EP3331935A1 - Amine pour compositions de résine époxyde à faible taux d'émission - Google Patents

Amine pour compositions de résine époxyde à faible taux d'émission

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Publication number
EP3331935A1
EP3331935A1 EP16750760.7A EP16750760A EP3331935A1 EP 3331935 A1 EP3331935 A1 EP 3331935A1 EP 16750760 A EP16750760 A EP 16750760A EP 3331935 A1 EP3331935 A1 EP 3331935A1
Authority
EP
European Patent Office
Prior art keywords
amine
formula
epoxy resin
bis
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.)
Withdrawn
Application number
EP16750760.7A
Other languages
German (de)
English (en)
Inventor
Urs Burckhardt
Ursula Stadelmann
Andreas Kramer
Edis Kasemi
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 EP3331935A1 publication Critical patent/EP3331935A1/fr
Withdrawn legal-status Critical Current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
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
    • C07C217/30—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring
    • C07C217/32—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring being further substituted
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
    • C07C217/30—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring
    • C07C217/32—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring being further substituted
    • C07C217/34—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines having the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring being further substituted by halogen atoms, by trihalomethyl, nitro or nitroso groups, or by singly-bound oxygen atoms
    • 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
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the invention relates to the field of amines, hardeners for epoxy resins, epoxy resin compositions, and their use, in particular as a coating, coating or coating.
  • suitable epoxy resin compositions should have the lowest possible viscosity so that they are easy to process at ambient temperature. Furthermore, they should harden as quickly as possible and without disruption, even in damp, cold conditions, and thereby form a level surface without turbidity, spots or craters. Finally, a cured coating should have a high hardness with low brittleness in order to withstand mechanical stress as well as possible. For optically demanding applications, such as floor coverings, a coating should also have a high degree of gloss and the lowest possible tendency to yellowing under the influence of light.
  • Prior art curing agents for epoxy coatings typically contain reaction products (“adducts”) from the reaction of polyamines with epoxies, particularly bisphenol liquid resins. Such adducts allow for rapid cure, but are highly viscous, therefore the hardeners are for use in setting
  • the non-adducted polyamines are typically odor-intensive and lead to increased occurrence of blushing effects.
  • “Blushing effects” are hardening surface defects such as opacities, stains Roughness and stickiness, which are caused by blushing of amines with carbon dioxide (CO 2 ) from the air and occur especially at high humidity and low temperatures
  • the diluents typically reduce Blushing E.
  • diluents such as, for example, benzyl alcohol, can therefore only be used sparingly or not at all.
  • the high viscosity and blushing susceptibility of the known adducts of polyamines with epoxides can be reduced not only by thinners but also in that the polyamine used in the adduction in large excess and the non-adducted excess is then removed by a separation process.
  • the removal of the polyamines commonly used for adducting, such as IPDA, MXDA, DETA or TETA is technically complicated and is usually incomplete, and the resulting reaction products are usually still highly viscous and / or prone to blushing, so that diluents are hardly dispensed with can.
  • aqueous epoxy resin coatings typically consist of an aqueous or water-dilutable hardener, which typically contains emulsified adducts of polyamines with epoxides, and an aqueous epoxy resin emulsion.
  • Aqueous or water-dilutable hardeners typically have water contents in the range of 10 to 80% by weight.
  • Aqueous epoxy resin products are usually low viscosity and low odor, but have other disadvantages. They are more expensive and considerably more expensive to produce than nonaqueous products, can be applied only at a sufficiently high temperature and in a relatively thin layer per operation, and have an increased water sensitivity during and after curing.
  • the object of the present invention is therefore to provide a low-viscosity and low-odor amine for use in curing agents for room-temperature-curing epoxy resin compositions, which low-emission epoxy resin coatings with good processability and faster Curing allows coatings of high hardness and good surface quality.
  • the amine of formula (I) is so low viscosity that it is easy to handle at room temperature even without dilution.
  • the amine of the formula (I) surprisingly scarcely tends to blushing effects. It can be prepared in a simple process in high purity, and reaction products from this process are low odor and good fluidity at room temperature and have a low content of unreacted diamine and not the formula (I) corresponding higher molecular weight by-products.
  • the amine of formula (I) is easier to produce in high purity, low viscosity and causes significantly less blushing effects.
  • the amine of formula (I) enables low-emission epoxy resin compositions which are easy to process, cure rapidly, form high-quality plastics of high hardness and a regular, non-sticky surface with high gloss and surprisingly hardly yellow under the influence of light.
  • the invention relates to the use of an amine of the formula (I) in a curing agent for epoxy resins,
  • n 1 to 3
  • X is 1, 2-ethylene or 1, 2-propylene
  • Y represents a mononuclear or polynuclear aromatic hydrocarbon radical.
  • primary amino group is meant an NH 2 group which is bonded to an organic radical and "secondary amino group” is an NH group which is bonded to two organic radicals, which may also be part of a ring together ,
  • amine hydrogen refers to the hydrogen atoms of primary and secondary amino groups.
