Diversity-oriented polymers of intrinsic microporosity and uses thereof

1. A microporous polymer according to the formula:

-[A-AB-B] n —,

or a salt thereof,

wherein:

n is an integer ranging from 10 to 10,000;

each monomer segment A-A is independently a monomer segment according to Formula (A), (B), (C), (D), (E), (F), (G) or (H):

each monomer segment B-B is independently a monomer segment according to Formula (a), (b), (c), (d), (e), or (f):

each R 11 is independently selected from the group consisting of —CH 2 NR 1 R 2 and H;

each R 12 is independently selected from the group consisting of —C(NOR 13 )N(R 14 ) 2 and —CN;

at least one R 11 in at least one monomer segment A-A is —CH 2 NR 1 R 2 , or at least one R 12 in at least one monomer segment B-B is —C(NOR 13 )N(R 14 ) 2 ;

each R 1 and R 2 is independently selected from the group consisting of (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, (C 3-8 )cycloalkyl(C 1-20 )alkyl, hetero(C 1-20 )alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C 1-20 )alkyl, 5- to 8-membered heteroaryl, heteroaryl(C 1-20 )alkyl,

wherein each R 1 and R 2 is optionally and independently substituted with one or more Z 1 ,

wherein each (C 1-20 )alkyl, (C 2-20 )alkenyl, and (C 2-20 )alkynyl in R 1 and R 2 optionally and independently comprises one or more heteroatoms independently selected from silicon, a chalcogenide, and a pnictide, and

wherein one or more atoms in R 1 and R 2 are optionally and independently present in oxidized form as C═O, C═S, N═O, N═S, S═O or S(O) 2 ; or

alternatively, each R 1 is optionally and independently taken together with R 2 , and the nitrogen atom to which both are attached, to form 3- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl, each of which is optionally substituted with one or more Z 2 ;

each Z 1 and Z 2 is independently selected from the group consisting of halogen, —OH, —NO 2 , —CN, (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 ) cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl, 3- to 8-membered heterocyclyl, 5- to 8-membered heteroaryl, (C 3-8 )cycloalkyl-(C 1-20 )alkyl, 3- to 8-membered heterocyclyl-(C 1-20 )alkyl, 5- to 8-membered heteroaryl-(C 1-20 )alkyl, halo(C 1-20 )alkyl, halo(C 1-20 )alkyloxy, —OR 6 , —SR 6 , —S(O)R 6 , —S(O) 2 R 6 , —SO 2 NR 6 R 7 , —NR 6 C(O)R 7 , —NR 6 S(O) 2 R 7 , —NR 6 C(O)NR 7 R 8 , —NR 6 R 7 , —CO 2 R 6 , —C(O)NR 6 R 7 , and —C(O)R 6 ;

each R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is independently selected from the group consisting of (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, (C 3-8 )cycloalkyl(C 1-20 )alkyl, hetero(C 1-20 )alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C 1-20 )alkyl, 5- to 8-membered heteroaryl, 5- to 8-membered heteroaryl-(C 1-20 )alkyl; or

alternatively, R 4 and R 5 are taken together to form (C 4-8 )cycloalkyl, (C 6-12 )aryl, 4- to 8-membered heterocyclyl, or 5- to 8-membered heteroaryl; or

alternatively, R 6 and R 7 are taken together to form 4- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl; or

alternatively, R 7 and R 8 are taken together to form 4- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl;

each R 13 is selected from the group consisting of H, (C 1-20 )alkyl, and (C 3-8 )cycloalkyl, wherein (C 1-20 )alkyl and (C 3-8 )cycloalkyl are optionally and independently substituted with one or more Z 3 ,

provided that R 13 is (C 1-20 )alkyl or (C 3-8 )cycloalkyl, each of which is optionally and independently substituted with one or more Z 3 , when all R 11 groups in monomer segments according to Formula (A) are H;

each R 14 is independently selected from the group consisting of H, (C 1-20 )alkyl, and (C 3-8 )cycloalkyl; and

each Z 3 is independently selected from the group consisting of halogen, —NO 2 , —CN, —OH, —SO 3 H, —NH 2 , (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 ) cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl, 3- to 8-membered heterocyclyl, 5- to 8-membered heteroaryl, (C 3-8 )cycloalkyl-(C 1-20 )alkyl, 3- to 8-membered heterocyclyl-(C 1-20 )alkyl, 5- to 8-membered heteroaryl-(C 1-20 )alkyl, halo(C 1-20 )alkyl, halo(C 1-20 )alkyloxy, —OR 6 , —SR 6 , —S(O)R 6 , —S(O) 2 R 6 , —SO 2 NR 6 R 7 , —NR 6 C(O)R 7 , —NR 6 S(O) 2 R 7 , —NR 6 C(O)NR 7 R 8 , —NR 6 R 7 , —CO 2 R 6 , —C(O)NR 6 R 7 , and —C(O)R 6 .

2. The microporous polymer of claim 1 , or the salt thereof, wherein:

each monomer segment A-A is independently a monomer segment according to Formula (A-i), (B-i), (C-i), (D-i), (E-i), (F-i), (G-i) or (H-i):

and each monomer segment B-B is independently a monomer segment according to Formula (a-i), (b-i), (c), (d), (e), or (f):

3. The microporous polymer of claim 1 , or the salt thereof, wherein:

each monomer segment A-A is independently a monomer segment according to Formula (A-i), (B-i), (C-i), (D-i), (E-i), (F-i), (G-i), (H-i), (B-ii), (C-ii), (C-ii), (E-ii), (F-ii), (G-ii), or (H-ii):

and each monomer segment B-B is independently a monomer segment according to Formula (a-ii) or (b-ii):

4. The microporous polymer of claim 1 , or the salt thereof, wherein:

each monomer segment A-A is independently a monomer segment according to Formula (A-i), (B-i), (C-i), (D-i), (E-i), (F-i), (G-i), (H-i), (B-ii), (C-ii), (D-ii), (E-ii), (F-ii), (G-ii), (H-ii), or (A-ii):

and each monomer segment B-B is independently a monomer segment according to Formula (a-iii), (b-iii), (a-iv), (b-iv), (a-v), (b-v), (a-vi), (b-vi), (a-vii), (b-vii), (a-viii), or (b-viii):

wherein A + is an inorganic cation or an organic cation.

5. The microporous polymer of claim 4 , or the salt thereof, wherein each monomer segment B-B is independently a monomer segment according to Formula (a-iii), (b-iii), (a-iv), (b-iv), (a-v), (b-v), (a-vi), or (b-vi).

6. The microporous polymer of claim 4 , or the salt thereof, wherein each monomer segment B-B is independently a monomer segment according to Formula (a-vii), (b-vii), (a-viii), or (b-viii).

7. The microporous polymer of claim 1 , or the salt thereof, wherein the microporous polymer has a surface area ranging from about 5 m 2 g −1 to about 1000 m 2 g −1 .

8. The microporous polymer of claim 1 , or the salt thereof, wherein the microporous polymer has pore sizes ranging from about 0.4 nm to about 5 nm.

9. The microporous polymer of claim 1 , or the salt thereof, wherein the microporous polymer has a porosity ranging from about 5% to about 40%.

10. A method for preparing a microporous polymer according to claim 1 , the method comprising

forming a polymerization mixture comprising

(1) a plurality of A-A monomers, wherein each A-A monomer is independently a compound according to Formula (I), (II), (III), (IV), (V), (VI), (VII), or (VIII)

or Formula (Ia), (Ha), (IIIa), (IVa), (Va), (VIa), (VIIa), or (VIIIa)

(2) a plurality of B-B monomers, wherein each B-B monomer is independently a compound according to Formula (i), (ii), (iii), (iv), (v), or (vi):

wherein X is a halide, and

(3) a base, and

heating the polymerization mixture, thereby forming the microporous polymer.

11. The method of claim 10 , wherein the polymerization mixture further comprises solid grinding media, liquid grinding media, or a combination thereof.

12. The method of claim 10 , wherein at least one monomer segment B-B in the microporous polymer is a monomer segment according to Formula (a-i) or Formula (b-i):

and the method further comprises combining the microporous polymer with hydroxyl amine under conditions sufficient to form a modified microporous copolymer having at least one monomer segment B-B according to Formula (a-ii) or Formula (b-ii):

13. The method of claim 12 , further comprising:

combining the modified microporous copolymer with a base and an alkylating agent under conditions sufficient to form an alkylated microporous polymer having at least one monomer segment B-B according to Formula (a-iii), (b-iii), (a-iv), (b-iv), (a-v), (b-v), (a-vi), or (b-vi):

14. The method of claim 13 , wherein the alkylating agent is selected from the group consisting of dimethyl sulfate, diethyl sulfate, propane sultone, and butane sultone.

15. The method of claim 13 , wherein:

the alkylated microporous polymer comprises at least one monomer segment B-B according to Formula (a-v), (b-v), (a-vi), or (b-vi); and

the method further comprises combining the alkylated microporous polymer with a salt A + X − under conditions sufficient to form a cation-exchanged microporous polymer, wherein the cation A + is a metal cation or an organic cation, and the anion X − is an organic anion or an inorganic anion.

16. The method of claim 12 , further comprising combining the modified microporous copolymer with an acid and carbocation-generating compound to form an alkylated microporous polymer having at least one B-B segment according to Formula (a-vii), (b-vii), (a-viii), or (b-viii):

17. An electrochemical cell comprising:

an anode;

an anode electrolyte in contact with h anode;

a separator in contact with the anode electrolyte, wherein said separator comprises a membrane comprising one or more microporous polymers according to claim 1 , or salts thereof, wherein said membrane has a thickness ranging from 0.1-1000 micrometers;

a cathode;

a cathode electrolyte in contact with the separator; and

a cathode electrolyte in contact with the cathode.

18. The electrochemical cell of claim 17 , wherein at least one repeat unit of the membrane is crosslinked with a non-adjacent repeat unit by a crosslinker.

19. The electrochemical cell of claim 18 , wherein the crosslinker is selected from the group consisting of 2,6-bis(4-azidobenzylidene)cyclohexanone, oxygen, 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone, 2,6-bis(4-azidobenzylidene)-4-ethylcyclohexanone, 4-azidophenylsulfone, and combinations thereof.

20. The electrochemical cell of claim 17 , wherein the membrane is in contact with a support comprising a poly(arylether), a poly(arylether) copolymer, a poly(arylether sulfone) copolymer, polyethylene, a polyethylene copolymer, polypropylene, a polypropylene copolymer, polyacrylonitrile, a polyacrylonitrile copolymer, poly(vinylidene fluoride), poly(tetrafluoroethylene), poly(vinyl chloride), a poly(vinylchloride) copolymer, poly(hexafluoropropylene), a poly(hexafluoropropylene) copolymer, a polyaramide, a polyaramide copolymer, a porous metal, a porous alloyed metal, a porous metal oxide, or a combination thereof.

21. The microporous polymer of claim 1 , wherein

each R 11 is independently selected from the group consisting of —CH 2 NR 1 R 2 ;

each R 12 is —CN;

each R 1 and R 2 is independently (C 1-20 )alkyl; or

alternatively, each R 1 is optionally and independently taken together with R 2 , and the nitrogen atom to which both are attached, to form 3- to 8-membered heterocyclyl, each of which is optionally substituted with one or more Z 2 ;

each Z 2 is independently selected from the group consisting of halogen, —OH, —NO 2 , —CN, (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 ) cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, hetero(C 1-20 )alkyl, 3- to 8-membered heterocyclyl, 5- to 8-membered heteroaryl, (C 3-8 )cycloalkyl-(C 1-20 )alkyl, 3- to 8-membered heterocyclyl-(C 1-20 )alkyl, 5- to 8-membered heteroaryl-(C 1-20 )alkyl, halo(C 1-20 )alkyl, halo(C 1-20 )alkyloxy, —OR 6 , —SR 6 , —S(O)R 6 , —S(O) 2 R 6 , —SO 2 NR 6 R 7 , —NR 6 C(O)R 7 , —NRS(O) 2 R 7 , —NR 6 C(O)NR 7 R 8 , —NR 6 R 7 , —CO 2 R 6 , —C(O)NR 6 R 7 , and —C(O)R 6 ; and

each R 6 , R 7 , and R 8 is independently selected from the group consisting of (C 1-20 )alkyl, (C 2-20 )alkenyl, (C 2-20 )alkynyl, (C 6-12 )aryl, (C 3-8 )cycloalkyl, (C 6-12 )aryl(C 1-20 )alkyl, (C 3-8 )cycloalkyl(C 1-20 )alkyl, hetero(C 1-20 )alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C 1-20 )alkyl, 5- to 8-membered heteroaryl, 5- to 8-membered heteroaryl-(C 1-20 )alkyl; or

alternatively, R 6 and R 7 are taken together to form 4- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl; or

alternatively, R 7 and R 8 are taken together to form 4- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl.

22. The microporous polymer of claim 1 , having the structure of:

23. The microporous polymer of claim 1 , having the structure of:

24. The microporous polymer of claim 1 , having the structure of:

25. The microporous polymer of claim 1 , having the structure of:

26. The microporous polymer of claim 1 , having the structure of:

27. The microporous polymer of claim 1 , having the structure of:

28. The microporous polymer of claim 1 , having the structure of: