EP3962984A1 - Composition de durcisseur pour résine époxyde, résine époxyde et système de résine époxyde à plusieurs composants ayant un meilleur durcissement à basse température - Google Patents

Composition de durcisseur pour résine époxyde, résine époxyde et système de résine époxyde à plusieurs composants ayant un meilleur durcissement à basse température

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Publication number
EP3962984A1
EP3962984A1 EP20718346.8A EP20718346A EP3962984A1 EP 3962984 A1 EP3962984 A1 EP 3962984A1 EP 20718346 A EP20718346 A EP 20718346A EP 3962984 A1 EP3962984 A1 EP 3962984A1
Authority
EP
European Patent Office
Prior art keywords
epoxy resin
salts
component
composition
hardener
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20718346.8A
Other languages
German (de)
English (en)
Inventor
Nicole Behrens
Alexander Bornschlegl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hilti AG
Original Assignee
Hilti AG
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Filing date
Publication date
Application filed by Hilti AG filed Critical Hilti AG
Publication of EP3962984A1 publication Critical patent/EP3962984A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/40—Macromolecules 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/68—Macromolecules 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 catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/68—Macromolecules 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 catalysts used
    • C08G59/686—Macromolecules 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 catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates 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
    • C08G59/18—Macromolecules 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
    • C08G59/68—Macromolecules 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 catalysts used
    • C08G59/687—Macromolecules 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 catalysts used containing sulfur

Definitions

  • the invention relates to a hardener composition for a multi-component epoxy resin compound for the chemical fastening of structural elements, an epoxy resin compound and a multi-component epoxy resin system.
  • the invention also relates to a method for chemical fastening of structural elements in boreholes.
  • the invention also relates to the use of a combination of a salt (S) with a phenol derivative in an epoxy resin compound for the chemical fastening of construction elements, in particular at low temperatures ( ⁇ 0 ° C.), to improve the hardening and the pull-out strength.
  • Multi-component mortars based on curable epoxy resins and amine hardeners have been known for a long time and are used as adhesives and fillers for filling cracks and chemical dowels for fastening structural elements such as anchor rods, rebars and screws in boreholes on various substrates.
  • these mortar masses often show extremely long curing times at low temperatures ⁇ 0 ° C or it is not possible to achieve a sufficient curing reaction, so that corresponding masses are not suitable for chemical fastening of construction elements due to the non-existent or very poor load capacity (failure loads) .
  • multicomponent mortar masses based on curable epoxy resins and amine hardeners are described, which show a very good load-bearing capacity at high temperatures.
  • the as yet unpublished European applications with application numbers 18195417.3, 18195422.3 and 18195415.7 describe multi-component epoxy resin systems in which the hardener component is a salt (S) selected from the group consisting of salts of nitric acid, salts of nitric acid, salts of halogens and salts which contains trifluoromethanesulfonic acid.
  • S salt
  • These multi-component mortar masses all show an inadequate load-bearing capacity as soon as they are used at low temperatures ⁇ 0 ° C Drilled hole are applied and cured at correspondingly low temperatures. Accordingly, it is not possible to use these multi-component mortars in certain countries in winter or in countries with low average temperatures.
  • the object of the invention is therefore to provide a hardener component for multicomponent epoxy resin compounds, the mortar compound produced from the multi-component epoxy resin compound being suitable for fastening purposes and having an improved pull-out strength at low temperatures ( ⁇ 0 ° C) compared to conventional mortar compounds.
  • the mortar compound produced from the multicomponent epoxy resin compound should have a similar or, if possible, even slightly improved pull-out strength at standard temperatures (20 to 25 ° C.) compared to conventional mortar compounds.
  • hardener composition (B) according to claim 1.
  • Preferred embodiments of the hardener composition (B) according to the invention are specified in the subclaims, which can optionally be combined with one another.
  • the invention also relates to an epoxy resin composition according to claim 9 and a multicomponent epoxy resin system according to claim 11.
  • Preferred embodiments of the epoxy resin composition according to the invention and the multicomponent epoxy resin system are specified in the dependent claims, which can optionally be combined with one another.
  • the subject matter of the invention is also a method for the chemical fastening of construction elements in boreholes according to claim 13.
  • the invention further comprises the use of at least one salt (S) selected from the group consisting of salts of nitric acid, salts of nitrous acid, salts of halogens and salts of trifluoromethanesulfonic acid in combination with at least one phenol derivative to improve the pull-out strengths of Epoxy resin compositions at low temperatures, preferably at ⁇ 0 ° C, preferably in a range from 0 ° C to -10 ° C, according to claim 14.
  • S salt selected from the group consisting of salts of nitric acid, salts of nitrous acid, salts of halogens and salts of trifluoromethanesulfonic acid in combination with at least one phenol derivative to improve the pull-out strengths of Epoxy resin compositions at low temperatures, preferably at ⁇ 0 ° C, preferably in a range from 0 ° C to -10 ° C, according to claim 14.
  • a hardener composition (B) for an epoxy resin compound which contains at least one amine reactive towards epoxy groups and at least one salt (S) selected as an accelerator from the group consisting of salts of nitric acid, salts of nitrous acid, salts of halogens, salts of trifluoromethanesulphonic acid and combinations thereof, wherein the hardener component (B) additionally comprises at least one phenol derivative as an accelerator.
  • the use of the hardener composition (B) according to the invention in an epoxy resin composition for fastening purposes leads to a considerable improvement in the curing reaction at temperatures ⁇ 0 ° C and thus also to a considerable improvement in the pull-out strengths at temperatures of ⁇ 0 ° C.
  • the cured compositions show excellent pull-out strength at temperatures of ⁇ 0 ° C, preferably in a range of ⁇ 0 ° C to -10 ° C. Compared to conventional masses, the masses according to the invention can be loaded after a shorter time (90% of the reference load).
  • the hardener composition (B) according to the invention and the epoxy resin compositions produced therefrom are therefore particularly suitable for use in countries with a cold temperature profile.
  • Aliphatic compounds are acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds;
  • Cycloaliphatic compounds are compounds with a carbocyclic ring structure, excluding benzene derivatives or other aromatic systems;
  • “Araliphatic compounds” are aliphatic compounds with an aromatic backbone, so that in the case of a functionalized araliphatic compound, an existing functional group is attached to the aliphatic and not the aromatic part of the compound; “Aromatic compounds” are compounds that follow the Hückel (4n + 2) rule;
  • Amines are compounds which are derived from ammonia by replacing one, two or three hydrogen atoms with hydrocarbon groups and have the general structures RNH 2 (primary amines), R 2 NH (secondary amines) and R 3 N (tertiary amines) ( see: IUPAC Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”), Compiled by AD McNaught and A. Wilkinson, Blackwell Scientific Publications, Oxford (1997));
  • Salts are compounds made up of positively charged ions (cations) and negatively charged ions (anions). Ionic bonds exist between these ions.
