# US 10,696,025 B2 · Asymmetric polymeric membranes containing a metal-rich dense layer with a controlled thickness and method of making same

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- Number: US 10,696,025 B2
- Document ID: US10696025B2
- Status: Granted
- Kind: B2
- Application number: 15/326,750
- Filed: 2015-07-13
- Published: 2017-07-27
- Granted: 2020-06-30
- Earliest claimed: 2014-07-18
- Assignees: King Abdullah University of Science and Technology
- Applicants: King Abdullah University of Science and Technology
- Inventors: Klaus-Viktor Peinemann; Luis Francisco Villalobos Vazquez de la Parra
- Web page: https://patentgrep.com/patent/US10696025B2

## CPC

- B32B 27/065: {of foam}
- B01D 67/00791: {Different components in separate layers}
- B01D 69/02: characterised by their properties
- B01D 69/107: {Organic support material}
- B01D 69/1214: {Chemically bonded layers, e.g. cross-linking}
- B01D 71/58: Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D 71/62: Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D 71/76: Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 (rubbers in general B01D71/24)
- B29C 37/0025: {Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing (moulding on preformed layers as inserts B29C70/68; applying fluent material to surfaces in general B05)}
- B29C 41/22: Making multilayered or multicoloured articles
- B29C 44/1285: {the preformed part being foamed}
- B32B 5/32: {at least two} layers being foamed {and next to each other}
- B01D 2323/2189: Metal-organic compounds or complexes
- B01D 2323/30: Cross-linking
- B01D 2325/10: Catalysts being present on the surface of the membrane or in the pores
- B29L 2031/755: {Membranes, diaphragms}
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B29L: INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES

## Abstract

A structure, and methods of making the structure are provided in which the structure can include: a membrane having a first layer and a second layer, the first layer comprising polymer chains formed with coordination complexes with metal ions, and the second layer consisting of a porous support layer formed of polymer chains substantially, if not completely, lacking the presence of metal ions. The structure can be an asymmetric polymeric membrane containing a metal-rich layer as the first layer. In various embodiments the first layer can be a metal-rich dense layer. The first layer can include pores. The polymer chains of the first layer can be closely packed. The second layer can include a plurality of macro voids and can have an absence of the metal ions of the first layer.

## Claims

### Claim 1

A method of making a structure, comprising:
(i) forming a solution of a polymer and a first solvent, and casting the solution to form a viscous polymer solution film;
(ii) immersing the viscous polymer solution film in a first bath having metal ions and a second solvent such that the metal ions react with a portion of the viscous polymer solution film to form a first layer of polymer-metal complexes, while also leaving an unreacted portion of the viscous polymer solution film; and
(iii) placing the film resulting from step (ii) in a second bath comprising a non-solvent to cause the unreacted portion of the viscous polymer solution film to precipitate and form a second layer that is substantially free of metal ions.

### Claim 2 (depends on 1)

The method of claim 1, where the structure formed is a hollow fiber, a particle, or a film.

### Claim 3 (depends on 1)

The method of claim 1, wherein the first layer of polymer-metal complexes is a dense first layer and acts as a barrier delaying diffusion of metal ions in the second solvent of the first bath to the remaining polymer solution, thereby forming the unreacted portion of the viscous polymer solution film.

### Claim 4 (depends on 1)

The method of claim 1, wherein the second layer comprises a porous support layer for the dense first layer.

### Claim 5 (depends on 1)

The method of claim 1, wherein the second solvent is a solvent that is capable of dissolving a metal salt to form the metal ions and does not cause the formed solution of the polymer and solvent to phase separate.

### Claim 6 (depends on 1)

The method of claim 1, wherein the polymer is a polymer that forms intermolecular complexes with metal ions.

### Claim 7 (depends on 6)

The method of claim 6, wherein the polymer is selected from the group consisting of poly-thiosemicarbazide (PTSC), poly-thiourea (PTU), polybenzimidazole (PBI), polymers containing azole groups in their backbone, or azole groups as pendant groups, polyazoles, copolyazoles, polyoxadiazoles, poly(5-vinyl tetrazole), copolymers of 5-vinyl tetrazole with acrylonitrile, poly(N-alkyl-5-vinyl tetrazole)s, polysulfone bearing triazole functions, and tetrazole-containing polymers.

### Claim 8 (depends on 1)

The method of claim 1, wherein the metal ions are selected from the group consisting of palladium, gold, silver, platinum, copper, cobalt, nickel, iron, zinc, and mercury.

### Claim 9 (depends on 1)

The method of claim 1, wherein the first solvent and second solvent are selected from the group consisting of Dimethyl sulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), Dimethylacetamide (DMAc), and Acetonitrile (MeCN).

### Claim 10 (depends on 1)

The method of claim 1, wherein the non-solvent bath comprises water, methanol, ethanol and/or isopropanol.

### Claim 11 (depends on 1)

The method of claim 1, wherein the first solvent and the second solvent are the same.

### Claim 12 (depends on 1)

The method of claim 1, wherein the first layer and the second layer comprise the same polymer.

### Claim 13 (depends on 1)

The method of claim 1, wherein phase inversion is not performed between steps (i) and (ii).

### Claim 14 (depends on 1)

The method of claim 1, wherein the unreacted portion of the viscous polymer solution is also an unprecipitated portion.