Functionalized ionic polymers and their uses

Abstract

The present disclosure relates to a composition comprising a first structure of formula, or a salt thereof: [Formula 1] TIFF2025534249000032.tif16159In formula, R 1 , R 2 , R 3 , Ar 1 and n are defined herein. Materials, devices, and methods for using such compositions are also described.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 376,405, filed September 20, 2022, which is incorporated by reference as if fully set forth herein. [Background technology]

[0002] One component of an electrochemical cell includes a polymer-based electrolyte membrane, the physical and chemical properties of which can affect the performance of such cells. Summary of the Invention

[0003] The present disclosure relates to compositions comprising a first polymer structure comprising an ionizable or ionic moiety. The compositions may comprise a polymer, copolymer, polymer blend, block copolymer, or other polymer-based form.

[0004] The present disclosure also relates to methods of making the compositions described herein, wherein a terminating agent (e.g., toluene) is added to a polymerization reaction mixture in such a way that any resulting exotherm is minimized or eliminated. This also provides a safe and efficient strategy for making polymers of the type described herein. In some embodiments, adding a terminating agent to a polymerization reaction generates an exotherm. For example, an exotherm is observed when the polymerization is terminated with methanol. In some embodiments, when the polymerization reaction is terminated in methanol, the reaction temperature can rise, for example, to about 40°C. In contrast, when the polymerization is terminated with toluene and then precipitated into methanol, the reaction temperature remains at room temperature (e.g., 25°C). One strategy for controlling the observed exotherm is to terminate over a long period of time.

[0005] Those skilled in the art will understand that the polydispersity index (PD)I describes the molecular weight distribution of a particular sample; thus, the closer the PDI is to unity (i.e., the closer the PDI is to 1.0), the more uniform the distribution. In some embodiments, when the polymerization is terminated with toluene, the polydispersity index (PDI) of the resulting polymer may be less than 2.7, less than 2.5, less than 2.6, less than 2.4, less than 2.3, less than 2.2, less than 2.1, or less than 2.0, as determined by gel permeation chromatography (GPC). In some embodiments, when the polymerization reaction is terminated using methanol, the PDI of the resulting polymer may be higher (e.g., up to 2.7 or 3.3) compared to the PDI of a polymer terminated with toluene. In some embodiments, when the polymerization reaction is terminated using methanol, the PDI of the resulting polymer may be comparable to the PDI of a toluene-terminated polymer. In some embodiments, the PDI of the polymers described by the present invention can be from 1 to 3, such as from 2 to 3, from 2.5 to 3, from 2.1 to 2.7, from 2.2 to 2.6, or from 2 to 2.5.

[0006] definition As used herein, the term "about" means + / - 10% of any stated value. As used herein, this term modifies any stated value, range of values, or one or more of the endpoints of a range.

[0007] As used herein, the terms "top," "bottom," "upper," "above," "below," "over," "above," and "below" are used to indicate relative relationships between structures. The use of these terms does not indicate or require that a particular structure must be located in a particular location within the device.

[0008] "Aliphatic" means a group containing at least 1 to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10"Aliphatic" refers to a hydrocarbon group having an alkyl group, including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), and cyclic versions thereof, including straight-chain and branched-chain arrangements, and all stereoisomers and positional isomers. Such aliphatic groups can be unsubstituted or substituted with one or more groups, such as the alkyl groups described herein.

[0009] The terms "acyl" or "alkanoyl," as used interchangeably herein, refer to a hydrogen attached to the parent molecular group through an alkyl group, as defined herein, or a carbonyl group, as defined herein. This group is exemplified by formyl, acetyl, propionyl, butanoyl, and the like. An alkanoyl group can be substituted or unsubstituted. For example, an alkanoyl group can be substituted with one or more substituents as described herein for alkyl. In some embodiments, an unsubstituted acyl group is C 2-7 It is an acyl group or an alkanoyl group. In certain embodiments, the alkanoyl group is -C(O)-Ak, where Ak is an alkyl group as defined herein.

[0010] "Alkoxy" refers to -OR, where R is an alkyl group optionally substituted as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy, e.g., trifluoromethoxy. An alkoxy group can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 Examples include alkoxy groups.

[0011] "Alkoxyalkyl" means an alkyl group, as defined herein, that is substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include those having 2 to 12 carbons (C 2-12 alkoxyalkyl), as well as alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms (e.g., C 1-6 Alkoxy-C 1-6 alkyl).

[0012] The terms "alkyl" and the prefix "alk" refer to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. An alkyl group can be cyclic (e.g., C 3-24 The alkyl group may be branched or unbranched. The alkyl group may be substituted or unsubstituted. For example, the alkyl group, in the case of an alkyl group of 1, 2, 3, or more than 2 carbons, may be substituted with four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., —O-Ak, where Ak is an optionally substituted C 1-6 alkyl); (2) C 1-6 Alkylsulfinyl (e.g., —S(O)—Ak, where Ak is an optionally substituted C 1-6 Alkyl; (3) C 1-6 Alkylsulfonyl (e.g., —SO—Ak, where Ak is an optionally substituted C 1-6 alkyl); (4) amino (e.g., -NR N1 R N2 , where R N1 and R N2 each is independently H or optionally substituted alkyl, or R N1 and R N2each taken together with the nitrogen atom to which it is attached forms a heterocyclyl group; (5) aryl; (6) arylalkoxy (e.g., -OL-Ar, where L is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl); (7) aryloyl (e.g., -C(O)-Ar, where Ar is an optionally substituted aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) carboxaldehyde (e.g., -C(O)H); (11) C 3-8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3-8 (12) halo (e.g., F, Cl, Br, or I); (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified); (14) heterocyclyloxy (e.g., -O-Het, where Het is a heterocyclyl as described herein); (15) heterocyclyloyl (e.g., -C(O)-Het, where Het is a heterocyclyl as described herein); (16) hydroxyl (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =0) or hydroxyimino (e.g., =N-OH); (20) C 3-8 Spirocyclyl (e.g., an alkylene or heteroalkylene diradical, both ends of which are attached to the same carbon atom of a parent group); (21) C 1-6 Thioalkoxy (e.g., -S-Ak, where Ak is an optionally substituted C 1-6 alkyl); (22) thiol (e.g., -SH); (23) -CO2R A , where RA is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 Aryl)C 1-6 alkyl (e.g., -L-Ar, where L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (24) -C(O)NR B RC , where R B and R C each of which is independently (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 Aryl)C 1-6 alkyl (e.g., -L-Ar, where L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (25) -SO2R D , where R D is (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) (C 4-18 Aryl)C 1-6 alkyl (e.g., -L-Ar, where L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (26) -SO 2 NR E R F , where R E and R F each of which is independently (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 (27) -NR G R H , where R G and R H are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds); (e) C 2-6 Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C 4-18 Aryl, (g) (C 4-18 Aryl)C 1-6alkyl (e.g., L-Ar, where L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (h) C 3-8 cycloalkyl, (i) (C 3-8 Cycloalkyl)C 1-6 Alkyl (e.g., -L-Cy, where L is a divalent form of an optionally substituted alkyl group and Cy is an optionally substituted cycloalkyl as described herein), where in one embodiment, the two groups are not attached to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 It is an alkyl group.

[0013] "Alkylene" refers to polyvalent (e.g., divalent, trivalent, tetravalent, etc.) forms of alkyl groups as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, an alkylene group is a C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24It is an alkylene group. The alkylene group can be branched or unbranched. The alkylene group can be saturated or unsaturated (e.g., having one or more double or triple bonds). The alkylene group can be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substituents described herein for alkyl. In one example, the substituted alkylene group can include an optionally substituted haloalkylene (e.g., an alkylene optionally substituted with one or more hydroxyl groups, as defined herein), an optionally substituted haloalkylene (e.g., an alkylene optionally substituted with one or more halo groups, as defined herein), and the like.

[0014] "Alkyleneoxy" means an alkylene group, as defined herein, attached to the parent molecular group through an oxygen atom.

[0015] What is "Amino" -NR N1 R N2 where R N1 and R N2 each is independently H, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, or R N1 and R N2 together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl group or heterocycle, as defined herein; or R N1 and R N2 taken together form an optionally substituted alkylene or heteroalkylene (eg, as described herein).

[0016] "Aminoalkyl" means an alkyl group, as defined herein, substituted with an amino group, as defined herein. Non-limiting aminoalkyl groups include -L-NR N1 R N2 where L is a polyvalent alkyl group as defined herein; R N1 and R N2each is independently H, optionally substituted alkyl, or optionally substituted aryl; or R N1 and R N2 taken together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0017] "Ammonium" refers to the protonated nitrogen atom N + Exemplary ammonium groups include groups containing -N + R N R N2 R N3 In the formula, R N1 , R N2 , and R N3 each is independently H, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl; or R N1 and R N2 are taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl group or heterocycle; R N1 and R N2 taken together form an optionally substituted alkylene or heteroalkylene (e.g., as described herein); or R N1 and R N2 and R N3 taken together with the nitrogen atom to which each is attached form a heterocycle, such as an optionally substituted heterocyclyl group or heterocyclic cation.

[0018] "Aromatic," unless otherwise specified, refers to a cyclic, conjugated group or portion thereof of 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl). That is, at least one ring, and optionally multiple fused rings, have a contiguous, delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Hückel's rule (4n + 2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. Such aromatics may be unsubstituted or substituted with one or more groups, such as those described herein for alkyl or aryl groups. Further substituents may include aliphatic, haloaliphatic, halo, nitrate, cyano, sulfonate, sulfonyl, or others.

