Mixtures of amines with guanidine derivatives

Patent metadata

Field	Value
Publication number	US-9328058-B2
Application number	US-200913054945-A
Country	US
Kind code	B2
Filing date	Jul 17, 2009
Priority date	Jul 22, 2008
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

The present invention provides a mixture comprising at least three hardener components a1), a2), and b), the ratio of hardener component a1) to a2) being in the range from 0.1 to 10:1, and hardener component b) being present at 5% to 55% by weight, based on the mixture, a process for preparing this mixture, the use of the mixture of the invention for curing epoxy resins, the use of the mixture of the invention with epoxy resins as adhesives, and an epoxy resin cured with the mixture of the invention.

First claim

The invention claimed is:

1. A mixture comprising a hardener component a1), a hardener component a2) and a hardener component b), wherein:
a weight ratio of the hardener component a1) to the hardener component a2) is from 3:2 to 5:1;
the hardener component a1) is a difunctional polyetheramine selected from the group consisting of
3,6-dioxa-1,8-octanediamine,
4,7,10-trioxa-1,13-tridecanediamine,
4,7-dioxa-1,10-decanediamine,
4,9-dioxa-1,12-dodecanediamine,
a polyetheramine based on triethylene glycol with an average molar mass of 148,
a difunctional, primary polyetheramine prepared by aminating an ethylene glycol grafted with propylene oxide, with an average molar mass of 176,
an aliphatic polyetheramine based on polyethylene glycol grafted with propylene oxide, with an average molar mass of 600,
a difunctional, primary polyetheramine prepared by aminating a diethylene glycol grafted with propylene oxide, with an average molar mass of 220,
a difunctional, primary polyetheramine based on polypropylene glycol with an average molar mass of 230, and
a difunctional, primary polyetheramine based on polypropylene glycol with an average molar mass of 400,
the hardener component a2) is a cycloaliphatic amine having 2 primary amino groups, selected from the group consisting of
1,2-diaminocyclohexane,
1,3-bis(aminomethyl)cyclohexane,
1-methyl-2,4-diaminocyclohexane,
3,3′-dimethyl-4,4′-diaminodicyclohexylmethane,
an isophoronediamine,
a menthenediamine,
a norbornanediamine, and
4,8-diaminotricyclo[5.2.1.0]decane; and
the hardener component b) is 5% to 30% by weight, based on the sum of weights of a1), a2) and b), of a compound of formula I

where R1, R2, R3, R5 and R6 each independently are selected from the group consisting of hydrogen and an organic radical having 1 to 20 carbon atoms, and R4 is selected from the group consisting of an organic radical having 1 to 20 carbon atoms and a group —C(NH)NR5R6, wherein the organic radical having 1 to 20 carbon atoms is a saturated or unsaturated acyclic hydrocarbon radical containing no heteroatoms.

2. The mixture according to claim 1 , wherein
the polyetheramines of the hardener component a1) are selected from the group consisting of
a difunctional, primary polyetheramine based on polypropylene glycol, with an average molar mass of 230,
a difunctional, primary polyetheramine based on polypropylene glycol, with an average molar mass of 400, and
a difunctional, primary polyetheramine prepared by aminating a diethylene glycol grafted with propylene oxide, with an average molar mass of 220.

3. The mixture according to claim 1 , wherein the hardener component b) is at least one of tetramethylguanidine, and pentamethylbiguanide.

4. The mixture according to claim 1 , wherein
the hardener component a1) is selected from the group consisting of
a polyetheramine D 230 and
a polyetheramine D 400,

the hardener component a2) is selected from the group consisting of
an isophoronediamine, and
1,3-bis(aminomethyl)cyclohexane, and

the hardener component b) is tetramethylguanidine.

5. The mixture according to claim 1 , wherein
the hardener component a1) is a difunctional, primary polyetheramine based on polypropylene glycol with an average molar mass of 230,
the hardener component a2) is isophoronediamine, and
the hardener component b) is tetramethylguanidine.

6. The mixture according to claim 1 , wherein the mixture further comprises a fiber-reinforcing material.

7. A process for preparing the mixture according to claim 1 , the process comprising mixing the hardener components a1), a2) and b) together at a temperature below 160° C.

8. A method for curing an epoxy resin, the method comprising reacting an epoxy resin and the mixture according to claim 1 .

9. A method for preparing a prepreg, a vacuum assisted resin transfer molding, a filament winding, a pultrusion, or a wet lay-up system, the method comprising mixing a prepreg, a vacuum assisted resin transfer molding, a filament winding, a pultrusion, or a wet lay-up system and the epoxy resin according to claim 8 .

10. A method for preparing a structural adhesive, the method comprising mixing at least one further material and the mixture according to claim 1 .

11. A structural adhesive comprising the mixture according to claim 1 .

12. A cured epoxy resin obtained by reacting an epoxy resin with the mixture according to claim 1 .

13. The mixture according to claim 1 , further comprising a fiber-reinforcing filler.

14. The mixture according to claim 1 , wherein said mixture comprising hardener component a1), hardener component a2) and hardener component b) has a pot life that is longer than a mixture comprising hardener component a1) and hardener component a2) but not comprising hardener component b).

15. The mixture according to claim 1 , wherein the hardener component b) is pentamethylbiguanide.

16. The mixture according to claim 1 , wherein the hardener component b) consists of tetramethylguanidine.

Assignees

• Wittenbecher Lars
• Henningsen Michael
• Daun Gregor
• Flick Dieter
• Geisler Joerg-Peter
• Schillgalies Juergen
• Jacobi Erhard
• Basf Se

Inventors

• Wittenbecher Lars
• Henningsen Michael
• Daun Gregor
• Flick Dieter
• Geisler Joerg-Peter
• Schillgalies Juergen
• Jacobi Erhard

Classifications

• C08G59/4021

  Ureas; Thioureas; Guanidines; Dicyandiamides · CPC title

• C07C279/04

  having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton · CPC title

• C09J163/00

  Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins · CPC title

• C07C211/36 Primary

  containing at least two amino groups bound to the carbon skeleton · CPC title

• C08G59/50

  Amines · CPC title