# US 11,897,884 B2 · Small molecules based free-standing films and hybrid materials

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- Number: US 11,897,884 B2
- Document ID: US11897884B2
- Status: Granted
- Kind: B2
- Application number: 16/621,278
- Filed: 2018-06-13
- Published: 2020-05-07
- Granted: 2024-02-13
- Earliest claimed: 2017-06-13
- Assignees: Yeda Research and Development Co. Ltd.
- Applicants: Yeda Research and Development Co. Ltd.
- Inventors: Boris Rybtchinski; Haim Weissman; Tamar Wolf; Angelica Elkan; Sounak Dutta; Raja Bhaskar Kanth Siram
- Web page: https://patentgrep.com/patent/US11897884B2

## CPC

- C09B 5/62: Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
- B01D 69/1216: {Three or more layers}
- C01B 32/174: Derivatisation; Solubilisation; Dispersion in solvents
- C07D 471/22: in which the condensed systems contains four or more hetero rings
- H10K 30/10: comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K 30/352: {the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer}
- H10K 85/221: {Carbon nanotubes}
- H10K 85/621: {Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide}
- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- B01D 61/027: {Nanofiltration}
- B01D 61/147: {Microfiltration}
- B01D 2325/0283: Pore size
- B01D 2325/20: Specific permeability or cut-off range
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- H10K 30/50: Photovoltaic [PV] devices
- Y02E 10/549: Organic PV cells
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- 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)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

This invention is directed to an aromatic material based free-standing film, a hybrid of organic crystalline materials and inorganic carbon nanomaterials, process of preparation and uses thereof. The film, which comprises a fibrous organic nanocrystals of an aromatic material, is mechanically and thermally stable. This film is optionally reinforced by hybridization with a reinforcement material, such as carbon nanotube, carbon material, a polysaccharide, a nanoclay a metal, metal alloy, or an organic polymer. The hybrid film of organic nanocrystals and carbon nanotubes (ONC/CNT) has high conductivity and high thermal stability. The films or hybrids of this invention are used as microfiltration membranes for various materials, in electrodes or perovskite solar cells.

## Claims

### Claim 1

A hybrid composition comprising a carbon nanotube (CNT) and organic nanocrystals (ONC), wherein the organic nanocrystal comprises a perylene diimide derivative, represented by the structure of formula IA, B3, II or III:
wherein,
X is —NR3;
Y is —NR4;
R1 is H, R5, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted; or R1 is joined together with R7 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring;
R2 is H, R5, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted; or R2 is joined together with R8 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring;
R3 and R4 are each independently H, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted;
R5 is OR6, OCH3, CF3, halide, COR6, COCl, COOCOR6, COOR6, OCOR6, OCONHR6, NHCOOR6, NHCONHR6, OCOOR6, CON(R6)2, SR6, SO2R6, SO2M, SOR6, SO3H, SO3M, SO2NH2, SO2NH(R6), SO2N(R6)2, NH2, NH(R6), N(R6)2, CONH2, CONH(R6), CON(R6)2, CO(N-heterocycle) NO2, OH, CN, cyanate, isocyanate, thiocyanate, isothiocyanate, mesylate, tosylate, triflate, PO(OH)2 or OPO(OH)2; wherein M is a monovalent cation;
R6 is H, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted;
R7 is H or is joined together with R1 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring; and
R8 is H or is joined together with R2 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring.

### Claim 2 (depends on 1)

The hybrid composition of claim 1, further comprising an organic polymer.

### Claim 3 (depends on 2)

The hybrid composition of claim 2, wherein said organic polymer is selected from the group consisting of: polyvinyl alcohol, polyethylene glycol (PEG), polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyamide, polyimide, polyester and any combination thereof.

### Claim 4 (depends on 3)

The hybrid composition of claim 3, wherein said organic polymer is polystyrene.

### Claim 5 (depends on 1)

The hybrid composition according to claim 1, wherein the carbon nanotubes are single walled carbon nanotubes (SWCNTs) or a multi walled carbon nanotubes (MWCNTs).

### Claim 6 (depends on 1)

The hybrid composition of claim 1, wherein the composition comprises one or more different perylene diimides derivatives.

### Claim 7 (depends on 1)

The hybrid composition of claim 1, wherein the perylene diimide derivative is represented by the structure of formula 1-3, 4a, 4b or 5:

### Claim 8 (depends on 7)

The hybrid composition of claim 7 wherein the perylenediimide derivative is a mixture of 4a and 4b.

### Claim 9 (depends on 1)

The hybrid composition according to claim 1, wherein the composition comprises between 3 wt % to 85 wt % of CNT.

### Claim 10 (depends on 1)

An electrode comprising a hybrid composition according to claim 1.

### Claim 11 (depends on 10)

The electrode of claim 10, wherein said electrode is a cathode or an anode.

### Claim 12 (depends on 10)

The electrode of claim 10, further comprising a binder, an additive, a current collector or any combination thereof.

