EP3861048A1 - Durcisseur pour adhésifs à base de résine époxyde - Google Patents

Durcisseur pour adhésifs à base de résine époxyde

Info

Publication number
EP3861048A1
EP3861048A1 EP19773880.0A EP19773880A EP3861048A1 EP 3861048 A1 EP3861048 A1 EP 3861048A1 EP 19773880 A EP19773880 A EP 19773880A EP 3861048 A1 EP3861048 A1 EP 3861048A1
Authority
EP
European Patent Office
Prior art keywords
amine
hardener
bis
epoxy resin
propylene
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
EP19773880.0A
Other languages
German (de)
English (en)
Inventor
Edis Kasemi
Andreas Kramer
Ursula Stadelmann
Urs Burckhardt
Ulrich Gerber
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP3861048A1 publication Critical patent/EP3861048A1/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
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • C08G59/502—Polyalkylene polyamines
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin

Definitions

  • the invention relates to the field of hardeners for epoxy resins, epoxy resin adhesives and their use for bonding, in particular steel.
  • Epoxy resin adhesives that can be hardened at room temperature are used for many applications, for example for reinforcing buildings using steel lamellas, for construction using prefabricated concrete parts, for fixing components such as railings, parapets or door frames or for repairs such as this Filling edges, holes or joints.
  • they For applications in the construction industry, they must be usable under construction site conditions; easy processability and reliable and quick curing at ambient temperatures outdoors are particularly important.
  • they should have high strength and adhesive strength on typical building materials such as concrete, steel and plastics.
  • the adhesive must not be too brittle for a high adhesive force, since otherwise it can break even at low loads despite good adhesion.
  • epoxy resin adhesives from the prior art contain amino-functional adducts of polyamines such as triethylene tetramine or isophorone diamine with aromatic epoxy resins as hardeners.
  • polyamines such as triethylene tetramine or isophorone diamine
  • aromatic epoxy resins as hardeners.
  • Such adducts enable quick curing and high strength.
  • the separate production of such adducts is complex and causes high viscosities, which makes processing, loading with fillers and wetting of the substrate surfaces more difficult.
  • dilution with solvents is not desirable for environmental reasons. If such amines are used in unadducted form as hardeners, the materials obtained with them are typically rather brittle, which is reflected in reduced strength and adhesive force.
  • such amines are susceptible to blushing, ie salt formation with carbon dioxide from the air, especially in cold and damp conditions.
  • Alkylated amines as described in EP 2,151, 461, EP 2,943,464, WO 2016/023839, EP 3,138,863 or EP 3,144,335 are significantly less sensitive on blushing. In the prior art, they are mainly used as a hardener for epoxy resin coatings, where a low viscosity and a low tendency to blushing effects are particularly important. If such alkylated amines are used as hardeners for epoxy resin adhesives, they result in inadequate adhesive forces, particularly on steel, and a low glass transition temperature.
  • the object of the present invention is therefore to provide a hardener for epoxy resins which overcomes the disadvantages of the prior art with regard to production, viscosity, blushing, adhesive force and glass transition temperature.
  • the hardener according to the invention is based on a certain combination of at least one alkylated amine A1 and at least one amine A2, which is a dimethylaminopolyalkylene amine.
  • the hardener according to the invention is easy to produce, low-viscosity and not sensitive to blushing. It enables low-emission epoxy resin adhesives with good processability, a sufficiently long pot life and open time with fast curing, high strength with surprisingly high adhesive forces, especially on steel, and a sufficiently high glass transition temperature.
  • the invention relates to a hardener for epoxy resins containing at least one amine A1 of the formula (I) and at least one amine A2 of the formula (II),)
  • A represents an alkylene radical with 2 to 10 C atoms which optionally contains nitrogen atoms or cyclic or aromatic components
  • Y represents an alkyl, cycloalkyl or aralkyl radical having 1 to 20 carbon atoms, x represents 1 or 2, and
  • weight ratio between amine A1 and amine A2 is in the range of 20/1 to 1/2.
