N-hydroxyl ethyl piperidine (NHEP): a novel curing agent for epoxy systems

Patent metadata

Field	Value
Publication number	US-10738147-B2
Application number	US-201715670329-A
Country	US
Kind code	B2
Filing date	Aug 7, 2017
Priority date	Dec 21, 2016
Publication date	Aug 11, 2020
Grant date	Aug 11, 2020

Abstract

The present invention relates to an amine-based curing agent comprising at least 1% by weight of at least one tertiary amine and, optionally, primary and/or secondary amines. The tertiary amine is preferably an N-substituted piperidine tertiary amine and, more preferably, N-hydroxyethyl piperidine (NHEP). The present invention also relates to an epoxy resin composition formed using this amine-based curing agent and a method of making the epoxy resin composition. These tertiary amines enhance desirable properties of epoxy resin compositions without the negative impact on mechanical properties in the cured product normally seen with tertiary amine-based curing agents.

First claim

What is claimed is:

1. A method for producing a cured epoxy resin composition, comprising:
(a) combining an epoxy resin component with an amine-based curing agent component to form an initial epoxy resin composition, the amine-based curing agent component comprising N-hydroxyethyl piperidine as a first amine component and a second amine component selected from the group consisting of aminopropyl cyclohexanamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, N-(2-aminoethyl)-1,3-propanediamine, N, N′-1,2-ethanediylbis-1,3-propanediamine, dipropylenetriamine, 1,3-bisaminocyclohexylamine, isophorone diamine, 4,4′-methylenebiscyclohexanamine, 4,4′-Methylenebis-(2-methyl-cyclohexanamine), and alpha-(2-aminomethylethyl) omega-(2-aminomethylethoxy);

and wherein the first amine component is present in an amount of 10%-60% by weight of the amine-based curing agent component; and
(b) allowing a chemical reaction to occur between the amine-based curing agent component and the epoxy resin component to form a cured epoxy resin composition.

2. The method of claim 1 , further comprising:
(c) performing steps (a) and (b) at a first ambient temperature; and
(d) maintaining a maximum internal temperature of the initial epoxy resin composition during steps (a) and (b) that is no more than 50 degrees C. above the first ambient temperature.

3. The method of claim 2 , wherein step (a) further comprises combining an epoxy resin component with an amine-based curing agent component to form an initial epoxy resin composition having a first viscosity that is at least 50 cps, and step (b) further comprises forming a cured epoxy resin composition having a T g of at least 70 degrees C.

4. The method of claim 1 , further comprising:
(c) applying the initial epoxy resin composition to a reinforcing fiber substrate after performing step (a) and before performing step (b).

5. A composition comprising the reaction product of:
an epoxy resin component; and
a curing agent component, wherein the curing agent component comprises:
N-hydroxyethyl piperidine as a first amine component and a second amine component selected from the group consisting of aminopropyl cyclohexanamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, N-(2-aminoethyl)-1,3-propanediamine, N, N′-1,2-ethanediylbis-1,3-propanediamine, dipropylenetriamine, 1,3-bisaminocyclohexylamine, isophorone diamine, 4,4′-methylenebiscyclohexanamine, 4,4′-Methylenebis-(2-methyl-cyclohexanamine), and alpha-(2-aminomethylethyl) omega-(2-aminomethylethoxy); and
wherein the first amine component is present in an amount of 10%-60% by weight of the curing agent component.

6. The composition of claim 5 , further comprising a stoichiometric ratio of the second amine component to the epoxy resin component, wherein the stoichiometric ratio is less than one.

7. The composition of claim 5 , wherein the epoxy resin component is present in an amount of about 30% to about 99% by weight of the composition.

8. The composition of claim 5 , wherein the epoxy resin component comprises a glycidyl ether of polyhydric phenol.

9. The composition of claim 5 , wherein the epoxy resin component comprises at least one glycidyl ether selected from the group consisting of glycidyl ethers of: resorcinol, hydroquinone, bis-(4-hydroxy-3,5-difluorophenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxy-3-methylphenyl)-propane, 2,2-bis-(4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis-(4-hydroxyphenyl)-propane, bis-(4-hydroxyphenyl)-methane, novolac resins, and combinations thereof.