  • the expression “salts of nitric acid” describes compounds which are derived from nitric acid (HNO 3 ) and which contain a nitrate (NO 3 ) as an anion.
  • the expression “salts of nitrous acid” describes compounds which are derived from nitrous acid (HNO 2 ) and which contain a nitrite (NO 2 ) as an anion.
  • salts of halogens describes compounds which contain an element of the 7th main group of the periodic table as an anion.
  • salts of the halogens is to be understood as meaning compounds which include a fluoride (F), chloride (CI), a bromide (Br) or iodide (I) as an anion.
  • salts of trifluoromethanesulfonic acid describes compounds which are derived from trifluoromethanesulfonic acid (CF 3 SO 3 H) and which include a triflate (CF 3 SO 3 ) as an anion.
  • salt (S) in the context of the present invention also includes the corresponding hydrates of the salts.
  • the salts (S) which are used as accelerators are also referred to as salts in the context of the present invention;
  • Phenol derivatives is a collective term for all compounds derived from phenol (empirical formula C 6 H 5 OH). In the case of the phenol derivatives, one or more of the hydrogen atoms bonded to the aromatic ring is substituted by hydrocarbon groups which may contain heteroatoms.
  • Novolak resin is the name for polycondensation products made from formaldehyde or formaldehyde precursors with phenolic compounds such as phenol, cresol, bisphenol A or F and cardanol derivatives.
  • the hardener composition (B) comprises at least one amine which is reactive toward epoxy groups.
  • Corresponding amines are generally known to the person skilled in the art.
  • the at least one amine which is reactive towards epoxide groups is preferably selected from the group consisting of aliphatic, alicyclic, aromatic and araliphatic amines and which has on average at least two reactive hydrogen atoms bound to a nitrogen atom per molecule.
  • 1,2-diaminoethane ethylenediamine
  • 1,2-propanediamine 1,3-propanediamine
  • 1,4-diaminobutane 2,2 -Dimethyl-1,3-propanediamine (neopentanediamine), diethylaminopropylamine (DEAPA)
  • 2-methyl-1,5-diaminopentane 1,3-diaminopentane
  • 2,2,4- or 2,4,4-trimethyl-1, 6- diaminohexane and mixtures thereof TMD
  • 1,3-bis (aminomethyl) -cyclohexane 1,2-bis (aminomethyl) cyclohexane, hexamethylenediamine (HMD), 1,2 and 1,4-diaminocyclohexane (1,2 -DACH and 1, 4-DACH)
  • Diaminodicyclohexylmethane (PACM), diethylmethylbenzenediamine (DETDA), 4,4'-diaminodiphenyl sulfone (Dapsone), mixed polycyclic amines (MPCA) (e.g.
  • Ancamine 2168 dimethyldiaminodicyclohexylmethane (Laromin C260), 2,2-bis (4-yl) aminocyclo (3 (4), 8 (9) bis (aminomethyldicyclo [5.2.1.0 2 ' 6 ] decane) (Mixture of isomers, tricyclic primary amines; TCD-diamine), methylcyclohexyl-diamine (MC DA), N, N'-diaminopropyl-2-methyl-cyclohexane-1, 3-diamine, N, N'-diaminopropyl-4-methyl- cyclohexan-1,3-diamine, N- (3-aminopropyl) cyclohexylamine, and 2- (2, 2,6,6-tetramethylpiperidin-4-yl) propane-1,3-diamine.
  • TCD-diamine methylcyclohexyl-diamine
  • MC DA methylcyclohexy
  • Preferred amines in the hardener composition (B) according to the invention are polyamines, such as 2-methylpentanediamine (DYTEK A), 3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1,3-benzene dimethanamine (m-xylylenediamine, MXDA), 1 , 4-benzenedimethanamine (p-xylylenediamine, PXDA), 1,6-diamino-2,2,4-trimethylhexane (TMD), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), N -Ethylaminopiperazine (N-EAP), (3 (4), 8 (9) bis (aminomethyl) dicyclo [5.
  • DYTEK A 2-methylpentanediamine
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexane
  • IPDA 1,3-
  • decane (mixture of isomers, tricyclic primary amines; TCD diamine), 1, 14- Diamino-4,11-dioxatetradecane, dipropylenetriamine, 2-methyl-1,5-pentanediamine, N, N'-dicyclohexyl-1,6-hexanediamine, N, N'-dimethyl-1,3-diaminopropane, N, N ' -Diethyl-1,3-diaminopropane, N, N-dimethyl-1,3-diaminopropane, secondary polyoxypropylenedi- and triamines, 2,5-diamino-2,5-dimethylhexane, bis (aminomethyl) tricyclopentadiene, 1,8 -Diamino-p-menthane, bis (4-amino-3,5-dimethylcyclohexyl) methane, 1,3-bis (aminomethyl)
  • the amines can be used either individually or as a mixture of two or more of the amines mentioned.
  • the amine (s) reactive towards epoxy groups is / are in the hardener composition preferably in a proportion of 10 to 90% by weight, particularly preferably 35 to 70% by weight, based on the total weight of the hardener composition (B) contain.
  • thiols, dithiols and / or polythiols can also be used, which are preferably selected from the group consisting of aliphatic, alicyclic, aromatic and araliphatic thiols and mixtures thereof. It is also possible for the at least one amine which is reactive towards epoxide groups to comprise at least one Mannich base. This can be used alone or in combination with the aforementioned amines.
  • the Mannich bases used are the reaction products of an amine and an aldehyde with a phenolic compound consisting of phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol, bisphenols such as bisphenol F. or bisphenol A, and combinations thereof.
  • a phenolic compound consisting of phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol, bisphenols such as bisphenol F. or bisphenol A, and combinations thereof.
  • the phenolic compound is reacted with a preferably primary or secondary amine and an aldehyde or an aldehyde precursor which decomposes to give an aldehyde.
  • the aldehyde or the aldehyde precursor can advantageously be added to the reaction mixture as an aqueous solution, in particular at an elevated temperature of about 50 ° C. to 90 ° C., and reacted with the amine and the phenolic compound.
  • Phenol or a styrenated phenol, resorcinol, styrenated resorcinol, bisphenol A or bisphenol F, particularly preferably phenol or a styrenated phenol, styrenated resorcinol or bisphenol A, are used as the phenolic compound to form the Mannich base.
  • the aldehyde used to form the Mannich base is preferably an aliphatic aldehyde, particularly preferably formaldehyde.
  • Trioxane or paraformaldehyde which decompose to formaldehyde by heating in the presence of water, can preferably be used as the aldehyde precursor.