  • the “primary amino group” refers to an amino group that is attached to a single organic residue and carries two hydrogen atoms
  • “secondary amino group” refers to an amino group that is bonded to two organic radicals, which can also be part of a ring, and has a hydrogen atom
  • the term “tertiary amino group” refers to an amino group that is attached to three organic radicals, which can also be part of one or more rings in groups of two or three, and does not carry a hydrogen atom.
  • the “hydrogen amine” refers to the hydrogen atoms of primary and secondary amino groups.
  • amine hydrogen equivalent weight is the mass of an amine or an amine-containing composition which contains one molar equivalent of amine hydrogen.
  • Substance names such as polyamine or polyepoxide beginning with “poly” refer to substances that formally contain two or more of the functional groups in their name per molecule.
  • a “thinner” is a substance that is soluble in an epoxy resin and lowers its viscosity, which is not chemically incorporated into the epoxy resin polymer during curing.
  • the “molecular weight” is the molar mass (in grams per mole) of a molecule.
  • the “average molecular weight” is the number average M n of a poly-disperse mixture of oligomeric or polymeric molecules, which is usually determined using gel permeation chromatography (GPC) against polystyrene as the standard.
  • GPC gel permeation chromatography
  • the “pot life” refers to the processing time of an epoxy resin composition, ie the maximum possible time between the mixing of the components and the application of the mixed composition, in which it is in a sufficiently flowable state and can wet the substrate surfaces.
  • the “open time” of an adhesive is the maximum possible time for a positive connection between the application of the adhesive and the joining of the parts to be glued.
  • room temperature A temperature of 23 ° C is referred to as "room temperature”.
  • A is preferably a divalent radical selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1 , 2-propylene, 1, 3-pentylene, 1, 5-pentylene, 2,2-dimethyl-1, 3-propylene, 1, 6-hexylene, 2-methyl-1, 5-pentylene, 1, 7-heptylene , 1, 8-octylene, 2,5-dimethyl-1, 6-hexylene, 1, 9-nonylene, 2,2 (4), 4-trimethyl-1, 6-hexylene, 1, 10-decylene, 1, 11 -ndene-cylene, 2-butyl-2-ethyl-1, 5-pentylene, 1, 12-dodecylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, (1, 5 , 5-Trimethylcyclohexan-1-yl) methan-1, 3, 4 (2)
  • 1,4-cyclohexylene-bis methylene
  • 1,3-phenylene-bis methylene
  • 1,4-phenylene-bis methylene
  • 3-aza-1,5-pentylene 3,6-diaza-1 , 8-octylene, 3,6,9-triaza-1, 11-undecylene, 3-aza-1, 6-hexylene or 3,7-diaza-1, 9-nonylene.
  • the radical A is particularly preferably free of nitrogen atoms. Such a hardener is particularly less sensitive to blushing effects.
  • A thus stands for a divalent radical selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1, 2-propylene, 1, 3-pentylene, 1, 5-pentylene, 2,2-dimethyl-1, 3-propylene, 1, 6-hexylene, 2-methyl-1, 5-pentylene, 1, 7-heptylene, 1, 8-octylene, 2,5-dimethyl-1, 6-hexylene, 1, 9-nonylene, 2,2 (4), 4-trimethyl-1, 6-hexylene, 1, 10-decylene, 1, 11 -Ndecylene, 2-butyl-2-ethyl-1, 5-pentylene, 1, 12-dodecylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexy
  • These amines A1 of the formula (I) are comparatively low-viscosity and enable adhesives with good processability.
  • A is particularly preferably 1,2-ethylene or 1,2-propylene. These amines A1 of the formula (I) enable adhesives with a particularly low tendency to yellow.
  • A is 1,2-ethylene.
  • These amines A1 of the formula (I) are particularly low-viscosity, particularly easy to obtain and enable particularly rapid curing.
  • Y is preferably flexyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl or an optionally substituted 1-phenylethyl-, 2-phenylethyl-,
  • Y particularly preferably represents a radical selected from 2-ethylhexyl, 2-phenylethyl, benzyl, 1-naphthylmethyl and cyclohexylmethyl.
