EPOXY RESIN COMPOSITION COMPRISING 2-(3-(AMINOMETHYL)-3,5,5-TRIMETHYLCYCLOHEXYL)PROPANE-1,3-DIAMINE (AM-CPDA) AS HARDENER

Abstract

An epoxy resin composition including A) at least one epoxy compound and B) a hardener composition including B1) 0.1%-100% by weight of 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine, and B2) 99.9%-0% by weight of at least one further diamine and/or polyamine, where the stoichiometric ratio of the epoxy groups of A) and the number of active hydrogen atoms of the functional groups of B) varies from 1:2 to 2:1.

Claims

1. An epoxy resin composition comprising: A) at least one epoxy compound and B) a hardener composition comprising: B1) from 0.1%400% by weight of 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine, and B2) from 99.9%-0% by weight of at least one further diamine and/or polyamine, where the stoichiometric ratio of the epoxy groups of A) and the number of active hydrogen atoms of the functional groups of B) varies from 1:2 to 2:1, C) optionally from 0.1% to 10% by weight of at least one hardening accelerator, D) optionally at least one latent hardener, where the amounts of A)-D) add up to 100% by weight, E) optionally further additives.

2. An epoxy resin composition consisting of: A) at least one epoxy compound and B) a hardener composition comprising: B1) from 0.1%400% by weight of 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine, and B2) from 99.9%-0% by weight of at least one further diamine and/or polyamine, where the stoichiometric ratio of the epoxy groups of A) and the number of hydrogen atoms of the functional groups of B) varies from 1:2 to 2:1, C) optionally from 0.1% to 10% by weight of at least one hardening accelerator, D) optionally at least one latent hardener, where the amounts of A)-D) add up to 100% by weight, E) optionally further additives.

3. The epoxy resin composition according to claim 1, wherein epoxy compounds A) selected from saturated, unsaturated, aliphatic, cycloaliphatic, aromatic and heterocyclic epoxy compounds are present, and these may also have hydroxyl groups.

4. The epoxy resin composition according to claim 1, wherein epoxy compounds A) selected from glycidyl ethers, glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and/or bisphenol F, glycidyl methacrylates are present.

5. The epoxy resin composition according to claim 1, wherein epoxy compounds A) selected from the group comprising epoxy resins based on bisphenol A diglycidyl ether, epoxy resins based on bisphenol F diglycidyl ether, 4,4′-methylenebis[N,N-bis(2,3-epoxypropyl)aniline], hexanediol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, propane-1,2,3-triol triglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl hexahydrophthalate, aliphatic or cycloaliphatic epoxy resin types are present.

6. The epoxy resin composition according to claim 1, wherein component B2) used comprises the following amines, alone or in mixtures: aliphatic amines, such as the polyalkylenepolyamines, preferably selected from ethylene-1,2-diamine, propylene-1,2-diamine, propylene-1,3-diamine, butylene-1,2-diamine, butylene-1,3-diamine, butylene-1,4-diamine, 2-(ethylamino)ethylamine, 3-(methylamino)propylamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, N-(2-aminoethyl)ethane-1,2-diamine, N-(3-aminopropyl)propane-1,3-diamine, N,N″-1,2-ethanediylbis(1,3-propanediamine), dipropylenetriamine, adipic dihydrazide, hydrazine; oxyalkylenepolyamines selected from polyoxypropylenediamine and polyoxypropylenetriamine (e.g. Jeffamine® D-230, Jeffamine® D-400, Jeffamine® T-403, Jeffamine® T-5000), 1,13-diamino-4,7,10-trioxatridecane, 4,7-dioxadecane-1,10-diamine; cycloaliphatic amines selected from isophoronediamine (3,5,5-trimethyl-3-aminomethylcyclohexylamine), 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane and 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, N-cyclohexyl-1,3-propanediamine, 1,2-diaminocyclohexane, 3-(cyclohexylamino)propylamine, piperazine, N-aminoethylpiperazine, TCD diamine (3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0.sup.2,6]decane), 4-methylcyclohexane-1,3-diamine araliphatic amines such as xylylenediamines; aromatic amines selected from phenylenediamines, phenylene-1,3-diamine, phenylene-1,4-diamine, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, alone or in mixtures of the isomers; adduct hardeners which are the reaction products of epoxy compounds, especially glycidyl ethers of bisphenol A and F, with excess amine; polyamidoamine hardeners which are obtained by condensation of mono- and polycarboxylic acids with polyamines, especially by condensation of dimer fatty acids with polyalkylenepolyamines; Mannich base hardeners which are obtained by reaction of mono- or polyhydric phenols with aldehydes, especially formaldehyde, and polyamines; Mannich bases, for example based on phenol and/or resorcinol, formaldehyde and m-xylylenediamine, and also N-aminoethylpiperazine and blends of N-aminoethylpiperazine with nonylphenol and/or benzyl alcohol, phenalkamines which are obtained in a Mannich reaction from cardanols, aldehydes and amines.

