# US 11,027,242 B2 · Nanofiltration membranes and methods of use

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- Number: US 11,027,242 B2
- Document ID: US11027242B2
- Status: Granted
- Kind: B2
- Application number: 16/283,257
- Filed: 2019-02-22
- Published: 2019-08-22
- Granted: 2021-06-08
- Earliest claimed: 2013-12-07
- Assignees: Novomer, Inc.
- Applicants: Novomer, Inc.
- Inventors: Robert E. Lapointe; Scott D. Allen; Han Lee; Thomas Widzinski; Jay J. Farmer
- Web page: https://patentgrep.com/patent/US11027242B2

## CPC

- B01D 67/0093: {Chemical modification}
- B01D 61/027: {Nanofiltration}
- B01D 71/56: Polyamides, e.g. polyester-amides
- B01D 71/60: Polyamines
- B01D 71/641: {Polyamide-imides}
- B01D 71/701: {Polydimethylsiloxane}
- 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 71/82: characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
- C07D 305/12: Beta-lactones
- B01D 2323/30: Cross-linking
- B01D 2323/36: Introduction of specific chemical groups
- B01D 2325/30: Chemical resistance
- 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)
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention provides nanofiltration membranes with reduced chemical reactivity that can be utilized in manufacturing processes where reactive feedstocks and/or products are utilized or produced. Methods of making and using the membranes are also provided.

## Claims

### Claim 1

A method of carbonylating epoxide comprising the steps of:
a) contacting epoxide with carbon monoxide in the presence of a homogenous carbonylation catalyst to provide a process stream comprising beta lactone and the homogenous catalyst,
b) flowing the process stream over a nanofiltration membrane to provide a permeate stream comprising beta lactone and a retentate stream comprising homogenous catalyst, and
c) returning the retentate stream to step (a),
wherein the concentration of the catalyst in the retentate stream is higher than the catalyst concentration in the permeate stream; and
wherein the nanofiltration membrane comprises a co-polymer, the co-polymer comprising a monomer of Formula M1 and one or more monomers of Formulae M1a, M2 and M3:
wherein:
each Ar1 is a tetravalent aromatic moiety;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
n is any integer up to about 100,000;
Z is a functional group that does not contain a nitrogen atom;
Z1 is H, aliphatic, acyl or aryl;
Z2 is selected from the group consisting of: aliphatic, aryl, acyl, —C(O)ORx, —SO2Rx and —C(O)NHRx;
where Z1 and Z2 may optionally be taken together to form a ring,
Rz is an optionally substituted aliphatic or optionally substituted aromatic group; and
Rx is an optionally substituted aliphatic or optionally substituted aromatic group.

### Claim 2 (depends on 1)

The method of claim 1, wherein the co-polymer comprises a monomer of Formulae M2a to M2j:
wherein:
Ra is —H, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl;
each of Rb and Rc are independently selected from the group consisting of: —H; optionally substituted C1 to C12 aliphatic; optionally substituted 3- to 14-membered carbocyclic; and optionally substituted 3- to 14 membered heterocyclic, where Rb and Rc may be taken together with intervening atoms to form one or more optionally substituted rings;
Re is one or more moieties selected from the group consisting of: —H, halogen, —OR, —NR2, —SR, —CN, —SO2R, —SOR, —CO2R, —C(O)R, —OC(O)R, SO2NR2; —CNO, —NRSO2R, —N3, —SiR3; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
R is H, optionally substituted aliphatic or optionally substituted aromatic;
is a single or double bond;
ring A is an optionally substituted aryl ring or an optionally substituted saturated or partially unsaturated mono- or polycyclic ring optionally containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; and
ring B represents an optionally substituted 5- or 6-membered saturated, partially unsaturated or aromatic ring optionally containing one or more additional heteroatoms, selected from the group consisting of nitrogen, oxygen, and sulfur, which may be part of a larger fused ring system.

### Claim 3 (depends on 1)

The method of claim 1, wherein the co-polymer comprises a monomer of Formulae M3a or M3b:
wherein
Xb is Cl, Br or I.

### Claim 4 (depends on 1)

The method of claim 1, wherein
each Ar1 is independently selected from the group consisting of:
and
Q is selected from the group consisting of:

### Claim 5

A method of carbonylating epoxide comprising the steps of:
a) contacting epoxide with carbon monoxide in the presence of a homogenous carbonylation catalyst to provide a process stream comprising beta lactone and the homogenous catalyst,
b) flowing the process stream over a nanofiltration membrane to provide a permeate stream comprising beta lactone and a retentate stream comprising homogenous catalyst, and
c) returning the retentate stream to step (a),
wherein the concentration of the catalyst in the retentate stream is higher than the catalyst concentration in the permeate stream; and
wherein said nanofiltration membrane comprises a co-polymer, the co-polymer comprising a monomer of Formula M4 and one or more of a monomer of Formula M5 and a group of Formula M6:
wherein:
each Ar2 is a trivalent aromatic moiety;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
n is any integer up to about 100,000;
Z1 is —H, aliphatic, acyl, or aryl;
Z2 is selected from the group consisting of: aliphatic, aryl, acyl, —C(O)ORx, —SO2Rx, and —C(O)NHRx;
where Z1 and Z2 may optionally be taken together to form a ring;
Rx is an optionally substituted aliphatic or optionally substituted aromatic group; and
Ra is —H, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl.

