Etheramines with enhanced thermal stability and their use as curatives or intermediates for polymer synthesis

Patent metadata

Field	Value
Publication number	US-9822215-B2
Application number	US-201415030110-A
Country	US
Kind code	B2
Filing date	Oct 17, 2014
Priority date	Oct 18, 2013
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

Implementations described herein relate to an etheramine mixture containing a cyclobutane based amine and its method of production by alkoxylating an initiator with an alkylene oxide to produce a precursor polyol and reductively aminating the precursor polyol to form the ehteramine mixture. The etheramine mixture may be used in a variety of applications including as a curing agent for an epoxy resin or as a reactant in the production of polyurea materials.

First claim

The invention claimed is:

1. An etheramine mixture comprising:
a cyclobutane based amine of formula (I):

wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical or different and are each, independently of one another, hydrogen, a linear or branched C 1 to C 5 alkyl group, a linear or branched C 2 -C 5 alkenyl group, or a substituted or unsubstituted C 6 -C 12 aryl group, x and y are each individually a number from 0 to 6 and x+y equals a number from 1 to 12.

2. The etheramine mixture of claim 1 , wherein x+y equals one.

3. The etheramine mixture of claim 1 , wherein R 1 and R 2 are independently selected from hydrogen, CH 3 and C 2 H 5 .

4. The etheramine mixture of claim 3 , wherein R 3 , R 4 , R 5 and R 6 are each CH 3 .

5. The etheramine mixture according to claim 1 , wherein the etheramine mixture contains at least about 10% by weight, based on the total weight of the etheramine mixture, of a monoetheramine of formula (I) wherein x+y equals one.

6. The etheramine mixture according to claim 1 , wherein the etheramine mixture contains from about 30% by weight to about 50% by weight, based on the total weight of the etheramine mixture, of a monoetheramine of formula (I) wherein x+y equals one.

7. A process for preparing an etheramine mixture comprising:
(i) charging an initiator to an alkoxylation reaction zone;
(ii) contacting the initiator with an alkylene oxide in the alkoxylation reaction zone to provide a precursor polyol; and
(iii) charging the precursor polyol to a reductive animation zone and reductively aminating the precursor polyol in the presence of a reductive amination catalyst, hydrogen and ammonia to form the etheramine mixture, wherein the etheramine mixture contains a cyclobutane based amine of formula (I):

wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical or different and are each, independently of one another, hydrogen, a linear or branched C 1 to C 5 alkyl group, a linear or branched C 2 -C 5 alkenyl group, or a substituted or unsubstituted C 6 -C 12 aryl group, x and y are each individually a number from 0 to 6 and x+y equals a number from 1 to 12.

8. The process of claim 7 , wherein the initiator is a cyclobutanediol or a cyclobutanedione.

9. The process of claim 8 , wherein the initiator is selected from 2,2,4,4-tetramethyl-1,3-cyclobutanedione and/or 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

10. The process of claim 7 , wherein the alkylene oxide is propylene oxide.

11. The process of claim 7 , wherein the alkylene oxide is butylene oxide.

12. The process of claim 7 , wherein the amount of alkylene oxide which is contacted with the initiator ranges from about 0.5 to 2 moles of alkylene oxide per mole of initiator.

13. The process of claim 7 , wherein the etheramine mixture contains at least about 10% by weight, based on the total weight of the etheramine mixture, of a monoetheramine of formula (I) wherein x+y equals one.

14. A process for producing a cured epoxy resin system comprising:
(i) providing an etheramine mixture of claim 1 ;
(ii) providing an epoxy resin;
(iii) contacting the etheramine mixture and the epoxy resin to form an epoxy resin system; and
(iv) curing the epoxy resin system.

15. The process of claim 14 , wherein curing the epoxy resin system comprises curing the epoxy resin system from about 3 to about 6 hours at 70 or 80° C.

16. A process for producing a polyurea material comprising reacting the etheramine mixture of claim 1 with an organic polyisocyanate.

17. A polyurea material produced by the process of claim 16 .

Assignees

• Huntsman Petrochemical Llc

Inventors

• Zhou Hui
• Lewis David C
• Klein Howard P
• Renken Terry L

Classifications

• C08L71/02

  Polyalkylene oxides · CPC title

• C08G65/3255

  Ammonia · CPC title

• C08G65/2603

  the other compounds containing oxygen · CPC title

• C08G65/26

  from cyclic ethers and other compounds · CPC title

• C08G65/2609

  containing aliphatic hydroxyl groups · CPC title