Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
  • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
• • 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
  • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5046—Amines heterocyclic
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the invention relates to the field of amines, hardeners for epoxy resins, epoxy resin products and their use, in particular as coatings, coatings and paints.
• Epoxy resin products suitable for coating should have as low a viscosity as possible to be readily processable and self-leveling at ambient temperature. Furthermore, they should cure as quickly as possible and trouble-free, even in humid-cold conditions, and thereby form a smooth surface without turbidity, stains 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 the lowest possible tendency to yellowing under the influence of light.
• thinners are commonly used in prior art epoxy coatings.
• the thinners improve processability, reduce the brittleness of the coating and improve the surface quality by reducing the occurrence of blushing effects.
• “Blushing effects” refer to surface defects such as turbidity, stains, roughness and stickiness during curing, which are caused by salting ("blushing") of amines with carbon dioxide (CO 2 ) from the air and especially at high air humidity and low temperatures occur.
• the thinners usually used are unreactive with respect to epoxy resins at room temperature and are therefore not incorporated into the resin matrix during curing.
• Today, however, increasingly low-emission products are desired which, after curing, have a low content of substances which can be released by evaporation or diffusion processes.
• Low-emission epoxy resin products can therefore be used only in very small amounts or not at all.
• Another way to dilute epoxy resins is to use increased amounts of small primary amines in the hardener component.
• Such amines such as, for example, diethylenetriamine, isophoronediamine or xylylenediamine, are odor-intensive, strongly irritating to the skin and the eyes, and sensitizing, and they increasingly lead to blushing effects.
• No. 5,426,157 describes epoxy resin compositions containing ⁇ , ⁇ '-dimethylated diamines.
• No. 5,739,209 describes monoalkylated diamines starting from 2-methyl-1,5-pentanediamine as a hardener for epoxy resins with increased flexibility and stability. The diamines described dilute low-emission epoxy resin coatings but insufficient.
• the amine of formula (I) solves this problem very well. It is low in odor and low in volatility, yet very low in viscosity and thins epoxy resin coatings surprisingly well without slowing down the cure rate too much or causing blushing effects. During curing, it is incorporated into the resin matrix and, with high hardness, very effectively contributes to the reduction of the sputtering. In contrast to similar amines, such as 1, 3-bis (benzylaminomethyl) benzene or 1, 3-bis (2-phenylethylaminomethyl) benzene, it surprisingly does not cause any increased yellowing of the cured coating.
• curing agents are available for low-emission, room-temperature-curing epoxy resins which fulfill the conditions for eco-labels, for example Emicode (EC1 Plus), AgBB, DIBt, Blue Angel, AFSSET, RTS (M1) and US Green Building Council (LEED), meet and At the same time meet high demands in terms of processing and use properties.
• the invention provides an amine of the formula (I).
• 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.
• non-incorporable diluent refers to a substance soluble in an epoxy resin and having a viscosity-reducing substance, 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.
• the amine of formula (I) is 1, 3-bis (2-ethylhexylaminomethyl) benzene.
• the amine of formula (I) can be obtained particularly advantageously by reductive alkylation of 1, 3-bis (aminomethyl) benzene (meta-xylylenediamine or MXDA) with 2-ethyl-hexanal.
• the reductive alkylation can be carried out directly with molecular hydrogen or indirectly by hydrogen transfer from other reagents. gentien.
• molecular hydrogen is used.
• the conditions are advantageously chosen so that on the one hand the primary amino groups are readily alkylated with good selectivity and on the other hand, the benzene ring is not hydrogenated.
• Preferred as a catalyst are palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams catalyst and Raney nickel, in particular palladium on carbon and platinum on carbon.
• the preparation of the amine of formula (I) by reductive alkylation in the manner described is particularly advantageous for use as a component of curing agents for epoxy resins, since primary amino groups are readily alkylated with good selectivity, while secondary amino groups are hardly further alkylated.
• the product from the described preparation process can therefore be used without further treatment for curing epoxy resins in the manner described.
