogenic
  • the fillers can be present in one or more components of a multi-component kit according to the invention, for example in one or both components (a) and (b) of a corresponding two-component kit; the proportion, based on the total weight of the curable substance, is preferably from 0 to 70% by weight, preferably from 5 to 60% by weight.
  • plasticisers for individual components or for a plurality of components of the compositions according to the invention or for use according to the invention there can be present plasticisers, non-reactive diluents or flexibilisers, stabilisers, catalysts, such as e.g. curing catalysts (for example salicylic acid), rheology auxiliaries, thixotropic agents, agents for controlling the reaction rate, e.g. accelerators, wetting agents, colouring additives, such as dyes or especially pigments, for example for staining the components different colours for better monitoring of the intermixing thereof, or additives, or the like, or mixtures of two or more thereof.
  • curing catalysts for example salicylic acid
  • rheology auxiliaries for example salicylic acid
  • thixotropic agents agents for controlling the reaction rate
  • accelerators e.g. accelerators, wetting agents
  • colouring additives such as dyes or especially pigments, for example for staining the components different colours for better monitoring of the intermixing thereof,
  • Such further additional ingredients can preferably be present, in total, in proportions by weight of in total from 0 to 30%, for example from 0 to 5%, based on the total curable substance. They can be present in individual components or in a plurality of components, e.g. (a) and/or (b), or in the Mannich base formulation (which is accordingly to be referred to as an “extended Mannich base formulation”) or can have been added to the mixtures of styrenated phenols with low molecular weight amines themselves.
  • the invention relates to the use of a Mannich base, as described above, in the production of hardeners for epoxy resins, especially having an enlarged processing temperature range, for increasing the load-bearing capacity at temperatures above room temperature or above 50° C., and/or for increasing the bond stress in the cured state, even at high temperatures, for example at from 70 to 80° C., in comparison with other Mannich bases, such as especially those produced with 1,2-diaminocyclohexane as amine.
  • a variant of the invention relates to the use of the Mannich bases mentioned above (especially as described above further as being preferred) or mentioned in the Examples in a multi-component kit characterised above and below as being preferred.
  • the invention relates also to a curable substance or especially to the use thereof in fixing, which curable substance contains an epoxy component (a) which contains curable epoxides (epoxy component), and a hardener component (b) which comprises a mixture of styrenated phenols with low molecular weight amines.
  • curable substance contains an epoxy component (a) which contains curable epoxides (epoxy component), and a hardener component (b) which comprises a mixture of styrenated phenols with low molecular weight amines.
  • the invention relates also to the use of a mixture of styrenated phenols with low molecular weight amines as hardener component in the production of a curable substance having curable epoxides for fixing purposes.
  • the mixture of styrenated phenols with low molecular weight amines and the curable epoxides are mixed together and brought to reaction, preferably on-site, with the fixing of fixing elements, such as anchoring elements, taking place simultaneously or immediately afterwards.
  • An embodiment of the invention relates also to the use of a Mannich base described hereinabove and hereinbelow in the production of a composition, especially the hardener component of a multi-component kit containing the components of such a composition, for the fixing of anchoring elements in drilled holes.
  • An embodiment of the invention relates also to the use of a mixture of one or more styrenated phenols with one or more low molecular weight amines, as described hereinabove and hereinbelow, in the production of a composition, especially the hardener component of a multi-component kit containing the components of such a composition, for the fixing of anchoring elements in drilled holes.
  • the invention relates also to the use of a mixture of styrenated phenols with low molecular weight amines as hardener component in the production of a curable substance containing curable epoxides for fixing purposes for increasing the load-bearing capacity at temperatures above room temperature or above 50° C., and/or for increasing the bond stress in the cured state in comparison with corresponding curable substances without the styrenated phenols.
  • Enhanced thermal stability results, for example, in better scope for use for fixing purposes, even in the event of relatively high temperatures e.g. in the drilled hole region of façade anchorings that are exposed to strong sunlight or otherwise increased temperatures.
  • tertiary amino compounds organic acids, such as carboxylic acids, e.g. salicylic acid, or sulfonic acids, e.g. p-toluenesulfonic acid, advantageously a tert-aminophenol (preferably added to component (b)), especially a 2,4,6-tris(di-C 1 -C 6 alkylamino)phenol, preferably 2,4,6-tris(dimethylamino)phenol, in hardener components (b) (especially containing Mannich base formulations used according to the invention) as a constituent of (especially multi-component, such as two-component) epoxy mortars.
  • organic acids such as carboxylic acids, e.g. salicylic acid, or sulfonic acids, e.g. p-toluenesulfonic acid
  • a tert-aminophenol preferably added to component (b)
  • the invention relates also to the use of curable substances according to the invention, especially in the form of multi-component kits, especially two-component kits, for the fixing of fibres, non-crimp fabrics, woven fabrics or composites, especially made of high-modulus fibres, preferably of carbon fibres, especially for reinforcement of buildings, for example of walls or ceilings or floors; or, further, for the fixing of building components, such as panels or blocks, e.g.
  • anchoring means such as anchor rods, bolts or the like
  • cavities such as drilled holes
  • the components of the multi-component kit after being mixed beforehand and/or while being mixed (for example by means of a static mixer or by rupturing a capsule or foil sachet or by mixing components from multi-chambered buckets or sets of buckets) are applied to the surface of a substrate or, in the case of anchoring means, introduced into cavities, such as drilled holes, in a substrate (e.g. masonry or concrete, or wood or metal).
  • a substrate e.g. masonry or concrete, or wood or metal
  • the invention relates especially to those variants of the embodiments of the invention in which the compositions are not aliphatic monoamines, or are not (meth)acrylate copolymers or they are non-aqueous, or those variants wherein two or more of those properties are realised.
  • 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).
  • Mortar component A (corresponding to (a) in the general part) is produced in accordance with the following formulation:

