Polyamides and amidoamines derived from hyroxyalkylpolyamines: epoxy curing agents with improved properties

Patent metadata

Field	Value
Publication number	US-2020308339-A2
Application number	US-201716470510-A
Country	US
Kind code	A2
Filing date	Dec 15, 2017
Priority date	Dec 19, 2016
Publication date	Oct 1, 2020
Grant date	—

Abstract

Polyamide and amidoamine curing agents comprising a selectively modified amine. The selectively modified amine is formed by a substitution reaction between a polyamine and an epoxide, resulting in a multifunctional amine having a hydroxyl substituent. The curing agents are used to form epoxy resins having improved properties when cured.

First claim

What is claimed:

1 . A curing agent comprising the reaction product of
(1) an amine component comprising at least one selectively modified multifunctional amine of the following structure:

where X and Y are independently selected from C2 through C16 linear, cyclic, and branched alkyl, alkenyl, and alkaryl groups, or (R1-NH—R2) m , where m=1 to 3, and R1, R2=alkylene groups of at least one C atom, and
(2) a fatty acid component.

2 . The curing agent of claim 1 , wherein the fatty acid component comprises at least one of tall oil fatty acid, a monomer fatty acid, a dimer fatty acid, a trimer fatty acid, a polymer fatty acid, or an ester of monomer, dimer, trimer, and polymer fatty acid.

3 . The curing agent of claim 1 , wherein a viscosity of the curing agent ranges from about 6000 MPa s to about 100,000 MPa s.

4 . The curing agent of claim 1 wherein the at least one selectively modified multifunctional amine comprises hydroxyethyl polyethylenepolyamine, hydroxypropyl polyethylenepolyamine, or propylhydroxy triethylenetetramine.

5 . The curing agent of claim 1 wherein the amine component comprises at least one unmodified polyalkylamine.

6 . The curing agent of claim 1 , wherein the fatty acid component comprises a mono functional fatty acid.

7 . The curing agent of claim 1 , wherein the at least one selectively modified multifunctional amine comprises a compound having a structural formula selected from the group consisting of:

8 . The curing agent of claim 1 , wherein the fatty acid component comprises at least one dimeric acid, at least one trimeric acid and at least one mono acid.

9 . The curing agent of claim 8 , wherein the dimeric acid comprises about 50 wt % to about 95 wt % of the fatty acid component.

10 . The curing agent of claim 8 , wherein the trimeric acid comprises about 3 wt % to about 40 wt % of the fatty acid component.

11 . The curing agent of claim 1 wherein the fatty acid component comprises monocarboxylic acids containing from about 8 to about 20 carbon atoms and from about 0 to about 4 units of unsaturation.

12 - 13 . (canceled)

14 . The curing agent of claim 1 wherein the ratio of the fatty acid component to the amine component ranges from about 1:1 to about 2:1, on a molecular basis, for monomeric fatty acids.

15 . A method for forming a selectively modified multifunctional amine of the following structure:

where X and Y are independently selected from C2-C16 linear, cyclic, and branched alkyl, alkenyl, and alkaryl groups, or (R1-NH—R2) m , where m=1 to 3, and R1, R2=alkylene groups of at least one C atom comprising:
contacting at least one polyamine with at least one epoxide.

16 . The method of claim 15 , wherein the at least one polyamine comprises at least one of diethylenetriamine, triethylenetetramine, 1,3-bisaminocyclohexyl amine, isophoronediamine, N-aminoethylpiperazine, 4,7-dioxadecane-1, 10-diamine, 1-propanamine, 3,3′-(oxybis(2, 1-ethanediyloxy)), poly(oxy(methyl-1, 2-ethanediyl)), alpha-(2-aminomethylethyl)omega-(2-aminomethylethoxy, triethylene glycol diamine, and poly(oxy(methyl-1, 2-ethanediyl))alpha, alpha′-(oxy(di-2,1-ethanediyl))bis(omega-(aminomethylethoxy)) or a mixture thereof.

17 . The method of claim 15 wherein the at least one polyamine comprises at least one or more multifunctional amines having the structure:

where R1 is CH2CH2CH2NH2; and R2, R3 and R4 independently are H or CH2CH2CH2NH2; and X is CH2CH2 or CH2CH2CH2.

18 . The method of claim 17 , wherein no more than one of R2 and R3 are H.

19 . The method of claim 15 , wherein the at least one polyamine comprises at least one compound having the structure selected from the group consisting of:

20 . The method of claim 15 , wherein the polyamine is a polyalkylenepolyamine.

21 . The method of claim 15 , wherein the epoxide is ethylene oxide.

22 . A method for forming a curing agent, comprising:
(i) reacting (1) at least one selectively modified multifunctional amine of the following structure:

where X and Y are independently selected from C2-C16 linear, cyclic, and branched alkyl, alkenyl, and alkaryl groups, or (R1-NH—R2) m , where m=1 to 3, and R1, R2=alkylene groups of at least one C atom, with (2) a fatty acid component.

23 . The method of claim 22 , wherein the fatty acid component comprises at least one of tall oil fatty acid, a monomer fatty acid, a dimer fatty acid, a trimer fatty acid, a polymer fatty acid, or an ester of monomer, dimer, trimer, and polymer fatty acid.

24 . The method of claim 23 , further comprising adding a defoamer to the mixture.

25 . An amine-epoxy composition comprising the reaction product of:
(1) the curing agent of claim 1 ; and (2) an epoxy composition comprising at least one multi-functional epoxy resin

26 . The amine-epoxy composition of claim 25 , wherein the epoxy composition further comprises at least one polyepoxy compound.

27 . The amine-epoxy composition of claim 26 wherein the at least one polyepoxy compound comprises at least one of the diglycidyl ethers of bisphenol-A, the advanced diglycidyl ethers of bisphenol-A, the diglycidyl ethers of bisphenol-F, and the epoxy novolac resins.

28 . The amine-epoxy composition of claim 25 , wherein the stoichiometric ratios of epoxy groups to amine hydrogen ranges from about 1.5 to 1 to about 1 to 1.5.

29 . The amine-epoxy composition of claim 26 , wherein the at least one polyepoxy compound comprises at least one dihydric phenol of the following structure:

where m is 0 to 7.

30 . An article of manufacture comprised of the amine-epoxy composition of claim 25 .

31 . The curing agent of claim 1 wherein the reaction product comprises amidoamine compounds having the general structure:

where R represents an alkyl or aryl group of 1-30 carbon atoms.

32 . The curing agent of claim 1 wherein the reaction product comprises polyamide compounds having the general structure:

where A and B are, independently, alkyl or aryl groups of 1-30 carbon atoms.

Assignees

• Evonik Operations Gmbh

Inventors

• Lal Gauri Sankar
• Ananthachar Sudhir
• Boyce Stephen Michael

Classifications

• C08G69/44

  Polyester-amides · CPC title

• C08G59/44 Primary

  Amides · CPC title

• C08G59/4042

  Imines; Imides · CPC title

• C08G69/34 Primary

  using polymerised unsaturated fatty acids · CPC title

• C08G73/028

  Polyamidoamines · CPC title