• Another object of the invention is thus a process for the preparation of the amine of formula (I) by reductive alkylation of 1, 3-bis (aminomethyl) benzene with 2-ethylhexanal and hydrogen.
• a molar ratio of ⁇ 1 .4 / 1 can lead to unsatisfactory results in terms of dilution effect and blushing when used in epoxy resin hardeners, while a molar ratio> 2.4 / 1 requires a costly post-purification.
• a molar ratio of about 2/1 is particularly preferred.
• the amine of the formula (I) is obtainable in high purity without additional workup and, as a constituent of epoxy resin hardeners, has an excellent diluting and brittleness-reducing action.
• the resulting reaction mixture in addition to the amine of the formula (I) also contains considerable amounts of N-2-ethylhexyl-1, 3-bis (aminomethyl) benzene. It has as Part of epoxy resin hardeners a good diluting effect, a moderate brittleness reducing effect and allows a particularly rapid curing.
• the amine of the formula (I) can also be obtained in other ways than by reductive alkylation, in particular by reacting 1,3-bis (aminomethyl) benzene with 2-ethylhexyl chloride or 2-ethylhexyl bromide in a suitable ratio. This gives rise to reaction mixtures which typically have a considerable proportion of doubly alkylated amino groups.
• the amine of formula (I) is a low volatile, low odor substance of very low viscosity. It has such a low reactivity with respect to CO 2 that, in contrast to many amines known from the prior art, it does not tend to form crusts, or precipitate or increase in viscosity in air. It shows excellent compatibility with other amines and with epoxy resins. Despite the presence of the aromatic ring, it surprisingly does not lead to increased yellowing under the influence of light in the cured epoxy resin coating.
• Another object of the invention is the use of the amine of formula (I) as a diluent, especially in curing agents for epoxy resins.
• the amine of formula (I) has a comparatively high amine hydrogen equivalent weight. As a result, it can be used in a considerable amount in curing agents for epoxy resins and dilute them, without affecting the curing reaction too much.
• the amine of formula (I) can significantly reduce their viscosity.
• Another object of the invention is a curing agent, suitable for curing epoxy resins comprising the amine of formula (I) and at least one polyamine A, which has at least three amine hydrogens reactive toward epoxide groups.
• Suitable polyamines A are, in particular, the following polyamines:
• aliphatic, cycloaliphatic 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 -Neodiamin), 1, 6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2,4- and 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- and 1, 4-diaminocyclohexane, bis (4-aminocyclohexyl) methane (H12-MDA), bis (4-
• aliphatic, cycloaliphatic or arylaliphatic primary triamines in particular 4-aminomethyl-1,8-octanediamine, 1,3,5-tris (aminomethyl) benzene,
• aliphatic primary diamines 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 and higher oligomers of these diamines, bis ( 3-aminopropyl) polytetrahydrofurans and other poly-tetrahydrofuran-diamine, cycloaliphatic ether groups-containing diamines from the propoxylation and subsequent amination of 1, 4-dimethylol cyclohexane, sold in particular as Jeffamine ® RFD 270 (of Hunts- man),
• Particularly suitable polyoxyalkylene diamines are Jeffamine ® D-230, Jeffamine ® D-400, Jeffamine ® D-2000, Jeffamine ® EDR-104, Jeffamine ® EDR-148 and Jeffamine ® EDR-176, and corresponding amines by BASF or Nitroil;
• primary polyoxyalkylene triamines which are typically products from the amination of Polyoxyalkylentnolen and obtainable for example are available under the name Jeffamine ® (from Huntsman), under the name of the polyetheramines (from BASF) or under the name PC amines ® (of Nitroil), especially Jeffamine ® T -403, Jeffamine ® T-3000, Jeffamine ® T-5000, and corresponding amines by BASF or Nitroil;
• tertiary amino group-containing polyamines having two primary aliphatic amino groups in particular N, N'-bis (aminopropyl) piperazine, N, N-bis (3-aminopropyl) methylamine, N, N-bis (3-aminopropyl) ethylamine, N, N-bis (3-aminopropyl) propylamine, N, N-bis (3-aminopropyl) cyclohexylamine, N, N-bis (3-aminopropyl) -2-ethyl-hexylamine, and the products of the double cyanoethylation and subsequent reduction of fatty amines, which are derived from natural fatty acids, such as N, N-bis (3-aminopropyl) dodecylamine, and N, N-bis tallowalkylamine (3-aminopropyl) available as Triameen ® Y12D and Triameen YT ® (ex Akzo
• tertiary amino-containing polyamines having three primary aliphatic amino groups, in particular tris (2-aminoethyl) amine, tris (2-aminopropyl) amine and tris (3-aminopropyl) amine;
• secondary amino-containing polyamines having two primary aliphatic amino groups in particular 3- (2-aminoethyl) aminopropylamine, bis (hexamethylene) triamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA ) and higher homologs of linear polyethyleneamines such as polyethylenepolyamine with 5 to 7 ethylenepolyamines (HEPA), products of 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, N5
• a polyamine containing a primary and a secondary amino group such as in particular N-butyl-1,2-ethanediamine, N-hexyl-1,2-ethanediamine, N- (2-ethyl-hexyl) -1,2-ethanediamine, N- Cyclohexyl-1,2-ethanediamine, 4-aminomethylpiperidine, N- (2-aminoethyl) piperazine, N-methyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N- (2- Ethylhexyl) -1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 3-methylamino-1-pentylamine, 3-ethylamino-1-pentylamine, 3-cyclohexylamino-1-pentylamine fatty diamine such as N-cocoalkyl -1, 3-propanediamine and products from the Michael-type addition reaction of primary ali
• aromatic polyamines in particular m- and p-phenylenediamine, 4,4'-, 2,4 'and 2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 2,4- and 2,6-toluene diamine, mixtures of 3,5-dimethyl methylthio-2,4- and -2,6-toluene diamine (available as Ethacure 300 ® of Albe- Marle), mixtures of 3,5- Diethyl 2,4- and -2,6-toluenediamine (DETDA), 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA), 3,3', 5,5 ' Tetraethyl 2,2'-dichloro-4,4'-diaminodiphenylmethane (M-CDEA), 3,3'-d
• Adducts of said polyamines with epoxides and epoxy resins in particular adducts with diepoxides in a molar ratio of about 2/1, adducts with monoepoxides in a molar ratio of at least 1/1, and reaction products of amines and epichlorohydrin, in particular that of 1, 3-bis - (aminomethyl) benzene, commercially available as gas fireplaces ® 328 (MGC);
• Polyamidoamines which are reaction products of a monohydric or polybasic carboxylic acid, or their esters or anhydrides, in particular a dinner fatty acid, and an aliphatic, cycloaliphatic or aromatic polyamine used in stoichiometric excess, in particular a polyalkyleneamine such as DETA or TETA , in particular the polyamidoamines commercially available Versamid ® 100, 125, 140 and 150 (from Cognis), Aradur ® 223, 250 and 848 (from Huntsman), Euretek ® 3607 and 530 (from Huntsman) and Beckopox ® EH 651, EH 654 EH 655, EH 661 and EH 663 (from Cytec); and
• phenalkamines and Mannich bases, which are reaction products of a Mannich reaction of phenols, in particular cardanol, which represent with aldehydes, especially formaldehyde, and polyamines, in particular the phenalkamines commercially available Cardolite ® NC-541, NC-557, NC-558, NC-566, Lite and Lite 2001 2002 (from Cardolite®) Wegur ® 3440, 3441, 3442 and 3460 (from Huntsman) and Beckopox® ® EH 614, EH 621, EH 624, EH 628 and EH 629 (Cytec).
• the polyamine A is selected from the group consisting of 1, 5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1, 5-pentanediamine (C1 1 -Ne- diamin), 1, 6- Hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1,12-dodecanediamine, 1,3-diaminocyclohexane, bis (4-aminocyclohexyl) - methane (HMDA), bis (4-amino-3-methylcyclohexyl) ethane, 1-amino-3-amino-methyl-3,5,5-tri-methylcyclohexane (IPD), 1, 3-bis (aminomethyl) cyclohexane, 1, 3-bis (aminonnethyl) benzene (MXDA), bishexamethylenetriamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (MPMD),
• These preferred polyamines A are particularly compatible with epoxy resins and allow high quality films.
• the polyamine A particularly preferably represents an adduct with an epoxide, in particular an adduct with an epoxy resin or with a monoepoxide.
• adducts show excellent properties as curing agents for epoxy resins, in particular a fast curing rate, even at low temperatures, and a slight tendency to blushing effects. They give films of excellent quality but, because of their high viscosity, are only suitable for coating applications when heavily diluted. This is typically achieved in the art by blends containing unincorporable diluents and larger amounts of small, relatively volatile primary diamines. However, if you do not want to install thinners that can not be incorporated, such hardeners are either too viscous or lead to strong blushing effects. By diluting such adducts with the amine of formula (I) are hardeners for epoxy resins with excellent properties for low-emission coatings accessible.
• the polyamine A is an adduct with an aromatic monoepoxide.
• Such adducts have a moderate viscosity and are well compatible with epoxy resins.
• Particularly preferred monoepoxides are aromatic glycidyl ethers, in particular the cresyl glycidyl ethers.
• Suitable as cresyl glycidyl ether are all isomeric cresyl glycidyl ether, and mixtures thereof, in particular commercially Avail- Liehe types such as in particular Araldite ® DY-K (from Huntsman), Polypox TM R6 (from Dow), Heloxy TM KR (from Hexion) or Erisys GE-10 ® (from CVC Spec. Chem.).
• Such an adduct has a particularly good compatibility with the usual epoxy resin products and allows cured films of high gloss and high hardness.
• the curing agent contains at least two different polyamines A, in particular at least one polyamine A1, which is preferably an adduct with an epoxide, and at least one polyamine A2, which is a non-adducted polyamine.
• polyamine A1 which is preferably an adduct with an epoxide
• polyamine A2 which is a non-adducted polyamine.
• the amine of the formula (I) is preferably present in the curing agent in an amount such that its amine hydrogens make up from 1 to 75%, preferably from 2 to 50%, in particular from 5 to 30%, of the total amine hydrogens present in the hardener.
• the amine of the formula (I) is present in the curing agent in such an amount that its weight fraction is from 1 to 95%, preferably from 5 to 75%, in particular in particular 5 to 50%, the sum of all epoxide-reactive amines makes up.
• Such hardeners are characterized by a low viscosity and allow epoxy resin coatings with high curing rate, little tendency to blushing effects and high hardness with low brittleness.
• the hardener may further contain at least one accelerator.
• 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; furthermore tertiary amines such as in particular 1,4-diazabicyclo [2.2.2] octane, benzyldimethylamine, ⁇ -methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles in particular N-methylimidazole,
• Preferred accelerators are salicylic acid and 2,4,6-tris (dimethylaminomethyl) phenol.
• the hardener may furthermore comprise at least one non-incorporable 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 dimer ethyl ether 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
• Benzyl alcohol, dodecyl phenol, tert-butylphenol, styrenated phenol, ethoxylated phenol and phenol-group-containing aromatic hydrocarbon resins in particular the Novares LS 500 ® types, LX 200, LA 300 and LA 700 are preferred (from Rutgers).
• the curing agent contains no or only a low content of non-incorporable diluents, particularly preferably less than 25% by weight, in particular less than 10% by weight and most preferably less than 5% by weight.
• no non-incorporable diluent is added to the hardener.