[0019] "Aryl" refers to a group containing any carbon-based aromatic group, for example, but not limited to, phenylbenzylanthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthylphenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, as well as fused benzo-C 4-8 Cycloalkyl radicals (e.g., as defined herein) include, for example, indanyl, tetrahydronaphthyl, fluorenyl, and the like. The term aryl also includes "heteroaryl," which is defined as a group containing an aromatic group with at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl within the term aryl defines a group containing an aromatic group that does not contain a heteroatom. An aryl group can be substituted or unsubstituted. An aryl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., —C(O)—Ak, where Ak is an optionally substituted C 1-6alkyl); (2) C 1-6 Alkyl; (3) C 1-6 Alkoxy (e.g., —O-Ak, where Ak is an optionally substituted C 1-6 alkyl); (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LO-Ak, where L is a divalent form of an optionally substituted alkyl group and Ak is an optionally substituted C 1-6アルキル (5) C 1-6 Alkylsulfinyl (e.g., —S(O)—Ak, where Ak is an optionally substituted C 1-6 Alkyl; (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -LS(O)-Ak, where L is a divalent form of an optionally substituted alkyl group and Ak is an optionally substituted C 1-6 alkyl), (7) C 1-6 Alkylsulfonyl (e.g., —SO—Ak, where Ak is an optionally substituted C 1-6 alkyl);(8)C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-Ak, where L is a divalent form of an optionally substituted alkyl group and Ak is an optionally substituted C 1-6 (9) aryl; (10) amino (e.g., —NR N1 R N2 , where R N1 and R N2 each is independently H or optionally substituted alkyl, or R N1 and R N2 each taken together with the nitrogen atom to which it is attached forms a heterocyclyl group; (11) C 1-6 Aminoalkyl (e.g., an alkyl group as defined herein, which is a group consisting of one or more —NR N1 R N2(12) heteroaryl (e.g., a subset of heterocyclyl groups (e.g., 5-, 6-, or 7-membered rings containing 1, 2, 3, or 4 non-carbon heteroatoms, unless otherwise specified), which are aromatic); (13) (C 4-18 Aryl)C 1-6 Alkyl (e.g., L-Ar, where L is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl), (14) aryloyl (e.g., —C(O)—Ar, where Ar is an optionally substituted aryl); (15) azido (e.g., —N); (16) cyano (e.g., —CN); (17) C 1-6 (18) carboxyaldehyde (e.g., —C(O)H); (19) carboxyaldehyde-C 1-6 Alkyl (e.g., an alkyl group as defined herein substituted with one or more carboxaldehyde groups as described herein); (20) C 3-8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3-8 Hydrocarbon group); (21) (C 3-8 Cycloalkyl)C 1-6 (21) alkyl (e.g., an alkyl group as defined herein substituted with one or more cycloalkyl groups as described herein); (22) halo (e.g., F, Cl, Br, or I); (23) C 1-6 (24) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified); (25) heterocyclyloxy (e.g., —O-Het, where Het is heterocyclyl as described herein); (26) heterocyclyloyl (e.g., —C(O)-Het, where Het is heterocyclyl as described herein); (27) hydroxyl (e.g., —OH); (28) C 1-6Hydroxyalkyl (e.g., an alkyl group as defined herein substituted with one or more hydroxyl groups as described herein); (29) nitro (e.g., —NO2); (30) C 1-6 Nitroalkyl (e.g., alkyl groups as defined herein, substituted with one or more nitro groups as described herein); (31) N-protected amino; (32) N-protected amino-C 1-6 Alkyl (e.g., alkyl groups as defined herein, substituted with one or more N-protected amino groups); (33) oxo (e.g., ═O) or hydroxyimino (e.g., ═N—OH); (34) C 1-6 Thioalkoxy (e.g., -S-Ak, where Ak is an optionally substituted C 1-6 Alkyl); (35) Thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LS-Ak, where L is a divalent form of optionally substituted alkyl and Ak is an optionally substituted C 1-6 alkyl), (36)-(CH2) r CO2R A , where r is an integer from 0 to 4, and R A is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C4 is aryl) C 1-6 Alkyl (e.g., -L-Ar, where L is a divalent form of optionally substituted alkyl and Ar is an optionally substituted aryl); (37) -(CH)CONR B R C In the formula, r is an integer from 0 to 4, and each R B and R C are independently (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 Aryl)C 1-6 alkyl (e.g., -L-Ar, where L is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl); (38) -(CH) r SO2R D, where r is an integer from 0 to 4, and R D is (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) (C 4-18 Aryl)C 1-6 Alkyl (e.g., -L-Ar, where L is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl); (39) -(CH) r SO2NR E R F , where r is an integer from 0 to 4, and R E and R F each of which is independently (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 Aryl)C 1-6 alkyl (e.g., -L-Ar, where L is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl); (40) -(CH) r NR G R H , where r is an integer from 0 to 4, where R G and R H are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds); (e) C 2-6 Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C 4-18 Aryl, (g) (C 4-18 Aryl)C 1-6 alkyl (e.g., -L-Ar, where L is a divalent form of optionally substituted alkyl and Ar is an optionally substituted aryl); (h) C 3-8 cycloalkyl, and (i) (C 3-8 Cycloalkyl)C 1-6Alkyl (e.g., -L-Cy, as described herein, where L is a divalent form of an optionally substituted alkyl and Cy is an optionally substituted cycloalkyl, and in one embodiment, the two groups are not attached to the nitrogen atom via a carbonyl or sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., an alkyl group in which each hydrogen atom is replaced with a fluorine atom); (43) perfluoroalkoxy (e.g., -ORF, where RF is an alkyl group in which each hydrogen atom is replaced with a fluorine atom); (44) aryloxy (e.g., -OAr, where Ar is an optionally substituted aryl; (45) cycloalkoxy (e.g., -O-Cy, where Cy is an optionally substituted cycloalkyl as described herein); (46) cycloalkylaralkoxy (e.g., -OL-Cy, where L is a divalent form of an optionally substituted alkyl group and Cy is an optionally substituted cycloalkyl as described herein), and (47) arylalkoxy (e.g., -OL-Ar, where L is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); in certain embodiments, an unsubstituted aryl group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 It is an aryl group.

[0020] "Arylalkoxy" means an arylalkylene group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -O-Ak-Ar, where Ak is an optionally substituted alkylene, as defined herein, and Ar is an optionally substituted aryl, as defined herein.

[0021] "(Aryl)(alkyl)ene" refers to a divalent form containing an arylene group, as described herein, attached to an alkylene or heteroalkylene group, as described herein. In some embodiments, the (aryl)(alkyl)ene group is -L-Ar- or -L-Ar-L- or -Ar-L-, where Ar is an arylene group and each L is independently an optionally substituted alkylene group or an optionally substituted heteroalkylene group.

[0022] "Arylalkylene" means an aryl group, as defined herein, attached to the parent molecular group via an alkylene group, as defined herein. In some embodiments, the arylalkylene group is -Ak-Ar, where Ak is an optionally substituted alkylene, as defined herein, and Ar is an optionally substituted aryl, as defined herein. The arylalkylene group can be substituted or unsubstituted. For example, the arylalkylene group can be substituted with one or more substituents described herein for aryl and / or alkyl. Exemplary unsubstituted arylalkylene groups are alkylene groups having 7 to 16 carbons (C 7-16 aryl alkylene), and also aryl groups having 4 to 18 carbons and alkylene groups having 1 to 6 carbons (i.e., (C 4-18 Aryl)C 1-6 alkylene).

[0023] "Arylene" refers to polyvalent (e.g., divalent, trivalent, tetravalent, etc.) forms of the aryl groups described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10The arylene group is an arylene group of the formula: The arylene group can be branched or unbranched. The arylene group can be substituted or unsubstituted. For example, the arylene group can be substituted with one or more of the substituents described herein for aryl.

[0024] "Aryleneoxy" means an arylene group, as defined herein, attached to the parent molecular group through an oxygen atom.

[0025] "Aryloxy" means an aryl group, as defined herein, attached to the parent molecular group through an oxygen atom.

[0026] "Aryloyl" refers to an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is C 7-11 Aryloyl or C-substituted 5-19 In certain embodiments, an aryloyl group is —C(O)—Ar, where Ar is an aryl group, as defined herein.

[0027] "Boranyl" refers to the group -BR2, where each R may independently be H, halo, or optionally substituted alkyl.

[0028] "Borono" refers to the -BOH2 group.

[0029] "Carboxyl" means a -CO2H group.

[0030] "Carboxylate anion" means a -CO2- group.

[0031] "Covalent bond" means a covalent interaction between two components. Non-limiting covalent bonds include single, double, triple, or spirocyclic bonds, in which at least two molecular groups are attached to the same carbon atom.

[0032] "Cyano" refers to the radical -CN.

[0033] The term "cyclic group" is used herein to refer to an aryl group, a non-aryl group (e.g., a cycloalkyl group or a heterocycloalkyl group), or both. A cyclic group has one or more ring systems that may be substituted or unsubstituted. A cyclic group can contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups.

[0034] "Cycloalkyl" means, unless otherwise specified, a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical of 3 to 10 carbons (e.g., C 3-8 or C 3-10 ) and are exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, and the like. The term cycloalkyl also includes "cycloalkenyl," which is defined as a non-aromatic carbon-based ring composed of 3 to 10 carbon atoms and containing at least one double bond, i.e., C=C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like. Cycloalkyl groups can be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups, including those described herein for alkyl.

[0035] "Halo" means F, Cl, Br, or I.

[0036] "Haloalkyl" means an alkyl group, as defined herein, substituted with one or more halo.

[0037] "Haloalkylene" means an alkylene group, as defined herein, substituted with one or more halo.

[0038] "Heteroaliphatic" means an aliphatic group, as defined herein, containing at least 1 heteroatom to 20 heteroatoms, e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms, which may be selected from oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof, within the group.

[0039] "Heteroalkyl" means an alkyl group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo).

[0040] "Heteroalkylene" means an alkylene group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). Heteroalkylene groups can be saturated or unsaturated (e.g., having one or more double or triple bonds). Heteroalkylene groups can be substituted or unsubstituted. For example, heteroalkylene groups can be substituted with one or more substituents described herein for alkyl.

[0041] "Heteroaryl" refers to a subset of heterocyclyl groups, as defined herein, that are aromatic, i.e., they contain 4n+2 pi-electrons in a monocyclic or polycyclic ring system.

[0042] The term "heterocycloalkyl" refers to a type of cycloalkyl group, as defined above, where at least one of the carbon atoms and the hydrogen atoms attached thereto, if present, is replaced by O, S, N, or NH. Heterocycloalkyl and heterocycloalkenyl groups can be substituted or unsubstituted. Cycloalkenyl and heterocycloalkenyl groups can be substituted with one or more of the following groups, including, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, sulfonic acid, sulfinic acid, fluoroacid, phosphonic acid, ester, ether, halide, hydroxy, ketone, nitro, cyano, azide, silyl, sulfonyl, sulfinyl, or thiol, as described herein.

