# US 12,179,157 B2 · Membranes of glassy polymer blends with peg-crosslinked intrinsic microporous polymers for gas separations

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- Number: US 12,179,157 B2
- Document ID: US12179157B2
- Status: Granted
- Kind: B2
- Application number: 17/513,510
- Filed: 2021-10-28
- Published: 2023-05-04
- Granted: 2024-12-31
- Earliest claimed: 2021-10-28
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Junyan Yang
- Web page: https://patentgrep.com/patent/US12179157B2

## CPC

- B01D 71/64: Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
- C08G 73/1039: {comprising halogen-containing substituents}
- B01D 53/228: {characterised by specific membranes}
- B01D 67/0006: {by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125)}
- B01D 69/02: characterised by their properties
- C08G 73/1042: {Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds}
- C08G 73/1067: {Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound}
- C08J 3/005: {Processes for mixing polymers}
- C08J 5/18: Manufacture of films or sheets
- C08L 79/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- B01D 71/76: Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 (rubbers in general B01D71/24)
- B01D 2256/245: Methane
- B01D 2257/504: Carbon dioxide
- B01D 2323/30: Cross-linking
- B01D 2325/34: Molecular weight or degree of polymerisation
- C08J 2379/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08J 2471/02: Polyalkylene oxides
- C08J 2479/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2205/03: containing three or more polymers in a blend
- C08L 2205/05: containing polymer components which can react with one another
- Y02C 20/40: of CO2
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]

## Abstract

This disclosure relates to blended polymeric membranes containing a polyimide polymeric matrix blended with a crosslinked polymer of intrinsic microporosity and methods of using the membranes for gas separation applications, such as removal of CO2 from natural gas.

## Claims

### Claim 1

A blended polymeric membrane comprising:
a co-polyimide polymeric membrane matrix;
a polymer of intrinsic microporosity (PIM); and
a polyethylene glycol-bisazide (PEG-bisazide) crosslinking agent having an average molecular weight (Mn) of about 200 to about 40,000,
wherein the PIM is crosslinked with the PEG-bisazide crosslinking agent.

### Claim 2 (depends on 1)

The blended polymeric membrane of claim 1, wherein the co-polyimide polymeric membrane matrix comprises a 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)-based polyimide.

### Claim 3 (depends on 2)

The blended polymeric membrane of claim 2, wherein the 6FDA-based polyimide has an average molecular weight (Mn) of about 150,000 to about 230,000.

### Claim 4 (depends on 2)

The blended polymeric membrane of claim 2, wherein the 6FDA-based polyimide is 6FDA-DAM: DABA.

### Claim 5 (depends on 4)

The blended polymeric membrane of claim 4, wherein the 6FDA-based polyimide is 6FDA-DAM: DABA (3:2).

### Claim 6 (depends on 1)

The blended polymeric membrane of claim 1, wherein the PIM is PIM-1.

### Claim 7 (depends on 1)

The blended polymeric membrane of claim 1, wherein the PIM has an average molecular weight (Mn) of about 70,000 to about 100,000.

### Claim 8 (depends on 1)

The blended polymeric membrane of claim 1, wherein the PEG-bisazide crosslinking agent has an average molecular weight (Mn) of about 600 to about 2,000.

### Claim 9 (depends on 1)

The blended polymeric membrane of claim 1, wherein the PEG-bisazide crosslinking agent has an average molecular weight (Mn) of about 1100.

### Claim 10 (depends on 1)

The blended polymeric membrane of claim 1, wherein the crosslinked PIM is blended with the co-polyimide polymeric membrane matrix.

### Claim 11 (depends on 1)

The blended polymeric membrane of claim 1, wherein the membrane demonstrates enhanced CO2 plasticization resistance up to 800 psi CO2 feed pressure as compared to the same blended polymeric membrane that does not incorporate a PIM crosslinked with a PEG-bisazide crosslinking agent.

### Claim 12 (depends on 1)

The blended polymeric membrane of claim 1, wherein the membrane exhibits a CO2-permeability increase of about 10% to about 100% as compared to the same blended polymeric membrane that does not incorporate a PIM crosslinked with a PEG crosslinking agent.

### Claim 13 (depends on 1)

The blended polymeric membrane of claim 1, wherein the membrane exhibits a CO2/CH4 selectivity increase of about 10% to about 100% as compared to the same blended polymeric membrane that does not incorporate a PIM crosslinked with a PEG crosslinking agent.

### Claim 14 (depends on 1)

The blended polymeric membrane of claim 1, wherein the membrane exhibits a CO2/CH4 single gas selectivity (αCO2/CH4) of about 50 to about 60 when tested at feed temperature of 25° C. and feed pressure of 800 psi.