7. The epoxy resin composition according to claim 1, wherein di- and/or polyamines B2) selected from isophoronediamine, 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, a mixture of the isomers of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, adduct hardeners based on the reaction products of epoxy compounds and di- and/or polyamines B2) or combination of the aforementioned di- and/or polyamines B2) are present.

8. The epoxy resin composition according to claim 1, wherein di- and/or polyamines B2) selected from a) isophoronediamine (3,5,5-trimethyl-3-aminomethylcyclohexylamine, IPD), b) or a combination of 1. isophoronediamine and 2. a mixture of the isomers of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine (TMD), alone or in mixtures of the isomers, 3. and/or a mixture of the isomers of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane and 2,2′-diaminodicyclohexylmethane (also referred to as PACM), alone or in mixtures of the isomers, c) or a combination of 1. a mixture of the isomers of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine (TMD), alone or in mixtures of the isomers, 2. and/or a mixture of the isomers of 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane and 2,2′-diaminodicyclohexylmethane (also referred to as PACM), alone or in mixtures of the isomers, d) and/or adduct hardeners based on the reaction products of epoxy compounds and the aforementioned amines B2) or combination of the aforementioned amines B2) are used.

9. The epoxy resin composition according to claim 1, wherein hardening accelerators C) present are imidazole and/or imidazole derivatives.

10. The epoxy resin composition according to claim 1, wherein latent hardeners D) selected from dicyandiamide, cyanoguanidines, aromatic amines, guanidines, modified polyamines, N-acylimidazoles, imidazoles, carbonyl hydrazides, triazine derivatives, melamine and derivatives thereof, N-cyanoacylamide compounds, acylthiopropylphenols are present.

11. Use of the epoxy resin compositions according to claim 1, comprising: A) at least one epoxy compound and B) a hardener composition consisting of: B1) 0.1%-100% by weight of 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine, and B2) 99.9%-0% by weight of at least one further diamine and/or polyamine, where the stoichiometric ratio of the epoxy groups of A) and the number of hydrogen atoms of the functional groups of B) varies from 1:2 to 2:1, C) optionally 0.1% to 10% by weight of at least one hardening accelerator, D) optionally at least one latent hardener, where the amounts of A)-D) add up to 100% by weight, E) optionally further additives, for production of composites.

12. The epoxy resin composition according to claim 1, comprising from 0.1% to 10% by weight of at least one hardening accelerator compounds.

13. The epoxy resin composition according to claim 12, wherein the hardening accelerators are imidazole and/or imidazole derivatives.

14. The epoxy resin composition according to claim 1, comprising at least one latent hardener.

15. The epoxy resin composition according to claim 14, wherein the at least one latent hardener is selected from dicyandiamide, cyanoguanidines, aromatic amines, guanidines, modified polyamines, N-acylimidazoles, imidazoles, carbonyl hydrazides, triazine derivatives, melamine and derivatives thereof, N-cyanoacylamide compounds, acylthiopropylphenols are present.

16. The epoxy resin composition according to claim 3, wherein di- and/or polyamines B2) selected from isophoronediamine, 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, a mixture of the isomers of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, adduct hardeners based on the reaction products of epoxy compounds and di- and/or polyamines B2) or combination of the aforementioned di- and/or polyamines B2) are present.

17. The epoxy resin composition according to claim 4, wherein di- and/or polyamines B2) selected from isophoronediamine, 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, a mixture of the isomers of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine, adduct hardeners based on the reaction products of epoxy compounds and di- and/or polyamines B2) or combination of the aforementioned di- and/or polyamines B2) are present.