[0043] "Heterocyclic" means a compound having one or more heterocyclyl moieties. Non-limiting heterocyclics include optionally substituted imidazole, optionally substituted triazole, optionally substituted tetrazole, optionally substituted pyrazole, optionally substituted imidazoline, optionally substituted pyrazoline, optionally substituted imidazolidine, optionally substituted pyrazolidine, optionally substituted pyrrole, optionally substituted pyrroline, optionally substituted pyrrolidine, optionally substituted tetrahydrofuran, optionally substituted furan, optionally substituted thiophene oxazole, optionally substituted isoxazole, optionally substituted isothiazole, optionally substituted thiazole, optionally substituted oxathiolane, optionally substituted oxadiazole, optionally substituted thiadiazole, optionally substituted sulfolane, optionally substituted succinimide, optionally substituted thiazolidinedione, optionally substituted oxazolidone, optionally substituted hydantoin, optionally substituted pyridine, optionally substituted piperidine, optionally substituted pyridazine, optionally substituted piperazine, optionally substituted pyrimidine, optionally substituted pyrazine, optionally substituted triazine, optionally substituted pyran, optionally substituted pyrylium, optionally substituted tetrahydropyran, optionally substituted dioxin, optionally substituted dioxanedithiane, optionally substituted trithiane, optionally substituted thiopyran, optionally substituted thiane, optionally substituted oxazine, optionally substituted morpholine, optionally substituted thiazine, optionally substituted thiomorpholine, optionally substituted cytosine, optionally substituted thymine, optionally substituted uracil, optionally substituted thiomorpholine dioxide, optionally substituted indene, optionally substituted indoline, optionally substituted indole, optionally substituted isoindole, optionally substituted indolizine, optionally substituted indazole, optionally substituted benzimidazole, optionally substituted azaindole,optionally substituted azaindazole, optionally substituted pyrazolopyrimidine, optionally substituted purine, optionally substituted benzofuran, optionally substituted isobenzofuran, optionally substituted benzothiophene, optionally substituted benzisoxazole, optionally substituted anthranil, optionally substituted benzisothiazole, optionally substituted benzoxazole, optionally substituted benzthiazole, optionally substituted benzthiadiazole, optionally substituted adenine, optionally substituted guanine, optionally substituted tetrahydroquinoline, optionally substituted dihydroquinoline, optionally substituted dihydroisoquinoline, optionally substituted quinoline, optionally substituted isoquinoline, optionally substituted quinolizine, optionally substituted quinoxaline, optionally substituted phthalazine, optionally substituted quinazoline, optionally substituted cinnoline, optionally substituted naphthyridine, optionally substituted pyridopyrimidine, optionally substituted optionally substituted pyridopyrazine, optionally substituted pteridine, optionally substituted chromene, optionally substituted isochromene, optionally substituted chromenone, optionally substituted benzoxazine, optionally substituted quinolinone, optionally substituted isoquinolinone, optionally substituted carbazole, optionally substituted dibenzofuran, optionally substituted acridine, optionally substituted phenazine, optionally substituted phenoxazine, optionally substituted phenothiazine, optionally substituted phenoxathiin, optionally substituted quinuclidine, optionally substituted azaadamantane, optionally substituted dihydroazepine, optionally substituted azepine, optionally substituted diazepine, optionally substituted oxepane, optionally substituted thiepine, optionally substituted thiazepine, optionally substituted azocane, optionally substituted azocine, optionally substituted thiocane, optionally substituted azonane, optionally substituted azecine, and the like. Optional substituents include those described herein for aryl. Heterocycles include:Also included are any of these cations and / or salts (e.g., any of those described herein, such as optionally substituted piperidinium, optionally substituted pyrrolidinium, optionally substituted pyrazolium, optionally substituted imidazolium, optionally substituted pyridinium, optionally substituted quinolinium, optionally substituted isoquinolinium, optionally substituted acridinium, optionally substituted phenanthridinium, optionally substituted pyridazinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted phenazinium, or optionally substituted morpholinium).

[0044] "Heterocyclyl," unless otherwise specified, means a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., a 5-, 6-, or 7-membered ring) containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). 3-membered rings have 0 to 1 double bonds, 4- and 5-membered rings have 0 to 2 double bonds, and 6- and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups, wherein any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocyclic groups include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaidazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxolyl, benzodithiepinyl, and benzimidazolyl. benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocin,Benzoxazepinyl, benzoxazinyl, benzoxazosinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., 3-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytodinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridineethionyl, diaziridinonyl, diaziridinyl , diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroipyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, Dioxanyl, dioxazinyl, dioxiindolyldioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolyl nyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthyridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl,Naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanoyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridyl nyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyrronyl, pyrrolidinyl, pyrrolidinyl, pyrrolidinyl Lidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydropyronyl, hydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thiethyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl,Examples of heterocyclyl groups include thiadiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, urisyl, uridinyl, xanthenyl, xanthinyl, xantthionyl, and the like, as well as variations thereof (e.g., one or more oxo and / or amino) and salts thereof. Heterocyclyl groups can be substituted or unsubstituted. For example, heterocyclyl groups can be substituted with one or more of the substituents described herein for aryl.

[0045] "Heterocyclyldiyl" refers to a divalent form of a heterocyclyl group described herein. In one example, a heterocyclyldiyl is formed by removing a hydrogen from a heterocyclyl group. Exemplary heterocyclyldiyl groups include piperzylidene, quinolinediyl, and the like. A heterocyclyldiyl group can be substituted or unsubstituted. For example, a heterocyclyldiyl group can be substituted with one or more substituents as described herein on the heterocyclyl group.

[0046] "Hydroxyl" refers to the group --OH.

[0047] "Hydroxyalkyl" means an alkyl group, as defined herein, substituted with one or more hydroxyl groups.

[0048] "Hydroxyalkylene" means an alkylene group, as defined herein, substituted with one or more hydroxyls.

[0049] "Nitro" refers to the -NO2 group.

[0050] "Phosphate" refers to a group derived from phosphoric acid. An example of a phosphate is -OP(=O)(OR P1 )(OR P2) or -O-[P(=O)(OR P1 )-O] P3 -R P2 groups, wherein R P1 and R P2 each is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted aryl, or optionally substituted arylalkylene, where P3 is an integer from 1 to 5. Still other examples of phosphates can include derivatives of phosphoric acid, such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, trimetaphosphoric acid, and / or phosphoric anhydride, or combinations thereof.

[0051] "Phosphono" or "phosphonic acid" refers to the group -P(O)(OH).

[0052] "Spirocyclyl" refers to an alkylene diradical, both ends of which are bonded to the same carbon atom of a parent group to form a spirocyclyl group, and a heteroalkylene diradical, both ends of which are bonded to the same atom. Non-limiting alkylene and heteroalkylene groups for use within a spirocyclyl group include C 12 , C 2-11 , C 2-10 , C 2-9 , C 2-8 , C 2-7 , C 2-6 , C 2-4 , or C 2-3 Alkylene groups, as well as C groups with one or more heteroatoms 1-12 , C 1-11 , C 1-10 , C 1-9 , C 1-8 , C 1-7 , C 1-6 , C 1-5 , C 1-4 , C 1-3 , or C 1-2 Examples include heteroalkylene groups.

[0053] "Sulfate" refers to a group derived from sulfuric acid. An example of a sulfate is -OS(=O)2(OR S1 ) groups, in which R S1 is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted arylalkylene.

[0054] "Sulfo" or "sulfonic acid" refers to the group -S(O)2OH.

[0055] "Sulfonyl" refers to the group -S(O2- or -S(O)2R, where R can be H, optionally substituted alkyl, or optionally substituted aryl. Non-limiting sulfonyl groups include trifluoromethylsulfonyl groups (-SO2-CF3 or Tf).

[0056] "Thiocyanato" refers to the group -SCN.

[0057] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein), including cationic or anionic compounds to form electrically neutral compounds or structures. Salts are well known in the art. For example, non-toxic salts are described in Berge SM et al., "Pharmaceutical Salts," J. Pharm. Sci. 1977 January; 66(1):1-19; and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth). Salts can be prepared during the final isolation and purification of the compounds of the invention, or in situ by reacting the free base with a suitable organic acid (to produce an anionic salt) or the acid group with a suitable metal or organic base (to produce a cationic salt).Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphor, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate glutamate glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydrogen iodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, Examples of suitable salts include laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphonate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, basic acetate, succinate, sulfate, tannate, tartrate, theophyllate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, and valerate. Representative cationic salts include metal salts, e.g., alkali or alkaline earth salts, such as barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron, and zinc; non-toxic ammonium, quaternary ammonium, and amine cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc. Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Still other salts include ammonium sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, Optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted prinium). Still other salts include halides (for example, F). - , Cl - , Br - , or I - ), hydroxides (e.g., OH -), borates (e.g., tetrafluoroborates (BF4 - ), carbonates (e.g., CO3 2- or HCO3 - ), or sulfates (e.g., SO4 2- ) and other anions.

[0058] "Leaving group" means an atom (or group of atoms) with electron-withdrawing ability that can take bonding electrons with it and be replaced as a stable species, or an atom (or group of atoms) that can be displaced by a substitution reaction. Examples of suitable leaving groups include H, halides, and sulfonates, including, but not limited to, triflate (-OTf), mesylate (-OM), tosylate (-OT), brosylate (-OB), acetate, Cl, Br, and I.

[0059] "Adhering," "attachment," or related word forms refer to either covalent or non-covalent interactions between two components. Non-covalent interactions include, but are not limited to, hydrogen bonding, ionic interactions, halogen bonding, electrostatic interactions, π-bonding interactions, hydrophobic interactions, inclusion complexes, clathration, van der Waals interactions, and combinations thereof. DETAILED DESCRIPTION OF THE INVENTION

[0060] Reference will now be made in detail to particular embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0061] The present disclosure relates to compositions comprising first (polymeric) structures, at least one of which comprises an ionizable or ionic moiety. Charge conduction through the composition can be controlled by the type and amount of charge provided by the ionizable / ionic moiety (e.g., anionic and / or cationic charge on the first structure). The properties of the composition can be tailored, inter alia, based on the groups present on the first structure. The first structure can comprise polymeric units. The polymeric units can be homopolymers, copolymers, block copolymers, or other useful combinations of repeating monomeric units.

[0062] The composition may include a plurality of first structures, each of which is identical (e.g., each Ar 1 , R 1 , R 2 , and rings a-c, if present, are identical in each monomer unit). In another example, the composition may include a plurality of first structures, at least two of the first structures being different (e.g., Ar 1 , R 1 , R 2 and at least one of rings a-c, if present, is different between the two monomer units.) Thus, the composition can be a homopolymer, copolymer, block copolymer, or other useful combination of repeating monomer units.

[0063] Thus, the composition comprises a plurality of first structures of formula (I): [ka] or a salt thereof (wherein R 1 and R 2 each is independently an electron-withdrawing moiety, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene; R 1and R 2 at least one of R contains an electron-withdrawing moiety; 1 and R 2 at least one of comprises an ionizable or ionic moiety; or R 1 and R 2 together with the carbon atoms to which they are attached form a cyclic group optionally substituted with ionizable or ionic moieties; R 3 is an optionally substituted aryl group; Ar 1 is an optionally substituted aromatic group or an optionally substituted arylene; where n is an integer greater than or equal to 1.

[0064] Each of the first structures can be the same, or at least two of the first structures can be different (e.g., the composition comprises a copolymer).

[0065] The compositions herein may contain any useful combination of repeating monomer units. In one example, the compositions may contain -AAA- or -[A]-, where A represents a monomer unit and [A] represents a block containing only A monomer units. A may be selected from those provided as the first or second structure.

[0066] In another example, the composition comprises -[A]-[A-combination-B]-[B]-, where A and B represent different monomer units. [A] and [B] represent polymer blocks containing only A monomer units and only B monomer units, respectively. An [A-combination-B] block refers to a block containing some combination of A and B monomer units. Each of A and B can be selected from those provided as the first and / or second structures. In some embodiments, A and B are both first structures.

[0067] In another example, the composition includes at least one alternating / periodic block, where the different monomers have an ordered sequence, for example, -[ABAB-...]-, -[ABCABC-...]-, -[AABBAABB-...]-, -[AABAAB-...]-, -[ABABBAAAABBB-...]-, etc. A, B, and C represent different monomer units. Examples in brackets represent polymer blocks, where the monomer sequence is repeated throughout the block.

[0068] In yet another example, the composition includes a specific unit covalently bonded between at least one pair of blocks, e.g., [A]-D-[B] or [A]-D-[B]-[C], where D can be a monomer unit or a linking moiety (e.g., any of those described herein). Multiple Ds can be present, such as [A]-DD-[B] or [A]-DDD-[B], and each C can be the same or different. [A] represents a block containing only A monomer units; [B] represents a block containing only B monomer units; [C] represents a block containing only C monomer units; and D can represent an individual monomer unit (e.g., any of those described herein) or a linking moiety (e.g., any of those described herein).