### Claim 6 (depends on 5)

The method of claim 5, wherein the co-polymer comprises a monomer of Formulae M5a to M5j:
wherein:
Re is one or more moieties selected from the group consisting of: —H, halogen, —OR, —NR2, —SR, —CN, —SO2R, —SOR, —CO2R, —C(O)R, —OC(O)R, SO2NR2; —CNO, —NRSO2R, —N3, —SiR3; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
R is H, or optionally substituted aliphatic or optionally substituted aromatic;
ring A is an optionally substituted aryl ring or an optionally substituted saturated or partially unsaturated mono- or polycyclic ring optionally containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; and
ring B represents an optionally substituted 5- or 6-membered saturated, partially unsaturated or aromatic ring optionally containing one or more additional heteroatoms, selected from the group consisting of nitrogen, oxygen, and sulfur, which may be part of a larger fused ring system.

### Claim 7 (depends on 5)

The method of claim 5, wherein
each Ar2 is independently selected from the group consisting of:
and
Q is selected from the group consisting of:

### Claim 8 (depends on 1)

The method of claim 1, wherein each
is independently a bivalent C2-20 aliphatic group, bivalent aromatic group, or derives from a bivalent diamine group

### Claim 9 (depends on 1)

The method of claim 1, wherein (i) each
is —CH2CH2—; —CH2CH2CH2—; —CH2(CH2)2CH2—; —CH2(CH2)3CH2—; —CH2(CH2)4CH2—; —CH2(CH2)6CH2—; —CH2(CH2)8CH2—; —CH2(CH2)10CH2—; —CH2(CH2)12CH2—; —CH2(CH2)14CH2—; or —CH2(CH2)16CH2—.

### Claim 10 (depends on 1)

The method of claim 1, wherein (i) each
wherein each X, X1, X2 and X3 is independently hydrogen, halogen, or an optionally substituted moiety selected from the group consisting of halogen, aliphatic, alkoxy, phenoxy, aryl, and phenyl; and
Q is selected from the group consisting of:

### Claim 11 (depends on 1)

The method of claim 1, wherein each
derives from a bivalent diamine group,
selected from the group consisting of:

### Claim 12 (depends on 1)

The method of claim 1, wherein the nanofiltration membrane has reduced chemical activity toward a reactive feedstock or product comprising a carbonylation catalyst.

### Claim 13

A method of carbonylating epoxide comprising the steps of:
a) contacting epoxide with carbon monoxide in the presence of a homogenous carbonylation catalyst to provide a process stream comprising beta lactone and the homogenous catalyst,
b) flowing the process stream over a nanofiltration membrane to provide a permeate stream comprising beta lactone and a retentate stream comprising homogenous catalyst, and
c) returning the retentate stream to step (a),
wherein the concentration of the catalyst in the retentate stream is higher than the catalyst concentration in the permeate stream; and
wherein said nanofiltration membrane comprises a co-polymer, the co-polymer comprising a monomer of Formula M4 and a monomer of Formula M13:
wherein:
each Ar2 is a trivalent aromatic moiety;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
n is any integer up to about 100,000;
Z is a functional group that does not contain a nitrogen atom; and
Ra is —H, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl.

### Claim 14 (depends on 13)

The method of claim 13, wherein the co-polymer comprises a monomer of Formulae M13a to M13d:
wherein
Xc is Cl, Br or I.

### Claim 15 (depends on 13)

The method of claim 13, wherein
each Ar2 is independently selected from the group consisting of:
and
Q is selected from the group consisting of:

### Claim 16

A method of carbonylating epoxide comprising the steps of:
a) contacting epoxide with carbon monoxide in the presence of a homogenous carbonylation catalyst to provide a process stream comprising beta lactone and the homogenous catalyst,
b) flowing the process stream over a nanofiltration membrane to provide a permeate stream comprising beta lactone and a retentate stream comprising homogenous catalyst, and
c) returning the retentate stream to step (a),
wherein the concentration of the catalyst in the retentate stream is higher than the catalyst concentration in the permeate stream; and wherein said nanofiltration membrane comprises a co-polymer, the co-polymer comprising (i) a monomer of Formulae M7, M8 or M9, and (ii) a monomer of Formulae M10 or M11, and/or a group of Formulae M12 or M6:
wherein:
each Ar2 is a trivalent aromatic moiety;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
each
represents a bivalent linker and may be the same or different at each occurrence in the co-polymer;
n is any integer up to about 100,000;
Z1 is —H, aliphatic, acyl, or aryl;
Z2 is selected from the group consisting of: aliphatic, aryl, acyl, —C(O)ORx, —SO2Rx, and —C(O)NHRx;
Rx is an optionally substituted aliphatic or optionally substituted aromatic group;
where Z1 and Z2 may optionally be taken together to form a ring; and
Ra is —H, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl.

### Claim 17 (depends on 16)

The method of claim 16, wherein
each Ar2 is independently selected from the group consisting of:
and
Q is selected from the group consisting of: