Low temperature anhydride epoxy cured systems

Patent metadata

Field	Value
Publication number	US-11286336-B2
Application number	US-201716468497-A
Country	US
Kind code	B2
Filing date	Dec 12, 2017
Priority date	Dec 12, 2016
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

A curing agent composition comprising anhydride and approximately equimolar amount of tertiary amine or imidazole and carboxylic acid, the amine being 1-piperidinylethanol (N-hydroxyethyl-piperidine, NHEP) represented by the structure below or an imidazole represented by the structure below:where R1=H, a C1-C20 straight chain or branched alkyl, or a monocyclic aryl; R2=a C1-C20 straight chain or branched alkyl, or a monocyclic aryl. The carboxylic acid is represented by RCOOH; R=a C1-C20 straight chain or branched alkyl, or a monocyclic aryl. The composition comprises a lower ratio of epoxy resin to anhydride (1:0.4-0.6) than typically used (1:0.8-1.1). In addition, it uses a higher loading of the hindered latent tertiary amine or the imidazole in combination with the carboxylic acid (wt % ratio of combined amine and carboxylic acid to anhydride ˜10%). With this composition a full cure can be achieved in less than 2 hr at a significantly lower temperature (˜100° C.).

First claim

The invention claimed is:

1. A curing agent composition for epoxy resin comprising: a carboxylic acid anhydride; and a component comprising approximately equimolar amounts of tertiary amine and carboxylic acid or approximately equimolar amounts of an imidazole and carboxylic acid, wherein the weight ratio of carboxylic acid anhydride to combined tertiary amine and carboxylic acid or combined imidazole and carboxylic acid is 50:50.

2. The curing agent composition of claim 1 wherein the carboxylic acid anhydride is selected from the group consisting of methylhexahydrophthalic anhydride (MHHPA), nadic methyl anhydride (NMA), dodecenylsuccinic anhydride (DDSA), methyltetrahydrophthalic anhydride (MTHPA), and hexahydrophthalic anhydride (HHPA).

3. The curing agent composition of claim 1 in which the tertiary amine is N-hydroxyethylpiperidine or the imidazole is represented by the structure below:

where R 1 =H, a C1-C20 straight chain or branched alkyl, or a monocyclic aryl; and R 2 =a C1-C20 straight chain or branched alkyl, or a monocyclic aryl.

4. The curing agent composition of claim 3 wherein the carboxylic acid is represented by RCOOH; R=a C1C20 straight chain or branched alkyl, or a monocyclic aryl.

5. A composition comprising the curing agent of claim 1 and epoxy resin.

6. The composition of claim 5 where the epoxy to carboxylic acid anhydride equivalent weight ratio is 1: 0.4-0.6.

7. The composition of claim 5 wherein the composition is capable of being cured at a temperature ranging from 80° C. to 100° C. for 1-2 hrs.

8. The composition of claim 4 wherein the epoxy resin is a liquid epoxy resin or a multifunctional epoxy resin.

9. The composition of claim 4 wherein the epoxy resin 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, and combinations thereof.

10. The composition of claim 5 further comprising an additive selected from the group consisting of epoxy tougheners, inorganic nano and micro fillers.

11. An article of manufacture comprising the composition of claim 5 , wherein the article is selected from the group consisting of an adhesive and a composite structural part.

12. An article of manufacture comprising the composition of claim 5 wherein the article is made from a process selected from the group consisting of resin transfer molding (RTM), high pressure resin transfer molding (HP RTM), light resin transfer molding (LRTM), compression molding (CM), resin infusion, filament winding, casting, pultrusion, molding, and combinations thereof.

Assignees

• Evonik Operations Gmbh

Inventors

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

Classifications

• C08G59/5073

  having two nitrogen atoms in the ring · CPC title

• C09J163/00

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

• C08G59/4238

  heterocyclic · CPC title

• C08G59/4215

  cycloaliphatic · CPC title

• C08L63/00

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