  • the amine used to react with the aldehyde and the phenolic compound to form the Mannich base is preferably one of the above-mentioned amines and preferably 1,3-benzenedimethanamine (MXDA), 3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA) , 1, 3-bis (aminomethyl) cyclohexane (1, 3-BAC), 1, 2- and 1, 4-diaminocyclohexane (1, 2-DACH and 1, 4-DACH), diaminodicyclohexylmethane (PACM), methylcyclohexyl-diamine (MCDA) and 5- (aminomethyl) bicyclo [[2.2.1] hept-2-yl] methylamine (NBDA).
  • MXDA 1,3-benzenedimethanamine
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexane
  • IPDA 3-bis (aminomethyl) cyclohexane
  • 1-BAC 1, 2- and
  • the amine is preferably present in an excess so that the Mannich base has free amino groups.
  • the amine used to react with the aldehyde and the phenolic compound to form the Mannich base can also be an aminosilane that is selected from the group consisting of 3-aminoalkyltrialkoxysilanes, such as 3-aminopropyltri (m) ethoxysilane, 3-aminoalkylalkyldialkoxysilane like 3-
  • Aminopropylmethyldi (m) ethoxysilane N- (aminoalkyl) -3-aminoalkyltrialkoxysilanes, such as N- (2-aminoethyl) -3-aminopropyltri (m) ethoxysilane, N- (aminoalkyl) -3-aminoalkyl-alkyldialkoxysilanes, such as N- (2 -Aminoethyl) -3-aminopropylmethyldi (m) ethoxysilane, 3- [2- (2-aminoethylamino) ethylamino] propyltri (m) ethoxysilane, bis- (gamma-
  • Trimethoxysilylpropyl) amine or mixtures thereof; or further selected from the group consisting of N-cyclohexyl-3-aminopropyltri (m) ethoxysilane, N-cyclohexylaminomethylmethyldiethoxysilane, N-cyclohexylaminomethyltriethoxysilane, 3-ureidopropyltri (m) ethoxysilane, N-methyl [3- (thoethoxysil - Trimethoxysilylmethyl-O-methylcarbamate and N-dimethoxy (methyl) silylmethyl-0-methylcarbamate.
  • the Mannich base is present in the hardener composition (B) in a proportion of 10% by weight to 70% by weight, preferably 15% by weight to 60% by weight, more preferably 20% % By weight to 50% by weight and particularly preferably from 25% by weight to 40% by weight, based on the total weight of the hardener composition (B).
  • the at least one amine which is reactive towards epoxide groups comprises at least one benzoxazine-amine adduct.
  • This can be used alone or in combination with the aforementioned amines.
  • the benzoxazine-amine adduct is selected from the group consisting of substances according to formula la, substances according to formula Ib and mixtures thereof, with the following structures:
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from H, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylalkyl, heteroalkyl, alkoxy, hydroxyl, Hydroxyalkyl, carboxyl, halo, haloalkyl, amino, aminoalkyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonylamino, aminosulfonyl, sulfonic acid or alkylsulfonyl radicals, in addition from combinations of two or more these radicals, it being possible for the radicals in each case to be unsubstituted or optionally substituted;
  • R 6 and R 7 each independently represent H or an amino, diamino or polyamino radical selected from the group consisting of aliphatic, alicyclic, aromatic amine radicals and also combinations of two or more of these radicals, the radicals in each case being selected may be unsubstituted or optionally substituted;
  • Z is selected from a direct bond, -C (O) -, -S-, -O-, -S (O) -, -S (0) 2 -, -C (R 8 ) (R 9 ) - , - [C (R 8 ) (R 9 )] m -C (R 8 ) (R 9 ) - [C (R 10 ) (R 11 )] n-, - [C (R 8 ) (R 9 ) ] m -C (R 8 ) (aryl) -
  • R 3 and R 5 are each H.
  • Z is also preferably selected from a direct bond, -C (R 8 ) (R 9 ) -, - C (R 8 ) (aryl) -, -C (O) -, -S-, -O-, - S (O) -, -S (0) 2 -, a divalent heterocycle, and - [C (R 8) (R 9)] m arylene [C (R 10) (R 1 1)] n -, where m and n are each independent of one another are 0 to 5.
  • Z is particularly preferably selected from a direct bond or -C (R 8 ) (R 9 ) -, where R 8 and R 9 are each independently selected from H or Cr C4-alkyl radicals, preferably H or methyl, or together a divalent lactone radical form.
  • R 3 and R 5 in the benzoxazine-amine adduct according to structures la and Ib are each H, and Z has the meaning given above.
  • the benzoxazine-amine adduct is present in the hardener composition (B) in a proportion of 10% by weight to 70% by weight, preferably 15% by weight to 60% by weight, more preferably from 20% by weight to 50% by weight and particularly preferably from 25% by weight to 40% by weight, based on the total weight of the hardener composition (B).
  • the benzoxazine-amine adduct is obtained by reacting at least one benzoxazine component with at least one amine component, preferably an aromatic or araliphatic amine, a diamine and / or polyamine component.
  • Suitable benzoxazines for the preparation of the benzoxazine-amine adduct without limiting the scope of the invention, preferably have the following structure:
  • R 3 and R 5 are each H, and Z is selected from a direct bond, -C (R 8 ) (R 9 ) -, -C (R 8 ) (aryl) -, -C ( O) -, -S-, -O-, -S (O) -, -S (0) 2 -, a divalent heterocycle and - [C (R 8 ) (R 9 )] m -
  • Z is particularly preferably selected from a direct bond or -C (R 8 ) (R 9 ) -, where R 8 and R 9 are each independently selected from H or Ci-C4-alkyl radicals, preferably H or methyl, or a divalent one together Form lactone residue.
  • the benzoxazines are preferably selected from the following structures:
  • Suitable amines for the preparation of the benzoxazine-amine adduct without restricting the scope of the invention are preferably selected from the group of the unbranched or branched C2-Cio-alkyldiamines, the C2-Cio-polyalkylene-polyamines and the aromatic and araliphatic amines, which preferably contain a substituted or unsubstituted benzene ring.
  • the amine can be used either alone or as a mixture of two or more of the amines mentioned. An amine mixture which is composed of two or more amines has proven advantageous.
  • benzoxazine and amine components for the preparation of a benzoxazine-amine adduct all of the substances mentioned above or mixtures thereof can be considered.
  • Various production processes for the benzoxazine-amine adduct are known to those skilled in the art known.
  • To prepare the benzoxazine-amine adduct one of the abovementioned benzoxazine components is preferably dissolved in a solvent and reacted with the amine component at an elevated temperature.
  • the amine is preferably added in excess.
  • the benzoxazine can also be dissolved in an excess of amine component.
