Patent Application
20240247096
The invention relates to amines and to the use thereof for curing of epoxy resins.
Epoxy resin compositions have various uses, including as adhesives or coatings in the building and manufacturing industries. For applications in which the compositions cure at ambient temperatures, rapid and reliable curing to high final hardness is desirable even at low temperatures. The curing agents known from the prior art are usually polyamines having two primary amino groups. They often show an inadequate curing rate and/or faulty curing with inadequate final hardness, and many give off a strong, unpleasant amine odor. Partial adduct formation with epoxy resins does enable faster curing, but the associated high viscosity is disadvantageous for many applications.
Alkylated amines as curing agents for epoxy resin coatings are known, for example from EP 3,180,383 or EP 3,344,677. They exhibit reliable curing at ambient temperatures and little tendency to blushing effects on two-dimensional application. But the curing rates achieved thereby are still in need of improvement.
It is therefore an object of the present invention to provide a low-viscosity, low-odor amine which, when used for curing of epoxy resins at ambient temperature, enables rapid and faultless curing and high final hardnesses.
Surprisingly, this object is achieved by an amine of the formula (I) as described in claim 1. The amine of the formula (I) is preparable in a simple process by reductive alkylation of an optionally substituted ethylenediamine with formyl- or acetylbenzonitrile and hydrogen. It has low odor and low viscosity, and shows excellent properties when used as curing agent for epoxy resins. In particular, it enables surprisingly rapid curing at room temperature and under cold conditions to give a material of high final hardness with a nice, faultless surface having high gloss. An amine of the formula (I) with R1 ═H enables particularly rapid curing, while an amine of the formula (I) with R1=benzyl, even in the case of two-dimensional application and under cold conditions, enables particularly nice surfaces and a particularly high final hardness.
The amine of the formula (I) is suitable as curing agent or co-curing agent for epoxy resin products such as coatings, adhesives or shaped bodies. It enables rapid, faultless curing at room temperature and under cold conditions, and high final hardnesses and nice surfaces.
Further aspects of the invention are the subject of further independent claims.
Particularly preferred embodiments of the invention are the subject of the dependent claims.
The invention provides an amine of the formula (I)
Substance names beginning with “poly”, such as polyamine or polyepoxide, refer to substances that formally contain two or more of the functional groups that occur in their name per molecule.
A “primary amino group” refers to an amino group that is attached to a single organic radical and bears two hydrogen atoms; a “secondary amino group” refers to an amino group that is attached to two organic radicals that may also together be part of a ring and bears one hydrogen atom; and a “tertiary amino group” refers to an amino group that is attached to three organic radicals, two or three of which may also be part of one or more rings, and does not bear any hydrogen atom.
“Amine hydrogen” refers to the hydrogen atoms of primary and secondary amine groups.
“Amine hydrogen equivalent weight” refers to the mass of an amine or an amine-containing composition that contains one molar equivalent of amine hydrogen. It is expressed in units of “g/eq”.
The “epoxide equivalent weight” refers to the mass of an epoxy group-containing compound or composition that contains one molar equivalent of epoxy groups. It is expressed in units of “g/eq”.
A “thinner” refers to a substance that is soluble in an epoxy resin and lowers its viscosity, and that is not chemically incorporated into the epoxy resin polymer during the curing process.
“Molecular weight” refers to the molar mass (in grams per mole) of a molecule.
“Average molecular weight” refers to the number-average molecular weight Mn of a polydisperse mixture of oligomeric or polymeric molecules, which is typically determined by gel-permeation chromatography (GPC) against polystyrene as standard.
“Pot life” refers to the maximum period of time from the mixing of the components and the application of an epoxy resin composition in which the mixed composition is in a sufficiently free-flowing state and has good ability to wet the substrate surfaces.
The “gel time” is the time interval from mixing the components of an epoxy resin composition until the gelation thereof.
“Room temperature” refers to a temperature of 23° C.
All industry standards and norms mentioned in the document refer to the versions valid at the date of first filing, unless stated otherwise.
Percent by weight (% by weight) values refer to the proportions by mass of a constituent in a composition based on the overall composition, unless stated otherwise. The terms “mass” and “weight” are used synonymously in the present document.
Preferably, R2 is H. This permits particularly rapid curing.
Preferably, A is 1,2-ethylene. These amines of the formula (I) enable particularly rapid curing.
Preferably, R1 is H, methyl, benzyl or cyclohexylmethyl, especially H or benzyl.
In a particularly preferred embodiment, R1 is H. These amines of the formula (I) are preparable in a particularly simple manner and enable particularly rapid curing under cold conditions, for example 8° C.
In a further particularly preferred embodiment, R1 is benzyl. These amines of the formula (I) enable particularly nice surfaces on two-dimensional application.
Preferably, the amine of the formula (I) is selected from the group consisting of N-(2-aminoethyl)-1,3-bis(aminomethyl)benzene, N-(3-(aminomethyl)benzyl)-N′-benzylethane-1,2-diamine, N-(2-aminoethyl)-1,4-bis(aminomethyl)benzene, N-(4-(aminomethyl)benzyl)-N′-benzylethane-1,2-diamine, N-(2-aminoethyl)-1,2-bis(aminomethyl)benzene and N-(2-(aminomethyl)benzyl)-N′-benzylethane-1,2-diamine.
The substituents on the benzene ring are preferably in 1,3 or 1,4 positions, especially in 1,3 positions.
The invention further provides a reaction product comprising at least one amine of the formula (I), obtained from the reductive alkylation of at least one amine of the formula (II) with at least one benzonitrile of the formula (III) and hydrogen
A preferred amine of the formula (II) is ethane-1,2-diamine, propane-1,2-diamine, N-methylethane-1,2-diamine, N-ethylethane-1,2-diamine, N-propylethane-1,2-diamine, N-isopropylethane-1,2-diamine, N-butylethane-1,2-diamine, N-hexylethane-1,2-diamine, N-cyclohexylmethylethane-1,2-diamine, N-benzylethane-1,2-diamine or N-benzylpropane-1,2-diamine. Particular preference is given to ethane-1,2-diamine or N-benzylethane-1,2-diamine.
A suitable benzonitrile of the formula (III) is 2-formylbenzonitrile, 3-formylbenzonitrile or 4-formylbenzonitrile, 2-acetylbenzonitrile, 3-acetylbenzonitrile or 4-acetylbenzonitrile. Preference is given to 2-formylbenzonitrile, 3-formylbenzonitrile or 4-formylbenzonitrile, especially 3-formylbenzonitrile or 4-formylbenzonitrile, greatest preference to 3-formylbenzonitrile.
If R1 is H, the reductive alkylation is conducted preferably in such a way that the amine of the formula (II) is used in a molar ratio of at least 2/1 relative to the benzonitrile of the formula (III) and excess amine of the formula (II) is removed after the reaction. Preference is given to a molar ratio of 2.5/1 to 5/1.
Preference is given to removing excess amine of the formula (II) by distillation or stripping. Preferably at least 50%, especially at least 80%, of the excess amine of the formula (II) is removed.
If R1 is not H, the amine of the formula (II) and the benzonitrile of the formula (III) are preferably used roughly stoichiometrically.
The reductive alkylation can be effected directly with molecular hydrogen, or indirectly by hydrogen or hydride transfer from other reagents such as formic acid or LiAIH4. Preference is given to using molecular hydrogen.
The conditions in the reaction are advantageously chosen such that the nitrile group is likewise hydrogenated and the benzene ring is not hydrogenated.
Preference is given to conducting the reaction at a temperature of 40 to 120° C., and in the presence of a suitable catalyst. Preferred catalysts are palladium on charcoal (Pd/C), platinum on charcoal (Pt/C), Adams' catalyst or Raney nickel, especially palladium on charcoal or Raney nickel.
When molecular hydrogen is used, preference is given to working in a pressure apparatus at a hydrogen pressure of 5 to 150 bar, especially 10 to 120 bar.
The volatile components, especially any solvent present, water, and any excess of amine of the formula (II) present, are preferably removed from the reaction product after the reaction, especially by distillation or stripping.
The reaction product can be purified further, especially by distillation. This affords a reaction product having a particularly high content of amine of the formula (I).