10. The composition of claim 5 , wherein the epoxy resin component comprises at least one dihydric phenol of the following structure:

wherein m is 0 to 25 and R is a divalent hydrocarbon radical.

11. The composition of claim 5 , wherein the epoxy resin component comprises at least one member selected from the group consisting of: bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, vinylcyclohexene diepoxides; limonene diepoxide; bis(3,4-epoxycyclohexylmethyl)pimelate; dicyclopentadiene diepoxide, 3,3-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate; 3,3-epoxy-1-methylcyclohexyl-methyl-3,4-epoxy-1-methylcyclohexane carboxylate; 6-methyl-3,4-epoxycyclohexylmethylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate; 3,4-epoxy-2-methylcyclohexyl-methyl-3,4-epoxy-3-methylcyclohexane carboxylate, and combinations thereof.

12. The composition of claim 5 , further comprising a reinforcing fiber.

13. The composition of claim 12 , wherein the reinforcing fiber is selected from the group consisting of woven fabrics, non-crimp fabrics, nonwoven webs, nonwoven mats, fiber stands, staple fiber formed of continuous fiber, staple fiber formed of discontinuous fiber, and combination thereof.

14. The composition of claim 12 , wherein the reinforcing fiber is selected from the group consisting of fiberglass, carbon fiber, carbon nanotubes, nano composite fibers, polyaramide fibers, poly(p-phenylene benzobisoxazole) fiber, Aramid fiber, ultrahigh molecular weight polyethylene fiber, high density polyethylene fibers, low density polyethylene fibers, polypropylene fibers, nylon fibers, cellulose fibers, natural fibers, biodegradable fibers and combinations thereof.

15. The composition of claim 12 , wherein the composition is made from a process selected from the group consisting of resin infusion, vacuum assisted resin transfer molding (VARTM), resin transfer molding (RTM), filament winding (FW), compression molding (CM), wet/hand lay-up, vacuum bagging, injection molding, prepreg, fiber impregnation, casting and combinations thereof.

16. An article of manufacture comprising the composition as set forth in claim 12 , wherein the article is selected from the group consisting of low pressure pipes, high pressure pipes, low pressure fittings, high pressure fittings, low pressure vessels, high pressure vessels, storage tanks, wind turbine blade, automotive structural parts, aerospace structural parts, oil buoyance modules, gas buoyance modules, rigs, well plugs, cure-in-place-pipe (CIPP), structural bonding adhesives, structural bonding laminates, encapsulation, a semiconductor, corrosion resistance coatings, and a composite liner.

17. A method for producing a cured epoxy resin composition, comprising:
(a) combining an epoxy resin component with an amine-based curing agent component to form an initial epoxy resin composition, the amine-based curing agent component consisting of N-hydroxyethyl piperidine; and
(b) allowing a chemical reaction to occur between the amine-based curing agent component and the epoxy resin component to form a cured epoxy resin composition.

18. The method of claim 17 , further comprising:
(c) performing steps (a) and (b) at a first ambient temperature; and
(d) maintaining a maximum internal temperature of the initial epoxy resin composition during steps (a) and (b) that is no more than 50 degrees C. above the first ambient temperature.

19. The method of claim 17 , wherein step (a) further comprises combining an epoxy resin component with an amine-based curing agent component to form an initial epoxy resin composition having a first viscosity that is at least 50 cps, and step (b) furth

Assignees

• Evonik Operations Gmbh

Inventors

• Patel Pritesh G
• Lal Gauri Sankar
• La Comare Douglas M

Classifications

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08J2363/00

  Characterised by the use of epoxy resins; Derivatives of epoxy resins · CPC title

• C08J5/04

  Reinforcing macromolecular compounds with loose or coherent fibrous material · CPC title

• C08G59/64 Primary

  Amino alcohols · CPC title

• C08G59/506 Primary

  having one nitrogen atom in the ring · CPC title