Triptycene-based dianhydrides, polyimides, methods of making each, and methods of use

Patent metadata

Field	Value
Publication number	US-9751985-B2
Application number	US-201414894617-A
Country	US
Kind code	B2
Filing date	Jun 9, 2014
Priority date	Jun 6, 2013
Publication date	Sep 5, 2017
Grant date	Sep 5, 2017

Abstract

A triptycene-based monomer, a method of making a triptycene-based monomer, a triptycene-based aromatic polyimide, a method of making a triptycene-based aromatic polyimide, methods of using triptycene-based aromatic polyimides, structures incorporating triptycene-based aromatic polyimides, and methods of gas separation are provided. Embodiments of the triptycene-based monomers and triptycene-based aromatic polyimides have high permeabilities and excellent selectivities. Embodiments of the triptycene-based aromatic polyimides have one or more of the following characteristics: intrinsic microporosity, good thermal stability, and enhanced solubility. In an exemplary embodiment, the triptycene-based aromatic polyimides are microporous and have a high BET surface area. In an exemplary embodiment, the triptycene-based aromatic polyimides can be used to form a gas separation membrane.

First claim

We claim at least the following:

1. A composition, comprising:
a triptycene-based aromatic polyimide having the following structure:

wherein n is 1 to 10,000 wherein X is:

wherein Y is a divalent organic group, wherein AR is a substituted or un-substituted aromatic moiety, wherein R1 is a substituted or un-substituted branched alkyl group, wherein R2 is hydrogen, a substituted or un-substituted alkyl group, substituted or un-substituted branched alkyl group, or substituted or un-substituted phenyl group.

2. The composition of claim 1 , wherein the divalent organic group is selected from the group consisting of: aromatic diamine, aromatic triamine, and aromatic tetramine.

3. The composition of claim 1 , wherein the substituted or un-substituted aromatic moiety is selected from the group consisting of: phenyl and naphthyl.

4. The composition of claim 1 , wherein substituted or un-substituted R1 and R2 are independently is selected from the group consisting of: substituted or un-substituted branched C3 to C5 alkyl groups.

5. The composition of claim 1 , wherein AR is

6. The composition of claim 1 , wherein Y is AR′, and AR′ is

7. A composition, comprising a monomer as shown in the following structure:

wherein AR is a substituted or un-substituted aromatic moiety, wherein R1 is hydrogen or a substituted or un-substituted branched alkyl group, and wherein R2 is hydrogen, or a substituted or un-substituted alkyl group, substituted or un-substituted branched alkyl group, or substituted or un-substituted phenyl group.

8. The composition of claim 7 , wherein AR is

9. The composition of claim 7 , wherein the substituted or un-substituted aromatic moiety is selected from the group consisting of: phenyl and naphthyl.

10. The composition of claim 7 , wherein substituted or un-substituted R1 and R2 are independently is selected from the group consisting of: substituted or un-substituted branched C3 to C5 alkyl groups.

11. A method of making a dianhydride, comprising:

wherein AR is a substituted or un-substituted aromatic moiety, wherein R1, R2, and R are each independently selected from: wherein R1 is substituted or un-substituted branched alkyl group, and wherein R2 is hydrogen, a substituted or un-substituted alkyl group, substituted or un-substituted branched alkyl group, or substituted or un-substituted phenyl group.

12. The composition of claim 11 , wherein AR is

13. The composition of claim 11 , wherein the substituted or un-substituted aromatic moiety is selected from the group consisting of: phenyl and naphthyl.

14. The composition of claim 1 , wherein substituted or un-substituted R, R1, and R2 are each independently is selected from the group consisting of: substituted or un-substituted branched C3 to C5 alkyl groups.

15. A method for making a polyimide, comprising: reacting a monomer of claim 7 with a multi-amine to form a polyimide.

16. The method of claim 15 , wherein the multi-amine is selected from the group consisting of a diamine, triamine, tetramine, and an amine having 5 or more amino groups.

17. The method of claim 15 , wherein the reaction scheme is as follows:

wherein AR is a substituted or un-substituted aromatic moiety, wherein R1 is substituted or un-substituted branched alkyi group, and R2 is hydrogen, a substituted or un-substituted alkyi group, substituted or un-substituted branched alkyi group, or substituted or un-substituted phenyl group, and DA is a linking group derived from the diamine.

18. The method of claim 17 , wherein the diamine includes

19. The method of claim 18 , wherein the DA is derived from one of

20. A method for making a polyimide, comprising: reacting a monomer of claim 7 with a multi-amine to form a polypyrrolone.

21. The method of claim 20 , wherein the reaction scheme is as follows:

wherein each AR is independently selected.

22. A membrane, comprising: a polyimide of claim 1 .

23. A method of separating a gas from a gas mixture, comprising: separating a first gas from a first gas mixture with a membrane of claim 22 to form a second gas mixture.

24. The method of claim 23 , wherein the first gas is selected from the group consisting of: He, H 2 , CO 2 , H 2 S, O 2 , N 2 , CH 4 , saturated C 2 + hydrocarbons, C 2 H 4 , C 2 H 6 , C 3 H 6 , C 3 H 8 and a combination thereof.

25. The method of claim 23 , wherein the second gas mixture is oxygen enriched when compared to the first gas mixture.

26. The method of claim 23 , wherein the second gas mixture is nitrogen enriched when compared to the first gas mixture.

Assignees

• Univ King Abdullah Sci & Tech

Inventors

• Ghanem Bader
• Pinnau Ingo
• Swaidan Raja

Classifications

• B01D53/228

  characterised by specific membranes · CPC title

• C08G73/1078

  wholly aromatic in the diamino moiety · CPC title

• C08G73/1053

  with oxygen only in the tetracarboxylic moiety · CPC title

• C07D493/22

  in which the condensed system contains four or more hetero rings · CPC title

• C08G73/1075

  Partially aromatic polyimides · CPC title