The reaction product preferably contains a content of amine of the formula (I) of at least 70% by weight, more preferably at least 80% by weight, especially at least 90% by weight, based on the overall reaction product.
The reaction product may comprise the following compounds in particular as by-products:
with a hydrogenated benzene ring,
from the hydrogenation of unconverted benzonitrile of the formula (III),
The amine of the formula (I) is of low odor and low viscosity.
The amine of the formula (I) is particularly suitable for curing of epoxy resins.
The invention thus further provides for the use of at least one amine of the formula (I) or at least one reaction product comprising the amine of the formula (I) as described above for curing of epoxy resins.
Suitable epoxy resins are especially glycidyl ethers of commercial mono- or polyfunctional alcohols or phenols, especially the epoxy resins specified in this document.
Preference is given to mixing the amine of the formula (I), the epoxy resin and any further substances with one another, where the ratio of the groups reactive toward the epoxy groups, especially the amine hydrogens of the amine of the formula (I), and the epoxy groups is preferably in the range from 0.5 to 1.5, especially 0.7 to 1.2.
The curing can be effected at ambient temperature, especially in the range from 5 to 40° C., or at elevated temperature, especially in the range from 40 to 150° C., preferably 50 to 120° C. The curing is preferably effected at ambient temperature.
The amine of the formula (I) enables surprisingly rapid curing to give a material of high final hardness with a nice surface.
The amine of the formula (I) may be used in partly adducted form with at least one epoxy resin or monoepoxide, especially with an epoxy resin or monoepoxide having an average epoxy equivalent weight in the range from 150 to 500 g/eq, preferably 156 to 250 g/eq.
Preference is given to amine-functional adducts from the reaction of at least one amine of the formula (I) and at least one epoxy resin in a stoichiometric ratio in the range from 1 to 10, preferably 1 to 5, mol of amine of the formula (I) per molar equivalent of epoxy groups.
The invention further provides a curing agent for epoxy resins comprising at least one amine of the formula (I) and at least one further constituent selected from further amines A1, accelerators and thinners.
The further amine A1 is preferably not an amine of the formula (I).
The curing agent preferably contains 1% to 99% by weight, more preferably 2% to 90% by weight, especially preferably 5% to 75% by weight, in particular 10% to 50% by weight, of amine of the formula (I), based on the overall curing agent.
The curing agent is preferably not water-based. It preferably contains less than 15% by weight, especially less than 10% by weight, of water, based on the overall curing agent. Such a curing agent is particularly suitable for nonaqueous epoxy resin products.
The curing agent preferably comprises at least one further amine A1 having at least three aliphatic amine hydrogens.
The following are especially suitable for this purpose: N-benzylethane-1,2-diamine, N-benzylpropane-1,2-diamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-phenylethyl)-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-1,3-bis(aminomethyl)benzene, 2,2-dimethylpropane-1,3-diamine, pentane-1,3-diamine (DAMP), pentane-1,5-diamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethylpentane-1,5-diamine (C11-neodiamine), hexane-1,6-diamine, 2,5-dimethylhexane-1,6-diamine, 2,2(4),4-trimethylhexane-1,6-diamine (TMD), heptane-1,7-diamine, octane-1,8-diamine, nonane-1,9-diamine, decane-1,10-diamine, undecane-1,11-diamine, dodecane-1,12-diamine, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl-5-methylcyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), menthane-1,8-diamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-bis(aminomethyl)benzene (MXDA), 1,4-bis(aminomethyl)benzene, bis(2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-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 of these diamines, bis(3-aminopropyl)polytetrahydrofurans or other polytetrahydrofurandiamines, polyoxyalkylenediamines or -triamines, especially polyoxypropylenediamines or polyoxypropylenetriamines such as, in particular, Jeffamine® D-230, Jeffamine® D-400 or Jeffamine® T-403 (all from Huntsman), polyalkyleneamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA), N-(2-aminoethyl)propane-1,3-diamine (N3 amine), N,N′-bis(3-aminopropyl)ethylenediamine (N4 amine), N,N′-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methylpentane-1,5-diamine, N3-(3-aminopentyl)pentane-1,3-diamine, N5-(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine, N,N′-bis(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine, 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT), N-benzylated polyalkyleneamines having one or two benzyl groups, especially benzylated DETA, TETA, N3 amine, N4 amine or DPTA, N-aminoethylpiperazine, 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), amine-functional adducts of the amines mentioned with epoxides, or mixtures of two or more of these amines.
