HALO-CONTAINING ANION EXCHANGE MEMBRANES AND METHODS THEREOF
20180194892 ยท 2018-07-12
Inventors
Cpc classification
B01J41/13
PERFORMING OPERATIONS; TRANSPORTING
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M8/1039
ELECTRICITY
C08G61/10
CHEMISTRY; METALLURGY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C08G2261/312
CHEMISTRY; METALLURGY
H01M8/1023
ELECTRICITY
B01J47/12
PERFORMING OPERATIONS; TRANSPORTING
International classification
C08G61/10
CHEMISTRY; METALLURGY
H01M8/1039
ELECTRICITY
H01M8/1023
ELECTRICITY
B01J47/12
PERFORMING OPERATIONS; TRANSPORTING
B01J41/13
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention relates to functionalized polymers including a poly(phenylene) structure having modifications suitable for an anion exchange membrane. Exemplary modifications include use of a cationic moiety and a halo moiety. Methods and uses of such structures and polymers are also described herein.
Claims
1. A composition comprising a structure having the formula (I): ##STR00013## or a salt thereof or a form thereof including a counter ion, wherein: each and every R.sup.AF comprises a cationic moiety or a halo; each R.sup.1 and R.sup.3 is, independently, H, halo, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 haloalkyl, optionally substituted C.sub.1-12 perfluoroalkyl, optionally substituted C.sub.1-12 heteroalkyl, R.sup.S, R.sup.P, R.sup.C, or R.sup.E, wherein R.sup.S is an acidic moiety comprising a sulfonyl group, R.sup.P is an acidic moiety comprising a phosphoryl group, R.sup.C is an acidic moiety comprising a carbonyl group, and R.sup.E is an electron-withdrawing moiety; each Ar.sup.L is, independently, a bivalent linker comprising optionally substituted arylene; each Ar.sup.M is, independently, a bivalent linker comprising optionally substituted arylene; each q is, independently, an integer of from 0 to 5; each a is, independently, an integer of from 0 to 5, wherein at least one a is not 0; and m is an integer of from about 1 to 1000.
2. The composition of claim 1, wherein at least one R.sup.AF is an aryl, an alkyl, or a heteroalkyl substituted with the cationic moiety.
3. The composition of claim 1, wherein the cationic moiety comprises an onium cation.
4. The composition of claim 3, wherein the onium cation comprises an ammonium cation.
5. The composition of claim 1, wherein at least one R.sup.AF is an aryl, an alkyl, or a heteroalkyl substituted with the halo.
6. The composition of claim 1, wherein at least one R.sup.AF is an optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 haloalkyl, optionally substituted C.sub.1-12 perfluoroalkyl, optionally substituted C.sub.1-12 heteroalkyl, halo, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryl-C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryloxy, optionally substituted C.sub.5-19 aryloxycarbonyl, optionally substituted C.sub.5-19 aryloyl, optionally substituted C.sub.4-18 arylcarbonyl-C.sub.1-12 alkyl, optionally substituted C.sub.4-18 arylsulfonyl, or optionally substituted C.sub.4-18 arylsulfonyl-C.sub.1-12 alkyl.
7. The composition of claim 6, wherein each and every R.sup.AF comprises an optionally substituted aryl group.
8. The composition of claim 1, wherein: at least one R.sup.AF is -L.sup.A-Ar.sup.AF and/or -L.sup.A-Ak.sup.AF, or a salt thereof or a form thereof including a counter ion; L.sup.A is a covalent bond, carbonyl, oxy, thio, azo, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo, optionally substituted C.sub.1-12 alkylene, optionally substituted C.sub.1-12 alkyleneoxy, optionally substituted C.sub.1-12 heteroalkylene, optionally substituted C.sub.1-12 heteroalkyleneoxy, optionally substituted C.sub.4-18 arylene, or optionally substituted C.sub.4-18 aryleneoxy; Ar.sup.AF is an optionally substituted aryl comprising the cationic moiety or the halo; and Ak.sup.AF is an optionally substituted alkyl comprising the cationic moiety or the halo; or an optionally substituted heteroalkyl comprising the cationic moiety or the halo.