  • the reaction time is preferably 30 hours or less, more preferably 26 hours or less and particularly preferably at most about 24 hours.
  • the hardener composition (B) contains at least one salt (S) as an accelerator.
  • the salt (S) is at least one salt selected from the group consisting of salts of nitric acid, salts of nitric acid, salts of halogens, salts of trifluoromethanesulphonic acid and combinations thereof.
  • the salt (S) is preferably at least one salt selected from the group consisting of salts of nitric acid, salts of halogens, salts of trifluoromethanesulfonic acid and combinations thereof.
  • the salt (S) is selected from the group consisting of nitrates (NOt), iodides (I), triflates (CF3SO3) and combinations thereof. It is particularly preferred that the salt (S) comprises at least one nitrate (NO3)
  • Particularly suitable salts of nitric acid are alkali metal nitrates, alkaline earth metal nitrates, lanthanoid nitrates, aluminum nitrate, ammonium nitrate and mixtures thereof.
  • Corresponding salts of nitric acid are commercially available.
  • the salts of nitric acid used are preferably alkali metal nitrates and / or alkaline earth metal nitrates, such as Ca (NO 3 ) 2 or NaN0 3 .
  • a solution of a salt in nitric acid is used as the salt (S), such as, for example, a solution containing Ca (NO 3 ) 2 / HN0 3 . To prepare this solution, CaC0 3 is dissolved in HNO 3 .
  • Particularly suitable salts of nitrous acid are alkali metal nitrites, alkaline earth metal nitrites, lanthanoid nitrites, aluminum nitrite, ammonium nitrite and mixtures thereof.
  • Corresponding salts of nitrous acid are commercially available.
  • the salts of nitrous acid used are preferably alkali metal nitrites and / or alkaline earth metal nitrites, such as, for example, Ca (N0 2 ) 2 .
  • Particularly suitable salts of the halogens are alkali metal halides, alkaline earth metal halides, lanthanide halides, aluminum halides,
  • halogens are commercially available.
  • the halogens are preferably selected from the group consisting of chloride, bromide, iodide and mixtures thereof, iodides in particular being used with preference.
  • Particularly suitable salts of trifluoromethanesulfonic acid are alkali metal triflates, alkaline earth metal triflates, lanthanoid triflates, aluminum triflate, ammonium triflate and mixtures thereof.
  • Corresponding salts of trifluoromethanesulfonic acid are commercially available.
  • the salts of trifluoromethanesulfonic acid used are preferably alkali metal nitrates and / or alkaline earth metal nitrates, such as Ca (CF 3 S0 3 ) 2, for example.
  • the cations of the salt (S) can be organic, inorganic or a mixture thereof.
  • the cation of the salt (S) is preferably an inorganic cation.
  • Suitable organic cations are, for example, with organic radicals, such as, for example, ammonium cations substituted with Ci-C 6 -alkyl radicals, such as tetraethylammonium cations.
  • the inorganic cations of the salt (S) are preferably cations selected from the group consisting of alkali metals, alkaline earth metals, lanthanoids, aluminum, ammonium (NH 4 + ) and mixtures thereof, more preferably from the group consisting of alkali metals, alkaline earth metals, Aluminum, ammonium and mixtures thereof, and even more preferably from the group consisting of alkali metals, alkaline earth metals, aluminum and mixtures thereof. It is particularly preferred that the cation of the salt (S) is selected from the group consisting of sodium, calcium, aluminum, ammonium and mixtures thereof.
  • the following compounds or components are therefore particularly suitable as salt (S): Ca (NC> 3 ) 2 (calcium nitrate, usually used as Ca (NC> 3 ) 2 Tetrahydrate), a mixture of Ca (N0 3 ) 2 / HNC> 3 , KNO3 (potassium nitrate), NaNCh (sodium nitrate), Mg (NÜ3) 2 (magnesium nitrate, usually used as Mg (NC> 3) 2 hexahydrate), AI ( NC> 3) 3 (aluminum nitrate, usually used as AI (NC> 3) 3 nonahydrate), NH4NO3 (ammonium nitrate), Ca (NÜ2) 2 (calcium nitrite), NaCI (sodium chloride), NaBr (sodium bromide), Nal (sodium iodide), Ca (CF3SC> 3) 2 (calcium triflate), Mg (CF 3 S0 3 ) 2 (magnesium triflate), Li (CF3SC
  • the hardener composition (B) according to the invention can have one or more salts (S).
  • the salts can be used either individually or as a mixture of two or more of the salts mentioned.
  • the salt (S) is dissolved in a suitable solvent and used accordingly as a solution.
  • Organic solvents such as methanol, ethanol or glycerine are suitable for this.
  • water can also be used as the solvent, optionally also as a mixture with the aforementioned organic solvents.
  • the salt (S) is added to the solvent and stirred, preferably until it is completely dissolved.
  • the salt (S) is preferably contained in the hardener composition (B) in a proportion of 0.1 to 15% by weight, based on the total weight of the hardener composition (B).
  • the salt (S) is preferably present in a proportion of 0.2 to 12% by weight, more preferably in a proportion of 0.8 to 10% by weight, even more preferably in a proportion of 1.0 to 8.0% by weight. -% based on the total weight of the hardener composition (B) contained in the hardener composition (B).
  • the hardener composition (B) also comprises at least one phenol derivative in addition to the at least one salt (S) as an accelerator.
  • the phenol derivative is preferably selected from the group consisting of polyphenols from the group of novolak resins, styrenated phenols, phenolic lipids and combinations thereof.
  • Compounds of the following formula (III) are preferably used as polyphenols from the group of novolak resins:
  • R20 and R21 each independently represent H or -CH3;
  • R 22 , R 23 , R 24 and R 25 each independently represent H, —CH 3 or an aliphatic radical, preferably a linear, optionally partially unsaturated, unbranched hydrocarbon chain with up to 15 carbon atoms, or an alkaryl radical, preferably -CsHg; and where
  • a is 0-20, preferably 0-15.
  • the polyphenol from the group of novolak resins particularly preferably corresponds to the following formula (IV):
  • R26 denotes a C1-C15-alkyl radical, preferably a methyl radical or tert-butyl radical;
  • b is 0, 1 or 2, and is preferably 1;
  • c is 0-15, and preferably 0-6.
  • the novolak resin very particularly preferably corresponds to the above formula (IV), in which R26 is CH3 and b is 1 or 2, or R26 is tert-butyl or a C1 -C15 alkyl radical and b is 1, and where c is 0 to 15, preferably 1 to 15.
  • styrenated phenols includes the electrophilic substitution products of phenols such as phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol or p-cresol with styrene or styrene analogs, such as vinyltoluene or vinylpyrinylbenzidine, in particular Understand styrene.