### Claim 13 (depends on 10)

The electrode of claim 10, wherein said hybrid composition is used as a binder, an additive, a current collector or any combination thereof.

### Claim 14 (depends on 1)

A process for the preparation of the hybrid composition of claim 1, the process comprises:
mixing a hydrophobic organic compound and a carbon nanotube (CNT) in a first organic solvent;
optionally drying the mixture;
adding to the mixture a second organic solvent and water to obtain an aqueous medium and mixing for a period of time to obtain the hybrid; wherein if the first organic solvent and the second organic solvent are the same, only water is added to the mixture.

### Claim 15 (depends on 1)

A process for the preparation of the hybrid composition of claim 1, the process comprises:
mixing a hydrophobic organic compound and a carbon nanotube (CNT) in a first organic solvent;
optionally drying the mixture;
optionally, adding to the mixture a second organic solvent to obtain an organic medium and mixing for a period of time to obtain the hybrid.

### Claim 16 (depends on 14)

The process of claim 14, wherein the hybrid is further purified by centrifugation, or precipitation to yield a homogenous dispersion of ONC/CNT hybrid composition.

### Claim 17 (depends on 15)

The process of claim 15, wherein the hybrid is further purified by centrifugation, or precipitation to yield a homogenous dispersion of ONC/CNT hybrid composition.

### Claim 18 (depends on 14)

The process according to claim 14, wherein the CNT is (6,5)-SWCNT, (7,6)-SWCNT, MWCNT or combination thereof.

### Claim 19 (depends on 15)

The process according to claim 15, wherein the CNT is (6,5)-SWCNT, (7,6)-SWCNT, MWCNT or combination thereof.

### Claim 20 (depends on 14)

The process according to claim 14, wherein the hydrophobic organic compound is perylenediimide (PDI) derivative, represented by the structure of formula IA, IB II or III:
wherein,
X is —NR3;
Y is —NR4;
R1 is H, R5, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted; or R1 is joined together with R7 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring;
R2 is H, R5, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted; or R2 is joined together with R8 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring;
R3 and R4 are each independently H, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted;
R5 is OR6, OCH3, CF3, halide, CORE, COCl, COOCOR6, COOR6, OCOR6, OCONHR6, NHCOOR6, NHCONHR6, OCOOR6, CON(R6)2, SR6, SO2R6, SO2M, SOR6, SO3H, SO3M, SO2NH2, SO2NH(R6), SO2N(R6)2, NH2, NH(R6), N(R6)2, CONH2, CONH(R6), CON(R6)2, CO(N-heterocycle), NO2, OH, CN, cyanate, isocyanate, thiocyanate, isothiocyanate, mesylate, tosylate, triflate, PO(OH)2 or OPO(OH)2; wherein M is a monovalent cation;
R6 is H, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted;
R7 is H or is joined together with R1 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring; and
R8 is H or is joined together with R2 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring.

### Claim 21 (depends on 15)

The process according to claim 15, wherein the hydrophobic organic compound is perylenediimide (PDI) derivative, represented by the structure of formula IA, IB II or III:
wherein,
X is —NR3;
Y is —NR4;
R1 is H, R5, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted; or R1 is joined together with R7 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring;
R2 is H, R5, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted; or R2 is joined together with R8 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring;
R3 and R4 are each independently H, (C1-C10)alkyl, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted;
R5 is OR6, OCH3, CF3, halide, CORE, COCl, COOCOR6, COOR6, OCOR6, OCONHR6, NHCOOR6, NHCONHR6, OCOOR6, CON(R6)2, SR6, SO2R6, SO2M, SOR6, SO3H, SO3M, SO2NH2, SO2NH(R6), SO2N(R6)2, NH2, NH(R6), N(R6)2, CONH2, CONH(R6), CON(R6)2, CO(N-heterocycle), NO2, OH, CN, cyanate, isocyanate, thiocyanate, isothiocyanate, mesylate, tosylate, triflate, PO(OH)2 or OPO(OH)2; wherein M is a monovalent cation;
R6 is H, (C1-C10)haloalkyl, (C3-C8)cycloalkyl, aryl or heteroaryl, wherein said alkyl, haloalkyl, cycloalkyl, aryl or heteroaryl groups are optionally substituted;
R7 is H or is joined together with R1 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring; and
R8 is H or is joined together with R2 to form a substituted or unsubstituted five or six membered ring, or a substituted or unsubstituted five or six membered fused ring.

### Claim 22 (depends on 14)

The process according to claim 14, wherein the aqueous medium is a mixture of THF, DMSO, NMP, DMF, acetonitrile acetone or combination thereof with water.

### Claim 23 (depends on 1)

A film comprising the hybrid composition according to claim 1.

### Claim 24 (depends on 23)

The film according to claim 23, wherein the film is a free-standing film.

### Claim 25 (depends on 23)

A conductive colorant comprising the film according to claim 23.

### Claim 26 (depends on 23)

A membrane for the separation of nanoparticles, biomolecules, comprising the film according to claim 23.