18. The epoxy resin composition according to claim 3, wherein component B2) used comprises the following amines, alone or in mixtures: aliphatic amines, such as the polyalkylenepolyamines, preferably selected from ethylene-1,2-diamine, propylene-1,2-diamine, propylene-1,3-diamine, butylene-1,2-diamine, butylene-1,3-diamine, butylene-1,4-diamine, 2-(ethylamino)ethylamine, 3-(methylamino)propylamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, N-(2-aminoethyl)ethane-1,2-diamine, N-(3-aminopropyl)propane-1,3-diamine, N,N″-1,2-ethanediylbis(1,3-propanediamine), dipropylenetriamine, adipic dihydrazide, hydrazine; oxyalkylenepolyamines selected from polyoxypropylenediamine and polyoxypropylenetriamine (e.g. Jeffamine® D-230, Jeffamine® D-400, Jeffamine® T-403, Jeffamine® T-5000), 1,13-diamino-4,7,10-trioxatridecane, 4,7-dioxadecane-1,10-diamine; cycloaliphatic amines selected from isophoronediamine (3,5,5-trimethyl-3-aminomethylcyclohexylamine), 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane and 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, N-cyclohexyl-1,3-propanediamine, 1,2-diaminocyclohexane, 3-(cyclohexylamino)propylamine, piperazine, N-aminoethylpiperazine, TCD diamine (3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0.sup.2,6]decane), 4-methylcyclohexane-1,3-diamine araliphatic amines such as xylylenediamines; aromatic amines selected from phenylenediamines, phenylene-1,3-diamine, phenylene-1,4-diamine, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, alone or in mixtures of the isomers; adduct hardeners which are the reaction products of epoxy compounds, especially glycidyl ethers of bisphenol A and F, with excess amine; polyamidoamine hardeners which are obtained by condensation of mono- and polycarboxylic acids with polyamines, especially by condensation of dimer fatty acids with polyalkylenepolyamines; Mannich base hardeners which are obtained by reaction of mono- or polyhydric phenols with aldehydes, especially formaldehyde, and polyamines; Mannich bases, for example based on phenol and/or resorcinol, formaldehyde and m-xylylenediamine, and also N-aminoethylpiperazine and blends of N-aminoethylpiperazine with nonylphenol and/or benzyl alcohol, phenalkamines which are obtained in a Mannich reaction from cardanols, aldehydes and amines.

19. The epoxy resin composition according to claim 4, wherein component B2) used comprises the following amines, alone or in mixtures: aliphatic amines, such as the polyalkylenepolyamines, preferably selected from ethylene-1,2-diamine, propylene-1,2-diamine, propylene-1,3-diamine, butylene-1,2-diamine, butylene-1,3-diamine, butylene-1,4-diamine, 2-(ethylamino)ethylamine, 3-(methylamino)propylamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, N-(2-aminoethyl)ethane-1,2-diamine, N-(3-aminopropyl)propane-1,3-diamine, N,N″-1,2-ethanediylbis(1,3-propanediamine), dipropylenetriamine, adipic dihydrazide, hydrazine; oxyalkylenepolyamines selected from polyoxypropylenediamine and polyoxypropylenetriamine (e.g. Jeffamine® D-230, Jeffamine® D-400, Jeffamine® T-403, Jeffamine® T-5000), 1,13-diamino-4,7,10-trioxatridecane, 4,7-dioxadecane-1,10-diamine; cycloaliphatic amines selected from isophoronediamine (3,5,5-trimethyl-3-aminomethylcyclohexylamine), 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane and 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, N-cyclohexyl-1,3-propanediamine, 1,2-diaminocyclohexane, 3-(cyclohexylamino)propylamine, piperazine, N-aminoethylpiperazine, TCD diamine (3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0.sup.2,6]decane), 4-methylcyclohexane-1,3-diamine araliphatic amines such as xylylenediamines; aromatic amines selected from phenylenediamines, phenylene-1,3-diamine, phenylene-1,4-diamine, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, alone or in mixtures of the isomers; adduct hardeners which are the reaction products of epoxy compounds, especially glycidyl ethers of bisphenol A and F, with excess amine; polyamidoamine hardeners which are obtained by condensation of mono- and polycarboxylic acids with polyamines, especially by condensation of dimer fatty acids with polyalkylenepolyamines; Mannich base hardeners which are obtained by reaction of mono- or polyhydric phenols with aldehydes, especially formaldehyde, and polyamines; Mannich bases, for example based on phenol and/or resorcinol, formaldehyde and m-xylylenediamine, and also N-aminoethylpiperazine and blends of N-aminoethylpiperazine with nonylphenol and/or benzyl alcohol, phenalkamines which are obtained in a Mannich reaction from cardanols, aldehydes and amines.