  • amine hydrogen equivalent weight denotes the weight fraction of a hardener or of an amine per amine hydrogen present in the hardener or in the amine.
  • a “thinner” is a soluble in an epoxy resin and its viscosity-reducing substance is referred to, which is not covalently incorporated into the resin matrix during the curing of the epoxy resin.
  • viscosity in the present document refers to the dynamic viscosity or shear viscosity, which is defined by the ratio between the shear stress and the shear rate (velocity gradient) and determined as described in the exemplary embodiments A dashed line in the formulas in this document in each case represents the bond between a substituent and the associated molecular residue.
  • Molecular weight as used herein means the molar mass (in grams per mole) of a molecule.
  • Average molecular weight refers to the number average M n of an oligomeric or polymeric mixture of molecules, which is usually determined by gel permeation chromatography (GPC) against polystyrene as standard.
  • room temperature refers to a temperature of 23 ° C.
  • m is 0 or 1 or 2, particularly preferably 0 or 1, in particular 0.
  • These amines allow particularly low-viscosity epoxy resin compositions.
  • the amine of the formula (I) is preferably in the form of a technical mixture which consists mainly of amines of the formula (I) in which m is 0 or 1.
  • m stands on the average for a value of less than 0.2.
  • m stands on average for a value in the range from 0 to 0.18, in particular 0 to 0.15.
  • the hardener is preferably a non-aqueous hardener.
  • a “non-aqueous hardener” is a hardener which contains less than 5% by weight, preferably less than 2% by weight, in particular less than 1% by weight, of water.
  • X is 1, 2-propylene. Its methyl group may be either in the 1-position or in the 2-position to the adjacent primary amino group.
  • Such an amine of the formula (I) enables epoxy resin products with particularly low viscosity and particularly beautiful surfaces.
  • Y is preferably an aromatic hydrocarbon radical having 6 to 25, in particular 6 to 18, carbon atoms.
  • Y is particularly preferably an aromatic hydrocarbon radical
  • R is a hydrogen radical or methyl radical.
  • Such an amine of formula (I) is particularly low viscosity, particularly accessible and particularly inexpensive.
  • the amine of formula (I) is derived from a bisphenol A liquid resin or from a bisphenol F liquid resin or from a mixture of bisphenol A and bisphenol F liquid resin, as are commercially available are.
  • amines of formula (I) are particularly low viscosity, particularly easy to access, particularly inexpensive and particularly compatible in conventional epoxy resin compositions.
  • m stands on the average for a value of less than 0.2.
  • m stands on average for a value in the range from 0 to 0.18, in particular 0 to 0.15.
  • Such an amine is particularly accessible and has a particularly low tendency to blushing effects.
  • An amine of formula (I) is preferably obtained from the reaction of at least one diamine selected from 1, 2-ethylenediamine and 1, 2-propylenediamine with at least one Di lycidylether of formula (II).
  • m and Y have the meanings already mentioned.
  • the amine of the formula (I) is preferably used for the described use in the form of a reaction product from the reaction of at least one diamine selected from 1,2-ethylenediamine and 1,2-propylenediamine with at least one diglycidyl ether of the formula (II).
  • Preferred diamine for the reaction described is 1,2-propylenediamine.
  • Such a reaction product is particularly low viscosity and allows epoxy resin products with particularly beautiful surfaces.
  • Suitable diglycidyl ethers of the formula (II) are mononuclear or polynuclear aromatic diglycidyl ethers, in particular technical epoxy resins, in particular the glycidylation products of:
  • Dihydroxybenzene derivatives such as resorcinol, hydroquinone or pyrocatechol;
  • bisphenols 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 (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) cyclohexane (bisphenol-Z), 1, 1-bis (4-hydroxyphenyl) -3,3,5
  • Preferred diglycidyl ethers of the formula (II) are bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, bisphenol A / F diglycidyl ethers, resorcinol diglycidyl ethers or hydroquinone diglycidyl ethers, in particular commercially available technical grades.
  • bisphenol A diglycidyl ether bisphenol F diglycidyl ether or bisphenol-A F-diglycidyl ether
  • Araldite ® GY 240 Araldite ® GY 250, Araldite ® GY 281, Araldite ® GY 282, Araldite ® GY 285, Araldite ® PY 304 or Araldite ® PY 720 (all available from Huntsman), or DER ® 330, DER ® 331, DER ® 332, DER ® 336, DER ® 351, DER ® 352, DER ® 354 or DER ® 356 (all ex Dow) ,
  • the ratio between the number of primary amino groups and the number of epoxide groups is preferably in the range from 2.5: 1 to 25: 1, in particular 4: 1 to 15: 1.
  • the temperature in the reaction is preferably in the range from 40 to 120.degree. C., in particular from 60 to 100.degree.
  • Excess unreacted diamine is preferably removed after the reaction by means of distillation, in particular by means of thin film or short path distillation in vacuo.
  • a prepared in the manner described amine of formula (I) has a particularly low content of higher molecular weight by-products and is characterized by a particularly low viscosity and thus particularly good properties in the inventive use.
  • the amine of formula (I) is thus preferably in the form of a reaction product of the reaction of at least one diamine selected from 1, 2-ethylenediamine and 1, 2-propylenediamine with at least one diglycidyl ether Formula (II) used, wherein the ratio between the number of primary amino groups and the number of epoxy groups is at least 2.5: 1 and excess diamine is removed by distillation after the reaction.
  • the ratio between the number of primary amino groups and the number of epoxide groups is preferably in the range from 2.5: 1 to 25: 1, in particular 4: 1 to 15: 1.
  • a reaction product from this preparation is so low viscosity that it is easy to handle at room temperature even without dilution.
  • the reaction product is substantially free of 1, 2-ethylenediamine and / or 1, 2-propylenediamine. It contains in particular less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight, of 1, 2-ethylenediamine and / or 1, 2-propylenediamine.
  • the amine of formula (I) is used in a curing agent for epoxy resins.
  • the hardener is stable on its own; that is, it can be stored at room temperature in a suitable container for a prolonged period of time, typically for 3 to 6 months and longer, without its storage and application properties changing to a relevant extent and thus its utility as Hardener for epoxy resins loses.
  • the amine of formula (I) is preferably used in combination with other amines and / or accelerators.
  • Another object of the invention is accordingly a hardener, in particular a non-aqueous hardener, for epoxy resins containing at least one amine of formula (I) and at least one further amine and / or at least one accelerator.
  • the further amine is in particular not 1,2-ethylenediamine, not 1,2-propylenediamine, no amine of the formula (I), no amine of the formula (I) with values of m> 3 and / or no higher molecular weight by-product in the form of repeatedly adducted diamine.
  • a hardener has a particularly low viscosity and / or a particularly high reactivity with respect to epoxy resins.
  • Suitable accelerators are substances which accelerate the reaction between amino groups and epoxide groups, in particular acids or compounds hydrolyzable to acids, in particular 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 in particular phosphoric acid, or mixtures of the abovementioned acids and acid esters; tertiary amines such as in particular 1, 4-diazabicyclo [2.2.2] octane, benzyldimethylamine, ⁇ -methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1, 2-dimethylimi
  • salicylic acid or 2,4,6-tris (dimethylaminomethyl) phenol or a combination thereof.
  • polyamines which have at least two, in particular at least three, amino acid reactive toward epoxide groups, in particular the following polyamines:
  • Polyamines having one or two secondary amino groups in particular products of the reductive alkylation of primary aliphatic polyamines with aldehydes or ketones, in particular N-benzyl-1,2-propanediamine, N, N'-dibenzyl-1,2-propanediamine, N-benzyl Benzyl 1, 3-bis (aminomethyl) benzene, N, N'-Dibenzyl-1,3-bis (aminonnethyl) benzene, N-2-ethylhexyl-1,3-bis (aminomethyl) benzene, N, N'-bis (2-ethylhexyl) -1, 3 bis (aminonnethyl) benzene, or partially styrenated polyamines such as styrenated MXDA
  • aliphatic, cydoaliphatic or arylaliphatic primary diamines especially 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 (C1 1 -nododiamine), 1, 6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2 (4), 4-trimethylhexamethylenediamine ( TMD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 1 1-undecanediamine, 1, 12-dodecanediamine, 1, 2, 1, 3 or 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane (H 2 -MDA), bis (4-amino-3-methylcycl
  • Ether group-containing aliphatic primary di- or triamines in particular bis (2-aminoethyl) ether, 3,6-dioxaoctane-1, 8-diamine, 4,7-dioxadecane-1, 10-diamine, 4,7-dioxadecan-2 , 9-diamine, 4,9-dioxadodecane-1, 12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1, 13-diamine or higher oligomers these diamines, polytetrahydrofurans bis (3-aminopropyl) or other Polytetrahydrofurandiamine, cydoaliphatician ether groups-containing diamines of the propoxylation and subsequent amination of 1, 4-dimethylol cyclohexane, available as Jeffamine ® particular RFD 270 (of Hunts- man), or
  • Particularly suitable polyoxyalkylene or -triami- ne are Jeffamine ® D-230, Jeffamine ® D-400, Jeffamine ® D-2000, Jeffamine EDR-104, Jeffamine ® EDR-148, Jeffamine ® EDR-176, Jeffamine ® T-403 , Jeffamine ® T-3000, Jeffamine ® T-5000, or the corresponding amines by BASF or Nitroil;
  • secondary amino-containing polyamines having two primary aliphatic amino groups in particular 3- (2-aminoethyl) aminopropylamine bis (hexamethylene) triamine (BHMT), diethylenetriamine (DETA), triethylenetetamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) or higher homologs of linear polyethyleneamines such as polyethylenepolyamine having 5 to 7 ethylenepolyamines (HEPA), products of the multiple cyanoethylation or cyanobutylation and subsequent hydrogenation of primary di- and polyamines having at least two primary amino groups, such as dipropylenetriamine ( DPTA), N- (2-aminoethyl) -1,3-propanediamine (N3-amine), N, N'-bis (3-aminopropyl) ethylenediamine (N4-amine), N, N'-bis (3 -aminopropyl) -1,4-diaminobutane,
  • aliphatic, cycloaliphatic or arylaliphatic primary triamines in particular 4-aminomethyl-1, 8-octanediamine, 1, 3,5-tris (aminomethyl) benzene, 1, 3,5-tris (aminomethyl) cyclohexane, tris (2-aminoethyl) amine Tris (2-amino-propyl) amine or tris (3-aminopropyl) amine;
  • aromatic polyamines in particular m- and p-phenylenediamine, 4,4'-, 2,4 'and / or 2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) diisocyanate, 2,4- and / or 2,6-toluene diamine, mixtures of 3,5-dimethylthio-2,4- and -2,6-toluene diamine (available as Ethacure 300 from Albermarle ®), mixtures of 3,5-diethyl -2,4- and -2,6-toluenediamine (DETDA), 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA),
  • Polyamidoamines in particular reaction products of a mono- or polybasic carboxylic acid, or their esters or anhydrides, in particular a dinner fatty acid, with an aliphatic, cycloaliphatic or aromatic polyamine used in stoichiometric excess, in particular a polyalkyleneamine such as DETA or TETA, especially those commercially available polyamidoamines Versamid ® 100, 125, 140 or 150 (from Cognis), Aradur ® 223, 250 or 848 (from Huntsman), Euretek ® 3607 or 530 (from Huntsman) or Beckopox ® EH 651, EH 654, EH 655, EH 661 or EH 663 (from Cytec);
  • Called phenalkamines, and Mannich bases in particular reaction products of a Mannich reaction of phenols, in particular Carda- nol, with aldehydes, especially formaldehyde, in particular the commercially available phenalkamines
  • Cardolite ® NC-541, NC-557, NC-558, NC 566, Lite 2001 Lite 2002, NX-4943, NX-5607 or NX-5608 from Cardolite®
  • Aradur ® 3440, 3441, 3442 or 3460 Hauntsman
  • Beckopox® ® EH 614, EH 621, EH 624, EH 628 or EH 629 from Cytec
  • Adducts of 1,2-ethylenediamine or 1,2-propylenediamine with reactive diluents having epoxide groups in particular monoglycidyl ethers of phenols, mono- or diglycidyl ethers of aliphatic or cycloaliphatic alcohols, diols or glycols, in particular phenyl glycidyl ether, cresyl glycidyl ethers, guaiacol glycidyl ethers, 4-methoxyphenyl glycidyl ethers, 4-n-butyl-phenylglycidyl ether, 4-tert-butylphenylglycidyl ether, 4-nonylphenylglycidyl ether, 4-dodecylphenylglycidyl ether, cardanolglycidyl ether, benzylglycidyl ether, allylglycidyl ether, buty
  • Preferred as a further amine are polyamines having one or two secondary amino groups, in particular N-benzyl-1,2-propanediamine, N-benzyl-1,3-bis (aminomethyl) benzene, N-2-ethylhexyl-1,3-bis (aminomethyl) benzene or styrenated MXDA.
  • Such amines give particularly low-viscosity hardeners that allow epoxy resin compositions with particularly rapid curing and beautiful surface.
  • Also preferred as a further amine are primary diamines, in particular MPMD, TMD, H 12 -MDA, IPDA, 2- or 4-methyl-1,3-diaminocyclohexane or mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4 Bis (aminomethyl) cyclohexane, NBDA or MXDA.
  • primary diamines in particular MPMD, TMD, H 12 -MDA, IPDA, 2- or 4-methyl-1,3-diaminocyclohexane or mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4 Bis (aminomethyl) cyclohexane, NBDA or MXDA.
  • Such amines give particularly low viscosity hardeners.
  • ether groups-containing aliphatic primary di- or triamines in particular polyoxyalkylene or triamines having an average molecular weight in the range of 200 to 500 g / mol, especially Jeffamine ® D-230 or Jeffamine ® T-403 (both from Huntsman), or cycloaliphatic diamines containing ether groups of the propoxylation and subsequent amination of 1, 4-dimethylolcyclohexane, especially Jeffamine ® RFD-270 (from Huntsman).
  • Such amines give particularly low viscosity hardeners.
  • amine As another amine also preferred are adducts of 1, 2-ethylene diamine or 1, 2-propylene diamine with epoxide having reactive, especially with cresyl glycidyl ether or C 2 - to C 14 -Alkylglycidylether or 1, 4-butanediol diglycidyl ether, or 1, 6-hexanediol diglycidyl ether.