The curing agent preferably comprises at least one further amine A1 selected from the group consisting of N-benzylethane-1,2-diamine, MPMD, TMD, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, NBDA, MXDA, DETA, TETA, TEPA, N3 amine, N4 amine, DPTA, BHMT, DMAPAPA, polyoxypropylene diamines having an average molecular weight Mn in the range from 200 to 500 g/mol, and polyoxypropylene triamines having an average molecular weight Mn in the range from 300 to 500 g/mol.
Among these, preference is given to N-benzylethane-1,2-diamine. This affords coatings having particularly nice surfaces.
Among these, preference is also given to MXDA, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane. This permits particularly rapid curing.
Among these, preference is also given to IPDA. This enables a high glass transition temperature.
Among these, preference is also given to DETA, TETA, TEPA or N4 amine. These enable inexpensive adhesives having particularly high bonding power.
The curing agent may especially comprise more than one further amine A1.
Suitable accelerators are especially acids or compounds hydrolyzable to acids, especially organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic esters, other organic or inorganic acids, such as phosphoric acid in particular, or mixtures of the abovementioned acids and acid esters; nitrates such as calcium nitrate in particular; tertiary amines such as in particular 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, salts of such tertiary amines, quaternary ammonium salts, such as benzyltrimethylammonium chloride in particular, amidines, such as 1,8-diazabicyclo[5.4.0]undec-7-ene in particular, guanidines, such as 1,1,3,3-tetramethylguanidine in particular, phenols, especially bisphenols, phenolic resins or Mannich bases such as in particular 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol or polymers produced from phenol, formaldehyde and N,N-dimethylpropane-1,3-diamine, phosphites such as in particular di- or triphenyl phosphites, or compounds having mercapto groups.
Preference is given to acids, nitrates, tertiary amines or Mannich bases, especially salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol, or a combination of these accelerators.
Suitable thinners are especially n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, n-hexanol, 2-ethylhexanol, 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 glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, 2,2,4-trimethylpentane-1,3-diol monoisobutyrate, diphenylmethane, diisopropylnaphthalene, mineral oil fractions, for example Solvesso® grades (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, cardanol, styrenated phenol, bisphenols, aromatic hydrocarbon resins, especially types containing phenol groups, alkoxylated phenol, especially ethoxylated or propoxylated phenol, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphoric or sulfonic esters or sulfonamides.
Preference among these is given to thinners having a boiling point of more than 200° C., especially benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenol groups, such as in particular the Novares® grades LS 500, LX 200, LA 300 or LA 700 (from Ruitgers), diisopropylnaphthalene or cardanol, especially benzyl alcohol.
Thinners containing phenol groups are effective also as accelerators.
The curing agent may comprise further constituents, especially:
The invention further provides an epoxy resin composition comprising
A suitable epoxy resin is obtained in a known manner, especially from the reaction of epichlorohydrin with polyols, polyphenols or amines.
Suitable epoxy resins are especially aromatic epoxy resins, especially the glycidyl ethers of:
Further suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, especially
The epoxy resin is preferably a liquid resin or a mixture comprising two or more liquid epoxy resins.
“Liquid epoxy resin” refers to an industrial polyepoxide having a glass transition temperature below 25° C.
The resin component optionally additionally contains proportions of solid epoxy resin.
The epoxy resin is especially a liquid resin based on a bisphenol or novolak, especially one having an average epoxy equivalent weight in the range from 156 to 210 g/eq.
A bisphenol A diglycidyl ether and/or bisphenol F diglycidyl ether, such as those commercially available from Olin, Huntsman or Momentive, is particularly suitable. These liquid resins have low viscosity for epoxy resins and permit rapid curing and high hardnesses. They may contain proportions of solid bisphenol A resin or novolak epoxy resins.
