Nanofiltration membranes and methods of use

Patent metadata

Field	Value
Publication number	US-11027242-B2
Application number	US-201916283257-A
Country	US
Kind code	B2
Filing date	Feb 22, 2019
Priority date	Dec 7, 2013
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

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.

First claim

What is claimed is:

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 Ar 1 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;
Z 1 is H, aliphatic, acyl or aryl;
Z 2 is selected from the group consisting of: aliphatic, aryl, acyl, —C(O)OR x , —SO 2 R x and —C(O)NHR x ;
where Z 1 and Z 2 may optionally be taken together to form a ring,
R z is an optionally substituted aliphatic or optionally substituted aromatic group; and
R x is an optionally substituted aliphatic or optionally substituted aromatic group.

2. The method of claim 1 , wherein the co-polymer comprises a monomer of Formulae M2a to M2j:

wherein:
R a is —H, or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic, C 1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl;
each of R b and R c are independently selected from the group consisting of: —H; optionally substituted C 1 to C 12 aliphatic; optionally substituted 3- to 14-membered carbocyclic; and optionally substituted 3- to 14 membered heterocyclic, where R b and R c may be taken together with intervening atoms to form one or more optionally substituted rings;
R e is one or more moieties selected from the group consisting of: —H, halogen, —OR, —NR 2 , —SR, —CN, —SO 2 R, —SOR, —CO 2 R, —C(O)R, —OC(O)R, SO 2 NR 2 ; —CNO, —NRSO 2 R, —N 3 , —SiR 3 ; or an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20 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.

3. The method of claim 1 , wherein the co-polymer comprises a monomer of Formulae M3a or M3b:

wherein
X b is Cl, Br or I.

4. The method of claim 1 , wherein
each Ar 1 is independently selected from the group consisting of:

and
Q is selected from the group consisting of:

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 Ar 2 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 1 is —H, aliphatic, acyl, or aryl;
Z 2 is selected from the group consisting of: aliphatic, aryl, acyl, —C(O)OR x , —SO 2 R x , and —C(O)NHR x ;
where Z 1 and Z 2 may optionally be taken together to form a ring;
R x is an optionally substituted aliphatic or optionally substituted aromatic group; and
R a is —H, or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic, C 1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl.

6. The method of claim 5 , wherein the co-polymer comprises a monomer of Formulae M5a to M5j:

wherein:
R e is one or more moieties selected from the group consisting of: —H, halogen, —OR, —NR 2 , —SR, —CN, —SO 2 R, —SOR, —CO 2 R, —C(O)R, —OC(O)R, SO 2 NR 2 ; —CNO, —NRSO 2 R, —N 3 , —SiR 3 ; or an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20 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 optional

Assignees

• Novomer Inc

Inventors

• Lapointe Robert E
• Allen Scott D
• Lee Han
• Widzinski Thomas
• Farmer Jay J

Classifications

• B01D71/641

  Polyamide-imides · CPC title

• B01D71/701

  Polydimethylsiloxane · CPC title

• B01D71/60

  Polyamines · CPC title

• B01D67/0093 Primary

  Chemical modification · CPC title

• B01D2323/30

  Cross-linking · CPC title