# US 10,245,562 B2 · Pervaporation membranes derived from polycyclo-olefinic block copolymers

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- Number: US 10,245,562 B2
- Document ID: US10245562B2
- Status: Granted
- Kind: B2
- Application number: 14/827,624
- Filed: 2015-08-17
- Published: 2016-02-25
- Granted: 2019-04-02
- Earliest claimed: 2014-08-15
- Assignees: Promerus, LLC; Sumitomo Bakelite Co., Ltd.
- Applicants: Promerus, LLC; Sumitomo Bakelite Co., Ltd
- Inventors: Andrew Bell; Oleksandr Burtovyy; Tamami Takigawa
- Web page: https://patentgrep.com/patent/US10245562B2

## CPC

- B01D 71/80: Block polymers
- B01D 61/362: {Pervaporation}
- B01D 67/0002: {Organic membrane manufacture}
- B01D 67/0009: {by phase separation, sol-gel transition, evaporation or solvent quenching}
- B01D 67/0095: {Drying}
- B01D 69/08: Hollow fibre membranes (manufacture of hollow fibres D01D5/24, D01F1/08)
- B01D 69/087: {Details relating to the spinning process}
- B01D 69/1213: {Laminated layers}
- B01D 69/125: {In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction}
- C07F 15/006: {Palladium compounds}
- C08F 32/04: having one carbon-to-carbon double bond
- C08F 299/02: from unsaturated polycondensates
- B01D 2323/12: Specific ratios of components used
- B01D 2323/36: Introduction of specific chemical groups
- C08F 4/80: selected from iron group metals or platinum group metals
- 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)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A pervaporation membrane formed from a series of vinyl addition block polymers derived from functionalized norbornene monomers are disclosed and claimed. Also disclosed are the fabrication of membranes which exhibit unique separation properties, and their use in the separation of organic volatiles from biomass and/or organic waste, including butanol, phenol, and the like.

## Claims

### Claim 1

A pervaporation membrane comprising a block copolymer of the formula (VI):
(A)m-b-(B)n (VI);
where each of m and n is an integer of at least 15;
b denotes a bond;
A and B are different from each other and independently selected from a repeat unit represented by formula (IVA), said repeat unit is derived from a monomer of formula (IV):
wherein:
denotes a place of bonding with another repeat unit;
p is an integer 0, 1 or 2;
R3, R4, R5 and R6 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C1-C16)alkyl, hydroxy(C1-C16)alkyl, perfluoro(C1-C12)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, perfluoro(C6-C10)aryl, perfluoro(C6-C10)aryl(C1-C3)alkyl, di(C1-C2)alkylmaleimide(C3-C6)alkyl, di(C1-C2)alkylmaleimide(C2-C6)alkoxy(C1-C2)alkyl, hydroxy, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl, (C5-C10)heteroaryloxy(C1-C3)alkyl, (C6-C10)aryloxy, (C5-C10)heteroaryloxy or (C1-C6)acyloxy, where each of the aforementioned substituents are optionally substituted with halogen or hydroxy.

### Claim 2 (depends on 1)

The pervaporation membrane according to claim 1 wherein said polymer further comprises a third repeat unit forming a block terpolymer represented by formula (VII):
(A)m-b-(B)n-b-(C)o (VII);
where m, n and b are as defined in claim 1 and o is an integer of at least 15;
C is same or different from A or B and independently selected from a repeat unit represented by formula (IVA), said repeat unit is derived from a monomer of formula (IV) as defined in claim 1.

### Claim 3 (depends on 1)

The pervaporation membrane according to claim 1, wherein the copolymer is selected from the group consisting of:
a block copolymer derived from 5-hexylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and 1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (C4F9NB-b-BuDMMINB);
a block copolymer of derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2-(bicyclo[2.2.1]kept-5-en-2-yl)bicyclo[2.2.1]heptane (HFANB-b-NBANB); and
a block copolymer of derived from 5-hexylbicyclo[2.2.1]hept-2-ene and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HexNB-b-NBANB).

### Claim 4 (depends on 2)

The pervaporation membrane according to claim 2, wherein the terpolymer is selected from the group consisting of:
a block terpolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo[2.2.1]hept-2-ene (BuNB-b-HFANB-b-BuNB); and
a block terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo[2.2.1]hept-2-ene, and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

### Claim 5 (depends on 1)

The pervaporation membrane according to claim 1 in a form of a tubular composite, hollow fiber, a dense film flat sheet, or a thin film composite.

### Claim 6 (depends on 1)

The pervaporation membrane according to claim 1, which is capable of preferential permeability to a volatile organic over water, said permeability increasing with increasing organic concentration of a feed stream.

### Claim 7 (depends on 6)

The pervaporation membrane according to claim 6, wherein said volatile organic comprises butanol.

### Claim 8 (depends on 6)

The pervaporation membrane according to claim 6, wherein said volatile organic comprises phenol.