Also particularly suitable are phenol-formaldehyde novolak glycidyl ethers, especially having an average functionality in the range from 2.3 to 4, preferably 2.5 to 3. They may contain proportions of other epoxy resins, especially bisphenol A diglycidyl ether or bisphenol F diglycidyl ether.
The resin component may comprise a reactive diluent.
Preferred reactive diluents are reactive diluents containing epoxy groups, especially butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane di- or triglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, guaiacol glycidyl ether, 4-methoxyphenyl glycidyl ether, p-n-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-dodecylphenyl glycidyl ether, cardanol glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, or glycidyl ethers of natural alcohols, such as in particular C8 to C10 or C12 to C14 or C13 to C15 alkyl glycidyl ethers.
The epoxy resin composition preferably comprises at least one further constituent selected from the group consisting of thinners, accelerators, stabilizers, surface-active additives, fillers and pigments.
Suitable thinners, accelerators, stabilizers and surface-active additives are especially those already mentioned.
Suitable fillers are, in particular, ground or precipitated calcium carbonate, which is optionally coated with fatty acid, especially stearates, baryte (heavy spar), talc, quartz powder, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, zinc oxide, aluminum-doped zinc oxide, aluminum hydroxide, magnesium hydroxide, silica, cement, gypsum, fly ash, carbon black, graphite, groundwood, metal powders such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow beads. Preference among these is given to calcium carbonate, baryte, quartz powder, talc, or a combination thereof.
Suitable pigments are especially titanium dioxides, iron oxides, chromium(III) oxides, anticorrosion pigments, organic pigments or carbon black, especially titanium dioxides.
The epoxy resin composition may optionally comprise further auxiliaries and additives, especially the following:
The epoxy resin composition preferably has only a low content of thinners. It preferably contains less than 30% by weight, more preferably less than 20% by weight, in particular less than 10% by weight, of thinner, based on the overall epoxy resin composition.
The epoxy resin composition preferably has only a low content of water, preferably less than 5% by weight, especially less than 1% by weight, of water, based on the overall epoxy resin composition.
The resin component and the curing agent component of the epoxy resin composition are stored in separate containers. Further constituents of the epoxy resin composition may be present as a constituent of the resin component or of the curing agent component; further constituents reactive toward epoxy groups are preferably a constituent of the curing agent component. It is likewise possible for further constituents to be present as a separate, further component.
A suitable container for storage of the resin component or the curing agent component is especially a vat, a hobbock, a bag, a bucket, a can, a cartridge or a tube. The components are storable, meaning that they can be stored prior to use for several months up to one year or longer without any change in their respective properties to a degree relevant to their use.
The resin component and curing agent component are mixed shortly before or during application. The mixing ratio is preferably chosen such that the molar ratio of the groups reactive toward epoxy groups relative to the epoxy groups is in the range from 0.5 to 1.5, especially 0.7 to 1.2. In parts by weight, the mixing ratio between the resin component and the curing agent component is typically within a range from 1:2 to 20:1.
The components are mixed continuously or in batches by means of a suitable method, taking care to ensure that not too much time elapses between the mixing of the components and the application, and that application takes place within the pot life. Mixing and application can be effected at ambient temperature, which is typically in the range from about 5 to 40° C., preferably about 10 to 35° C., or at elevated temperature, especially in the range from 40 to 150° C., preferably 50 to 120° C.
With the mixing of the components, the curing of the epoxy resin composition by chemical reaction commences. Primary and secondary amino groups, and any further groups present that are reactive toward epoxy groups, react with the epoxy groups, resulting in ring opening thereof. As a result primarily of these reactions, the composition polymerizes and thereby cures.
Curing typically extends over a few hours to days. The duration depends on factors including the temperature, the reactivity of the constituents, the stoichiometry thereof, and the presence/amount of accelerators. The amine of the formula (I) enables particularly rapid curing, especially also at low temperatures.
When freshly mixed, the epoxy resin composition has low viscosity. The viscosity at 20° C. 5 minutes after the resin component and curing agent component have been mixed is preferably in the range from 0.2 to 20 Pa·s, preferably 0.3 to 10 Pa·s, especially 0.3 to 5 Pa·s, measured using a cone-plate viscometer at a shear rate of 10 s−1.