9. The composition of claim 8, wherein L.sup.A is a covalent bond, carbonyl, sulfonyl, NR.sup.L3, (CR.sup.L1R.sup.L2).sub.La, C(O)NR.sup.L3, NR.sup.L3C(O), SO.sub.2NR.sup.L3, NR.sup.L3SO.sub.2, (CR.sup.L1R.sup.L2).sub.LaC(O)NR.sup.L3, (CR.sup.L1R.sup.L2).sub.LaNR.sup.L3C(O), (CR.sup.L1R.sup.L2).sub.LaSO.sub.2NR.sup.L3, or SO.sub.2NR.sup.L3(CR.sup.L1R.sup.L2).sub.La; wherein each of R.sup.L1, R.sup.L2, and R.sup.L3 is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkoxy, optionally substituted alkaryl, optionally substituted aryl, or halo; and wherein Ar.sup.AF or Ak.sup.AF is optionally substituted with one or more substituents selected from the group consisting of halo, cyano, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted nitroalkyl, and optionally substituted alkyl.
10. The composition of claim 8, wherein the composition comprises a structure having any one of formulas (Ia) to (Ij), or a salt thereof or a form thereof including a counter ion; and wherein R.sup.AF is R.sup.A comprising the cationic moiety or R.sup.F comprising the halo.
11. The composition of claim 1, wherein: R.sup.S is SO.sub.2R.sup.S1 or SO.sub.2NR.sup.N1R.sup.S2 or SO.sub.2NR.sup.N1SO.sub.2R.sup.S3, wherein each R.sup.S1 is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted aryl, optionally substituted alkaryl, or hydroxyl; each R.sup.N1 is, independently, H or optionally substituted C.sub.1-12 alkyl, optionally substituted aryl, or optionally substituted alkaryl; each R.sup.S2 is, independently, H, hydroxyl, optionally substituted alkyl, optionally substituted alkylsulfonyl, optionally substituted aryl, or optionally substituted alkaryl; and each R.sup.S3 is, independently, H, hydroxyl, optionally substituted alkyl, optionally substituted C.sub.1-12 haloalkyl, optionally substituted perfluoroalkyl, optionally substituted aryl, or optionally substituted alkaryl; R.sup.P is P(O)(OH).sub.2 or OPO(OH).sub.2 or P(O)<R.sup.P1R.sup.P2 or P(O)<R.sup.ArR.sup.P2 or P(O)<R.sup.ArR.sup.Ar, and wherein each of R.sup.P1 and R.sup.P2 is, independently, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted alkaryl, optionally substituted aryloxy, hydroxyl, or H; and each of R.sup.Ar is, independently, optionally substituted aryl, optionally substituted alkaryl, or optionally substituted aryloxy; R.sup.C is CO.sub.2H, C(O)R.sup.C1, or R.sup.CAC(O)R.sup.C1, and wherein each R.sup.C1 is, independently, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted alkaryl, optionally substituted aryloxy, hydroxyl, or H; and each R.sup.CA is, independently, oxy, optionally substituted alkylene, or optionally substituted heteroalkylene; and R.sup.E is optionally substituted aryloyl, carboxyaldehyde, optionally substituted alkanoyl, or optionally substituted alkyl.
12. The composition of claim 1, wherein Ar.sup.L and/or Ar.sup.M is optionally substituted phenylene, optionally substituted naphthylene, or optionally substituted phenanthrylene.
13. The composition of claim 12, wherein the optional substitution for Ar.sup.L is R.sup.AF, R.sup.H, R.sup.S, R.sup.P, R.sup.C, or R.sup.E; and wherein the optional substitution for Ar.sup.M is R.sup.AF, R.sup.H, R.sup.S, R.sup.P, R.sup.C, R.sup.E, or a label.
14. The composition of claim 1, wherein the composition comprises a structure having any one of formulas (I-1) to (I-8), (IV-3), (IV-5), (IV-8), (IV-10), or (IV-11), or a salt thereof or a form thereof including a counter ion; wherein each and every R.sup.AF1, if present, comprises the cationic moiety or the halo; wherein each and every R.sup.A1, if present, comprises the cationic moiety; wherein each and every R.sup.F1, if present, comprises the halo; wherein L.sup.A is a covalent bond, carbonyl, oxy, thio, azo, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo, optionally substituted C.sub.1-12 alkylene, optionally substituted C.sub.1-12 alkyleneoxy, optionally substituted C.sub.1-12 heteroalkylene, optionally substituted C.sub.1-12 heteroalkyleneoxy, optionally substituted C.sub.4-18 arylene, or optionally substituted C.sub.4-18 aryleneoxy; and wherein m is an integer of from about 1 to 500.
15. The composition of claim 14, wherein: R.sup.F1 is the halo, an optionally substituted aryl having the halo, an optionally substituted alkyl having the halo, or an optionally substituted heteroalkyl having the halo; and/or R.sup.A1 is the cationic moiety, an optionally substituted aryl having the cationic moiety, an optionally substituted alkyl having the cationic moiety, or an optionally substituted heteroalkyl having with the cationic moiety.
16. A composition comprising a structure having the formula (VI) or (VII): ##STR00014## or a salt thereof or a form thereof including a counter ion, wherein: each and every R.sup.AF comprises a cationic moiety or a halo; each R.sup.1 and R.sup.3 is, independently, H, halo, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 haloalkyl, optionally substituted C.sub.1-12 heteroalkyl, optionally substituted C.sub.1-12 perfluoroalkyl, R.sup.S, R.sup.P, R.sup.C, or R.sup.E, wherein R.sup.S is an acidic moiety comprising a sulfonyl group, R.sup.P is an acidic moiety comprising a phosphoryl group, R.sup.C is an acidic moiety comprising a carbonyl group, and R.sup.E is an electron-withdrawing moiety; each Ar.sup.L is, independently, a bivalent linker comprising optionally substituted arylene; each Ar.sup.M is, independently, a bivalent linker comprising optionally substituted arylene; each q is, independently, an integer of from 0 to 5; each a is, independently, an integer of from 0 to 5, wherein at least one h is not 0; each of m and n is, independently, an integer of from about 1 to 1000; L is a sublink; Ar* is a hydrophobic segment; and each R.sup.L is, independently, a reactive end group.
17. The composition of claim 16, wherein L comprises a covalent bond, optionally substituted C.sub.1-12 alkylene, optionally substituted C.sub.1-12 alkyleneoxy, optionally substituted C.sub.1-12 heteroalkylene, optionally substituted C.sub.1-12 heteroalkyleneoxy, optionally substituted C.sub.4-18 arylene, optionally substituted C.sub.4-18 aryleneoxy, optionally substituted polyphenylene, or a structure of formula (II).
18. The composition of claim 16, wherein R.sup.L is optionally substituted C.sub.7-11 aryloyl or optionally substituted C.sub.6-18 aryl.
19. The composition of claim 16, wherein the composition comprises a structure having the formula (VIa) to (VId), or a salt thereof or a form thereof including a counter ion; or the formula (VIII) or (VIIIa), or a salt thereof or a form thereof including a counter ion.
