Etheramines and their Use as Curatives or Intermediates for Polymer Synthesis

Patent metadata

Field	Value
Publication number	US-2016257778-A1
Application number	US-201415033704-A
Country	US
Kind code	A1
Filing date	Oct 30, 2014
Priority date	Nov 5, 2013
Publication date	Sep 8, 2016
Grant date	—

Abstract

Implementations described herein generally relate to etheramine mixtures formed from a mixture of two or more multifunctional alcohol initiators, processes for the etheramine mixtures production, and its use as a curing agent or as a raw material in the synthesis of polymers. In one implementation, the process comprises mixing a polyol initiator having a melting point greater than a processing temperature and a polyol initiator having a melting point less than the processing temperature to form a polyol initiator mixture having a melting point less than the processing temperature, charging the polyol initiator mixture to an alkoxylation reaction zone, contacting the polyol initiator mixture with an alkylene oxide in the alkoxylation reaction zone to provide a mixture of alkoxylated precursor polyols and charging the mixture of alkoxylated precursor polyols to a reductive amination zone and reductively aminating the mixture of alkoxylated precursor polyols to form the etheramine mixture.

First claim

1 . A process for preparing an etheramine mixture, comprising:
(a) mixing a first polyol initiator having a melting point greater than a processing temperature and a second polyol initiator having a melting point less than the processing temperature to form a polyol initiator mixture having a melting point less than the processing temperature; (b) charging the polyol initiator mixture to an alkoxylation reaction zone in the presence of an alkali metal hydroxide catalyst; (c) contacting the polyol initiator mixture with an alkylene oxide in the alkoxylation reaction zone to provide a mixture of alkoxylated precursor polyols; and (d) charging the mixture of alkoxylated precursor polyols to a reductive amination zone and reductively aminating the mixture of alkoxylated precursor polyols in the presence of a reductive amination catalyst and ammonia to form the etheramine mixture.

2 . (canceled)

3 . (canceled)

4 . (canceled)

5 . The process of claim 1 , wherein the first polyol initiator is neopentyl glycol.

6 . The process of claim 5 , wherein the second polyol initiator is selected from the group consisting of: 1,4-cyclohexanedimethanol, 1,4-butanediol, ethylene glycol and combinations thereof.

7 . The process of claim 5 , wherein the alkylene oxide is selected from the group consisting of: propylene oxide, butylene oxide, ethylene oxide and combinations thereof.

8 . The process of claim 1 , wherein the melting point of the second polyol initiator mixture is less than 60° C. and the melting point of the first polyol initiator is greater than 60° C.

9 . The process of claim 8 , wherein the melting point of the first polyol initiator is greater than 100° C.

10 . The process of claim 1 , wherein the weight ratio of the first polyol initiator to the second polyol initiator is between 30:70 and 90:10

11 . The process of claim 1 , further comprising:
(e) contacting the etheramine mixture with an epoxy resin to form an epoxy resin system; and (f) curing the epoxy resin system.

12 . The process of claim 1 , further comprising:
(e) reacting the etheramine mixture with an organic polyisocyanate to produce a polyurea.

13 . (canceled)

14 . The process of claim 1 , wherein the first polyol initiator is a solid and the second polyol initiator is a liquid.

15 . The process of claim 14 , wherein the polyol initiator mixture is a liquid.

16 . A composition comprising an etheramine mixture that comprises the reaction product of ammonia and a mixture of alkoxylated precursor polyols;
wherein the reaction is conducted under reductive amination reaction conditions; wherein the mixture of alkoxylated polyols is the reaction product of a polyol initiator mixture having a melting point less than a processing temperature with an alkylene oxide; and wherein the polyol initiator mixture comprises a first polyol initiator having a melting point greater than the processing temperature and a second polyol initiator having a melting point less than the processing temperature.

17 . The composition of claim 16 , wherein the etheramine mixture comprises an etheramine of formula (I):

wherein L is a linear or branched C 2 -C 18 alkylene, preferably C 2 -C 12 alkylene and particularly preferably C 2 -C 6 alkylene; C 3 -C 12 cycloalkylene, preferably C 4 -C 8 cycloalkylene and particularly preferably C 5 -C 8 cycloalkylene; C 2 -C 4 alkylene-C 3 -C 12 cycloalkylene and preferably C 2 -C 4 alkylene-C 5 -C 6 cycloalkylene; C 2 -C 4 alkylene-C 3 -C 12 cycloalkylene-C 2 -C 4 alkylene and preferably C 2 -C 4 alkylene-C 5 -C 6 cycloalkylene-C 2 -C 4 alkylene;
wherein R 3 and R 4 may be identical or different and may each be, 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; and
wherein m and n may each individually be a number from 0 to 6 wherein at least one of m and n is 1 or more.

18 . The composition of claim 16 , wherein the etheramine mixture comprises an etheramine of formula (I):

wherein 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 and m+n equals a non-zero whole number between one and six.

19 . The composition of claim 18 , wherein the etheramine mixture further comprises at least one of:

wherein R 7 and R 8 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 and x+y equals a non-zero whole number between one and six;

wherein R 9 and R 10 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 and x+y equals a non-zero whole number between one and six; and

wherein R 11 and R 12 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 and x+y equals a non-zero whole number between one and six.

20 . (canceled)

21 . (canceled)

22 . (canceled)

23 . (canceled)

24 . (canceled)

25 . (canceled)

26 . The composition of claim 25 , wherein the composition is clear and has a melting point of 60° C. or less.

27 . The composition of claim 16 , wherein the composition is a polyurea composition.

28 . The composition of claim 16 , wherein the composition is an epoxy resin system.

29 . (canceled)

30 . (canceled)

31 . A composition comprising:

wherein L is a linear or branched C 2 -C 18 alkylene, preferably C 2 -C 12 alkylene and particularly preferably C 2 -C 6 alkylene; C 3 -C 12 cycloalkylene, preferably C 4 -C 8 cycloalkylene and particularly preferably C 5 -C 8 cycloalkylene; C 2 -C 4 alkylene-C 3 -C 12 cycloalkylene and preferably C 2 -C 4 alkylene-C 5 -C 6 cycloalkylene; C 2 -C 4 alkylene-C 3 -C 12 cycloalkylene-C 2 -C 4 alkylene and preferably C 2 -C 4 alkylene-C 5 -C 6 cycloalkylene-C 2 -C 4 alkylene;
wherein R 3 and R 4 may be identical or different and may each be, 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 unsubstitut

Assignees

• Huntsman Petrochemical Llc

Inventors

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

Classifications

• C08G65/2609

  containing aliphatic hydroxyl groups · CPC title

• C08G18/3228

  acyclic · CPC title

• C07C217/42

  having etherified hydroxy groups and at least two amino groups bound to the carbon skeleton · CPC title

• C08G65/2696

  characterised by the process or apparatus used · CPC title

• C08G59/184

  with amines · CPC title