Nanofiltration membranes and methods of use

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 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.

7. The method of claim 5 , wherein

each Ar 2 is independently selected from the group consisting of:

and

Q is selected from the group consisting of:

8. The method of claim 1 , wherein each

is independently a bivalent C 2-20 aliphatic group, bivalent aromatic group, or derives from a bivalent diamine group

9. The method of claim 1 , wherein (i) each

is —CH 2 CH 2 —; —CH 2 CH 2 CH 2 —; —CH 2 (CH 2 ) 2 CH 2 —; —CH 2 (CH 2 ) 3 CH 2 —; —CH 2 (CH 2 ) 4 CH 2 —; —CH 2 (CH 2 ) 6 CH 2 —; —CH 2 (CH 2 ) 8 CH 2 —; —CH 2 (CH 2 ) 10 CH 2 —; —CH 2 (CH 2 ) 12 CH 2 —; —CH 2 (CH 2 ) 14 CH 2 —; or —CH 2 (CH 2 ) 16 CH 2 —.

10. The method of claim 1 , wherein (i) each

wherein each X, X 1 , X 2 and X 3 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:

11. The method of claim 1 , wherein each

derives from a bivalent diamine group,

selected from the group consisting of:

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

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 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 is a functional group that does not contain a nitrogen atom; 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.

14. The method of claim 13 , wherein the co-polymer comprises a monomer of Formulae M13a to M13d:

wherein

X c is Cl, Br or I.

15. The method of claim 13 , wherein

each Ar 2 is independently selected from the group consisting of:

and

Q is selected from the group consisting of:

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 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 ;

R x is an optionally substituted aliphatic or optionally substituted aromatic group;

where Z 1 and Z 2 may optionally be taken together to form a ring; 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.

17. The method of claim 16 , wherein

each Ar 2 is independently selected from the group consisting of:

and

Q is selected from the group consisting of: