# US 12,109,548 B2 · Superhydrophobic covalent organic framework materials

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- Number: US 12,109,548 B2
- Document ID: US12109548B2
- Status: Granted
- Kind: B2
- Application number: 16/961,152
- Filed: 2019-01-12
- Published: 2020-11-19
- Granted: 2024-10-08
- Earliest claimed: 2018-01-12
- Assignees: University of South Florida
- Applicants: University of South Florida
- Inventors: Shengqian Ma; Qi Sun
- Web page: https://patentgrep.com/patent/US12109548B2

## CPC

- B01J 20/226: {Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- C08J 9/405: {with polymerisable compounds}
- B01J 20/262: {obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation (macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G)}
- B01J 20/28009: {Magnetic properties}
- B01J 20/28011: {Other properties, e.g. density, crush strength}
- B01J 20/28026: {Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin}
- B01J 20/28045: {Honeycomb or cellular structures; Solid foams or sponges}
- B01J 20/321: {consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds}
- B01J 20/3212: {consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds}
- B01J 20/3217: {Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond}
- B01J 20/3268: {Macromolecular compounds}
- B01J 20/3278: {Polymers being grafted on the carrier}
- B01J 20/3293: {Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers}
- C08J 2361/28: with melamine
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)

## Abstract

A variety of superhyrdophobic porous materials are provided including a covalent organic framework having a plurality of perfluoroalkyl or perfluorheteroalkyl moieties covalently attached thereto. The materials can include a polymeric foam matrix made of a three-dimensional network of polymer fibers, and the covalent organic framework can be made encasing at least a portion of the polymer fibers. The covalent organic framework can be intertwined within the polymeric foam matrix such that the covalent organic framework encasing the portion of the polymer fibers is stable to mechanical compression of the polymeric foam matrix. Surfaces and other articles are provided including the superhyrdophobic porous materials are also provided, as are methods of making the superhyrdophobic porous materials, and methods of use for oil recovery among other things.

## Claims

### Claim 1

A superhydrophobic porous material comprising:
a polymeric foam matrix comprising a three-dimensional network of polymer fibers;
a covalent organic framework encasing at least a portion of the polymer fibers, wherein the covalent organic framework comprises a plurality of perfluoroalkyl or perfluorheteroalkyl moieties covalently attached thereto.

### Claim 2 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the polymeric foam matrix comprises a foam selected from the group consisting of polyurethane foam, polyurea foam, polyvinyl chloride foam, polypropylene foam, polyethylene foam, polystyrene foam, polyvinyl acetate foam, and melamine foam.

### Claim 3 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the covalent organic framework is intertwined within the polymeric foam matrix such that the covalent organic framework encasing the portion of the polymer fibers is stable to mechanical compression of the polymeric foam matrix.

### Claim 4 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the covalent organic framework is intertwined within the polymeric foam matrix such that the polymeric foam matrix maintains about the same level of mechanical compressibility as the otherwise same polymeric foam matrix except without the covalent organic framework.

### Claim 5

A superhydrophobic porous material comprising a covalent organic framework, wherein the covalent organic framework comprises a plurality of perfluoroalkyl or perfluoroheteroalkyl moieties covalently attached thereto;
wherein the covalent organic framework has a structure according to the following formula:
where each occurrence of R1 and R2 is independently a hydrogen, alkyl, alkenyl, heteroalkyl, alkoxy, perfluoroalkyl partially fluorinated alkyl, perfluorheteroalkyl, or partially fluorinated heteroalkyl so long as at least one occurrence of R1 or R2 comprises a perfluoroalkyl, partially fluorinated alkyl, perfluorheteroalkyl, or partially fluorinated heteroalkyl, and
where n is an integer from 2 to 12.

### Claim 6 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the covalent organic framework has a structure according to the following formula
where each occurrence of R1 and R2 is independently a hydrogen, alkyl, alkenyl, heteroalkyl, alkoxy, perfluoroalkyl, partially fluorinated alkyl, perfluorheteroalkyl, or partially fluorinated heteroalkyl so long as at least one occurrence of R1 or R2 comprises a perfluoroalkyl, partially fluorinated alkyl, perfluorheteroalkyl, or partially fluorinated heteroalkyl, and
where n is an integer from 2 to 12.

### Claim 7 (depends on 6)

The superhydrophobic porous material according to claim 6, wherein each occurrence of R2 is a hydrogen, and wherein each occurrence of R1 is independently a hydrogen or a -LR3,
where L is none or is an alkyl or thioalkyl, and where each occurrence of R3 is a perfluoroalkyl.

### Claim 8 (depends on 6)

The superhydrophobic porous material according to claim 6, wherein the perfluoralkyl comprises 6 to 15 carbon atoms.

### Claim 9 (depends on 6)

The superhydrophobic porous material according to claim 6, wherein R1 is hydrogen, alkenyl, or —R4SR5B1, where R4 is a C1-C5 alkyl, R5 is a C1-C3 alkyl, and B1 is a C6-C12 perflouoroalkyl;
wherein R2 is a hydrogen; and
n is 4 to 6.

### Claim 10 (depends on 9)

The superhydrophobic porous material according to claim 9, wherein R4 is C2 alkyl, R5 is C2 alkyl, and B1 is C8 perfluoroalkyl.

### Claim 11 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the covalent organic framework exhibits a water adsorption capacity of about 50-80 milligrams water per gram of the covalent organic framework.

### Claim 12 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the covalent organic framework exhibits a toluene adsorption capacity of about 500-800 milligrams toluene per gram of the covalent organic framework.

### Claim 13 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein a water contact angle on the covalent organic framework is about 150° or more.

### Claim 14 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein a nitrobenzene contact angle on the covalent organic framework is about 10° or less.

### Claim 15 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the composition has an oil absorption capacity of about 50 to 150 times the weight of the composition.

### Claim 16 (depends on 1)

The superhydrophobic porous material according to claim 1, wherein the oil absorption capacity is measured for one or more oils selected from the group consisting of CHCl3, nitrobenzene, dimethylformamide, toluene, bromobenzene, ethanol, hexane, mineral oil, pump oil, soybean oil, and a mixture thereof.

### Claim 17 (depends on 1)

A surface comprising a superhydrophobic porous material according to claim 1.

### Claim 18 (depends on 6)

A droplet comprising an aqueous central region surrounded by an outer surface according to claim 6.

### Claim 19 (depends on 18)

The droplet of claim 18, wherein the aqueous central region comprises a plurality of magnetic particles.