• the hardener may contain further substances which are reactive toward epoxide groups, for example monoamines, such as hexylamine and benzylamine; secondary aliphatic polyamines; Mercapto-containing compounds, 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 and 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 and G 4;
• Mercaptan-terminated polyoxyalkylene ethers obtainable, for example, by reaction of polyoxyalkylene di- and 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 and 3-800;
• Polyesters of thiocarboxylic acids for example pentaerythritol tetramer capoacetate, trimethylolpropane trimercaptoacetate, glycol dimercaptoacetate, pentaerythritol tetra- (3-mercaptopropionate), trimethylolpropane tri- (3-mercaptopropionate) and glycoldi- (3-mercaptopropionate), as well as the esterification products of polyoxyalkylene diols and triols ethoxylated trimethylolpropane and polyester diols with thiocarboxylic acids such as thioglycolic acid and 2- or 3-mercaptopropionic acid; and
• Another object of the invention is an epoxy resin composition containing at least one epoxy resin and the previously described hardener.
• 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 which have a glass transition temperature below 25 ° C.
• 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 and 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) -cyclohe
• 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), 4,4 '- [1,3-phenylene-bis (1-methylethylidene)] bisaniline (bisaniline-M).
• epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular
• Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C 2 -C 30 -alcohols in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexane, neopentyl glycol, Dibromo-neopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythrol, sorbitol or glycerol, as well as alkoxylated glycerol or alkoxylated trimethylolpropane;
• N-glycidyl derivative of amides or heterocyclic nitrogen bases such as triglycidyl cyanurate and triglycidyl isocyanurate, as well as reaction products of epichlorohydrin and hydantoin.
• the epoxy resin is preferably a bisphenol-based liquid resin, in particular a diglycidyl ether of bisphenol A, bisphenol F or bisphenol A / F, as are commercially available, for example, from Dow, Huntsman and Hexion. These liquid resins have a low viscosity for epoxy resins and in the cured state good properties as a coating. They may optionally be present in combination with bisphenol A solid resin or bisphenol F novolac epoxy resin.
• the epoxy resin may contain a reactive diluent, in particular a reactive diluent having at least one epoxide group.
• Suitable reactive diluents are the glycidyl ethers of monohydric or polyhydric phenols and aliphatic or cycloaliphatic alcohols, in particular in particular, the above-mentioned polyglycidyl ethers of diols or polyols, and also especially phenylglycidyl ether, cresyl glycidyl ether, benzylglycidyl ether, p-tert-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonyl phenylglycidyl ether, allylglycidyl ether, butylglycidyl ether, hexylglycidyl ether, 2-ethylhexylglycidyl ether, as well as glycidyl ethers of natural alcohols, such as, for example, Cs to C
• 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 reactive diluents having epoxide groups, as mentioned above, epoxidized soybean oil or linseed oil, acetoacetate-containing compounds, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes and furthermore isocyanates and 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 and alkyl (meth) acrylates, in particular chlorosulfonated polyethylenes and fluorine-containing polymers, sulfonamide-modified Melamine and purified montan waxes;
• inorganic and organic fillers for example ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barite, talc, quartz flour, quartz sand, iron mica, dolomites, wollastonites, kaolins, mica (potassium aluminum Silicate), molecular sieves, aluminum oxides, aluminum hydroxides, Magnesium hydroxide, silicas, cements, plasters, flyashes, soot, graphite, metal powders such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow spheres;
• fatty acids in particular stearates, barite, talc, quartz flour, quartz sand, iron mica, dolomites, wollastonites, kaolins, mica (potassium aluminum Silicate), molecular sieves, aluminum oxides, aluminum hydroxides, Magnesium hydroxide, silicas, cements, plasters, flyashes, soot, graphite, metal powders such
• Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;
• titanium dioxide and iron oxides in particular titanium dioxide and 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 (diphenyl phosphate), resorcinol diphosphate oligomer, tetraphenyl resorcinol diphosphite, ethylenediamine diphosphate and bisphenol A bis (diphenyl phosphate), tris (chloroethyl) phosphate, tris (chloropropyl) phosphate and tris (dichloroisopropyl) phosphate, Tris [3
• Biocides such as algicides, fungicides or fungal growth inhibiting substances.
• the epoxy resin composition contains other auxiliaries and additives, in particular wetting agents, leveling agents, defoamers, stabilizers. ren, pigments and catalysts, in particular salicylic acid or 2,4,6-tris (dimethylaminomethyl) phenol.