The epoxy resin composition is applied to at least one substrate and/or to at least one casting mold.
Suitable substrates are especially:
The substrates can if required be pretreated prior to application, especially by physical and/or chemical cleaning methods or the application of an activator or a primer.
The substrates are especially coated and/or adhesively bonded.
A suitable casting mold is an apparatus into which the mixed, liquid epoxy resin composition can be poured and in which it can be cured, and from which it can be demolded/removed after curing, where the cured composition forms a shaped body.
The invention further provides a cured composition obtained from the epoxy resin composition described after mixing of the resin component and the curing agent component.
The epoxy resin composition is preferably used as coating, primer, adhesive, sealant, potting compound, casting resin, impregnating resin, or as shaped body or matrix for composite materials such as, in particular, CFRP (containing carbon fibers) or GFRP (containing glass fibers) or wood composites.
The invention further provides a method of coating, comprising the steps of
Suitable substrates are those already mentioned.
Preference is given here to using the epoxy resin composition as a primer, in which case the substrate is especially concrete, mortar, cement screed, or a metal, especially steel. Such an epoxy resin composition is preferably largely free of fillers and serves to strengthen the substrate, to close any pores, and to ensure good adhesion between the substrate and further layers.
Further preferably, the epoxy resin composition is used as a floor coating. Such an epoxy resin composition preferably comprises fillers and pigments and is applied two-dimensionally in one or more operations overall, especially in a layer thickness of 0.1 to 5 mm, preferably as a self-leveling coating, and left to cure. The substrate is preferably an optionally primer-pretreated concrete, mortar, cement screed.
Further preferably, the epoxy resin coating is used as a protective coating, especially as an anticorrosion coating on steel, or as a topcoat on floor coatings. Such a coating is preferably applied in a spraying method, especially in a layer thickness of 0.05 to 0.5 mm.
The invention further provides a method of bonding, comprising the applying of the mixed epoxy resin composition
An “anchor” refers here more particularly to a rebar, a threaded rod or a bolt. An anchor is in particular thus adhesive-bonded or anchored in a wall, ceiling or foundation in such a way that a portion thereof is bonded in a force-fitting manner and a portion thereof protrudes and can be subjected to a construction load.
Identical or different substrates may be bonded.
The invention further provides a method of producing a shaped body, comprising the introducing of the mixed epoxy resin composition into a casting mold, followed by the curing of the mixed composition, optionally under pressure and optionally by means of supplied heat.
The epoxy resin composition, before being cured, may be admixed with fibers, powders or pellets, especially with carbon fibers, glass fibers or wood powder and/or pellets, in order to obtain a composite material.
The shaped body may be produced in one shot in the casting mold, or it may be built up in layers.
After curing, the shaped body is preferably removed from the casting mold. It can be processed further, especially by cutting, drilling, drawing, grinding or polishing.
The use of an amine of the formula (I) for curing of epoxy resins, or a method of coating, bonding or producing a shaped body, gives rise to an article.
The article is preferably a built structure or part thereof, especially a built structure above or below ground, an office, an industrial hall, a sports hall, a cold room, a silo, a bridge, a roof, a staircase, a floor, a balcony, a terrace or a parking deck, or an industrial good or a consumer good, especially a lamella, a panel, a pier, an offshore platform, a lock gate, a crane, a bulkhead, a pipeline, a container or a rotor blade of a wind turbine, or a mode of transport such as in particular an automobile, a truck, a rail vehicle, a ship, an aircraft or helicopter, or an installable component thereof.
Working examples are adduced hereinafter, which are intended to further elucidate the invention described. The invention is of course not limited to these described working examples.
The chemicals used were from Sigma-Aldrich Chemie GmbH, unless stated otherwise.
Viscosity was measured on a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm). Low-viscosity samples having a viscosity of less than 100 mPa·s were measured at a shear rate of 100 s−1, higher-viscosity samples at a shear rate of 10 s−1.
Amine value was determined by titration (with 0.1 N HClO4 in acetic acid against crystal violet).
Gas chromatograms (GC) were measured within the temperature range of 60 to 320° C. with a heating rate of 15° C./min and a run time of 10 min at 320° C. The injector temperature was 250° C. A Zebron ZB-5 column was used (L=30 m, ID=0.25 mm, dj=0.5 μm) with a gas flow rate of 1.5 ml/min. Detection was by flame ionization (FID).