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  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170107189A1 (en) * 2015-10-15 2017-04-20 Dow Global Technologies Llc Tristyrylphenol monogycidyl ether
US10711116B2 (en) 2014-09-23 2020-07-14 Fischerwerke Gmbh & Co. Kg Fixing systems having fine-particle fillers
US11542363B2 (en) 2017-11-06 2023-01-03 Hilti Aktiengesellschaft Multicomponent epoxide resin composition and curing agent component therefor
US11542419B2 (en) * 2016-12-06 2023-01-03 Illinois Tool Works Inc. Cycloaliphatic-based epoxy adhesive composition

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015109125A1 (de) 2014-07-04 2016-01-07 Fischerwerke Gmbh & Co. Kg Epoxidbasiertes Befestigungskunstmörtelsystem mit Siloxanoligomeren
DE102015111484A1 (de) 2014-09-17 2016-03-17 Fischerwerke Gmbh & Co. Kg Härterzusammensetzung für additionspolymerisationsbasierte Befestigungskunstmörtelsysteme, dessen Verwendung und Herstellung
DE102015113351A1 (de) 2014-09-20 2016-03-24 Fischerwerke Gmbh & Co. Kg Härtbares Kunstharz mit erheblichen Anteilen an cyclischen Carbonatgruppen, sowie/und Cyclocarbonatharz-basierte Befestigungssysteme, deren Herstellung und Verwendung
EP3218421B1 (en) * 2014-11-11 2020-03-11 Dow Global Technologies LLC Fast curing high glass transition temperature epoxy resin system
DE102015115942A1 (de) 2014-11-20 2016-05-25 Fischerwerke Gmbh & Co. Kg Mannich-Basen, deren Herstellung und ihre Verwendung als Härter beispielsweise in Kunstharzzusammensetzungen
DE102015000875A1 (de) 2015-01-23 2016-07-28 Fischerwerke Gmbh & Co. Kg Resorcinbasierte Mannichbasen und Silane in Kunstharzzusammensetzungen für Befestigungszwecke
CN105331285A (zh) * 2015-11-11 2016-02-17 广东鸿博科技有限公司 一种用于高压开关铜排易散热绝缘涂料及其制备方法
RU2652797C1 (ru) * 2017-12-12 2018-05-03 Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д. И. Менделеева" (РХТУ им. Д. И. Менделеева) Аминный отвердитель для эпоксидных лакокрасочных композиций
JP7182699B2 (ja) * 2018-09-19 2022-12-02 ヒルティ アクチエンゲゼルシャフト エポキシ樹脂組成物用の硬化剤、エポキシ樹脂組成物、および多成分エポキシ樹脂系
EP3786133A1 (de) 2019-08-27 2021-03-03 Hilti Aktiengesellschaft Mörtelmasse mit mannichbasen für befestigungszwecke mit verbesserter temperaturfestigkeit
KR102391491B1 (ko) * 2019-11-20 2022-04-27 주식회사 엘지화학 경화성 조성물
EP3838981A1 (de) * 2019-12-18 2021-06-23 Hilti Aktiengesellschaft Reaktivharzkomponente, diese enthaltendes reaktivharzsystem und deren verwendung
JP6816319B1 (ja) * 2020-02-21 2021-01-20 日進化成株式会社 コンクリート接着用の二液混合型接着剤およびコンクリート補強方法
EP4310124A1 (de) 2022-07-20 2024-01-24 Hilti Aktiengesellschaft Mehrkomponenten-zusammensetzung für befestigungszwecke mit nicht stöchiometrischen eew/ahew anteilen, daraus hergestellte mörtelmasse und daraus hergestellter chemischer dübel

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010035111A1 (en) * 2000-01-21 2001-11-01 Roland Gienau Curable two-component mortar composition and its use
JP2008088348A (ja) * 2006-10-04 2008-04-17 Aica Kogyo Co Ltd エポキシ樹脂組成物
US20120010329A1 (en) * 2009-02-24 2012-01-12 Hunter Gary A Curable epoxy resin compositions and cured products therefrom