  • the styrenated phenol is particularly preferably selected from the reaction products of styrene and phenol which contain mixtures of compounds or individual compounds of the following formulas:
  • 2,6-distyrylphenol such as oligo- and polystyrene compound components or compounds (products from the cationic polymerization of styrenes in phenols, oligo- or polymeric products obtained).
  • phenolic lipids is a collective term for a class of natural products that includes long aliphatic chains and phenolic rings.
  • the phenolic lipid is selected from alkyl catechols, alkyl phenols, alkyl resorcinols and anacardic acids.
  • the at least one phenolic lipid is particularly preferably an alkylphenol selected from propylphenol, butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol and cardanol-based compounds.
  • the hardener composition (B) according to the invention can have one or more phenol derivatives.
  • the phenol derivatives can be used either individually or as a mixture of two or more of the phenol derivatives mentioned.
  • the hardener composition (B) according to the invention contains the phenol derivative preferably in a proportion of 4 to 25% by weight, preferably in a proportion of 10 to 20% by weight, based on the total weight of the hardener composition.
  • the phenol derivative is at least one polyphenol selected from the group of novolak resins and is combined with a salt (S) selected from the group of nitrates.
  • the weight percentage ratio of all phenol derivatives, in particular the polyphenols from the group of novolak resins, to all salts (S) in the hardener composition (B) according to the invention is preferably 250: 1 to 1: 4, preferably 40: 1 to 1: 2.
  • the hardener composition (B) comprises at least one further additive selected from the group of further accelerators, adhesion promoters, thickeners and fillers.
  • Non-reactive diluents can preferably be present in an amount of up to 30% by weight, based on the total weight of the hardener composition, for example from 1 to 20% by weight.
  • suitable solvents are alcohols such as methanol, ethanol or glycols, lower alkyl ketones such as acetone, di-lower alkyl lower alkanoylamides such as dimethylacetamide, lower alkylbenzenes such as xylenes or toluene, phthalic acid esters or paraffins.
  • the amount of solvents is preferably ⁇ 5% by weight based on the total weight of the hardener composition.
  • Tertiary amines or imidazoles, organophosphines, Lewis bases or acids such as phosphoric acid esters, or mixtures of two or more thereof can be used as further accelerators.
  • the further accelerators are contained in the hardener composition (B) in a weight proportion of 0.001 to 20% by weight, preferably 0.001 to 5% by weight, based on the total weight of the hardener composition (B).
  • suitable accelerators are in particular tris-2,4,6-dimethylaminomethylphenol, 2,4,6-tris (dimethylamino) phenol and bis [(dimethylamino) methyl] phenol.
  • a suitable accelerator mixture contains 2,4,6-tris (dimethylaminomethyl) phenol and bis (dimethylaminomethyl) phenol.
  • Such mixtures are commercially available, for example as Ancamine® K54 (Evonik).
  • adhesion promoter improves the cross-linking of the borehole wall with the mortar compound, so that the adhesion increases in the hardened state.
  • Suitable adhesion promoters are selected from the group of silanes that have at least one Si-bonded hydrolyzable group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-
  • Epoxycyclohexyl) ethyltrimethoxysilane N-2- (aminoethyl) -3-aminopropylmethyl-diethoxysilane, N-2- (aminoethyl) -3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminoethyl- 3-aminopropyl-trimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-
  • AMMO 3-aminopropyl-trimethoxysilane
  • AMO 3-aminopropyltriethoxysilane
  • DAMO 2- Aminoethyl-3-aminopropyl-trimethoxysilane
  • Trimethoxysilylpropyldiethylenetetramine (TRIAMO) is preferred. Further silanes are described, for example, in EP3000792 A1, the content of which is hereby included in the present application.
  • the adhesion promoter can be present in an amount of up to 10% by weight, preferably 0.1% by weight to 8% by weight, more preferably 1.0 to 5% by weight, based on the total weight of the hardener composition.
  • Silicas are preferably used as thickeners.
  • a thickener can be present in an amount of up to 10% by weight, preferably 0.1% by weight to 8% by weight, based on the total weight of the hardener composition (B).
  • Inorganic fillers in particular cements such as Portland cement or high-alumina cement and other hydraulically setting inorganic substances, quartz, glass, corundum, porcelain, earthenware, barite, light spar, gypsum, talc and / or chalk and mixtures thereof serve as fillers.
  • thickeners such as pyrogenic silica can also be used as inorganic fillers.
  • non-surface-treated quartz flours, fine quartz flours and very fine quartz flours, such as Millisil W3, Millisil W6, Millisil W8 and Millisil W12, preferably Millisil W12 come into consideration as fillers.
  • silanized quartz flours, fine quartz flours and very fine quartz flours can be used.
  • Silbond product series from Quarzwerke.
  • the product series Silbond EST (epoxysilane-modified) and Silbond AST (aminosilane-treated) are particularly preferred.
  • the inorganic fillers can be added in the form of sands, flours or moldings, preferably in the form of fibers or spheres.
  • the fillers can be present in any or all of the components of the multi-component epoxy resin system described below.
  • the hardener composition (B) has an AHEW (Amine Hydrogen Equivalent Weight) of 20 to 1000 g / EQ, preferably from 30 to 500 g / EQ, more preferably from 40 to 350 g / EQ, even more preferably from 50 to 225 g / EQ and particularly preferably from 50 to 150 g / EQ.
  • the AHEW value can be obtained experimentally by determining the glass transition temperature (Tg) of a mixture of epoxy resin (with a known EEW) and amine component.
  • Tg glass transition temperature
  • the glass transition temperatures of epoxy resin / amine mixtures with different ratios are determined.
  • the sample is cooled from 21 to -70 ° C at a heating rate of -20 K / min, heated to 250 ° C in a first heating run (heating rate 10 K / min), then cooled again to -70 ° C (heating rate -20 K / min) and in the last step heated to 200 ° C (20 K / min).
  • the mixture with the highest glass transition temperature in the second heating run (“Tg2") has the optimal ratio of epoxy resin and amine.
  • the AHEW value can be calculated from the known EEW and the optimal epoxy resin / amine ratio.
  • the present invention also relates to an epoxy resin composition which contains at least one curable epoxy resin and a hardener composition (B) as described above includes.
  • the epoxy resin compound is preferably a multi-component epoxy resin compound, preferably a two-component epoxy resin compound.
  • a large number of the commercially available compounds known to the person skilled in the art and commercially available, which on average contain more than one epoxy group, preferably two epoxy groups, per molecule can be used as the hardenable epoxy.
  • These epoxy resins can be both saturated and unsaturated and aliphatic, alicyclic, aromatic or heterocyclic and also contain hydroxyl groups. They can also contain those substituents which do not cause any disruptive side reactions under the mixing or reaction conditions, for example alkyl or aryl substituents, ether groups and the like. Trimeric and tetrameric epoxides are also suitable for the purposes of the invention.