[0069] Other alternative configurations are also encompassed by the compositions herein, such as branched configurations, diblock copolymers, triblock copolymers, random or statistical copolymers, stereoblock copolymers, gradient copolymers, graft copolymers, and combinations of any of the blocks or regions described herein.

[0070] The compositions herein can be characterized by a first molecular weight (MW) of a first structure (e.g., as a polymer unit) or the total MW of the composition. For example, the first MW or total MW is a weight average molecular weight (MW) of at least 10,000 g / mol, at least 20,000 g / mol, about at least 50,000 g / mol, or about 5,000 to 2,500,000 g / mol, e.g., 10,000 to 2,500,000 g / mol, 50,000 to 2,500,000 g / mol, 10,000 to 250,000 g / mol, 20,000 to 250,000 g / mol, or 20,000 to 200,000 g / mol. The first MW or total MW is a number average molecular weight (M) of at least 20,000 g / mol or at least 40,000 g / mol; or from about 2,000 to 2,500,000 g / mol, e.g., from 5,000 to 750,000 g / mol or from 10,000 to 400,000 g / mol. n ) can be.

[0071] The composition can include any useful number n of monomer units, e.g., 1 or more, 20 or more, 50 or more, 100 or more; 1 to 1,000,000, 10 to 500, 100 to 1,000, 100 to 300, 10 to 1,000,000, 100 to 1,000,000, 200 to 1,000,000, 500 to 1,000,000, or 1,000 to 1,000,000.

[0072] The compositions herein can be characterized by their polydispersity index (PDI). For example, the PDI of the polymer units can be less than 2.7, less than 2.5, less than 2.6, less than 2.4, less than 2.3, less than 2.2, less than 2.1, or less than 2.0, as determined by gel permeation chromatography (GPC). In other examples, the PDI of the polymer units can be 1 to 3, e.g., 2 to 3, 2.5 to 3, 2.1 to 2.7, 2.2 to 2.6, or 2 to 2.5.

[0073] First structure Within the present compositions, the first structure may comprise a polymer unit, which in turn may comprise one or more ionizable or ionic moieties. In a non-limiting example, the polymer unit may have an arylene-containing backbone, which provides an organic scaffold to which the ionizable / ionic moieties may be added.

[0074] The arylene-containing backbone may also provide an aromatic group that facilitates the addition of a reactive carbocation (e.g., by reacting with a Friedel-Crafts alkylation reagent). In this manner, monomer units having aromatic groups can be reacted together to form polymer units. Such addition / polymerization reactions can be facilitated in any useful manner, for example, by including an electron-withdrawing group adjacent to the carbocation. Thus, in some non-limiting examples, the first structure may include both an optionally substituted aromatic group and an electron-withdrawing group.

[0075] The reactive carbocation can also provide a functional group that can be further modified. For example, the reactive carbocation can be attached to a L-A-R group, where L A is a linking moiety (e.g., any of those described herein) and RG is a reactive group (e.g., halo). A After adding the -RG group to the polymer unit, the RG group can be reacted with an ionizable reagent (e.g., an amine, NR N1 R N2 R 3 etc.) to form ionic moieties (e.g., ammonium, -N + R N1 R N2 R N3 etc.) can be provided.

[0076] Thus, the first structure can include a polymer unit (e.g., any of those described herein) having an ionizable / ionic moiety and an electron-withdrawing group. In some cases, the polymer unit is formed by using one or more monomer units. Non-limiting monomer units include one or more of the following: [ka] or a salt thereof, wherein R 1 and R 2 each is independently an electron-withdrawing moiety, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene; R 1 and R 2 at least one of R contains an electron-withdrawing moiety; 1 and R 2 at least one of comprises an ionizable or ionic moiety; or R 1 and R 2 together with the carbon atoms to which they are attached form a cyclic group optionally substituted with ionizable or ionic moieties; Ar 1 is an optionally substituted aromatic group or an optionally substituted arylene; where n is an integer greater than or equal to 1.

[0077] Ar 1 Non-limiting examples include, for example, phenylene (e.g., 1,4-phenylene, 1,3-phenylene, etc.), biphenylene (e.g., 4,4'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene, etc.), terphenylene (e.g., 4,4'-terphenylene), triphenylene, diphenyl ether, anthracene (e.g., 9,10-anthracene), naphthalene (e.g., 1,5-naphthalene, 1,4-naphthalene, 2,6-naphthalene, 2,7-naphthalene, etc.), tetrafluorophenylene (e.g., 1,4-tetrafluorophenylene, 1,3-tetrafluorophenylene), etc., as well as others described herein.

[0078] Thus, for example, Ar 1 teeth, [ka] wherein: R 4 and R 5 each can independently be H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, or R 4 and R 5 together with the carbon atoms to which they are attached form an optionally substituted cyclic group; Each of ring a, ring b, and / or ring c can be optionally substituted; and One or more of rings a-c optionally includes an ionizable or ionic moiety.

[0079] Ar 1 For example, [ka] for example: [ka] is.

[0080] Thus, the monomer units may include one or more of the following: [ka] (and combinations thereof); whereby the first structure of formula (I) is, respectively: [ka]

[0081] Ring a, Ring B, Ring C, R 1, and R 2 Further substitutions of may include one or more optionally substituted arylene, as well as any of the alkyl or aryl groups described herein.

[0082] Ring a, ring b, and / or ring c contain an ionizable or ionic moiety. 2 comprises an ionizable or ionic moiety. In certain embodiments, the ionic moiety is -L A -X A Contains or -L A -X A where L A is a linking moiety (e.g., an optionally substituted aliphatic, alkylene, heteroaliphatic, heteroalkylene, aromatic, or arylene); X A is an acidic moiety, a basic moiety, a multiionic moiety, a cationic moiety, or an anionic moiety. A Non-limiting examples of include amino, ammonium cation, heterocyclic cation, piperidinium cation, azepanium cation, phosphonium cation, phosphazenium cation, or others herein.

[0083] In other embodiments, R 1 includes electron-withdrawing moieties. Non-limiting electron-withdrawing moieties include optionally substituted haloalkyl (e.g., C 1-6 Haloalkyl (e.g., halomethyl, perhalomethyl, haloethyl, perhaloethyl, etc.), cyano (CN), phosphate (e.g., —O(P═O)(OR P1 )(OR P2 ) or -O-[P(=O)(OR P1 )-O]P3-R P2 ), sulfate (e.g., —OS(═O)2(ORS1)), sulfonate (—SO3H), sulfonyl (e.g., —SO2—CF3), difluoroboranyl (—BF2), borono (—B(OH)2), thiocyanato (—SCN), or piperidinium. In further embodiments, R 1contains an electron-withdrawing moiety, and R 2 comprises an ionizable / ionic moiety. Still other non-limiting phosphate groups can include derivatives of phosphoric acid, such as orthophosphate, pyrophosphate, tripolyphosphate, tetrapolyphosphate, trimetaphosphate, and / or phosphoric anhydride, or combinations thereof.

[0084] Non-limiting haloalkyl groups include fluoroalkyl (e.g., —C x F y H z ), perfluoroalkyl (e.g., -C x F y ), chloroalkyl (e.g., -C x Cl y Hz), perchloroalkyl (e.g., -C x Cl y ), bromoalkyl (e.g., -C x Br y Hz), perbromoalkyl (e.g., -C x Br y ), iodoalkyl (e.g., -C x I y Hz), or periodoalkyl (e.g., -C x I y In some embodiments, x is 1 to 6, y is 1 to 13, and z is 0 to 12. In particular embodiments, z=2x+1-y. In other embodiments, x is 1 to 6, y is 3 to 13, and z is 0 (e.g., y=2x+1).

[0085] In any of the aforementioned non-limiting polymer units, R 2 , R 4 or R 5 is the formula -L A -X A or -L A -(X A wherein each L A is independently a linking moiety and each X A or X A ' is independently an acidic or basic moiety.

[0086] The polymer units can include one or more substitutions on the cyclic portion (e.g., provided by aromatic or arylene groups) or the linear portion (e.g., provided by aliphatic or alkylene groups) of the unit. Non-limiting substituents include lower unsubstituted alkyl (e.g., C 1-6 alkyl), low-substituted alkyl (e.g., optionally substituted C 1-6 alkyl), lower haloalkyl (e.g., C 1-6 haloalkyl), halo (e.g., F, Cl, Br, or I), unsubstituted aryl (e.g., phenyl), halo-substituted aryl (e.g., 4-fluoro-phenyl), substituted aryl (e.g., substituted phenyl), and others.

[0087] As described herein, R 1 and R 2 and R 4 and R 5 can form a cyclic group together with the carbon atom to which they are attached, which can be optionally substituted. For example, R 1 and R 2 and R can be taken together to form an optionally substituted spirocyclyl group, as defined herein. The spirocyclyl group can be independently substituted with one or more ionizable or ionic moieties (e.g., any of those described herein). 1 and R 2 and R 4 and R 5 Examples of compounds that form a spirocyclic group include: [ka] or a salt thereof. 1’ and R 2 and R 4’ and R 5’taken together form an optionally substituted alkylene group or an optionally substituted heteroalkylene group, which can be independently substituted with one or more ionizable or ionic moieties.

[0088] Further polymer units The compositions and first structure(s) described herein may comprise two or more polymer units, which are attached to each other directly or indirectly (e.g., via a linking moiety). See, for example, U.S. Patent Application Publication No. 2022 / 0119641, which is incorporated by reference as if fully set forth herein (e.g., the "second structure" described therein). The polymer units may be homopolymers, copolymers, block copolymers, polymer blends, or other useful combinations of repeating monomer units. The following provides additional usable monomer units and polymer units.

[0089] The monomer unit may include an optionally substituted aliphatic group, an optionally substituted aromatic group, and a combination thereof. Non-limiting examples of the monomer unit include an optionally substituted arylene, an optionally substituted aryleneoxy, an optionally substituted alkylene, or a combination thereof, such as an optionally substituted (aryl)(alkyl)ene (e.g., -Ak-Ar- or -Ak-Ar-Ak- or -Ar-Ak-, where Ar is an optionally substituted arylene and Ak is an optionally substituted alkylene).

[0090] Further, other monomer units may include: [ka] wherein Ar is an optionally substituted arylene or an optionally substituted aromatic compound; Ak is an optionally substituted alkylene or an optionally substituted haloalkylene, an optionally substituted heteroalkylene, an optionally substituted aliphatic, or an optionally substituted heteroaliphatic; L is a linking moiety (e.g., any moiety described herein) or -C(R 1 )(R 2 )-. One or more of the monomer units can be optionally substituted with one or more ionizable or ionic moieties (e.g., as described herein). In certain embodiments, at least one of the monomer units is substituted with one or more ionizable or ionic moieties.

[0091] One or more monomer units can be combined to form a polymer unit. Non-limiting polymer units include any of the following: [ka] wherein Ar is an optionally substituted arylene or an optionally substituted aromatic compound, Ak is an optionally substituted alkylene or an optionally substituted aliphatic, L is a linking moiety (e.g., any moiety described herein), each n is independently an integer greater than or equal to 1, and each m is independently an integer greater than or equal to 0 or 1. Any number and type of monomer units can be combined to form a polymer unit.

[0092] In certain embodiments, the polymer unit comprises multiple arylene groups, for example, a polymer unit having this structure: [ka] wherein n may be greater than 1 and / or Ar may contain two or more aromatic or arylene groups. The presence of such aromatic groups may be used to build linear chains within the composition.

[0093] In other embodiments, L is optionally substituted C 1-6 Aliphatic, optionally substituted C 1-6 Alkylene, optionally substituted C 1-6 The use of short linkers may provide for more extensive polymer networks because they minimize self-cyclization reactions.

[0094] The polymer units can include one or more substitutions on the cyclic portion (e.g., provided by aromatic or arylene groups) or the linear portion (e.g., provided by aliphatic or alkylene groups) of the unit. Non-limiting substituents include lower unsubstituted alkyl (e.g., C 1-6 alkyl), low-substituted alkyl (e.g., optionally substituted C 1-6 alkyl), lower haloalkyl (e.g., C 1-6 haloalkyl), halo (e.g., F, Cl, Br, or I), unsubstituted aryl (e.g., phenyl), halo-substituted aryl (e.g., 4-fluoro-phenyl), substituted aryl (e.g., substituted phenyl), and others.

[0095] In some embodiments of the polymer unit, L is a covalent bond, —O—, —NR N1 -, -C(O)-, -SO2-, optionally substituted alkylene (e.g., -CH2- or -C(CH3)2-), optionally substituted alkyleneoxy, optionally substituted haloalkylene (e.g., -CF2- or -C(CF3)2-), optionally substituted heteroalkylene, optionally substituted arylene, optionally substituted aryleneoxy, optionally substituted heterocyclyldiyl, -SO2-NRN1-Ak-, -(O-Ak) L1 -SO2-NRN1-Ak-, -Ak-, -Ak-(O-Ak) L1 -, -(O-Ak) L1 -, -(Ak-O) L1-, -C(O)O-Ak-, -Ar-, or -Ar-O-, and combinations thereof. In certain embodiments, Ak is optionally substituted alkylene or optionally substituted haloalkylene; R N1 is H or optionally substituted alkyl or optionally substituted aryl; Ar is optionally substituted arylene; and L1 is an integer from 1 to 3.

[0096] In some instances, the polymer subunits may lack ionic moieties. Alternatively, the polymer subunits may include ionic moieties on the Ar group, the L group, both the Ar and L groups, or incorporated as part of the L group. Non-limiting examples of ionizable and ionic moieties include cationic groups, anionic groups, and multi-ionic groups described herein.

[0097] Further polymer units include poly(benzimidazole) (PBI), polyphenylene (PP), polyimide (PI), poly(ethyleneimine) (PEI), sulfonated polyimide (SPI), polysulfone (PSF), sulfonated polysulfone (SPSF), poly(ether ether ketone) (PEEK), PEEK containing cardo groups (PEEK-WC), polyethersulfone (PES), sulfonated polyethersulfone (SPES), sulfonated poly(ether ether ketone) (SPEEK), SPEEK with cardo groups (SPEEK-WC), poly(p-phenylene oxide) (PPO), sulfonated polyphenylene oxide (SPPO), ethylene tetrafluoroethylene (ETFE), polytetrafluoroethylene (PTFE), and polytetrafluoroethylene (PTFE). tetrafluoroethylene (PTFE), poly(epichlorohydrin) (PECH), poly(styrene) (PS), sulfonated poly(styrene) (SPS), hydrogenated poly(butadiene-styrene) (HPBS), styrene divinylbenzene copolymer (SDVB), styrene-ethylene-butylene-styrene (SEBS), sulfonated bisphenol-A-polysulfone (SPSU), poly(4-phenoxybenzoyl-1,4-phenylene) (PPBP), sulfonated poly(4-phenoxybenzoyl-1,4-phenylene) (SPPBP), poly(vinyl alcohol) (PVA), poly(phosphazenes), poly(aryloxyphosphazenes), polyetherimides, and combinations thereof.

[0098] Ionizable and Ionizable Moieties The compositions herein may include one or more ionizable or ionic moieties.

[0099] Such moieties can contain an anionic or cationic charge, such as in an ionic moiety. Alternatively, the ionizable moiety includes a functional group that can be readily converted to an ionic moiety, such as the ionizable moiety of a carboxy group (-COH), which can be readily deprotonated to form a carboxylate anion (-CO). As used herein, the terms "ionizable" and "ionic" are used interchangeably.

[0100] The ionizable or ionic moieties can be provided in the composition in any useful way. In one embodiment, the first structure comprises one or more ionizable / ionic moieties.

[0101] Moieties can be characterized as acidic moieties (e.g., moieties that can be deprotonated or that can carry a negative charge) or basic moieties (e.g., moieties that can be protonated or that can carry a positive charge). In certain embodiments, moieties can be multi-ionic moieties, which can include multiple acidic moieties, multiple basic moieties, or combinations thereof (e.g., zwitterionic moieties, etc.). Further moieties can include zwitterionic moieties, such as those that include an anionic moiety (e.g., hydroxyl or deprotonated hydroxyl) and a cationic moiety (e.g., ammonium).

[0102] The ionic moieties herein can be connected to the parent structure via one or more linking moieties. Furthermore, a single ionic moiety can extend from a single linking moiety, or multiple ionic moieties can have one or more linking moieties between them.

[0103] For example, the ionic moiety may have the following structure: A -X A or -L A -(L A’ -X A )2 or -L A -(X A -L A’ -X A’ )2 or -L A -X A -L A’ -X A’ -X A’ -L A’’ -X A’’、 -L A’’ -X A’’ wherein each L A , L A’ , and L A’’ is the linking part; each X A , XA’ , and X A’’ independently comprises an acidic moiety, a basic moiety, or a multi-ionic moiety; and L2 is an integer of 1, 2, 3, or more (e.g., 1-20).

[0104] Non-limiting linking moieties (e.g., L A , L A’ , and L A’’ (in the case of ) includes covalent bonds, spirocyclic bonds, -O-, -NR N1 -, -SO2-NR N1 -Ak-, -(O-Ak) L1 -SO2-NR N1 -Ak-, -Ak-, -(O-Ak) L1 -, -(O-Ak)L1-, -(Ak-O) L1 -, -C(O)O-Ak-, -Ar-, or -Ar-O-, where Ak is optionally substituted alkylene or optionally substituted haloalkylene; R N1 is H or optionally substituted alkyl, Ar is optionally substituted arylene, and L is an integer from 1 to 3. In certain embodiments, L A is -(CH2) L1 -, -O(CH2) L1 -, -(CF2) L1 -, -O(CF2) L1 - or -S(CF2) L1 wherein L1 is an integer of 1 to 3.

[0105] In some cases, the linker is attached to two or more ionizable moieties. In some embodiments, the ionizable moiety is -L A -(L A’ -X A )2, wherein L A and L A’ is the linking part, and X A is an acidic moiety, a basic moiety, or a multi-ionic moiety. In one example, L A provides one, two, or three links. Acan be -CX2(CX2-), -CX(CX2-)2, or -C(CX2-)3, where X is H, alkyl, or halo. A’ can provide a point of attachment to an ionic moiety. For example, LA1′ can be —(CH2) L1 -, -O(CH2) L1 -, -(CF2) L1 -, -O(CF2) L1 - or -S(CF2) L1 -, L1 is an integer from 1 to 3; X A is any ionizable or ionic moiety described herein. For example, each L A is an optionally substituted alkylene, for example, an optionally substituted C 1-10 Alkyl (e.g., C such as ethyl, propyl, butyl, pentyl, and hexyl) 2-6 alkyl).

[0106] Non-limiting ionic moieties include carboxy (-COH), carboxylate anion (-CO - ), guanidine cations (e.g., -NR N1 -C(=NR N2 R N3 )(NR N4 R N5 ) or >N=C(NR N2 R N3 )(NR N4 R N5 )) or a salt form thereof. N1 , R N2 , R N3 , R N4 , and R N5 Each non-limiting example of R is independently H, optionally substituted alkyl, optionally substituted aryl, or optionally substituted amino; or N1 and R N2 , R N2 and R N3 , R N3 and R N4 , R N1 and R N2 , or R N1 and R N4taken together with the nitrogen atom to which each is attached, form an optionally substituted heterocyclyl, heterocyclic, or heterocyclic cation, as defined herein.

[0107] Some ionic moieties may contain one or more sulfur atoms. Non-limiting sulfur-containing moieties include sulfo (-SOOH), sulfonate anion (-SOO-), sulfonium cation (e.g., -SR S1 R S2 ), sulfates (e.g., -OS(=O)2(OR S1 )), sulfate anion (-OS(=O)2O - ) or a salt form thereof. S1 and R S2 Non-limiting examples of each of R are independently H, optionally substituted alkyl, optionally substituted aryl, or optionally substituted amino; or R S1 and R S2 together with the sulfur atom to which each is attached form an optionally substituted heterocyclyl, heterocyclic, or heterocyclic cation, as defined herein; or R S1 and R S2 taken together form an optionally substituted alkylene or heteroalkylene (eg, as described herein).

[0108] Other ionic moieties may contain one or more phosphorus atoms. Non-limiting phosphorus-containing moieties include phosphono (e.g., -P(=O)(OH)), phosphonate anions (e.g., -P(=O)(OH)), and phosphonate anions (e.g., -P(=O)(OH). - )2 or -P(=O)(OH)(O - )), phosphates (e.g., -OP(=O)(OR P1 )(OR P2 ) or -O-[P(=O)(OR P1 )-O] P3 -R P2 ), phosphate anion (e.g., -OP(=O)(OR P1 )(O-) or -OP(=O)(O - )2), phosphonium cations (e.g., -P+ R P1 R P2 R P3 ), phosphazenium cations (e.g., -P + (=N RN1 R N2 )R P1 R P2 Contains R N1 and R N2 Each of R is independently an optionally substituted alkyl or an optionally substituted aryl, or a salt form thereof. P1 , R P2 , and R P3 Non-limiting examples of each of R are independently H, optionally substituted alkyl, optionally substituted aryl, or optionally substituted amino; or R P1 and R P2 are each taken together with the phosphorus atom to which they are attached to form an optionally substituted heterocyclyl, heterocyclic, or heterocyclic cation, as defined herein; or R P1 and R P2 and R P3 each taken together with the phosphorus atom to which it is attached forms an optionally substituted heterocyclyl, heterocyclic, or heterocyclic cation, as defined herein; a single, double, or delocalized pi bond (provided that the combination of bonds results in tetravalent phosphorus), or R P1 , R P2 , and R P3 two of which together form an optionally substituted alkylene or heteroalkylene (eg, as described herein).

[0109] Still other ionic moieties can contain one or more nitrogen atoms. Non-limiting nitrogen-containing moieties include amino (e.g., —NR N1 R N2 ), ammonium cations (e.g., -N + R N1 R N2 R N3 or -N+R N1 R N2-), heterocyclic cations (e.g., piperidinium, 1,1-dialkyl-piperidinium, pyrrolidinium, 1,1-dialkyl-pyrrolidinium, pyridinium, 1-alkylpyridinum, (1,4-diazabicyclo[2.2.2]octan-1-yl) (DABCO), 4-alkyl-(1,4-diazabicyclo[2.2.2]octan-1-yl), etc.), or salt forms thereof. N1 , R N2 , and R N3 Each non-limiting example of R is independently H, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl; or R N1 and R N2 are taken together with the nitrogen atom to which they are each attached to form an optionally substituted heterocyclyl, heterocyclic, or heterocyclic cation, as defined herein; R N1 and R N2 and R N3 together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl, heterocyclic, or heterocyclic cation, as defined herein; R N1 , R N2 , and R N3 two of which together form an optionally substituted alkylene or heteroalkylene (e.g., as described herein); or a single, double, or delocalized pi bond (provided that the combination of bonds results in a tetravalent nitrogen).