• auxiliaries and additives in particular wetting agents, leveling agents, defoamers, stabilizers. ren, pigments and catalysts, in particular salicylic acid or 2,4,6-tris (dimethylaminomethyl) phenol.
• the epoxy resin composition preferably contains no or only a small content of non-incorporable diluents, more preferably less than 10% by weight, in particular less than 5% by weight, most preferably less than 2% by weight.
• the ratio of the number of epoxy groups relative 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 epoxy resin composition is a two-part composition consisting of
• the components of the two-component composition are each stored in a separate container.
• Other constituents of the two-component epoxy resin composition may be present as a constituent of the resin component or of the hardener component, with further constituents reactive toward epoxide groups 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 being reflected in their respective properties to a degree that is relevant to their use.
• the resin and hardener components are mixed shortly before or during application.
• the mixing ratio between the two components is preferably selected such that the groups which are reactive toward epoxide groups of the hardener component are in a suitable ratio to the epoxide groups of the resin component, as described above.
• 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 inter alia on the temperature, the reactivity of the constituents and their stoichiometry and the presence of accelerators.
• Another object of the invention is thus also a cured composition obtained from the curing of an epoxy resin composition as described in this document.
• the application of the epoxy resin composition takes place on at least one substrate, the following being particularly suitable: - glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble;
• metals and alloys such as aluminum, iron, steel and non-ferrous metals, including surface-treated metals and alloys, such as galvanized and chromium-plated metals;
• resins for example phenolic, melamine or epoxy resins, bonded wood-based materials, resin-textile composites and other so-called polymer composites;
• plastics especially hard and soft PVC, ABS, polycarbonate (PC), polyamide (PA), polyester, PMMA, epoxy resins, PUR, POM, PO, PE, PP,
• EPM and EPDM wherein the plastics are optionally surface treated by means of plasma, corona or flame;
• 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 processes, 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 epoxy resin composition described is advantageously usable as a fiber composite material (composite), potting compound, sealant, adhesive, coating, coating, paint, varnish, sealant, primer or primer.
• potting compound, sealant and adhesive such as, for example, as an electrical potting compound, sealant, body adhesive, sandwich element adhesive, half-shell adhesive, for example for wind turbine wind turbine blades, bridge element adhesive or anchoring adhesive; and further as a coating, coating, paint, varnish, sealer, primer and primer for construction and industrial applications, such as in particular as floor covering and 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 surface sealing of wooden constructions , Vehicles, cargo areas, tanks, silos, shafts, pipelines, pipelines, machinery or steel structures, for example of ships, piers, offshore platforms, floodgates, hydroelectric power plants, river structures, swimming pools, wind turbines, bridges, chimneys, cranes or sheet piling; and furthermore as a primer, adhesive coating, anticorrosion primer or for the hydrophob
• 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 another material, in particular a polyurethane or polyurea coating.
• the described epoxy resin composition can be used particularly advantageously as a coating.
• Coating is understood to mean surface-applied coatings of all kinds, in particular paints, lacquers, sealants, primers and primers, as described above.
• Particularly advantageous is the described epoxy resin composition in low-emission epoxy resin products with eco-labels, for example Emicode (EC1 Plus), AgBB, DIBt, The Blue Angel, AFSSET, RTS (M1) and US Green Building Council (LEED).
• 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 can be applied in particular as a self-leveling 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 from 300 to 2 ⁇ 00 mPa s, preferably in the range from 300 to 1'500 mPa s, particularly preferably in the range from 300 to 1'200 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 then evenly distributing with the aid of, for example, a sprocket or a dental trowel.
• the application can also be carried out 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, low brittleness and a low tendency to yellowing, which have good adhesion to a wide variety of substrates.
• a film of high hardness and low brittleness preferably has a king hardness (pendulum hardness according to König, measured according to DIN EN ISO 1522) in the range of 100 to 200 s, in particular 120 to 180 s.