  • the epoxy resins are preferably glycidyl ethers derived from polyhydric alcohols, in particular from polyhydric phenols such as bisphenols and novolaks, in particular those with an average glycidyl group functionality of 1.5 or greater, in particular 2 or greater, for example 2 until 10.
  • polyhydric phenols used to produce the epoxy resins are resorcinol, hydroquinone, 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), isomer mixtures of dihydroxyphenylmethane (bisphenol F), tetrabromo-bisphenol A, novolaks, 4,4 '-Dihydroxyphenylcyclohexane and 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane.
  • the epoxy resin is preferably a diglycidyl ether of bisphenol A or of bisphenol F or a mixture thereof.
  • Liquid diglycidyl ethers based on bisphenol A and / or F with an epoxy equivalent weight (EEW) of 150 to 300 g / EQ are particularly preferably used.
  • Another object of the present invention is a multicomponent epoxy resin system comprising an epoxy resin component (A) and a hardener component, the epoxy resin component (A) containing a curable epoxy resin and the hardener component comprising an amine that is reactive towards epoxy groups.
  • the multi-component epoxy resin system also comprises, as accelerator, the combination of at least one salt (S) selected from salts of nitric acid, salts of nitrous acid, salts of halogens, salts of trifluoromethanesulphonic acid and combinations thereof and at least one phenol derivative.
  • S salts of nitric acid, salts of nitrous acid, salts of halogens, salts of trifluoromethanesulphonic acid and combinations thereof and at least one phenol derivative.
  • the salt (S) used as accelerator can be contained in the epoxy resin component (A) or in the hardener component or both in the epoxy resin component (A) and in the hardener component.
  • the hardener composition (B) described above is used in the multi-component epoxy resin system.
  • the proportion of epoxy resin in the epoxy resin component (A) is> 0% by weight to 100% by weight, preferably 10% by weight to 70% by weight and particularly preferably 30% by weight to 60% by weight , based on the total weight of the epoxy resin component (A).
  • the epoxy resin component (A) can optionally contain at least one reactive thinner.
  • the reactive diluents used are glycidyl ethers of aliphatic, alicyclic or aromatic mono- or, in particular, polyalcohols, which have a lower viscosity than epoxides containing aromatic groups.
  • reactive diluents are monoglycidyl ethers, for example o-cresyl glycidyl ether, and glycidyl ethers with an epoxide functionality of at least 2, such as 1,4-butanediol diglycidyl ether (BDDGE), cyclohexanedimethanol diglycidyl ether and Hexanediol diglycidyl ether, and tri- or higher glycidyl ethers, such as glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolpropane triglycidyl ether (TMPTGE) or trimethylolethane triglycidyl ether (TMETGE), trimethylolethane triglycidyl ether being preferred.
  • BDDGE 1,4-butanediol diglycidyl ether
  • Mixtures of two or more of these reactive diluents can also be used, preferably mixtures containing triglycidyl ether, particularly preferably as a mixture of 1,4-butanediol diglycidyl ether (BDDGE) and trimethylolpropane triglycidyl ether (TMPTGE) or 1,4-butanediol diglycidyl ether (TMDGE) and trimethylolethane ether (BDDGE) .
  • BDDGE 1,4-butanediol diglycidyl ether
  • TMPTGE trimethylolpropane triglycidyl ether
  • TMDGE 1,4-butanediol diglycidyl ether
  • BDDGE trimethylolethane ether
  • the reactive diluents are preferably present in an amount from 0% by weight to 60% by weight, more preferably from 1% by weight to 20% by weight, based on the total weight of the epoxy resin component (A).
  • Suitable epoxy resins and reactive thinners can also be found in the standard work by Michael Dornbusch, Ulrich Christ and Rob Rasing, "Epoxy resins", Vincentz Network GmbH & Co KG (2015), ISBN 13: 9783866308770. These compounds are incorporated herein by reference.
  • the epoxy resin component (A) can contain a co-accelerator, provided this is compatible with the epoxy resins.
  • a co-accelerator for example, tertiary amines or imidazoles, organophosphines, Lewis bases or acids such as phosphoric acid esters, or mixtures of two or more thereof can be used as co-accelerators.
  • These co-accelerators can also, as mentioned above, be present in the hardener composition (B).
  • the proportion of the epoxy resin component (A) in the total mass of the multicomponent epoxy resin system is preferably 5% by weight to 90% by weight, preferably 20% by weight to 80% by weight, more preferably 30% by weight to 70% by weight % or more preferably 40% to 60% by weight.
  • the epoxy resins can have an EEW of 120 to 2000 g / eq, preferably 140 to 400 g / eq, in particular 150 to 300 g / eq. Mixtures of several epoxy resins can also be used.
  • the proportion of the hardener component in the total mass of the multi-component epoxy resin system is preferably 10% by weight to 95% by weight, preferably 15% by weight to 80% by weight, more preferably 15% by weight to 60% by weight or particularly preferably 20% by weight to 40% by weight.
  • epoxy resin component (A) can contain customary additives, in particular adhesion promoters and fillers, as already described for the hardener composition (B).
  • the adhesion promoter can contain up to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably 1.0 to 5.0% by weight, based on the total weight of the epoxy resin component (A) his.
  • the inorganic fillers described above are preferably used as fillers.
  • the fillers can be present in one or in all components of the multi-component epoxy resin system.
  • the proportion of fillers is preferably 0% by weight to 90% by weight, for example 10% by weight to 90% by weight, preferably 15% by weight to 75% by weight, more preferably 20% by weight % to 50% by weight, and more preferably 25% by weight to 40% by weight, based on the total weight of the multi-component epoxy resin system.
  • additives to the multicomponent epoxy resin system are also thixotropic agents such as optionally organically aftertreated pyrogenic silica, bentonites, alkyl and methyl celluloses and castor oil derivatives, plasticizers such as phthalic acid or sebacic acid esters, stabilizers, antistatic agents, thickeners, flexibilizers, hardening agents such as rheology aids, wetting agents Dyes or pigments, for example for different coloring of the components for better control of their mixing, as well as Wetting agents, phlegmatizers, dispersants and other reaction rate control agents, or mixtures of two or more thereof.
  • plasticizers such as phthalic acid or sebacic acid esters, stabilizers, antistatic agents, thickeners, flexibilizers, hardening agents such as rheology aids, wetting agents Dyes or pigments, for example for different coloring of the components for better control of their mixing, as well as Wetting agents, phlegmatizers, dispersants and other reaction rate control agents,
  • non-reactive diluents can preferably be present in an amount of up to 30% by weight, based on the total weight of the respective component (epoxy resin and / or hardener component), for example from 1% by weight to 20% by weight. %.