  • N-benzyl-1,2-propanediamine Very particularly preferred as a further amine is N-benzyl-1,2-propanediamine. This amine gives very particular low viscosity hardeners, which are particularly easy-to-process epoxy resin products with fast curing and a beautiful surface.
  • the hardener according to the invention contains preferably 1 to 80% by weight, preferably 2 to 70% by weight, particularly preferably 5 to 60% by weight, in particular 10 to 50% by weight, of amine of the formula (I).
  • Such hardeners are characterized by a low viscosity and allow epoxy resin coatings with high curing speed, high hardness and beautiful surfaces.
  • a particularly preferred hardener for epoxy resins contains
  • the amine of the formula (I), N-benzyl-1,2-propanediamine and the further amine are present in an amount such that all of the amine hydrogens of the hardener
  • Such a curing agent has a low viscosity and, in particular, cures quickly and largely without blushing effects to give cured films of high gloss and high hardness.
  • the hardener is preferably substantially free of amines having a molecular weight below 120 g / mol, in particular below 150 g / mol.
  • the hardener preferably contains less than 2% by weight, in particular less than 1% by weight, of amines having a molecular weight of less than 120 g / mol, in particular less than 150 g / mol.
  • the hardener may further contain at least one diluent, in particular 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 dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene
  • Benzyl alcohol, dodecyl phenol, tert-butylphenol, styrenated phenol, ethoxylated phenol, or phenol group-containing aromatic hydrocarbon resins in particular the Novares LS 500 ® types, LX 200, LA 300 or LA 700 are preferred (from Rutgers).
  • the hardener contains no or only a small content of thinners.
  • the hardener preferably contains a maximum of 5% by weight of thinner.
  • the hardener may contain further substances which are reactive toward epoxide groups, for example monoamines such as hexylamine or benzylamine, or compounds containing mercapto groups, in particular the following: - liquid mercaptan-terminated polysulfide polymers, known under the trade name Thiokol ® (from Morton Thiokol, for example, available from SPI Supplies, or by Toray Fine Chemicals), in particular the types of LP-3, LP-33, LP-980, LP 23, LP-55, LP-56, LP-12, LP-31, LP-32 or LP-2; and also known under the brand name Thioplast ® (ex Akzo Nobel), in particular the types of G 10, G 1 12 G 131, G 1, G 12, G 21, G 22, G 44 or G 4;
  • monoamines such as hexylamine or benzylamine
  • compounds containing mercapto groups in particular the following: - liquid mercaptan-terminated polysulf
  • Mercaptan-terminated polyoxyalkylene ethers obtainable, for example, by reaction of polyoxyalkylene di- or triols with either epichlorohydrin or with an alkylene oxide, followed by sodium hydrogen sulfide;
  • Capcure ® from Cognis, in particular the types WR-8, L ⁇ F or 3-800;
  • Polyesters of thiocarboxylic acids for example pentaerythritol tetramer capoacetate, trimethylolpropane trimercaptoacetate, glycol dimercaptoacetate, pentaerythritol tetra- (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate) or glycoldi- (3-mercaptopropionate), or esterification products of polyoxyalkylene diols or triols, ethoxylated Trimethylolpropane or polyester diols with thiocarboxylic acids such as thioglycolic acid or 2- or 3-mercaptopropionic acid; or
  • Another object of the invention is an epoxy resin composition comprising
  • the resin and hardener components are typically present in separate containers and only become available immediately before application mixed together so that their reactive groups come into contact with each other and the composition hardens.
  • the hardener component is preferably non-aqueous and preferably contains less than 5% by weight, more preferably less than 2% by weight, in particular less than 1% by weight, of water.
  • the hardener component preferably comprises a hardener containing at least one amine of the formula (I) and at least one further amine and / or at least one accelerator, as described above.
  • epoxy resin customary technical epoxy resins are suitable. These are obtained in a known manner, for example from the oxidation of the corresponding olefins or from the reaction of epichlorohydrin with the corresponding polyols, polyphenols or amines.
  • liquid resin So-called polyepoxide flux resins, hereinafter referred to as "liquid resin", which have a glass transition temperature below 25 ° C., are particularly suitable as epoxy resin.
  • an epoxy resin are so-called solid resins, which have a glass transition temperature above 25 ° C and can be comminuted at 25 ° C pourable powders.
  • Suitable epoxy resins are in particular aromatic epoxy resins, in particular the glycidylation products of:
  • 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 cyclohex
  • aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyl-di (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).
  • aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyl-di (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).
  • epoxy resins are aliphatic or cydoaliphatic poly epoxides, in particular
  • Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C 2 - to C 30 -alcohols in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl 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 hydantoin.
  • Epoxy resins from the oxidation of olefins in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododeca-, isoprene, 1, 5-hexadiene, butadiene, polybutadiene or divinylbenzene.
  • the epoxy resin in the resin component is a bisphenol-based liquid resin, particularly a diglycidyl ether of bisphenol-A, bisphenol-F or bisphenol-A / F, as commercially available from Dow, Huntsman or Momentive, for example.