  • Y very particularly preferably represents benzyl.
  • the amine A1 of the formula (I) is preferably selected from the group consisting of N-benzyl-1, 2-ethanediamine, N- (1-naphthylmethyl) -1, 2-ethanediamine, N-cyclohexylmethyl-1, 2- ethanediamine, N-benzyl-1, 2-propanediamine, N-benzyl-1, 3-bis (aminomethyl) benzene, N- (2-ethylhexyl) -1, 3-bis (aminomethyl) benzene, N- (2nd -Phenylethyl) - 1, 3-bis (aminomethyl) benzene (constituent of styrenated 1, 3-bis (aminomethyl) - benzene, available as Gaskamine ® 240 from Mitsubishi Gas Chemical), N-benzyldiethylenetriamine, N
  • amine A1 of formula (I) is N-benzyl-1, 2-ethanediamine. This enables particularly fast curing and particularly high adhesive forces.
  • the amine A1 of the formula (I) is preferably used as part of a reaction mixture from the partial alkylation of at least one amine of the formula A (NFl2) 2 with at least one alkylating agent.
  • the alkylation is preferably a reductive alkylation, an aldehyde or ketone and hydrogen being used as the alkylating agent.
  • the reductive alkylation is preferably carried out in the presence of a suitable catalyst.
  • a suitable catalyst Palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams catalyst or Raney nickel, in particular palladium on carbon or Raney nickel, are preferred as catalysts.
  • the reductive alkylation is preferably carried out in a pressure apparatus at a hydrogen pressure of 5 to 150 bar, in particular 10 to 100 bar. This can be done in a batch process or preferably in a continuous process.
  • the reductive alkylation is preferably carried out at a temperature in the range from 40 to 120 ° C., in particular 60 to 100 ° C.
  • set diamine is at least partially removed from the reaction mixture, in particular by means of stripping. If desired, the reaction mixture can then be further purified, in particular by at least partially removing the corresponding dialkylated amine from the monoalkylated amine A1 of the formula (I) by distillation.
  • X is preferably 1.
  • B is preferably 1,3-propylene.
  • the amine A2 of the formula (II) is preferably 3- (3- (dimethylamino) propylamino) propylamine.
  • the weight ratio between amine A1 and amine A2 is preferably in
  • the hardener preferably contains at least one further amine.
  • the hardener can preferably contain a combination of two or more of the further amines mentioned below.
  • the hardener contains at least one amine A3 of the formula (III),
  • the amine A3 is preferably a constituent of a reaction mixture from the partial alkylation of at least one amine of the formula A (NH2) 2 with at least one alkylating agent which also contains the corresponding monoalkylated amine A1.
  • Amine A3 is preferably present in an amount such that the weight ratio between amine A1 and amine A3 is in the range from 50/50 to 95/5, preferably 65/35 to 95/5, in particular 70/30 to 90/10.
  • Such a mixture of amine A1 and amine A3 is technically easily available and particularly inexpensive.
  • the hardener contains, as a further amine, at least one amine A4, which is an aliphatic polyamine with at least two primary amino groups.
  • at least one amine A4 enables a particularly high glass transition temperature.
  • Suitable as amine A4 are aliphatic, cycloaliphatic or arylaliphatic polyamines, in particular 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-diamino-2-methylpentane ( MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11 -neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1, 6-hexanediamine, 2,2 (4), 4-trimethyl -1, 6-hexanediamine (TMD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11 -ndecanediamine, 1, 12- dodecanediamine, 1, 2- , 1, 3- or 1, 4-diaminocyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (a
  • the amine A4 is preferably selected from the group consisting of TMD, 1, 2-, 1, 3- or 1, 4-diaminocyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane , Bis (4-aminocyclohexyl) methane, IPDA, 2 (4) -methyl-1, 3-diaminocyclohexane, MXDA, polyalkylene amines, adducts of these or other polyamines with mono- or diepoxides and Mannich bases.
  • IPDA or MXDA or their adducts with at least one epoxy resin is preferred.