  • suitable solvents are alcohols such as methanol or ethanol, lower alkyl ketones such as acetone, di-lower alkyl-lower alkanoylamides such as dimethylacetamide, lower alkylbenzenes such as xylenes or toluene, phthalic acid esters or paraffins.
  • Such further additives can preferably be added in proportions by weight of a total of 0% by weight to 40%, based on the total weight of the epoxy resin component.
  • the multi-component epoxy resin system is preferably in cartridges, cartridges or foil bags, which are characterized in that they comprise two or more separate chambers in which the epoxy resin component (A) and the hardener component of the mortar mass are arranged separately from one another in a reaction-inhibiting manner.
  • the epoxy resin component (A) and the hardener component are emptied from the separate chambers and mixed in a suitable device, for example a static mixer or a dissolver.
  • a suitable device for example a static mixer or a dissolver.
  • the mixture of epoxy resin component (A) and hardener component is then introduced into the previously cleaned borehole by means of a known injection device.
  • the component to be fixed is inserted into the epoxy resin compound and adjusted.
  • the reactive constituents of the hardener component react with the epoxy resins of the epoxy resin component (A) with polyaddition, so that the epoxy resin composition cures under ambient conditions within a desired time, preferably within a few hours.
  • the components of the multi-component epoxy resin system are preferably mixed in a ratio that results in a balanced stoichiometry in accordance with the EEW and AHEW values.
  • the epoxy resin composition according to the invention or the multi-component epoxy resin system according to the invention is preferably used for construction purposes.
  • the term "for building purposes” means the structural bonding of concrete / concrete, steel / concrete or steel / steel or one of the named materials on other mineral materials, the structural reinforcement of components made of concrete, masonry and other mineral materials, the reinforcement applications with fiber-reinforced polymers of construction objects, the chemical fastening to surfaces made of concrete, steel or other mineral materials, in particular the chemical fastening of construction elements and anchoring means, such as anchor rods, anchor bolts, (threaded) rods, (threaded) sleeves, concrete iron, screws and the like, in drill holes in different substrates such as (steel) concrete, masonry, other mineral materials, metals (e.g. steel), ceramics, plastics, glass and wood.
  • the epoxy resin compositions according to the invention and the multicomponent epoxy resin system according to the invention are very particularly preferably used for the chemical fastening of anchoring means.
  • Another object of the present invention is a method for chemically fastening structural elements in boreholes, an epoxy resin compound according to the invention or a multi-component epoxy resin system according to the invention as described above being used for chemical fastening of the construction elements.
  • the method according to the invention is particularly suitable for structural bonding of concrete / concrete, steel / concrete or steel / steel or one of the materials mentioned on other mineral materials, the structural reinforcement of components made of concrete, masonry and other mineral materials, the reinforcement applications with fiber-reinforced polymers from Construction objects, the chemical fastening on surfaces made of concrete, steel or other mineral materials, in particular the chemical fastening of construction elements and anchoring means, such as anchor rods, anchor bolts, (threaded) rods, (threaded) sleeves, concrete iron, screws and the like, in drill holes in different substrates such as (steel) concrete, masonry, other mineral materials, metals (e.g. steel), ceramics, plastics, glass and wood.
  • the method according to the invention is very particularly preferably used
  • Another object of the present invention is the use of 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 and at least one phenol derivative as an accelerator in an epoxy resin composition for chemical fastening of construction elements, in particular for anchoring fastening elements in boreholes, preferably to improve the curing reaction and the pull-out strengths at temperatures ⁇ 0 ° C, preferably in a range from ⁇ 0 ° C to -10 ° C.
  • the epoxy resin compound is in the form of a multi-component epoxy resin system which comprises the epoxy resin component (A) described above and a hardener component.
  • the salt (S) and the phenol derivative are contained in the hardener component and thus a hardener composition (B) as described above is used as the hardener component.
  • the epoxy resins used in the examples were the bisphenol A-based or bisphenol F-based epoxy resins available commercially under the names Araldite GY 240 and Araldite GY 282 (Huntsman). 3-Glycidyloxypropyl-trimethoxysilane available under the name Dynalsylan GLYMO TM (Evonik Industries) was used as the adhesion promoter.
  • composition of the epoxy resin components A1 to A9 used in the examples is given in Table 1 below.
  • Table 1 Compositions of the epoxy resin components A1 to A9 in% by weight
  • composition of the epoxy resin components VA1 to VA9 used in the comparative examples is given in Table 2 below.
  • the amines used were m-xylylenediamine (MXDA) and 1,3-cyclohexanedimethanamine (1,3-BAC) from MGC, Japan, and 2-methyl-1,5-pentamethylenediamine (Dytek A) from Invista, the Netherlands, 3-aminomethyl -3,5,5-trimethylcyclohexane (isophoronediamine.IPDA, trade name Vastamin IPD) from Evonik Degussa, Germany, methylcyclohexanediamine (Baxxodur EC 210, MCDA) from BASF SE, Germany, N- (2-aminoethyl) piperazine (N- AEP) from TCI Europe and 4,4'-methylenebiscyclohexylamine (PACM) from Evonik are used to produce the hardener composition (B).
  • MXDA m-xylylenediamine
  • 1,3-BAC 1,3-cyclohexanedimethanamine
  • the filler used was quartz (Millisil TM W12 or Millisil TM W4 from Quarzwerke Frechen) and calcium aluminate cement (Secar 80 from Kerneos SA) and the thickener was fumed silica (Cab-O-Sil TM TS-720 from Cabot Rheinfelden or Aerosil R 805 from Evonik).
  • Table 3 List of salts (S), novolak resins and other accelerators used
  • the salt calcium nitrate was used as a solution in glycerine (1,2,3-propanetriol, CAS No. 56-81-5, Merck, D).
  • glycerine (1,2,3-propanetriol, CAS No. 56-81-5, Merck, D).
  • 400.0 g of calcium nitrate tetrahydrate were added to 100.0 g of glycerol and the mixture was stirred at 50 ° C. until it was completely dissolved (3 hours).
  • the solution prepared in this way contained 80.0% calcium nitrate tetrahydrate.
  • a calcium nitrate / nitric acid solution was also used as an accelerator. To prepare this solution, 52.6 g calcium carbonate were slowly added to 135.2 g nitric acid and then stirred for 5 minutes
  • the liquid components were mixed. If the phenol derivative used as accelerator was a solid, it was added to the solution and dissolved at a slightly elevated temperature (up to 50 ° C.) with stirring. Liquid phenol derivatives and the salt (S) were added and then quartz powder and silica were added and the mixture was stirred in a dissolver (PC laboratory system, volume 1 L) at a negative pressure of 80 mbar at 2500 rpm for 10 min.
  • the composition of the hardener compositions (B) produced in this way is given in Table 4 below:
  • Table 4 Composition of the hardener composition (B) in% by weight
  • the liquid components were mixed. If the phenol derivative used as accelerator was a solid, it was added to the solution and dissolved at a slightly elevated temperature (up to 50 ° C.) with stirring. Liquid phenol derivatives and the salt (S) were added and quartz powder and silica were then added and the mixture was stirred in a dissolver (PC laboratory system, volume 1 L) at a vacuum of 80 mbar at 2500 rpm for 10 min. Table 5 shows the composition of the hardener components (B) of Comparative Examples CE1 to CE9.
  • Table 5 Composition of the hardener composition (B) in% by weight
  • the epoxy resin components A1 to A9 or VA1 to VA9 were each filled with the hardener composition B1 to B9 or VB1 to VB9 (A1 with B1, A2 with B2, VA1 with VB1 etc.) in hard cartridges with a volume ratio of 3: 1 and over a static mixer (Quadro TM mixer from Sulzer) is injected into the borehole.
  • the injection is usually carried out at room temperature.
  • the mortar mass is tempered to +5 ° C and injected into the borehole.
  • the pull-out strength of the mortar masses obtained by mixing the epoxy resin component (A or VA) and hardener composition (B or VB) according to the examples given above were determined using a high-strength anchor threaded rod M12 according to ETAG 001 Part 5, which was inserted into a hammer-drilled borehole with a diameter of 14 mm and a drill hole depth of 69 mm was dowelled with the respective mortar mass in C20 / 25 concrete.
  • the boreholes were cleaned with compressed air (2 x 6 bar), a wire brush (2 x) and then again compressed air (2 x 6 bar).
  • the boreholes were filled two-thirds from the bottom with the mortar mass to be tested.
  • the threaded rod was pressed in by hand.
  • the excess mortar was removed with a spatula.
  • the failure load was determined by centrically pulling out the threaded anchor rod with close support. The following tests were carried out:
  • the pull-out tests show that the mortar masses of the examples according to the invention each have significantly higher load values when hardening and pulling out at -5 ° C. than the mortar masses of the comparative examples.
  • Example 1 according to the invention had a gel time of 6:38 minutes, Comparative Example 1 a considerably longer gel time of 17:51 minutes and Comparative Example 2 a gel time of 5:10 minutes.
  • the curing of Comparative Example 1 is not yet complete even after 168 hours at -5 ° C.
  • Comparative example 2 and example 1 show acceptable load values after 168 hours at -5 ° C., but example 1 has the most advantageous combination for the user of the longest possible processing time and high final load after 168 hours.
  • the combination of phenolic accelerator and inorganic salt according to the invention therefore achieves the best overall property profile.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de durcisseur pour une résine époxyde pour le scellement chimique d'éléments de construction, une résine époxyde et un système de résine époxyde à plusieurs composants. L'invention concerne en outre un procédé de scellement chimique d'éléments de construction dans des trous forés. L'invention concerne également l'utilisation d'une combinaison d'un sel (S) avec un dérivé phénolique pour la fixation chimique d'éléments de construction, en particulier à basse température (≤ 0 °C), afin d'améliorer le durcissement et la résistance à l'arrachement.
EP20718346.8A 2019-04-30 2020-04-20 Composition de durcisseur pour résine époxyde, résine époxyde et système de résine époxyde à plusieurs composants ayant un meilleur durcissement à basse température Pending EP3962984A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19171884.0A EP3733731A1 (fr) 2019-04-30 2019-04-30 Composition durcissante pour une masse de résine époxy, masse de résine époxy et système de résine époxy multicomposant à durcissement à température basse amélioré
PCT/EP2020/060954 WO2020221608A1 (fr) 2019-04-30 2020-04-20 Composition de durcisseur pour résine époxyde, résine époxyde et système de résine époxyde à plusieurs composants ayant un meilleur durcissement à basse température

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EP19171884.0A Withdrawn EP3733731A1 (fr) 2019-04-30 2019-04-30 Composition durcissante pour une masse de résine époxy, masse de résine époxy et système de résine époxy multicomposant à durcissement à température basse amélioré
EP20718346.8A Pending EP3962984A1 (fr) 2019-04-30 2020-04-20 Composition de durcisseur pour résine époxyde, résine époxyde et système de résine époxyde à plusieurs composants ayant un meilleur durcissement à basse température

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US (1) US20220213259A1 (fr)
EP (2) EP3733731A1 (fr)
JP (1) JP2022532049A (fr)
KR (1) KR20220002400A (fr)
CN (1) CN113631624B (fr)
AU (1) AU2020264706A1 (fr)
CA (1) CA3132925A1 (fr)
WO (1) WO2020221608A1 (fr)

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EP3882294A1 (fr) * 2020-03-18 2021-09-22 Hilti Aktiengesellschaft Composition de durcisseur à base de diaminométhylcyclohexane et de 1,3-cyclo-hexane-bis(méthylamine) pour une masse de résine époxy, masse de résine époxy et système de résine époxy multicomposant
EP3945082A1 (fr) * 2020-07-28 2022-02-02 Hilti Aktiengesellschaft Durcisseur pour masses de résine époxy à des fins de fixation
EP4074671A1 (fr) * 2021-04-16 2022-10-19 Hilti Aktiengesellschaft Matériau de résine époxy à composants multiples avec des particules fines
IT202100028793A1 (it) * 2021-11-12 2023-05-12 Di Lodovico Srl Resina epossidica, relativo procedimento di realizzazione, e relativo procedimento di fabbricazione di modelli per stampi
CN113861386B (zh) * 2021-11-25 2024-01-19 浙江交工高等级公路养护有限公司 耐海水环氧涂料的固化剂及制备方法和耐海水环氧涂料
EP4310124A1 (fr) * 2022-07-20 2024-01-24 Hilti Aktiengesellschaft Composition à composants multiples à des fins de fixation comportant des fractions eew/ahew non stochiometriques, matière de mortier fabriquée à partir de celle-ci et cheville chimique fabriquée à partir de celle-ci
WO2024078879A1 (fr) * 2022-10-12 2024-04-18 Henkel Ag & Co. Kgaa Formulation époxy à deux composants (2k)

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KR20220002400A (ko) 2022-01-06
CN113631624B (zh) 2023-10-20
US20220213259A1 (en) 2022-07-07
WO2020221608A1 (fr) 2020-11-05
CN113631624A (zh) 2021-11-09
EP3733731A1 (fr) 2020-11-04
AU2020264706A1 (en) 2021-09-30
JP2022532049A (ja) 2022-07-13
CA3132925A1 (fr) 2020-11-05

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