• An even higher royal hardness also typically has increased brittleness and lower royal hardness is too soft for many coating applications.
• Another object of the invention is an article containing a cured composition obtained by the curing 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 viscosity and cures quickly and largely without blushing effects even in cold, damp conditions, with clear films of high hardness, low brittleness and low yellowing tendency available, even with low levels or without the use of non-incorporable thinners and with low levels or without the use of small, relatively volatile primary diamines. With the epoxy resin composition described are low-emission epoxy resin products accessible that meet the conditions for many eco-labels while meeting high standards of occupational safety, processing and performance properties.
• AHEW stands for the amine hydrogen equivalent weight.
• MMC Metal Organic Chemical
• the amine content that is the total content of amino groups in the compounds prepared, was determined by titration (with 0.1 N HClO 4 in glacial acetic acid, against crystal violet) and is always given in mmol N / g.
• FT-IR Infrared
• GC / MS was carried out under the following conditions: column Agilent VF-5ms, 30 mx0.25 mm, 0.25 ⁇ m film thickness; Heating rate 15 ° C / min from 60 ° C to 320 ° C, then 15 min. maintained at 320 ° C; Carrier gas He at a constant flow rate of 1 .1 ml / min; Injector split 25: 1, temperature 230 ° C; Ionization method Cl + (methanol).
• the viscosity was measured on a thermostatically controlled Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-to-plate distance 0.05 mm, shear rate 10-100 s -1 ).
• EP-adduct 1 1 reaction product of 16.0 GT 1, 5-diamino-2-methyl pentane and 182 Araldite GT ® DY-K;
• EP-adduct 2 reaction product of 136.2 GT 1, 3-bis (aminomethyl) - benzene and 182 Araldite GT ® DY-K;
• Amine 1 1, 3-bis (2-ethylhexylaminomethyl) benzene
• FT-IR 2956, 2923, 2857, 281 1, 1457, 1378, 1 156, 1 1 13, 776, 726, 699.
• Amin-2 reaction mixture containing 1, 3-bis (2-ethylhexylaminomethyl) benzene and N-2-ethylhexyl-1,3-bis (aminomethyl) benzene
• Amine-5 (Reference): 1,3-Bis (n-octylaminomethyl) benzene
• 25.6 g (0.20 mol) of 1-octanal and 13.6 g (0.10 mol) of 1,3-bis (aminomethyl) benzene were reacted. Obtained was a clear, slightly yellowish liquid having a viscosity of 130 mPa s at 20 ° C, an amine content of 5.45 mmol N / g and a theoretical AHEW of about 180.3 g / eq.
• Amine-6 (Reference): N, N'-Bis (2-ethylhexyl) -1, 5-diamino-2-methylpentane
• 25.6 g (0.20 mol) of 1-octanal and 1 1 .6 g (0.10 mol) of 1, 5-diamino-2-methylpentane (Dytek ® A from Invista) implemented. Obtained was a clear, slightly yellowish liquid having a viscosity of 140 mPa s at 20 ° C, an amine content of 5.80 mmol N / g and a theoretical AHEW of about 170.3 g / eq.
• HZ-1 to HZ-3 are hardeners according to the invention, and Ref-1 to Ref-3 are comparative examples.
• Table 1 Compositions, viscosities and AHEW of the hardener HZ-1 to
• Each curing agent of Table 1 contains the amine-1 or the amine-3 in such an amount that its amine hydrogens constitute 25% of the total present in the curing agent amine hydrogens. 5.
• “Beautiful” was a film that was clear and had a glossy and non-sticky surface without texture, and the "structure” is 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 stored immediately after the application for 7 days at 8 ° C and 80% relative humidity and then for 3 weeks in NK, or cured. 24 hours after application, a bottle cap made of polypropylene was placed on the film, under which was placed a damp sponge. 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.
• EZ-1 to EZ-4 are examples according to the invention, and Ref-4 to Ref-11 are comparative examples.

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• 2013
  • 2013-01-08 EP EP13150534.9A patent/EP2752403A1/de not_active Withdrawn
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