# US 9,751,985 B2 · Triptycene-based dianhydrides, polyimides, methods of making each, and methods of use

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- Number: US 9,751,985 B2
- Document ID: US9751985B2
- Status: Granted
- Kind: B2
- Application number: 14/894,617
- Filed: 2014-06-09
- Published: 2016-04-14
- Granted: 2017-09-05
- Earliest claimed: 2013-06-06
- Assignees: King Abdullah University of Science and Technology
- Applicants: King Abdullah University of Science and Technology
- Inventors: Bader Ghanem; Ingo Pinnau; Raja Swaidan
- Web page: https://patentgrep.com/patent/US9751985B2

## CPC

- C08G 73/1085: {Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties}
- B01D 53/228: {characterised by specific membranes}
- B01D 71/64: Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
- C07D 493/22: in which the condensed system contains four or more hetero rings
- C08G 73/1053: {with oxygen only in the tetracarboxylic moiety}
- C08G 73/1075: {Partially aromatic polyimides}
- C08G 73/1078: {wholly aromatic in the diamino moiety}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## 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.

## Claims

### Claim 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.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

The composition of claim 1, wherein AR is

### Claim 6 (depends on 1)

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

### Claim 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.

### Claim 8 (depends on 7)

The composition of claim 7, wherein AR is

### Claim 9 (depends on 7)

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

### Claim 10 (depends on 7)

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.

### Claim 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.

### Claim 12 (depends on 11)

The composition of claim 11, wherein AR is

### Claim 13 (depends on 11)

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

### Claim 14 (depends on 1)

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.

### Claim 15 (depends on 7)

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

### Claim 16 (depends on 15)

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.

### Claim 17 (depends on 15)

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.

### Claim 18 (depends on 17)

The method of claim 17, wherein the diamine includes

### Claim 19 (depends on 18)

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

### Claim 20 (depends on 7)

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

### Claim 21 (depends on 20)

The method of claim 20, wherein the reaction scheme is as follows:
wherein each AR is independently selected.

### Claim 22 (depends on 1)

A membrane, comprising: a polyimide of claim 1.

### Claim 23 (depends on 22)

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.

### Claim 24 (depends on 23)

The method of claim 23, wherein the first gas is selected from the group consisting of: He, H2, CO2, H2S, O2, N2, CH4, saturated C2+ hydrocarbons, C2H4, C2H6, C3H6, C3H8 and a combination thereof.

### Claim 25 (depends on 23)

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

### Claim 26 (depends on 23)

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