[0110] Y Still other heterocyclic cations include piperidinium cations such as dimethylpiperidinium, methylpiperidinium (e.g., 1-methyl-piperidinium-1-yl), ethylmethylpiperidinium, piperidinium ethyl (e.g., 1-ethyl-piperidinium-1-yl), propylmethylpiperidinium, propylpiperidinium (e.g., 1-propyl-piperidinium-1-yl), butylmethylpiperidinium, piperidinium butyl (e.g., 1-butyl-piperidinium), -1-yl), diethylpiperidinium, propylethylpiperidinium, butylethylpiperidinium, butylpropylpiperidinium, or spiro-1,1'-bipiperidinium; pyrrolidinium cations, for example, dimethylpyrrolidinium, ethylmethylpyrrolidinium, propylmethylpyrrolidinium, butylmethylpyrrolidinium, diethylpyrrolidinium, propylethylpyrrolidinium, butylethylpyrrolidinium, butylpropylpyrrolidinium, spiro-1,1'-bipyrrolidinium pyrazolium, spiro-1-pyrrolidinium-1'-piperidinium, or spiro-1-pyrrolidinium-1'-morpholinium; pyrazolium cations, such as dimethylpyrazolium, ethylmethylpyrazolium, or butylmethylpyrazolium; imidazolium cations, such as 3-alkylimidazolium, 1,2-dialkylimidazolium, such as 1,2-dimethyl-1H-imidazol-3-ium; those having one nitrogen and five or six carbon rings, such as pyridinium, 2- Examples include methylpyridinium, 3-methylpyridinium, 4-methylpyridinium, 2,6-dimethylpyridinium, quinolinium, isoquinolinium, acridinium, or phenanthridinium; those having two nitrogen ring members and four carbon ring members, such as pyridazinium, pyrimidinium, pyrazinium, or phenazinium; or those having one nitrogen ring member and one carbon ring member, such as morpholinium, 2-methylmorpholinium, or 3-methylmorpholinium.

[0111] Any heterocyclic cation can be attached to a polymer directly or indirectly (e.g., via a linker or linking moiety). Furthermore, any atom within the heterocyclic cation (e.g., within the ring of the heterocyclic cation) can be attached to the polymer. For example, piperidinium is a non-limiting heterocyclic cation, such a cation can be attached to the polymer via the cationic center or via an atom within the ring, and such attachment can be directly via a covalent bond or indirectly via L A (any linking moiety as described herein). [ka] (piperidin-1-ium-1-yl), [ka] piperidin-1-ium-1-yl attached via LA), [ka] (piperidin-1-ium-4-yl), or [ka] (Piperidin-1-ium-4-yl attached via LA). In addition to attachment at the 1 or 4 position of piperidin-1-ium, other attachment sites can be implemented at any point on the ring.

[0112] In some embodiments, the heterocyclic cation is or comprises a piperidinium cation or an azepanium cation. In one embodiment, the heterocyclic cation comprises the following structure: [ka] During the ceremony: R N1is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, or optionally substituted aryl; n is 1, 2, 3, 4, or 5; Each R a are independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, an ionizable moiety, or an ionic moiety; R N1 and at least one R a together with where at least two R a The groups may be taken together to form an optionally substituted cyclic group or an optionally substituted heterocyclic group. In one example, R N1 and R a can be taken together to form an optionally substituted alkylene group or an optionally substituted heteroalkylene group. In certain embodiments, the alkylene or heteroalkylene groups are independently substituted with one or more ionizable or ionic moieties (e.g., any of those described herein).

[0113] In another example, at least one R a is an optionally substituted aliphatic or an optionally substituted alkyl. a Non-limiting examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, neopentyl, 3-pentyl, sec-isopentyl, etc. In other embodiments, the heterocyclic cation has 1, 2, 3, 4, 5, or 6 R that are not H. aIn yet other embodiments, the heterocyclic cation has one, two, three, four, five, or six R a The cations herein may have rings bearing groups, i.e., independently, optionally substituted aliphatic or optionally substituted alkyl. While not wishing to be limited by mechanism, the presence of bulky substituents may result in more stable cations. In other embodiments, any ionizable or ionic moiety herein may have one or more R a It may be substituted with a group.

[0114] Additionally, other non-limiting piperidinium or azepanium cations include any of the following: [ka] etc.

[0115] In other parts, -L A -L A’ -X A wherein L A can be or include an optionally substituted aromatic compound, an optionally substituted arylene, an optionally substituted heterocycle, or an optionally substituted heterocyclyl (e.g., an optionally substituted phenylene or an optionally substituted aryleneoxy); L A’ is an optionally substituted aliphatic, optionally substituted alkylene, optionally substituted heteroaliphatic, or optionally substituted heteroalkylene (e.g., optionally substituted C 1-6 Alkylene or optionally substituted C 1-6 heteroalkylene); X Ais or includes an ionic moiety containing one or more nitrogen atoms. Non-limiting ionic moieties include pyridinium (e.g., pyridinium-1-yl, Pyrd; alkylpyridinium, e.g., 2-methylpyridinium-1-yl, 2MPyrd; or aromatic pyridinium, e.g., 1-benzylpyridinium-4-yl), imidazolium (e.g., 1,2-dialkylimidazolium-3-yl, e.g., 1,2-dimethylimidazolium-3-yl (1,2-DMim)), 4-aza-1-azoniabicyclo[2.2 .2]octan-1-yl (or 1,4-diazabicyclo[2.2.2]octane (DABCO) cation), 4-alkyl-1,4-diazoniabicyclo[2.2.2]octan-1-yl (e.g., 4-methyl-1,4-diazoniabicyclo[2.2.2]octan-1-yl (MAABCO) cation), 4-benzyl-1,4-diazoniabicyclo[2.2.2]octan-1-yl (or 1-benzyl-1,4-diazoniabicyclo[2.2.2]octane (BABCO) cation), aliphatic ammonium (e.g., hexyldimethylammonium-1-yl (DMHA), dicyclohexylmethylammonium-1-yl (MCH), methyldi-n-propylammonium-1-yl (MnPr), trimethylammonium-1-yl (TMA), or triethylammonium-1-yl (TEA)), aromatic ammonium (e.g., dialkylbenzylammonium, e.g., benzyldimethylammonium-1-yl, benzyldiethylammonium-1-yl, benzylhexylmethylammonium-1-yl, benzyldi-n-propylammonium-1-yl, benzylmethyl-n-propylammonium-1-yl, benzyldicyclohexylammonium- 1-yl, benzylcyclohexylmethylammonium-1-yl, (3-nitrobenzyl)dimethylammonium-1-yl, or (3-methoxybenzyl)dimethylammonium-1-yl; or dialkyl(phenylalkyl)ammonium, such as dimethyl(phenylhexyl)ammonium-1-yl), and piperidinium (e.g., aliphatic piperidinium, such as 1-methyl-piperidinium-1-yl (Mepip), 1,2-dialkyl-piperidinium, or 1,2-dimethyl-piperidinium-4-yl (DMP); or aromatic piperidinium, such as 1-benzyl-1-methyl-piperidinium-4-yl (BMP), as well as any piperidinium cation described herein).

[0116] In addition, other parts include -L A -X A L A is a covalent bond (including a spirocyclic bond), optionally substituted aliphatic, optionally substituted alkylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted substituted heterocyclic, or optionally substituted heterocyclyl (e.g., optionally substituted C 1-6 Alkylene, optionally substituted C 1-6heteroalkylene, optionally substituted phenylene, or optionally substituted aryleneoxy); X Ais or includes an ionic moiety containing one or more nitrogen atoms. Non-limiting ionic moieties include pyridinium (e.g., pyridinium-1-yl, Pyrd; alkylpyridinium, e.g., 2-methylpyridinium-1-yl, 2MPyrd; or aromatic pyridinium, e.g., 1-benzylpyridinium-4-yl), imidazolium (e.g., 1,2-dialkylimidazolium-3-yl, e.g., 1,2-dimethylimidazolium-3-yl (1,2-DMim)), 4-aza-1-azoniabicyclo[2.2. 2]octan-1-yl (or 1,4-diazabicyclo[2.2.2]octane (DABCO) cation), 4-alkyl-1,4-diazoniabicyclo[2.2.2]octan-1-yl (e.g., 4-methyl-1,4-diazoniabicyclo[2.2.2]octan-1-yl (MAABCO) cation), 4-benzyl-1,4-diazoniabicyclo[2.2.2]octan-1-yl (or 1-benzyl-1,4-diazoniabicyclo[2.2.2]octane (BABCO) cation), aliphatic ammonium (e.g., hexyldimethylammonium-1-yl (DMHA), dicyclohexylmethylammonium-1-yl (MCH), methyldi-n-propylammonium-1-yl (MnPr), trimethylammonium-1-yl (TMA), or triethylammonium-1-yl (TEA)), aromatic ammonium (e.g., dialkylbenzylammonium, e.g., benzyldimethylammonium-1-yl, benzyldiethylammonium-1-yl, benzylhexylmethylammonium-1-yl, benzyldi-n-propylammonium-1-yl, benzylmethyl-n-propylammonium-1-yl, benzyldicyclohexylammonium ammonium-1-yl, benzylcyclohexylmethylammonium-1-yl, (3-nitrobenzyl)dimethylammonium-1-yl, or (3-methoxybenzyl)dimethylammonium-1-yl; or dialkyl(phenylalkyl)ammonium, such as dimethyl(phenylhexyl)ammonium-1-yl), and piperidinium (e.g., aliphatic piperidinium, such as 1-methyl-piperidinium-1-yl, 1,2-dialkyl-piperidinium, or 1,2-dimethyl-piperidinium-4-yl (DMP); or aromatic piperidinium, such as 1-benzyl-1-methyl-piperidinium-4-yl (BMP), as well as any of the piperidinium cations described herein).

[0117] Such moieties can be associated with one or more counterions, for example, a cationic moiety can be associated with one or more anionic counterions, and an anionic moiety can be associated with one or more cationic counterions. arylene group

[0118] Certain moieties herein (e.g., polymer units, linking moieties, and the like) may contain optionally substituted arylene. Such arylene groups include any polyvalent (e.g., divalent, trivalent, tetravalent, etc.) group having one or more aromatic groups, which may include heteroaromatic groups. Non-limiting aromatic groups may include any of the following: [ka] During the ceremony: R 4 and R 5 each can independently be H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, or R 4 and R 5 together with the carbon atoms to which they are attached form an optionally substituted cyclic group; Each of ring a, ring b, and / or ring c can be optionally substituted; and One or more of rings a-c optionally includes an ionizable or ionic moiety, and each of rings a-c can be optionally substituted (e.g., with any optional substituent described herein for alkyl or aryl, or with any ionic moiety described herein).