  • These liquid resins have a low viscosity for epoxy resins and, when cured, good properties as a coating. They may contain portions of bisphenol A solid resin or bisphenol F novolacs.
  • the resin component may contain a reactive diluent, in particular a reactive diluent having at least one epoxide group.
  • Suitable reactive diluents are, in particular, the glycidyl ethers of monohydric or polyhydric phenols or aliphatic or cycloaliphatic alcohols, in particular the polyglycidyl ethers of diols or polyols already mentioned, or furthermore phenylglycidyl ether, cresyl glycidyl ether, benzylglycidyl ether, p-n-butylphenyl glycidyl ether, p-tert .Butylphenylglycidylether, nonyl phenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexy
  • the epoxy resin composition contains further constituents, in particular auxiliaries and additives commonly used in epoxy resin compositions, for example the following:
  • Reactive diluents in particular epoxide-containing reactive diluents, as mentioned above, epoxidized soybean oil or linseed oil, Acetoacetate-containing compounds, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes, and also isocyanates or silicones having reactive groups;
  • Polymers in particular polyamides, polysulfides, polyvinylformal (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, sulfonamide-modified melamines or purified montan waxes;
  • inorganic or organic fillers in particular ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barytes, talcs, quartz flour, quartz sand, iron mica, dolomites, wollastonites, kaolins, mica (potassium aluminum silicate) , Molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silicas, cements, gypsum, flyash, soot, graphite, metal powders such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow spheres;
  • Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;
  • Pigments in particular titanium dioxide and / or iron oxides
  • Rheology modifiers in particular thickeners or anti-settling agents
  • flame-retarding substances in particular aluminum hydroxide (ATH), magnesium dihydroxide (MDH), antimony trioxide, antimony pentoxide, boric acid (B (OH) 3 ), zinc borate, zinc phosphate, melamine borate, melamine cyanurate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, polybrominated diphenyl oxides or diphenyl ethers, phosphates in particular diphenylcresyl phosphate, resorcinol bis (diphenylphosphate), resorcinol diphosphate oligomer, tetraphenylresorcinol diphosphite, ethylenediamine diphosphate or Bisphenol A bis (diphenyl phosphate), tris (chloroethyl) phosphate, tris (chloropropyl) phosphate or tris (dichloroisopropyl) phosphate, tris [3-brom
  • Biocides such as algicides, fungicides or fungal growth inhibiting substances.
  • the epoxy resin composition preferably comprises further auxiliaries and additives, in particular wetting agents, leveling agents, defoamers, stabilizers, pigments and / or accelerators, in particular salicylic acid and / or 2,4,6-tris (dimethylaminomethyl) phenol.
  • auxiliaries and additives in particular wetting agents, leveling agents, defoamers, stabilizers, pigments and / or accelerators, in particular salicylic acid and / or 2,4,6-tris (dimethylaminomethyl) phenol.
  • the epoxy resin composition contains no or only a small content of thinners, preferably at most 5% by weight, in particular at most 2% by weight.
  • the ratio of the number of epoxy-reactive groups to the number of epoxy groups is preferably in the range of 0.5 to 1 .5, especially 0.7 to 1 .2.
  • the amine hydrogens present in the epoxy resin composition and, if appropriate, further epoxy-reactive groups react with the epoxide groups under their ring opening (addition reaction). As a result of these reactions, the composition polymerizes and eventually cures. It is known to the person skilled in the art that primary amino groups are difunctional with respect to epoxide groups and a primary amino group thus counts as two epoxide-reactive groups.
  • the two components of the epoxy resin composition are each stored in a separate container. Further constituents of the epoxy resin composition may be present as constituent of the resin component or of the hardener component, other epoxide-reactive further constituents preferably being a constituent of the hardener component.
  • 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 are storable, which means that they can be stored for several months to a year or more before being used, without changing their respective properties to a degree that is relevant to their use.
  • the resin and hardener components are mixed together shortly before or during application.
  • the mixing ratio between the two components is preferably selected so that the epoxy groups reactive groups of the curing agent component are in a suitable ratio to the epoxy groups of the resin component, as previously described. In parts by weight, the mixing ratio between the resin component and the hardener component is usually in the range of 1:10 to 10: 1.
  • the mixing of the two components takes place by means of a suitable method; it can be continuous or batchwise. If mixing occurs before application, care must be taken that there is not too much time between blending the components and the application, as this can lead to disturbances, such as a slow or incomplete build-up of adhesion to the substrate.
  • the mixing takes place in particular at ambient temperature, which is typically in the range of about 5 to 50 ° C, preferably at about 10 to 30 ° C.
  • the curing begins by chemical reaction, as previously described. Curing takes place especially at ambient temperature. It typically lasts for a few days to weeks until it is largely completed under the given conditions. The duration depends, among other things, on the temperature, the reactivity of the constituents and their stoichiometry and the presence of accelerators.