Infrared spectra (FT-IR) were measured as undiluted films on a Nicolet iS5 FT-IR instrument from Thermo Scientific equipped with a horizontal ATR measurement unit with a diamond crystal. Absorption bands are reported in wavenumbers (cm−1).
1H NMR spectra were measured on a spectrometer of the Bruker Ascend 400 type at 400.14 MHz; the chemical shifts 5 are reported in ppm relative to tetramethylsilane (TMS). No distinction was made between true coupling and pseudo-coupling patterns.
An initial charge of 60.1 g (1 mol) of ethane-1,2-diamine at room temperature was mixed with a solution of 26.2 g (0.2 mol) of 3-formylbenzonitrile (=3-cyanobenzaldehyde) in 750 ml of isopropanol and stirred at 40° C. for 1 hour.
Subsequently, the reaction mixture was hydrogenated at 80° C., hydrogen pressure 80 bar, and a flow rate of 5 ml/min on a continuous hydrogenation apparatus with a fixed-bed Raney nickel catalyst, and the hydrogenated solution was concentrated on a rotary evaporator at 65° C., removing unreacted ethane-1,2-diamine, water and isopropanol. What was obtained was 33.5 g of a yellowish oil with a viscosity at 20° C. of 65 mPa·s and an amine value of 887 mg KOH/g, which was purified by distillation.
At 90 to 100° C. (vapor temperature) and 0.06 mbar, 26.7 g of distillate was obtained as a clear, colorless oil with a viscosity at 20° C. of 44 mPa·s, an amine value of 927 mg KOH/g, and an N-(2-aminoethyl)-1,3-bis(aminomethyl)benzene content determined by GC of >97% (retention time 11.7 min), and a calculated AHEW of 35.8 g/eq, which was used hereinafter as amine A1.
1H NMR (CDCl3): 7.28 (m, 2H, Ar—H), 7.19 (m, 2H, Ar—H), 3.85 (d, 2H, Ar—CH2—N), 3.77 (d, 2H, Ar—CH2—N), 2.81 (m, 2H, CH2—N), 2.27 (m, 2H, CH2—N), 1.53 (br s, 5H, NH)
FT-IR: 3360, 3280, 3022, 2914, 2848, 1662, 1606, 1588, 1441, 1352, 1152, 1116, 1065, 976, 842, 777, 699
Amine A2: N-(3-(Aminomethyl)benzyl)-N′-benzylethane-1,2-diamine 26.2 g (0.2 mol) of 3-formylbenzonitrile (=3-cyanobenzaldehyde) was dissolved at 40° C. in 300 ml of isopropyl alcohol, then 30.1 g (0.2 mol) of N-benzylethane-1,2-diamine, prepared as described above, was added gradually while stirring, and the mixture was stirred for 1 hour. Subsequently, the reaction mixture was hydrogenated at 80° C., hydrogen pressure 80 bar, and a flow rate of 5 ml/min on a continuous hydrogenation apparatus with a fixed-bed Raney nickel catalyst, and the hydrogenated solution was concentrated on a rotary evaporator at 65° C., removing water and isopropanol. What was obtained was 49.7 g of a yellowish oil with a viscosity at 20° C. of 177 mPa·s and an amine value of 594 mg KOH/g, which was purified by distillation.
At 150 to 155° C. (vapor temperature) and 0.06 mbar, 19.9 g of distillate was obtained as a clear, colorless oil with a viscosity at 20° C. of 153 mPa·s, an amine value of 624 mg KOH/g, and an N-(3-(aminomethyl)benzyl)-N′-benzylethane-1,2-diamine content determined by GC of >97% (retention time 16.4 min), and a calculated AHEW of 67.3 g/eq, which was used hereinafter as amine A2.