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57195119A (en) * 1981-05-25 1982-11-30 Mitsubishi Gas Chem Co Inc Preparation of curing agent for epoxy resin
DE3233565A1 (de) 1982-09-10 1984-03-15 Hoechst Ag, 6230 Frankfurt Haertungsmittel fuer epoxidharze und verfahren zum haerten von epoxidharzen
DE4139069A1 (de) * 1991-04-13 1992-10-15 Koch Marmorit Gmbh Verfahren und mittel zum verankern von schrauben in bohrloechern
US5387266A (en) * 1993-06-11 1995-02-07 Ethyl Corporation Mannich base derivatives, and the production and uses thereof
DE4331052A1 (de) * 1993-09-13 1995-03-16 Hoechst Ag Härtungskomponente für Epoxidharze
DE4410785A1 (de) * 1994-03-28 1995-10-05 Hoechst Ag Amin-modifizierte Epoxidharz-Zusammensetzung
EP0872504A1 (en) 1995-08-04 1998-10-21 Asahi Denka Kogyo Kabushiki Kaisha Curable epoxy resin composition which gives flexible cured article
EP0870790A1 (en) 1995-08-04 1998-10-14 Asahi Denka Kogyo Kabushiki Kaisha Curable epoxy resin composition
DE19625344A1 (de) 1996-06-25 1998-01-08 Herberts Gmbh Wäßriges Überzugsmittel und dessen Verwendung zur Herstellung von Füllerschichten
RU2186802C1 (ru) * 2001-01-05 2002-08-10 Лапицкая Татьяна Валентиновна Полимерная композиция
DE10115587B4 (de) 2001-03-29 2017-06-14 Fischerwerke Gmbh & Co. Kg Verwendung eines Harzes mit bestimmten härtbaren Harnstoffderivaten zur Befestigung mit Hilfe von Verankerungsmitteln
DE10115591A1 (de) 2001-03-29 2002-10-02 Fischer Artur Werke Gmbh Mehrkomponentenkits und Kombinationen, ihre Verwendung und erhältliche Kunstmörtel
DE102004008464A1 (de) 2004-02-19 2005-09-15 Fischerwerke Artur Fischer Gmbh & Co. Kg Mehrkomponentenkit für Befestigungszwecke und dessen Verwendung
US7572506B2 (en) 2004-06-30 2009-08-11 E. I. Du Pont De Nemours And Company Aqueous primer surfacer compositions
JP5526618B2 (ja) * 2009-06-23 2014-06-18 三菱瓦斯化学株式会社 エポキシ樹脂硬化剤及びエポキシ樹脂組成物
CN102549041A (zh) * 2009-09-25 2012-07-04 陶氏环球技术有限责任公司 可固化环氧树脂组合物及由其制备的复合材料
DE202010018070U1 (de) 2010-03-16 2013-11-20 Fischerwerke Gmbh & Co. Kg Epoxidbasierter Befestigungsmörtel mit Silanzusätzen
DE102011015193A1 (de) 2011-03-25 2012-09-27 Momentive Specialty Chemicals Gmbh Epoxidierte Arylalkylphenole

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010035111A1 (en) * 2000-01-21 2001-11-01 Roland Gienau Curable two-component mortar composition and its use
JP2008088348A (ja) * 2006-10-04 2008-04-17 Aica Kogyo Co Ltd エポキシ樹脂組成物
US20120010329A1 (en) * 2009-02-24 2012-01-12 Hunter Gary A Curable epoxy resin compositions and cured products therefrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Yoshida et al., JP 2008-088348 A machine translation in English, 04/17/2008. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10711116B2 (en) 2014-09-23 2020-07-14 Fischerwerke Gmbh & Co. Kg Fixing systems having fine-particle fillers
US11795301B2 (en) 2014-09-23 2023-10-24 Fischerwerke Gmbh & Co. Kg Fixing systems having fine-particle fillers
US20170107189A1 (en) * 2015-10-15 2017-04-20 Dow Global Technologies Llc Tristyrylphenol monogycidyl ether
US11542419B2 (en) * 2016-12-06 2023-01-03 Illinois Tool Works Inc. Cycloaliphatic-based epoxy adhesive composition
US11542363B2 (en) 2017-11-06 2023-01-03 Hilti Aktiengesellschaft Multicomponent epoxide resin composition and curing agent component therefor

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US20160355437A1 (en) 2016-12-08
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CN104837887B (zh) 2019-01-29
DE202013012733U1 (de) 2018-12-12
BR112015013087B1 (pt) 2021-04-06
BR112015013087A2 (pt) 2017-07-11
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DE102013113465A1 (de) 2014-06-12
CN104837887A (zh) 2015-08-12

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