Etheramine mixture containing polyether diamines and method of making and using the same

Patent metadata

Field	Value
Publication number	US-11566107-B2
Application number	US-201916980485-A
Country	US
Kind code	B2
Filing date	Mar 18, 2019
Priority date	Mar 19, 2018
Publication date	Jan 31, 2023
Grant date	Jan 31, 2023

Abstract

An etheramine mixture comprising one or more polyether diamines, methods for its production, and its use as a curing agent for epoxy resins. The etheramine mixture may also be used in the preparation of polyamides and polyurea compounds.

First claim

What is claimed is:

1. An etheramine mixture comprising:
one or more polyether diamines of formula (I):

wherein: R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; n is in a range of from 1 to 3; x and y are each in a range of from 0 to 9 with the caveat that if one of x or y is 0, then the other is in a range of from 1 to 9; and the sum of x and y is in a range of from 1 to 10;
at least one or more polyether diamines of formula (III):

wherein: R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; n is in a range of from 1 to 3; x and y are each in a range of from 1 to 9; and the sum of x and y is in a range of from 2 to 10; and
less than 10 wt. % of a monoether diamine based on the total weight of the etheramine mixture.

2. The etheramine mixture of claim 1 , wherein x and y are each in a range of from 1 to 9 and the sum of x and y is in a range of from 2 to 10 for each of the one or more polyether diamines of formula (I) and formula (III).

3. The etheramine mixture of claim 1 , wherein the hydrophobic diol has 6 to 15 carbon atoms for each of the one or more polyether diamines of formula (I) and formula (III).

4. The etheramine mixture of claim 3 , wherein the hydrophobic diol is selected from a cycloaliphatic diol, a hydrogenated aromatic diol, a linear alkyl diol, or a combination thereof.

5. The etheramine mixture of claim 3 , wherein the hydrophobic diol is a cyclopentane diol or a cyclohexane diol.

6. The etheramine mixture of claim 1 , wherein the sum of x and y is in a range of from 3 to 6 for each of the one or more polyether diamines of formula (I) and formula (III).

7. The etheramine mixture of claim 1 , wherein at least 60% of the amine groups of the one or more polyether diamines of formula (I) are primary amines.

8. A method for producing an etheramine mixture, comprising:
charging a hydrophobic diol to an alkoxylation reaction zone;
contacting the hydrophobic diol with an ethylene oxide in the alkoxylation reaction zone to provide a precursor diol, wherein the ratio of moles of ethylene oxide to hydrophobic diol is in a range of from greater than 2:1 to 10:1; and
charging the precursor diol to a reductive amination zone and reductively aminating the precursor diol to form an etheramine mixture containing one or more polyether diamines of formula (I):

wherein: R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; n is in a range of from 1 to 3; x and y are each in a range of from 0 to 9 with the caveat that if one of x or y is 0, then the other is in a range of from 1 to 9; and the sum of x and y is in a range of from 1 to 10; one or more polyether diamines of the formula (III)

wherein: R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; n is in a range of from 1 to 3; x and y are each in a range of from 1 to 9; and the sum of x and y is in a range of from 2 to 10; and
less than 10 wt. % of monoether diamine based on the total weight of the etheramine mixture.

9. The method of claim 8 , wherein x and y are each in a range of from 1 to 9 and the sum of x and y is in a range of from 2 to 10 for each of the one or more polyether diamines of formula (I) and formula (III).

10. The method of claim 8 , wherein the hydrophobic diol has 6 to 15 carbon atoms for each of the one or more polyether diamines of formula (I) and formula (III).

11. The method of claim 10 , wherein the hydrophobic diol is selected from a cycloaliphatic diol, a hydrogenated aromatic diol, a linear alkyl diol, or a combination thereof.

12. A method for producing an epoxy resin system, comprising:
providing the etheramine mixture of claim 1 ;
providing an epoxy resin;
contacting the etheramine mixture and the epoxy resin to form an epoxy resin system.

13. A method for producing a cured epoxy resin system, comprising:
providing an etheramine mixture of claim 1 ;
providing an epoxy resin;
contacting the etheramine mixture and the epoxy resin to form an epoxy resin system; and
curing the epoxy resin system.

14. The method of claim 13 , wherein the step of curing the epoxy resin system comprises subjecting the epoxy resin system to a temperature ranging from about 5° C. to 30° C. for a time ranging from 6 to 24 hours.

15. A method for producing a polyurea comprising reacting the etheramine mixture of claim 1 with an organic polyisocyanate.

16. A polyurea produced by the method of claim 15 .

17. An etheramine mixture produced by a method comprising the steps of:
charging a hydrophobic diol to an alkoxylation reaction zone;
contacting the hydrophobic diol with an ethylene oxide in the alkoxylation reaction zone to provide a precursor diol, wherein the ratio of moles of ethylene oxide to hydrophobic diol is in a range of from greater than 2:1 to 10:1; and
charging the precursor diol to a reductive amination zone and reductively aminating the precursor diol to form the etheramine mixture containing one or more polyether diamines of formula (I):

wherein: R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; n is in a range of from 1 to 3; x and y are each in a range of from 0 to 9 with the caveat that if one of x or y is 0, then the other is in a range from 1 to 9; and the sum of x and y is in a range of from 1 to 10; one or more polyether diamines of the formula (III)

wherein: R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; n is in a range of from 1 to 3; x and y are each in a range of from 1 to 9; and the sum of x and y is in a range of from 2 to 10; and
less than 10 wt. % of monoether diamine based on the total weight of the etheramine mixture.

18. The mixture of claim 17 , wherein x and y are each in a range of from 1 to 9 and the sum of x and y is in a range of from 2 to 10 for each of the one or more polyether diamines of formula (I) and (formula (III).

19. A composite formed by the method of claim 13 .

Assignees

• Huntsman Petrochemical Llc

Inventors

• Klein Howard P
• Renken Terry L
• Li Cheng-Kuang

Classifications

• C08L79/02

  Polyamines · CPC title

• C08G73/024 Primary

  Polyamines containing oxygen in the form of ether bonds in the main chain · CPC title

• C08G59/504 Primary

  containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen · CPC title

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/5024 Primary

  containing primary and/or secondary amino groups · CPC title