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

Abstract

An epoxy resin composition including A) at least one epoxy compound, and B) a hardener composition including B1) from 0.1%-100% by weight of 2-(3,3,5-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.

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-(3,3,5-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 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%-100% by weight of 2-(3,3,5-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 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. The use of epoxy resin compositions according to claim 1, comprising: A) at least one epoxy compound and B) a hardener composition comprising: B1) 0.1%-100% by weight of 2-(3,3,5-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, preferably from 1:1.5 to 1.5:1 and more preferably from 1:1.25 to 1.25:1, 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

Examples: CPDA as Hardener in Epoxy Resin Systems

[0100] 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-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine (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.

Description of the Analysis Methods:

DSC

Glass Transition Temperature:

[0101] Instrument: Mettler DSC 1

[0102] Parameters: Temperature −30 to +250° C., heating rate 10 K/min

[0103] Determination of glass transition temperature (Tg): Half step-height method, midpoint DIN 51007

Determination of Conversion:

[0104] [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 Example Comparative 1 example A) Amount of epoxy resin (g) per 100 g 370 441 of hardener B) Hardener component 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. 53 38 Conversion % 81 59 DSC analysis after hardening at 70° C. for 1 h Tg ° C. 90 77 Conversion % 93 82 DSC analysis after hardening at 90° C. for 1 h Tg ° C. 109 107 Conversion % 96 90 DSC analysis after hardening at 110° C. for 1 h Tg ° C. 131 127 Conversion % 100 94 DSC analysis after hardening at 130° C. for 1 h Tg ° C. 138 144 Conversion % 100 98 DSC analysis after hardening at 150° C. for 1 h Tg ° C. 141 154 Conversion % 100 100 DSC analysis after hardening at 180° C. for 1 h Tg ° C. 144 154 Conversion % 100 100

[0105] As the skilled person can easily see from the examples, 2-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine (CPDA) is suitable as an excellent hardener component in epoxy resin systems. 2-(3,3,5-Trimethylcyclohexyl)propane-1,3-diamine (CPDA, see Example 1) exhibits a much higher reactivity than isophoronediamine (IPD, see comparative example), as apparent from the faster evolution of Tg and conversion, especially at relatively low hardening temperatures down to 70° C. 2-(3,3,5-Trimethylcyclohexyl)propane-1,3-diamine (CPDA) exhibits only a marginally lower final Tg than isophoronediamine (IPD).