  • the polyalkylene amines in particular TETA, TEPA, PEHA, N4-amine or BHMT, or their adducts with at least one are particularly preferred Epoxy resin.
  • a hardener enables particularly high adhesive forces and a particularly high glass transition temperature.
  • the hardener can contain a combination of two or more A4 amines.
  • the hardener may contain at least one thinner.
  • xylene 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ether , Ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl glycol, propylene glycol, propylene glycol, propylene glycol, ethylene glycol , Diphenylmethane, diisopropylnaphthalene, petroleum fractions such as Solvesso ® grades (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodec
  • Thinners with a boiling point of more than 200 ° C. are preferred.
  • the diluent is preferably selected from the group consisting of benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenol groups, in particular the Novares ® types LS 500, LX 200, LA 300 or LA 700 (from Rütgers), diisopropylnaphthalene and Cardanol. Phenol group-containing thinners also act as accelerators.
  • the hardener may contain at least one accelerator.
  • Suitable accelerators are substances which accelerate the reaction between amino groups and epoxy groups, in particular acids or acids Acids hydrolyzable compounds, especially organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids such as especially phosphoric acid, or mixtures of the above - called acids and acid esters; Nitrates such as in particular calcium nitrate; tertiary amines such as, in particular, 1,4-diazabicyclo [2.2.2] octane, benzyldimethylamine, a-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as in particular N-methylimidazole, N-viny
  • Preferred accelerators are acids, nitrates, tertiary amines or Mannich bases.
  • Salicylic acid or calcium nitrate or 2,4,6-tris (dimethylaminomethyl) phenol or a combination thereof is particularly preferred.
  • Another object of the invention is an epoxy resin composition comprising
  • a hardener component comprising the hardener described above, containing at least one amine A1 of the formula (I) and at least one amine A2 of the formula (II) in the weight ratio between amine A1 and amine A2 in the range from 20/1 to 1/2 .
  • a suitable epoxy resin is obtained in a known manner, in particular from the oxidation of olefins or from the reaction of epichlorohydrin with the polyols, polyphenols or amines.
  • Suitable epoxy resins are, in particular, aromatic epoxy resins, in particular the glycidyl ethers of:
  • Bisphenol-A bisphenol-F or bisphenol-A / F, where A stands for acetone and F for formaldehyde, which served as starting materials for the preparation of these bisphenols.
  • positional isomers can also be present, in particular derived of 2,4'- or 2,2'-hydroxyphenylmethane.
  • Dihydroxybenzene derivatives such as resorcinol, hydroquinone or pyrocatechol;
  • bisphenols or polyphenols such as bis (4-hydroxy-3-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol-C), bis (3,5-dimethyl-4- hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4- hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane (bisphenol-B), 3,3-bis (4-hydroxyphenyl) pentane, 3,4-bis (4-hydroxyphenyl) ) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2 -methylbutane, 1,1-bis (4-hydroxyphenyl)
  • Novolaks which are in particular condensation products of phenol or cresols with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde or 2-ethylhexanal or benzaldehyde or furfural;
  • aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi- (N-methyl) amine, 4,4 '- [1,4-phenylene bis ( 1-methylethylidene)] bisaniline (bisaniline-P) or 4,4 '- [1,3-phenylene-bis (1-methylethylidene)] bisaniline (bisaniline-M).
  • suitable epoxy resins are aliphatic or cycloaliphatic poly-epoxides, in particular
  • Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2 to C3o alcohols in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexane, neopentomethylene glycol, dophenylene glycol , Castor oil, trimethylolpropane, trimethylolethane, pentaerythrol, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane;
  • N-glycidyl derivative of amides or heterocyclic nitrogen bases such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with flydantoin.
  • Epoxy resins from the oxidation of olefins such as in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene,
  • Isoprene 1, 5-flexadiene, butadiene, polybutadiene or divinylbenzene.
  • the epoxy resin is preferably a liquid resin or a mixture comprising two or more liquid epoxy resins.
  • epoxy liquid resin A technical polyepoxide with a glass transition temperature below 25 ° C is called “epoxy liquid resin”.