[0119] Other non-limiting examples of arylene include phenylene (e.g., 1,4-phenylene, 1,3-phenylene, etc.), biphenylene (e.g., 4,4'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene, etc.), terphenylene (e.g., 4,4'-terphenylene), 9,10-anthracene, naphthalene (e.g., naphthalene 1,5-naphthalene, 1,4-naphthalene, 2,6-naphthalene, 2,7-naphthalene, etc.), tetrafluorophenylene (e.g., 1,4-tetrafluorophenylene, 1,3-tetrafluorophenylene), and the like.

[0120] connecting part Certain chemical functionalities herein may include a linking moiety between a parent structure and another moiety (e.g., an ionic moiety), or between two (or more) other moieties. A , L A’ , and others) can be any useful polyvalent group, such as any useful polyvalent form of optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0121] Non-limiting linking moieties (e.g., L A and L A’ ) can be a covalent bond, a spirocyclic bond, -O-, -NR N1 -, -C(O)-, -C(O)O-, -OC(O)-, -SO2-, optionally substituted alkylene, optionally substituted alkyleneoxy, optionally substituted haloalkylene, optionally substituted heteroalkylene, optionally substituted arylene, optionally substituted aryleneoxy, optionally substituted heterocyclyldiyl, -SO2-NR N1 -Ak-, -(O-Ak) L1 -SO2-NR N1 -Ak-, -Ak-, -Ak-(O-Ak) L1 -, -(O-Ak) L1 -, -(Ak-O) L1 In certain embodiments, A is an optionally substituted aliphatic, an optionally substituted alkylene, or an optionally substituted haloalkylene; N1 is H or optionally substituted alkyl or optionally substituted aryl, Ar is optionally substituted aromatic or optionally substituted arylene, and L1 is an integer from 1 to 3.

[0122] In some embodiments, the linking moiety is -(CH) L1 -, -O(CH2)L1 -, -(CF2) L1 -, -O(CF2) L1 - or -S(CF2) L1 wherein L1 is an integer from 1 to 3. In other embodiments, the linking moiety is -Ak-O-Ar-Ak-O-Ak- or -Ak-O-Ar-, where Ak is optionally substituted alkylene or optionally substituted haloalkylene, and Ar is optionally substituted arylene. Non-limiting examples of substitutions for Ar include -SO2-Ph, where Ph can be unsubstituted or substituted with one or more halo.

[0123] Methods for making polymers The present disclosure also encompasses methods for making polymers. One non-limiting method can include forming an initial polymer with a reactive group (e.g., a halo or another leaving group) and replacing the reactive group with an ionic moiety, resulting in an ionic polymer. Any useful synthetic scheme can be used to provide such ionizable or ionic moieties, for example, by introducing such ionizable / ionic moieties through sulfonation or oxidation, catalytic polymerization with a monomer bearing such ionizable / ionic moieties, etc.

[0124] A further step may involve exchanging a counterion present in the ionic polymer for another counterion (e.g., exchanging a halide counterion for a hydroxide counterion). Yet another step may involve exposing the ionic polymer to a cross-linking reagent to form one or more cross-linkers between polymer units, ionizable moieties, or combinations of ionic moieties.

[0125] One example for making the ionic polymers described herein is generally depicted in Scheme I: [ka]

[0126] Scheme I Scheme I provides a non-limiting reaction scheme for making a polymer. The reaction can proceed by providing a monomer unit (1) (e.g., meta-terphenyl) containing an optionally substituted arylene (-Ar1-). Also provided is a non-limiting Friedel-Crafts acylating agent (2) (e.g., 7-bromo-1,1,1-trifluoroheptan-2-one) optionally in the presence of a strong acid (e.g., methanesulfonic acid), which can be used to react between monomer units (1). For example, the Friedel-Crafts acylating agent can be used to react between monomer units (1) by forming a linking moiety (L A a haloalkyl or other electron-withdrawing moiety (e.g., R 1 After the electrophilic addition reaction, the resulting initial polymer (3) can be provided with an electron-withdrawing moiety (e.g., R 1 ) and arylene groups (-Ar 1 The polymerisation reaction can then be terminated by the addition of a terminating agent (8) (e.g., R 3 , where R3 is phenyl-(G 1 ) g wherein G 1 is C 1-10 alkyl, OR X , where R X is H or C 1-10 alkyl; and g is an integer from 0 to 3. Further reaction can involve contacting the reactive group RG with, for example, an ionizable reagent (4), thereby forming an ionic moiety (-X A A further step can be performed to provide an ionic polymer (11) having a counter ion (RG +) present in the ionic polymer. - ) to another counterion (A - ) (6) to provide additional ionic polymer (7).

[0127] Thus, in one example, the compound of formula (10) can be a compound of formula (a): [ka] This can be converted to a compound of formula (b) by reacting a compound of formula (a) with an amine such as trimethylamine to give a compound of formula (b): [ka] In some cases, a counter ion (A - , in this case Br - ) can be exchanged for another counterion, such as bicarbonate, such as compound (c). [ka]

[0128] use The compositions described herein can be used to form materials such as films, membranes (e.g., ion exchange membranes), or crosslinked polymer matrices. The compositions and materials can be used in devices or apparatuses such as electrochemical cells. In one embodiment, the electrochemical cell includes an anode, a cathode, and a polymer electrolyte membrane (PEM) disposed between the anode and the cathode. The PEM (or a component thereof) can include any of the compositions or materials described herein.

[0129] The compositions herein can be used as components of membrane electrode assemblies (MEAs). Non-limiting examples of MEAs include a cathode layer having a reduction catalyst and a first ion-conducting polymer, an anode layer having an oxidation catalyst and a second ion-conducting polymer, a membrane layer having a third ion-conducting polymer between the anode and cathode layers, and a cathode buffer layer having a fourth ion-conducting polymer between the cathode and membrane layers. The membrane layer (e.g., PEM) can provide ionic communication between the cathode and anode layers or can electrically connect the cathode and anode layers. The cathode buffer layer can electrically connect the cathode and membrane layers. Any of the polymers in the MEA (e.g., as the first, second, third, and / or fourth ion-conducting polymers) can include the compositions described herein.

[0130] In some embodiments, the cathode buffer layer has a first porosity of between about 0.01 and 95 volume percent (e.g., the first porosity is formed by inert filler particles, such as diamond particles, boron-doped diamond particles, polyvinylidene fluoride (PVDF) particles, and polytetrafluoroethylene (PTFE) particles).

[0131] In other embodiments, at least two of the first, second, third, and fourth ion-conducting polymers are from different classes of ion-conducting polymers. There are three classes of ion-conducting polymers: anion conductors, cation conductors, and cation and anion conductors. The ionic or ionizable moieties can be selected to provide any of these classes.

[0132] The term "ion-conducting polymer" is used herein to describe a polymer electrolyte having a specific conductivity of greater than about 1 mS / cm for anions and / or cations. The terms "anion conductor" and / or "anion-conducting polymer" refer to an ion-conducting polymer that conducts primarily anions (although there may still be a small amount of cation conduction) and has an anion mobility number greater than about 0.85 at a thickness of about 100 microns. The terms "cation conductor" and / or "cation-conducting polymer" refer to an ion-conducting polymer that conducts primarily cations (e.g., there may still be an incidental amount of anion conduction) and has a cation mobility number greater than about 0.85 at a thickness of about 100 microns. For ion-conducting polymers described as conducting both anions and cations ("cation and anion conductors"), neither the anions nor the cations have a mobility number greater than about 0.85 or less than about 0.15 at a thickness of about 100 microns. To say that a material conducts ions (anions and / or cations) is to say that the material is an ion-conducting material.

[0133] The compositions herein can be used in a reactor. Non-limiting examples of reactors include electrolytic cells, carbon dioxide reduction electrolytic cells, water electrolytic cells, electrochemical reactors, and gas-phase polymer electrolyte membrane electrolytic cells, but can additionally or alternatively include any other suitable reactor. The reactor may include one or more of the following: electrodes (e.g., anodes, cathodes), catalysts (e.g., within and / or adjacent to the cathode and / or anode), gas diffusion layers (e.g., adjacent to the cathode and / or anode), and / or flow fields (e.g., one or more channels defined within and / or adjacent to the electrodes and / or gas diffusion layers, through the gas diffusion layers facing the cathode, etc.). In some embodiments, the reactor includes a membrane stack or membrane electrode assembly (MEA) having one or more polymer electrolyte membranes (PEMs) that provide ionic communication between the anode and cathode of the reactor. In certain embodiments, the reactor comprises a membrane stack including: a cathode layer comprising a reduction catalyst and an ion-conducting polymer; a PEM membrane (e.g., a bipolar membrane, a monopolar membrane, etc.; a membrane comprising one or more anion conductors, such as an anion exchange membrane (AEM), a proton and / or cation conductor (e.g., a proton exchange membrane), and / or any other suitable ion-conducting polymer; a membrane comprising one or more buffer layers, etc.); and an anode layer comprising an oxidation catalyst and an ion-conducting polymer. The ion-conducting polymer in each layer may be the same ion-conducting polymer or different ion-conducting polymers. In certain embodiments, the membrane, membrane stack, membrane electrode assembly (MEA), polymer electrolyte membrane (PEM), and / or ion-conducting polymer comprise a composition described herein.

[0134] In one embodiment, the carbon dioxide reduction electrolyzer includes a membrane electrode assembly (MEA), which may include one or more ion-conducting polymer layers (such as, for example, any of the compositions described herein) and a cathode catalyst for promoting the chemical reduction of carbon dioxide to carbon monoxide.

[0135] In some configurations, the bipolar MEA has a stacked arrangement of cathode layer / cathode buffer layer (anion conducting layer) / cation conducting layer (which may be a PEM) / anode layer. In some implementations, the bipolar MEA has a cathode layer comprising an anion conducting polymer and / or an anode layer comprising a cation conducting layer. In some implementations, the bipolar MEA has an anode buffer layer that may comprise a cation conducting material between the cation conducting layer and the anode layer. The cathode layer, cathode buffer layer, anion conducting layer, cation conducting layer, and / or anode layer may comprise any of the compositions described herein.

[0136] In some configurations, the bipolar MEA has a stacked arrangement of cathode layer / cation conducting layer (which may be a PEM) / anion conducting layer / anode layer. In some applications, the bipolar MEA having this arrangement is configured in a system for reducing a carbonate and / or bicarbonate feedstock, such as an aqueous solution of carbonate and / or bicarbonate. The cathode layer, cation conducting layer, anion conducting layer, and / or anode layer can comprise any of the compositions described herein.

[0137] In some configurations, the MEA has a stacked arrangement of cathode layer / anion conducting layer / bipolar interface / cation conducting layer / anode layer. The bipolar interface may comprise, for example, cation and anion conducting polymers, a third polymer different from the polymers in the anion conducting polymer layer and the cation conducting polymer layer, a mixture of anion conducting polymer and cation conducting polymer, or crosslinked cation conducting polymer and anion conducting polymer. The cathode layer, anion conducting layer, bipolar interface, cation conducting layer, and / or anode layer may comprise any of the compositions described herein.