1H NMR (CDCl3): 7.25 (m, 8H, Ar—H), 3.86 (d, 2H, Ar—CH2—N), 3.77 (d, 4H, Ar—CH2—N), 2.78 (d, 4H, N—CH2—CH2—N), 1.85 (br s, 4H, NH)
FT-IR: 3290, 3024, 2912, 2813, 1605, 1588, 1493, 1451, 1355, 1336, 1198, 1154, 1111, 1027, 890, 779, 732, 696
An initial charge of 180.3 g (3 mol) of ethane-1,2-diamine at room temperature was mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol and stirred for 2 hours, then hydrogenated at 80° C., hydrogen pressure 80 bar, and a flow rate of 5 ml/min in a continuous hydrogenation apparatus with a fixed-bed Pd/C catalyst, and the hydrogenated solution was concentrated on a rotary evaporator at 65° C., removing unreacted ethane-1,2-diamine, water and isopropanol. The resulting reaction mixture was purified by distillation at 80° C. under reduced pressure. This gave a colorless liquid having an N-benzylethane-1,2-diamine content determined by GC of >97%.
Further substances and abbreviations used:
For each example, the ingredients of the resin component specified in table 1 were mixed in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) and stored with exclusion of moisture.
The ingredients of the curing agent component specified in table 1 were processed and stored in a similar manner.
The two components of each composition were then processed using the centrifugal mixer into a homogeneous liquid and this was tested immediately as follows:
For the examples suitable as coating, a film was applied to a glass plate in a layer thickness of 500 μm, and this was stored/cured under standard climatic conditions. König's hardness (König's pendulum hardness to DIN EN ISO 1522) was determined on this film after 1 day, 2 days, 7 days and 14 days (1d SCC), (2d SCC), (7d SCC), (14d SCC). After 14 days, the appearance (SCC) of the film was assessed. A clear film was described as “nice” if it had a glossy and nontacky surface with no structure. “Structure” refers to any kind of marking or pattern on the surface.
As a measure of yellowing, the change in color of the examples suitable as coating was determined after stress in a weathering tester. For this purpose, a further film was applied to a glass plate in a layer thickness of 500 μm and this was stored/cured under standard climatic conditions for 2 weeks and then stressed for 72 hours at a temperature of 65° C. in a model Q-Sun Xenon Xe-1 weathering tester having a Q-SUN Daylight-Q optical filter and a xenon lamp having a light intensity of 0.51 W/m2 at 340 nm (Q-Sun (72 h)). The difference in color ΔE of the thus stressed film versus the corresponding unstressed film was then determined using an NH310 colorimeter from Shenzen 3NH Technology Co. LTD equipped with silicon photoelectric diode detector, light source A, color space measurement interface CIE L*a*b*C*H*.
For the examples suitable as coating, a further film was applied to a glass plate in a layer thickness of 500 μm and this was immediately after application stored/cured for 7 days at 8° C. and 80% relative humidity and then for 2 weeks under standard climatic conditions. 24 hours after application, a polypropylene bottle top beneath which a damp sponge had been positioned was placed on the film. After a further 24 hours, the sponge and the bottle top were removed and positioned at a new point on the film, from which it was in turn removed and repositioned after 24 hours, this being done a total of 4 times. The appearance of this film was then assessed (designated “Appearance (8°/80%)” in the tables) in the same way as described for Appearance (SCC). Also reported in each case here was the number and nature of visible marks that had formed in the film as a result of the damp sponge or the bottle top on top. The number of white discolored spots was reported as “blushing”. A faint white discolored spot was designated as “(1)”. A clear white discolored spot was designated as “1”. The designation “ring” was reported if a ring-shaped imprint was present due to sinking of the first bottle top applied 24 hours after application. Such a ring-shaped impression indicates that the coating was not ready to be walked on. A weak imprint was designated as “(yes)”. König's hardness was again determined on the films thus cured, in each case after 7 days at 8° C. and 80% relative humidity (König hardness (7d 8°/80%)) and then after a further 2 days under SCC (König hardness (+2d SCC)), 7 days under SCC (König hardness (+7d SCC)), and 14 d under SCC (König hardness (+14d SCC)).
The results are reported in table 1.
Comparative examples are labelled “(Ref.)”.
1not measurable (too soft) “n.d.” stands for “not determined”
| Number | Date | Country | Kind |
|---|---|---|---|
| 21185058.1 | Jul 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/068829 | 7/7/2022 | WO |