  • the resin component may also contain proportions of solid epoxy resin.
  • the epoxy resin is in particular a liquid resin based on a bisphenol, in particular a bisphenol-A diglycidyl ether and / or bisphenol-F diglycidyl ether, as are commercially available for example from Olin, Huntsman or Momentive.
  • These liquid resins have a low viscosity for epoxy resins and enable fast curing and high hardness. They can contain parts of bisphenol A solid resin or novolak glycidyl ethers.
  • the resin component may contain a reactive diluent.
  • Preferred reactive diluents are epoxy group-containing reactive diluents, in particular butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylol propane or triglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, guaiacol glycidyl ether, 4-methoxyphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether Dodecylphenylglycidylether, Cardanolglycidylether, Benzylglycidylether, Allylglycidylether, Butylglycidylether, Hexylg
  • the epoxy resin composition preferably contains at least one further constituent selected from the group consisting of thinners, accelerators and fillers.
  • Suitable accelerators are those already mentioned, in particular salicylic acid, calcium nitrate or 2,4,6-tris (dimethylaminomethyl) phenol or a combination thereof.
  • Suitable diluents are those already mentioned, in particular those with a boiling point of more than 200 ° C.
  • the diluent is selected from the group consisting alcohol from Benzylal-, styrene istechnische-like compounds, especially the Novares ® grades LS 500, LX 200, LA 300 or LA 700 (from Rutgers), diisopropylnaphthalene and cardanol.
  • alcohol from Benzylal-, styrene is convincedm phenol, ethoxylated phenol, phenol group-containing aroma aromatic hydrocarbon resins, especially the Novares ® grades LS 500, LX 200, LA 300 or LA 700 (from Rutgers), diisopropylnaphthalene and cardanol.
  • the epoxy resin composition preferably contains only a low content of thinners. It preferably contains less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 1% by weight, of thinner. This enables low-emission or zero-emission epoxy resin products.
  • Suitable fillers are, in particular, ground or precipitated calcium carbonate, which is optionally coated with fatty acid, in particular stearates, barite (heavy spar), talc, quartz powder, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, kaolin, mica (potassium aluminum -Silicate), molecular sieve, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, cement, gypsum, fly ash, soot, graphite, metal powder such as aluminum, copper, iron, zinc, silver or steel, PVC powder or flute balls.
  • fatty acid in particular stearates, barite (heavy spar), talc, quartz powder, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, kaolin, mica (potassium aluminum -Silicate), molecular sieve, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, cement, gypsum, fly
  • Calcium carbonate, quartz powder and quartz sand are preferred.
  • the epoxy resin composition may contain further auxiliaries and additives, in particular the following:
  • - reactive diluents in particular the previously mentioned, or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes, isocyanates or silicones containing reactive groups;
  • amines in particular monoamines such as in particular benzylamine or furfurylamine or aromatic polyamines such as in particular 4,4'-, 2,4 'and / or 2,2'-diaminodiphenylmethane, 2,4- and / or 2,6-toluenediamine, 3 , 5-dimethyl-thio-2,4- and / or -2,6-toluenediamine, 3,5-diethyl-2,4- and / or -2,6-toluenediamine;
  • Polymers in particular polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers with carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene Copolymers, homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, Isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular chlorosulfonated polyethylenes or fluorine-containing polymers or sulfonamide-modified melamines;
  • Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;
  • Pigments especially titanium dioxide, iron oxides or chromium (III) oxide;
  • Flame retardant substances in particular the fillers already mentioned, aluminum hydroxide or magnesium hydroxide, antimony trioxide, antimony pentoxide, boric acid (B (OFI) 3), zinc borate, zinc phosphate, melamine borate, melamine cyanurate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, polybromated diphenyl phosphate or diphenyl oxide or Diphenyl cresyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol diphosphate oligomer, tetraphenyl resorcinol diphosphite, ethylenediamine diphosphate, bisphenol A-bis (diphenyl phosphate), tris (chloroethyl) phosphate, tris (chloropropyl) tris (chloropropyl) - tris (chloropropyl) - tris (chloropropyl)
  • Additives in particular dispersed paraffin wax, film-forming aids, wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides.