### Claim 9 (depends on 7)

The pervaporation membrane according to claim 7 having a flux for butanol of at least about 100 g/m2·h from a fermentation broth comprising at least about 1% by weight butanol, wherein the flux for butanol is an amount of butanol (g) that flows through an unit area (m2) of the pervaporation membrane per unit of time (h).

### Claim 10 (depends on 1)

A method of separating an organic product from a feedstock selected from a fermentation broth or a waste containing the organic product comprising:
charging the feedstock to a pervaporation module containing a pervaporation membrane formed by a polymer according to claim 1; and
collecting a permeate vapor containing the organic product from the pervaporation module.

### Claim 11 (depends on 10)

The method according to claim 10, wherein the fermentation broth charged to the pervaporation module has a temperature from about 30° C. to about 110° C.

### Claim 12 (depends on 10)

The method according to claim 10, wherein a vacuum from about 0.1 in Hg to about 25 in Hg is applied to the pervaporation module.

### Claim 13 (depends on 10)

The method according to claim 10, wherein the pervaporation membrane is formed by a polymer selected from:
a block copolymer derived from 5-hexylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and 1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (C4F9NB-b-BuDMMINB);
a block copolymer of derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HFANB-b-NBANB); and
a block copolymer of derived from 5-hexylbicyclo[2.2.1]hept-2-ene and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HexNB-b-NBANB).

### Claim 14 (depends on 10)

The method according to claim 10, wherein the pervaporation membrane is formed by a polymer selected from:
a block terpolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo[2.2.1]hept-2-ene (BuNB-b-HFANB-b-BuNB); and
a block terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo[2.2.1]hept-2-ene, and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

### Claim 15 (depends on 10)

The method according to claim 10, wherein the organic product is butanol, ethanol or phenol.

### Claim 16

A method of separating butanol or phenol from a feedstock selected from a fermentation broth or a waste containing butanol or phenol comprising:
charging the feedstock to a pervaporation module containing a pervaporation membrane formed by a polymer selected from:
a block copolymer derived from 5-hexylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and 1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (C4F9NB-b-BuDMMINB);
a block copolymer of derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2-(bicyclo[2.2.1]kept-5-en-2-yl)bicyclo[2.2.1]heptane (HFANB-b-NBANB);
a block copolymer of derived from 5-hexylbicyclo[2.2.1]hept-2-ene and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HexNB-b-NBANB);
a block terpolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo[2.2.1]hept-2-ene (BuNB-b-HFANB-b-BuNB); and
a block terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo[2.2.1]hept-2-ene, and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB); and
collecting a permeate vapor containing butanol or phenol from the pervaporation module.

### Claim 17

A method of forming a membrane comprising:
pouring a solution of a block copolymer of the formula (VI):
(A)m-b-(B)n (VI)
onto a suitable substrate;
where each of m and n is an integer of at least 15;
b denotes a bond;
A and B are different from each other and independently selected from a repeat unit represented by formula (IVA), said repeat unit is derived from a monomer of formula (IV):
wherein:
denotes a place of bonding with another repeat unit;
p is an integer 0, 1 or 2;
R3, R4, R5 and R6 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C1-C16)alkyl, hydroxy(C1-C16)alkyl, perfluoro(C1-C12)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, perfluoro(C6-C10)aryl, perfluoro(C6-C10)aryl(C1-C3)alkyl, di(C1-C2)alkylmaleimide(C3-C6)alkyl, di(C1-C2)alkylmaleimide(C2-C6)alkoxy(C1-C2)alkyl, hydroxy, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl, (C5-C10)heteroaryloxy(C1-C3)alkyl, (C6-C10)aryloxy, (C5-C10)heteroaryloxy or (C1-C6)acyloxy, where each of the aforementioned substituents are optionally substituted with halogen or hydroxy; and
drying the substrate at a suitable temperature to form the membrane.

### Claim 18 (depends on 17)

The method according to claim 17, wherein said polymer further comprises a third repeat unit and represented by formula (VII):
(A)m-b-(B)n-b-(C)o (VII);
where m, n and b are as defined in claim 17 and o is an integer of at least 15; and
C is same or different from A or B and independently selected from a repeat unit represented by formula (IVA), said repeat unit is derived from a monomer of formula (IV) as defined in claim 17.

### Claim 19 (depends on 17)

The method according to claim 17, wherein said copolymer is selected from the group consisting of:
a block copolymer derived from 5-hexylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b-HFANB);
a block copolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and 1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (C4F9NB-b-BuDMMINB);
a block copolymer of derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HFANB-b-NBANB); and
a block copolymer of derived from 5-hexylbicyclo[2.2.1]hept-2-ene and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HexNB-b-NBANB).

### Claim 20 (depends on 18)

The method according to claim 18, wherein said polymer is selected from the group consisting of:
a block terpolymer derived from 5-butylbicyclo[2.2.1]hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo[2.2.1]hept-2-ene (BuNB-b-HFANB-b-BuNB); and
a block terpolymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo[2.2.1]hept-2-ene, and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).