[0138] In some configurations, the MEA has a stacked arrangement of cathode layer / anion conducting layer / anode layer. In some implementations, the MEA does not have a cation conducting layer between the cathode layer and the anode layer. In some applications, an MEA containing only an anion conducting material between the cathode and anode is configured in a system for reducing carbon monoxide feedstock. The cathode layer, anion conducting layer, and / or anode layer can include any of the compositions described herein.

[0139] The compositions herein can be provided in a layer (e.g., a membrane layer or other layer herein) having any suitable porosity (e.g., no porosity, or a porosity of 0.01 to 95%, 0.1 to 95%, 0.01 to 75%, 1 to 95%, 1 to 90%, etc.). In some embodiments, the compositions can provide a layer (e.g., a membrane) that is chemically and mechanically stable at temperatures ranging from room temperature (e.g., 25°C) to 50°C. In other embodiments, the compositions are soluble in solvents used during fabrication of the layer (e.g., organic solvents such as dimethyl sulfoxide, dichloromethane, tetrahydrofuran, and ethanol or mixtures thereof). In certain embodiments, the compositions, their layers, or their membranes are characterized by an ion exchange capacity (IEC) of about 0.2 to 3 milliequivalents / g (meq / g), e.g., 0.5 to 3 meq / g, 1 to 3 meq / g, or 1.1 to 3 meq / g. In some embodiments, the composition, a layer thereof, or a film thereof is characterized by a water uptake (wt%) of about 2 to 180 wt%, e.g., 10 to 180 wt%, 20 to 180 wt%, 50 to 180 wt%, 10 to 90 wt%, 20 to 90 wt%, or 50 to 90 wt%. In other embodiments, the composition, a layer thereof, or a film thereof is characterized by an ionic conductivity of greater than about 10 mS / cm. In any embodiment herein, a layer, film, or film comprising the composition herein has a thickness of about 10 to 300 μm, e.g., 20 to 300 μm, 20 to 200 μm, or 20 to 100 μm. In any embodiment herein, the composition, a layer thereof, or a film thereof is characterized by minimal or no light absorption at wavelengths of about 350 nm to 900 nm, about 400 nm to 800 nm, or about 400 nm to 900 nm.

[0140] The layer or film can be formed by any useful method. In one embodiment, the composition (e.g., the initial polymer or ionic polymer) can be dissolved in a solvent (e.g., any organic solvent described herein, such as dimethyl sulfoxide, dichloromethane, tetrahydrofuran, and ethanol, or a mixture thereof) to form a casting solution. The casting solution can be optionally filtered, applied to a substrate, and then dried to form a film. Application to the substrate can include doctor blade coating, solution casting, spraying, dip coating, spin coating, extrusion, melt casting, or any combination of techniques. The film can optionally be further processed, for example, by immersion in any of the reagents described herein (e.g., ionizable reagents, crosslinking reagents, counterions, solvents including water, etc., and combinations thereof).

[0141] Other applications, membranes, assemblies, and configurations are described in U.S. Patent No. 15 / 586,182, filed May 3, 2017, published as U.S. Patent Application Publication No. 2017-0321334, Kuhl et al., entitled "Reactor with advanced architecture for the electrochemical reaction of CO, CO and other chemical compounds"; U.S. Patent No. 63 / 060,583, filed August 3, 2020, and WO 2021 / 044378, filed August 3, 2020, Flanders et al., entitled "System and method for carbon dioxide reactor control"; and U.S. Patent No. 62 / 939,960, filed November 25, 2019, WO 2021 / 108446, Huo et al., entitled "Membrane electrode assembly for CO reduction," each of which is incorporated herein by reference in its entirety.

[0142] Values ​​expressed in range format should be interpreted flexibly to include not only the numerical values ​​explicitly recited as limits of the range, but also all individual numerical values ​​or subranges subsumed within that range, as if each numerical value and subrange were explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5% within the stated range, but also individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%). The expression "about X to about Y" has the same meaning as "about X to about Y" unless otherwise specified. Similarly, the statement "about X, about Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise specified.

[0143] As used herein, the terms "a," "an," or "the" are used to include one or more unless the context clearly dictates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. Furthermore, it should be understood that any expressions or terms used herein and not otherwise defined are for descriptive purposes only and not for limiting purposes. Any use of section headings is intended to aid in the reading of this specification and should not be construed as limiting. Furthermore, information associated with a section heading may occur within or outside that particular section. Furthermore, all publications, patents, and patent documents mentioned herein are incorporated by reference in their entirety, as if individually incorporated by reference. In the event of inconsistent usage between this specification and the specification incorporated by reference, the usage in the incorporated reference should be considered supplementary to the usage in this document, and in the event of an irreconcilable inconsistency, the usage in this specification shall control.

[0144] In the methods described herein, the steps can be performed in any order without departing from the principles of the invention, unless a chronological or operational order is explicitly recited. Furthermore, certain steps can be performed simultaneously unless express claim language recites them as being performed separately. For example, a step recited in a claim performing X and a step recited in a claim performing Y can be performed simultaneously in a single operation, and the resulting process would fall within the scope as recited in the claimed process.

[0145] As used herein, the term "about" may allow for a degree of variation in a value or range, for example, within 10%, within 5%, or within 1% of a stated limit of a stated value or range.

[0146] As used herein, the term "substantially" refers to a majority or majority of at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999%, or more.

[0147] As used herein, the term "substantially free" refers to less than about 30%, 25%, 20%, 15%, 10%, 5%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, 0.001%, or about 0.0005% or less, or about 0% or less.

[0148] Those skilled in the art will understand that many modifications to the embodiments described herein are possible without departing from the scope of the present disclosure. Accordingly, this description is not intended to be, and should not be construed as, limited to the examples given, but should be accorded the full protection afforded by the appended claims and their equivalents. Furthermore, some features of the present disclosure can be used without the corresponding use of other features. Thus, the foregoing description of embodiments or exemplary implementations are provided for the purpose of illustrating the principles of the present disclosure and are not limited thereto, and can include modifications thereto and permutations thereof.

Claims

1. Composition containing the first structure of the formula: 【Chemistry 1】 or its salt (in the formula, R １ and R ２ Each of these is independently an electron-withdrawing moiety, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene; R １ and R ２ At least one of them includes an electron-withdrawing portion, R １ and R ２ At least one of them includes an ionizable moiety or an ionic moiety, R １ and R ２ These, together with the carbon atoms to which they are attached, form a cyclic group that is optionally substituted with an ionizable or ionic moiety; R ３ is an optionally substituted aryl group; Ar １ (wherein is an optionally substituted aromatic group or optionally substituted allylene; n is an integer greater than or equal to 1).

2. The composition according to claim 1 (wherein Ar １ teeth, 【Chemistry 2】 And in the formula: R ４ and R ５ Each of them independently is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted heteroaliphatic, optionally substituted heteroalkyl, optionally substituted aromatic, optionally substituted aryl, or optionally substituted arylalkylene, or R ４ and R ５ These, along with the carbon atoms to which they are attached, may form substituted cyclic groups; Each of ring a, ring b, and / or ring c may be substituted depending on the circumstances; and One or more of rings a to c may include an ionizable moiety or an ionic moiety.

3. The first structure is given by formula: 【Transformation 3】 The composition according to claim 1, having the following characteristics.

4. The first structure is given by formula: 【Chemistry 4】 The composition according to claim 1, having the following characteristics.

5. R ３ but, 【Transformation 5】 G １ However, C １－１０ Alkyl or OR Ｘ And R Ｘ However, H or C １－１０ It is alkyl, The composition according to claim 1, wherein g is an integer from 0 to 3.

6. The composition according to claim 1, wherein the electron-withdrawing portion is optionally a substituted haloalkyl, cyano(CN), phosphoric acid, sulfate, sulfonic acid, sulfonyl, difluoroboranyl, borono, thiocyanate, or piperidinium.

7. The ionizable portion or the ionic portion is -L Ａ -X Ａ or -L Ａ - (LA'-X Ａ ) 2 or -L Ａ - (X Ａ -L Ａ’ -X Ａ’ ) ２ or -L Ａ -X Ａ -LA'-X Ａ’ -L A'' -XA'' (wherein each L Ａ , LA', and LA'' are connecting parts; each X Ａ , X Ａ’ , and X Ａ’’ It independently comprises an acidic part, a basic part, a multiionic part, a cation part, or an anionic part. L ２ The composition according to claim 1, wherein is an integer of 1 or more.

8. In the ceremony, L Ａ , L Ａ’ , and L Ａ’’ The composition according to claim 7, wherein it independently comprises an optionally substituted alkylene, an optionally substituted alkylene oxy, an optionally substituted heteroalkylene, an optionally substituted allylene, and / or an optionally substituted allylene oxy.

9. The composition according to claim 7, wherein XA, XA', and XA'' independently comprise a sulfo, a sulfonic acid anion, a sulfonium cation, a carboxy, a carboxylate anion, a phosphono, a phosphonate anion, a phosphonium cation, a phosphazenium cation, an amino, an ammonium cation, a heterocyclic cation, a piperidinium cation, or an azepanium cation.

10. The composition according to claim 7, wherein LA, LA', and LA'' independently comprise optionally substituted alkylenes.

11. XA, X Ａ’ , and X Ａ’’ The composition according to claim 7, wherein independently, it comprises an amino or ammonium cation.

12. R １ However, it is a substituted haloalkyl in some cases: R ２ The composition according to claim 7, wherein the aliphatic is substituted in some cases.

13. R ２ However, -L Ａ -X Ａ And each L Ａ However, they are aliphatic compounds that may be substituted in some cases; each X Ａ However, independently, it includes a cationic moiety; L ２ The composition according to claim 7, wherein the value is an integer of 1 or more.

14. Each L Ａ The composition according to claim 13, wherein the alkylene is substituted in some cases.

15. L Ａ However, C may be substituted in some cases. １－１０ The composition according to claim 13, wherein it is alkyl.

16. X Ａ The composition according to claim 13, wherein the cation is an ammonium cation.

17. The composition according to claim 1, wherein the first structure has the following formula: 【Transformation 6】

18. The composition according to claim 1, wherein the first structure has the following formula: 【Transformation 7】

19. The composition according to claim 1, wherein the first structure has the following formula: 【Transformation 8】

20. The composition according to claim 1, wherein the first structure has a polydispersity index of less than 2.7 as determined by gel permeation chromatography (GPC).

21. It is an electrochemical cell, Node and; Cathode and; An electrochemical cell comprising a polymer electrolyte membrane disposed between the anode and the cathode, wherein the polymer electrolyte membrane comprises the composition described in any one of claims 1 to 20.

22. A method for producing polymers, The process involves contacting monomer units with a Friedel-Crafts acylating agent containing a reactive group in the presence of a strong acid to obtain an initial polymer, A method comprising contacting the initial polymer with a termination agent to obtain a polymer having the first structure described in any one of claims 1 to 20.

23. The method according to claim 22, further comprising contacting the reactive group with an ionizable reagent to obtain an ionic polymer containing a plurality of ionic moieties.

24. The method according to claim 22, further comprising exchanging a counterion present in the composition with another counterion.

25. The method according to claim 23, wherein the ionic portion is a cationic portion.

26. The method according to claim 22, further comprising the step of contacting the polymer with methanol.

27. The method according to claim 26, wherein contact with methanol does not cause exothermic reaction.

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