  • the ratio of the number of groups reactive towards epoxy groups to the number of epoxy groups is preferably in the range from 0.5 to 1.5, in particular 0.7 to 1.2.
  • the primary and secondary amino groups present in the epoxy resin composition and any other groups which are reactive towards epoxy groups react with the epoxy groups by opening them (Addition reaction). As a result of this reaction mainly, the composition polymerizes and thereby hardens.
  • the resin and hardener components of the epoxy resin composition are stored in separate containers. Further constituents of the epoxy resin composition can be present as a constituent of the resin or hardener component, further constituents reactive towards epoxy groups preferably being a constituent of the hardener component. It is also possible for other components to be present as separate components.
  • a suitable container for storing the resin or hardener component is in particular a barrel, a hobbock, a bag, a bucket, a can, a cartridge or a tube.
  • the components can be stored, which means that they can be stored for several months to a year or longer before they are used, without changing their respective properties to an extent relevant to their use.
  • the components are mixed with one another shortly before or during the application.
  • the mixing ratio between the resin component and the hardener component is preferably chosen such that the groups of the hardener component which are reactive towards epoxy groups are in a suitable ratio to the epoxy groups of the resin component, as described above. In parts by weight, the mixing ratio between the resin component and the hardener component is usually in the range from 1:10 to 10: 1.
  • the components are mixed using a suitable method; it can be carried out continuously or in batches. If mixing does not take place immediately before application, care must be taken to ensure that there is not too much time between the mixing of the components and the application and that the application takes place within the pot life.
  • Mixing takes place in particular at ambient temperature, which is typically in the range from about 5 to 40 ° C., preferably at about 10 to 35 ° C. With the mixing of the two components, the hardening by chemical reaction begins, as previously described. Curing typically takes place at a temperature in the range from 0 to 150 ° C. It is preferably carried out at ambient temperature and typically extends from a few days to weeks. The duration depends, among other things, on the temperature, the reactivity of the constituents and their stoichiometry, and the presence of accelerators.
  • the epoxy resin composition is applied to at least one substrate, the following being particularly suitable:
  • Metals or alloys such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-coated metals or alloys such as galvanized or chrome-plated metals
  • plastics such as hard and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO,
  • PE PE, PP, EPM or EPDM, each untreated or surface-treated, for example by means of plasma, corona or flame;
  • CFRP carbon fiber reinforced plastics
  • GTK glass fiber reinforced plastics
  • SMC sheet molding compounds
  • - Insulating foams in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);
  • - coated or lacquered substrates in particular lacquered tiles, coated concrete, powder-coated metals or alloys or lacquered sheets; - Coatings, paints or varnishes, in particular coated floors, which are covered with another layer of floor covering.
  • the substrates can be pretreated before application, in particular by physical and / or chemical cleaning processes or by applying an activator or a primer.
  • a cured composition is obtained from the curing of the epoxy resin composition described.
  • the epoxy resin composition described is preferably used as an adhesive, sealant, casting compound, casting resin, coating, primer or as a matrix for fiber composite materials (composites) such as, in particular, CFRP or GFRP.
  • coating also includes primers, paints, varnishes and seals.
  • the epoxy resin composition described is particularly preferably used as an adhesive. After mixing the components, it typically has a pasty consistency with pseudoplastic properties. During application, the mixed adhesive is applied to at least one of the substrates to be bonded within the pot life and the substrates are bonded within the open time of the adhesive.
  • the mixed adhesive is applied or applied in particular by means of a brush, roller, spatula, squeegee, trowel, or from a tube, cartridge or metering device.