  • a further subject of the invention is therefore also a cured composition obtained from the curing of an epoxy resin composition as described in the present document.
  • the application of the epoxy resin composition takes place on at least one substrate, the following being particularly suitable:
  • metals or alloys such as aluminum, iron, steel or non-ferrous metals, or surface-refined metals or alloys such as galvanized or chromium-plated metals;
  • Plastics in particular hard or soft PVC, ABS, polycarbonate (PC), polyamide (PA), polyester, PMMA, epoxy resins, PUR, POM, PO, PE, PP, EPM or EPDM, the plastics optionally being replaced by plasma, Corona or flames are surface treated;
  • CFRP Carbon Fiber Reinforced Plastics
  • GRP Glass Fiber Reinforced Plastics
  • SMC Sheet Molding Compounds
  • coated substrates such as powder-coated metals or alloys
  • the substrates may be pretreated if necessary prior to application of the epoxy resin composition.
  • pretreatments include, in particular, physical and / or chemical cleaning methods, for example grinding, sandblasting, shot peening, brushing and / or blowing off, as well as further treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer.
  • the described epoxy resin composition can advantageously be used as a fiber composite matrix for fiber composite materials (composites), in particular CFRP or GFRP, or as potting compound, sealant, adhesive, coating, coating, paint, varnish, sealant, primer or primer.
  • potting compound for example as electrical potting compound, or as adhesive, in particular as car body adhesive, sandwich element adhesive, half-shell adhesive for wind turbine rotor blades, bridge element adhesive or anchoring adhesive.
  • a coating, coating, painting, lacquer, sealant, primer or primer for construction and industrial applications, in particular as a floor covering or floor coating for interiors such as offices, industrial halls, gymnasiums or cold rooms, or outdoors for balconies, terraces, parking decks , Bridges or roofs, as a protective coating for concrete, cement, metals, plastics or wood, for example for the surface sealing of wooden constructions, vehicles, loading areas, tanks, silos, shafts, pipelines, pipelines, machines or steel constructions, such as ships, piers, Offshore platforms, floodgates, hydroelectric power plants, river structures, swimming pools, wind turbines, bridges, fireplaces, cranes or sheet piling.
  • it is furthermore usable as a primer, adhesive coating, anticorrosive primer or for the hydrophobization of surfaces.
  • the completely or partially cured epoxy resin composition in particular when it is used as a coating, coating or coating, it is possible to apply a further coating, a further coating, or a further coating, wherein this further coating may likewise be an epoxy resin composition but also a different material, in particular a polyurethane or polyurea coating.
  • the described epoxy resin composition is used as a coating.
  • a further subject of the invention is accordingly a coating containing an epoxy resin composition as described above.
  • Coating of all types of surface-applied coatings is understood as coating, in particular paints, varnishes, sealants, primers or primers, as described above, or floor coverings or protective coatings, especially those for heavy corrosion protection.
  • the described epoxy resin composition is particularly advantageously used in low-emission coatings with eco-labels, for example according to Emicode (EC1 Plus), AgBB, DIBt, Der Blaue Engel, AFSSET, RTS (M1) and US Green Building Council (LEED).
  • Emicode EC1 Plus
  • AgBB AgBB
  • DIBt DIBt
  • Der Blaue Engel AFSSET
  • RTS RTS
  • M1 US Green Building Council
  • the epoxy resin composition is advantageously used in a process for coating, wherein it has a liquid consistency with low viscosity and good flow properties and is applied in particular as a self-leveling or thixotropic coating on predominantly flat surfaces or as a paint.
  • the epoxy resin composition in this application immediately after mixing the resin and the hardener component has a viscosity, measured at 20 ° C, in the range of 300 to 4 ⁇ 00 mPa s, preferably in the range of 300 to 2 ⁇ 00 mPa s, especially preferably in the range of 300 to 1 '500 mPa s, on.
  • the blended composition is applied flat over the processing time as a thin film having a layer thickness of typically about 50 ⁇ m to about 5 mm onto a substrate, typically at ambient temperature.
  • the application is carried out in particular by pouring onto the substrate to be coated and subsequent uniform distribution using, for example, a doctor blade or a dental trowel.
  • the application can also be done with a brush or roller or as a spray application, for example as a corrosion protection coating on steel.
  • Curing typically produces largely clear, glossy and non-tacky films of high hardness, which have good adhesion to a wide variety of substrates.
  • the application of the epoxy resin composition results in an article comprising the cured composition from the cure of the described epoxy resin composition.
  • the cured composition is present in particular in the form of a coating.
  • the described epoxy resin composition is characterized by advantageous properties. It is low viscous and odorless and hardens quickly and largely without blushing effects, even at low levels or without the use of thinners, and especially without the use of volatile, odorous amines. In the areal use as a coating, clear, non-sticky films of high hardness and high surface quality are formed, which hardly yellow under the influence of light. With the epoxy resin composition described in particular low-emission epoxy resin products are available, which meet the conditions for many eco-labels and at the same time meet high standards of occupational safety, processing and performance characteristics.