20. The epoxy resin composition according to claim 5, wherein component B2) used comprises the following amines, alone or in mixtures: aliphatic amines, such as the polyalkylenepolyamines, preferably selected from ethylene-1,2-diamine, propylene-1,2-diamine, propylene-1,3-diamine, butylene-1,2-diamine, butylene-1,3-diamine, butylene-1,4-diamine, 2-(ethylamino)ethylamine, 3-(methylamino)propylamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, N-(2-aminoethyl)ethane-1,2-diamine, N-(3-aminopropyl)propane-1,3-diamine, N,N″-1,2-ethanediylbis(1,3-propanediamine), dipropylenetriamine, adipic dihydrazide, hydrazine; oxyalkylenepolyamines selected from polyoxypropylenediamine and polyoxypropylenetriamine (e.g. Jeffamine® D-230, Jeffamine® D-400, Jeffamine® T-403, Jeffamine® T-5000), 1,13-diamino-4,7,10-trioxatridecane, 4,7-dioxadecane-1,10-diamine; cycloaliphatic amines selected from isophoronediamine (3,5,5-trimethyl-3-aminomethylcyclohexylamine), 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane and 2,2′-diaminodicyclohexylmethane, alone or in mixtures of the isomers, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, N-cyclohexyl-1,3-propanediamine, 1,2-diaminocyclohexane, 3-(cyclohexylamino)propylamine, piperazine, N-aminoethylpiperazine, TCD diamine (3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0.sup.2,6]decane), 4-methylcyclohexane-1,3-diamine araliphatic amines such as xylylenediamines; aromatic amines selected from phenylenediamines, phenylene-1,3-diamine, phenylene-1,4-diamine, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, alone or in mixtures of the isomers; adduct hardeners which are the reaction products of epoxy compounds, especially glycidyl ethers of bisphenol A and F, with excess amine; polyamidoamine hardeners which are obtained by condensation of mono- and polycarboxylic acids with polyamines, especially by condensation of dimer fatty acids with polyalkylenepolyamines; Mannich base hardeners which are obtained by reaction of mono- or polyhydric phenols with aldehydes, especially formaldehyde, and polyamines; Mannich bases, for example based on phenol and/or resorcinol, formaldehyde and m-xylylenediamine, and also N-aminoethylpiperazine and blends of N-aminoethylpiperazine with nonylphenol and/or benzyl alcohol, phenalkamines which are obtained in a Mannich reaction from cardanols, aldehydes and amines.

Description

EXAMPLES

Example: 2-(3-(Aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine (AM-CPDA) as Hardener in Epoxy Resin Systems

[0102] The epoxy resin employed was the standard resin Epikote 828 from Hexion having an epoxy equivalent weight of 188 g/eq. The latter was blended as specified with the hardener component 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine (AM-CPDA) or isophoronediamine (IPD), and the glass transition temperature was determined after a delay time of one hour at a defined hardening temperature. For this purpose, 5 g in each case of formulation were hardened under the conditions specified in an aluminium pan of diameter 5 cm to give a pure resin casting having a thickness of 2 mm. The respective reaction conversions were determined via the recorded evolution of heat from the hardening reaction in relation to the maximum evolution of heat.

[0103] Description of the Analysis Methods:

[0104] DSC

[0105] Glass Transition Temperature:

[0106] Instrument: Mettler DSC 1

[0107] Parameters: Temperature −30 to +250° C., heating rate 10 K/min

[0108] Determination of glass transition temperature (Tg):

[0109] Half step-height method, midpoint DIN 51007

[0110] Determination of Conversion:

[00001]$100-\left(\frac{\mathrm{exothermic}.Math..Math.\mathrm{heat}.Math..Math.\mathrm{flux}.Math..Math.\mathrm{after}.Math..Math.\mathrm{hardening}\times 100}{\mathrm{exothermic}.Math..Math.\mathrm{heat}.Math..Math.\mathrm{flux}.Math..Math.\mathrm{before}.Math..Math.\mathrm{hardening}}\right)$

TABLE-US-00001 Comparative Example 1 example A) Amount of epoxy resin (g) per 100 g 492 441 of hardener B) Hardener component AM-CPDA (g) 100 C) Hardener component IPD 100 Epoxy groups from A):amino 1:1 1:1 hydrogens from B) DSC analysis after hardening at 50° C. for 1 h Tg ° C. 47 38 Conversion % 56 59 DSC analysis after hardening at 70° C. for 1 h Tg ° C. 84 77 Conversion % 71 82 DSC analysis after hardening at 90° C. for 1 h Tg ° C. 111 107 Conversion % 79 90 DSC analysis after hardening at 110° C. for 1 h Tg ° C. 129 127 Conversion % 91 94 DSC analysis after hardening at 130° C. for 1 h Tg ° C. 152 144 Conversion % 94 98 DSC analysis after hardening at 150° C. for 1 h Tg ° C. 170 154 Conversion % 100 100 DSC analysis after hardening at 180° C. for 1 h Tg ° C. 182 154 Conversion % 100 100

[0111] As the skilled person can easily see from the examples, 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine (AM-CPDA) is found to be an excellent hardener component in epoxy resin systems.

[0112] 2-(3-(Aminomethyl)-3,5,5-trimethylcyclohexyl)propane-1,3-diamine (AM-CPDA, see Example 1) exhibits a much higher glass transition temperature compared to isophoronediamine (IPD, see comparative example). It is thus possible, in applications which require glass transition temperatures in the region of 180° C., to achieve inexpensive and low-viscosity epoxy resin formulations, since it is possible to dispense with the use of special high-viscosity and costly high-Tg epoxy resins.