  • the adhesive is particularly suitable for use in the construction industry, in particular for the reinforcement of buildings by means of steel lamellas or lamellas made of carbon fiber reinforced composite plastics (CFRP), for constructions that contain glued precast concrete parts, especially bridges or concrete towers
  • CFRP carbon fiber reinforced composite plastics
  • CFRP carbon fiber reinforced composite plastics
  • Such an epoxy resin adhesive is also suitable for filling cavities such as cracks, crevices or boreholes, the adhesive being filled or injected into the cavity and filling it after curing and connecting the flanks of the cavity with one another in a force-locking manner or glued.
  • Another object of the invention is a method for gluing comprising the steps
  • a “reinforcing bar”, a threaded rod or a bolt is referred to as “anchor”.
  • anchor Such is particularly glued or anchored in a wall, wall, ceiling or in a foundation in such a way that a part of it is non-positively bonded and a part of it protrudes and can be structurally loaded.
  • An article is obtained from the application and curing of the epoxy resin composition described or from the process for gluing.
  • This article can be a structure or a part thereof, in particular a building or civil engineering structure, a bridge, a roof, a stairwell, a balcony, or it can be an industrial good or a consumer good, in particular a pier, an offshore Platform or a rotor blade of a wind power plant, or a means of transport such as, in particular, an automobile, a truck, a rail vehicle, a ship, an aircraft or a helicopter, or an attachment part thereof.
  • Another object of the invention is therefore an article obtained from the described use or the described method for gluing.
  • the epoxy resin composition described is characterized by advantageous properties. It is also easy to process without thinner, has a long pot life and open time with fast curing and hardens to a material of high strength, low brittleness, high adhesive forces and a sufficiently high glass transition temperature. Articles glued to it can withstand heavy mechanical and weather-related loads.
  • AHEW stands for the amine hydrogen equivalent weight.
  • NK standard climate
  • the viscosity was measured on a thermostatted Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10 s -1 ).
  • the amine number was determined by titration (with 0.1 N FICI04 in acetic acid against crystal violet).
  • Sikadur ® -30 component A, quartz-filled resin components of a structural epoxy resin adhesive, containing bisphenol A diglycidyl ether and 1,4-butanediol diglycidyl ether, EEW approx. 700 g / eq (from Sika)
  • DMAPAPA 3- (3- (dimethylamino) propylamino) propylamine, AHEW 53 g / Eq (DMAPAPA, from Arkema).
  • B-EDA is an amine A1 of the formula (I).
  • DMAPAPA is an amine A2 of formula (II).
  • the hydrogenated solution was then concentrated on a rotary evaporator at 65 ° C., unreacted 1, 2-ethylenediamine, water and isopropanol being removed.
  • the so The reaction mixture obtained was a clear, slightly yellowish liquid with an amine number of 678 mg KOH / g. 50 g of this were distilled under vacuum at 80 ° C., 31.3 g of distillate being collected at a steam temperature of 60 to 65 ° C. and 0.06 mbar.
  • the ingredients of the flärter component indicated in Tables 1 to 2 were mixed in the stated amounts (in parts by weight) using a centrifugal mixer (SpeedMixer TM DAC 150, FlackTek Inc.) and stored with the exclusion of moisture.
  • a centrifugal mixer SpeedMixer TM DAC 150, FlackTek Inc.
  • Sikadur ® -30 component A (from Sika) was used as the Flarz component in the amount given in Tables 1 to 2 (in parts by weight).
  • the pot life was determined in the standard climate by using a spatula to mix the adhesive every 5 minutes. was moved until the adhesive had thickened so much that it could no longer be processed.
  • the mechanical properties were determined by applying and curing the mixed adhesive in a silicone mold into dumbbell-shaped bars with a thickness of 10 mm, a length of 150 mm, a web length of 80 mm and a web width of 10 mm .
  • the tensile bars were released from the mold after 7 days of curing and the tensile strength and elongation at break were measured in accordance with EN ISO 527 at a tensile speed of 1 mm / min.
  • the condition of the surface was assessed on the dumbbell-shaped bars to determine the mechanical properties on the side exposed to the curing of the air.
  • a non-sticky surface was referred to as “smooth” and a sticky surface was referred to as “sticky”.
  • a sticky surface is a sign of blushing.