  • Another object of the invention is an amine of the formula (I), welh in wel-
  • n 0 to 1
  • X is 1, 2-propylene
  • Y is a radical of the formula where R is a
  • Hydrogen radical or methyl radical is.
  • m stands on the average for a value of less than 0.2.
  • m stands on average for a value in the range from 0 to 0.18, in particular 0 to 0.15.
  • This amine is especially suitable for use in a curing agent for epoxy resins, as previously described.
  • AHEW stands for the amine hydrogen equivalent weight.
  • NK stands for "standard climate”.
  • FT-IR Infrared
  • 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 HClO 4 in acetic acid against crystal violet).
  • Araldite ® GY 250 Bisphenol A diglycidyl ether, EEW about 187.5 g / eq (of
  • Araldite ® DY-E monoglycidyl ether of C 2 - to C 4 -alcohols, EEW approx. 290 g / Eq (from Huntsman)
  • Erisys RDGE ®-H resorcinol diglycidyl ether, EEW about 1 18.5 g / Eq (from
  • N-Benzyl-1, 2-pro reaction mixture prepared as described in the following pandiamin ben, AHEW about 54.75 g / eq N-Benzyl-1, 2-propanediamine:
  • the reaction was checked by IR spectroscopy to see if the imine band had disappeared at about 1665 cm -1 and then the hydrogenated solution was concentrated on a rotary evaporator at 65 ° C., removing unreacted 1,2-propanediamine and isopropanol of which 300 g were distilled under reduced pressure at 80 ° C., collecting 237.5 g of distillate at a vapor temperature of 60 to 63 ° C.
  • FT-IR 2955, 2921, 2869, 1589, 1490, 1450, 1286, 1263, 1 181, 1 145, 1039, 831, 760, 686.
  • the ingredients of the hardener component shown in Table 1 were mixed in the indicated amounts (in parts by weight) by means of a centrifugal mixer (Speed Mixer TM DAC 150, FlackTek Inc.) and stored with exclusion of moisture.
  • a centrifugal mixer Speed Mixer TM DAC 150, FlackTek Inc.
  • a first film was coated in a layer thickness of 500 ⁇ on a glass plate and this stored or cured under standard conditions.
  • the king's hardness pendulum hardness according to King, measured according to DIN EN ISO 1522
  • 1 day (“Königshärte (1 d NK)")
  • 2 days (“Königshärte (2d NK)”
  • 4 days King Hardness (4d NK) )
  • 7 days Royal Hardness (7d NK)
  • Royal Hardness (14d NK) was a film that was clear and had a glossy and non-sticky surface without any texture, meaning any kind of drawing or pattern on the surface.
  • a second film was applied in a layer thickness of 500 ⁇ on a glass plate and this immediately after the application for 7 days 8 ° C and 80% relative humidity and then stored for 3 weeks in NK, or cured. Twenty-four hours after application, a polypropylene bottle cap was placed on the film, under which a moist sponge was placed. After another 24 hours, the sponge and lid were removed and placed in a new location on the film, where it was removed and repositioned after 24 hours, a total of 4 times.

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  • Epoxy Resins (AREA)

Abstract

L'invention concerne l'utilisation d'une amine de formule (I) dans un durcisseur pour résines époxydes, un durcisseur pour résines époxydes contenant ladite amine de formule (I) et des compositions de résine époxyde ainsi obtenues qui peuvent s'utiliser en particulier comme revêtements de résine époxyde à faible taux d'émission et durcissant à température ambiante, qui présentent une bonne aptitude à la transformation, un durcissement rapide, une dureté renforcée et une meilleure qualité de surface. L'amine de formule (I) est peu odorante et bien manipulable à température ambiante également sans dilution et peut être préparée à un degré élevé de pureté selon un procédé simple.
EP16750760.7A 2015-08-07 2016-08-04 Amine pour compositions de résine époxyde à faible taux d'émission Withdrawn EP3331935A1 (fr)

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EP15180243 2015-08-07
PCT/EP2016/068704 WO2017025448A1 (fr) 2015-08-07 2016-08-04 Amine pour compositions de résine époxyde à faible taux d'émission

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WO2019192903A1 (fr) * 2018-04-06 2019-10-10 Basf Se Procédé de préparation d'amines
EP3677648A1 (fr) * 2019-01-03 2020-07-08 Sika Technology Ag Procédé de détection de l'usure dans des systèmes de revêtement de sol et compositions correspondantes
KR102273807B1 (ko) * 2019-03-14 2021-07-06 주식회사 케이씨씨 아민-아마이드 수지 조성물 및 이의 제조 방법
CN110591624A (zh) * 2019-10-25 2019-12-20 山东益丰生化环保股份有限公司 一种硫醇改性室温快速固化环氧胶粘剂预聚物及其制备方法

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CA877389A (en) 1971-08-03 Becker Wilhelm Curing epoxide resins
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