  • the compressive strength was determined by applying the mixed adhesive in a silicone mold to cuboids measuring 12.7 x 12.7 x 25.4 mm in a standard atmosphere and curing them in the standard climate. After 7 days, several such cuboids were removed from the mold and compressed to destruction at a test speed of 1.3 mm / min in accordance with ASTM D695, the value for the compressive strength being read at the maximum force in each case.
  • Table 1 Composition and properties of Examples 1 to 6.
  • Table 2 Composition and properties of Examples 7 to 11.

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

Abstract

La présente invention concerne un durcisseur pour résines époxydes contenant au moins une amine A1 de formule (I) et au moins une amine A2 de formule (II), le rapport pondéral entre l'amine A1 et l'amine A2 étant compris entre 20/1 et 1/2. Le durcisseur selon l'invention est particulièrement peu visqueux et non sensible à l'opalescence. Il permet d'obtenir des adhésifs à base de résine époxyde à faibles émissions présentant une bonne aptitude au façonnage, une durée de vie en pot et un temps ouvert suffisamment longs avec un durcissement rapide, une résistance élevée, une fragilité réduite, une forte adhérence, en particulier sur l'acier, et une température de transition vitreuse suffisamment élevée.
EP19773880.0A 2018-10-01 2019-09-30 Durcisseur pour adhésifs à base de résine époxyde Pending EP3861048A1 (fr)

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EP18198004 2018-10-01
PCT/EP2019/076494 WO2020070084A1 (fr) 2018-10-01 2019-09-30 Durcisseur pour adhésifs à base de résine époxyde

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US2739981A (en) * 1952-08-26 1956-03-27 American Home Prod Diamines and salts thereof
DD135623B1 (de) * 1977-12-23 1980-08-06 Hoerhold Hans Heinrich Verfahren zur Herstellung von Optik-Klebstoffen auf der Basis von Epoxidharz-Polyadditionspxodukten
DE50103081D1 (de) * 2000-07-03 2004-09-09 Vantico Gmbh & Co Kg Härtbare Zusammensetzungen aus Glycidylverbindungen, aminischen Härtern und niedrigviskosen Härtungsbeschleunigern
US8518547B2 (en) * 2007-02-07 2013-08-27 Air Products And Chemicals, Inc. Alkylated polyalkylene polyamines and uses thereof
US8168296B2 (en) 2007-02-07 2012-05-01 Air Products And Chemicals, Inc. Benzylated polyalkylene polyamines and uses thereof
US8143331B2 (en) * 2007-02-07 2012-03-27 Air Products And Chemicals, Inc. Alkylated polyalkyleneamines and uses thereof
EP2752437A1 (fr) * 2013-01-08 2014-07-09 Sika Technology AG Durcisseur pour produits à résine époxy pauvres en émissions
EP2752403A1 (fr) 2013-01-08 2014-07-09 Sika Technology AG Amine pour résines époxy à faibles émissions
MX2017001876A (es) 2014-08-13 2017-05-15 Sika Tech Ag Amina para composiciones de resina epoxi de baja emision.
EP3138863A1 (fr) 2015-09-01 2017-03-08 Sika Technology AG Composition de resine hepoxyde pauvre en emissions
EP3144335A1 (fr) 2015-09-17 2017-03-22 Sika Technology AG Amine pour compositions à resine époxyde pauvres en émissions
US10759946B2 (en) * 2016-02-15 2020-09-01 Sika Technology Ag Low-emission liquid film for sealing buildings
KR20180116366A (ko) * 2016-02-22 2018-10-24 에보닉 데구사 게엠베하 벤질화 마니히 염기 경화제, 조성물, 및 방법
EP3336120A1 (fr) * 2016-12-14 2018-06-20 Sika Technology AG Adhésif de résine époxyde à haute adhérence
US20210332181A1 (en) * 2018-10-01 2021-10-28 Sika Technology Ag Hardener for epoxy resins

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CN112789309B (zh) 2024-01-09
JP2022501481A (ja) 2022-01-06
CN112789309A (zh) 2021-05-11
US20220033568A1 (en) 2022-02-03

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