20. An anion exchange membrane comprising the composition of claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0166] The present invention relates to polymer structures having various functional groups including a cationic moiety or a halo group (e.g., a R.sup.AF group). In particular embodiments, R.sup.A is a functional group including the cationic moiety, and R.sup.F is a functional group including the halo group. The R.sup.AF groups can be provided on any useful site of the underlying polymer (e.g., pendent groups and/or backbone groups of the polymer). In some embodiments, the polymer includes both R.sup.A groups and R.sup.F groups (e.g., R.sup.A and R.sup.F on pendent groups and/or backbone groups of the polymer). Described herein are structures for such polymers having cationic moieties or halo groups, as well as methods for making and functionalizing such polymers.
Polymers
[0167] The present invention encompasses polymers, including copolymers. Exemplary polymer include any described herein, such as non-limiting generic structure provided in formulas (I), (Ia), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (VI), (VIa), (VIb), (VIc), (VId), (VII), (VIII), (VIIIa), and (IX), as well as particular structures provided as structures (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), (IV-3), (IV-5), (IV-8), (IV-10), and (IV-11) (see
[0168] Of these, formulas (VI), (VIa), (VIb), (VIc), (VId), (VIII), and (VIIIa) are considered to be reagents having one or more reactive end groups. Formula (VII) is considered to be a copolymer. In particular embodiments, the copolymer of the invention includes a first segment, a second segment, and at least one linking segment connecting at least one first segment with at least one second segment. The second segment can be a hydrophilic segment or a hydrophobic segment. The first segment can include at least one R.sup.AF.
[0169] In one embodiment, a polymer includes the structure of formula (I), including salts thereof and forms thereof including a counter ion. As can be seen in
[0170] The polymer can include any useful type of pendent substituents substituents R.sup.AF, R.sup.A, R.sup.F, and/or R.sup.3 on a pendent aryl group, such as those labeled with an R.sub.3 in formula (I) of
[0171] The polymer can also include any useful backbone structure. For instance, in formula (I), the backbone includes three groups, i.e., two R.sup.1-substituted aryl groups and a bridging group Ar.sup.L optionally including a functional group R.sup.AF. The polymer can include any useful type of backbone substituents (e.g., backbone substituents R.sup.1 or R.sup.H disposed on a backbone aryl group), as well as any useful number of such substituents on each group (e.g., a substituents for R.sup.AF and/or q substituents for R.sup.1, where each of a and q is, independently, 0, 1, 2, 3, 4, or 5, and/or where at least one a is not 0). For any structure described herein, each R.sup.1 is, independently, a functional group (R.sup.AF, R.sup.A, or R.sup.F), an acidic moiety (e.g., R.sup.S, R.sup.P, R.sup.C, or any described herein), an electron-withdrawing moiety (e.g., R.sup.E or any described herein), or an inert substituent (e.g., H, halo, optionally substituted alkyl, optionally substituted alkoxy, etc.). In some embodiments, each and every R.sup.1 is, independently, R.sup.AF, R.sup.A, R.sup.F, R.sup.H, R.sup.S, R.sup.P, R.sup.C, or R.sup.E.
[0172] Each of bridging group Ar.sup.L and connecting group Ar.sup.M can be any useful bivalent linker. In particular embodiments, each of Ar.sup.L and Ar.sup.M is, independently, includes an optionally substituted arylene group. In some embodiments, each of Ar.sup.L and Ar.sup.M is, independently, an optionally substituted arylene group. In other embodiments, each of Ar.sup.L and Ar.sup.M is, independently, substituted with 1, 2, 3, or 4 R.sup.AF substituent(s), R.sup.A substituent(s), R.sup.E substituent(s), R.sup.H substituent(s), R.sup.S substituent(s), R.sup.P substituent(s), R.sup.C substituent(s), R.sup.E substituent(s), or label(s). Exemplary labels include a detectable label, such as an NMR label (e.g., fluorine, such as .sup.19F; nitrogen, e.g., .sup.15N; or oxygen, e.g., .sup.17O), a spin label, an isotopic label, a mass label, a fluorescent label, a dye, etc.
[0173] In yet other embodiments, each of Ar.sup.L and Ar.sup.M is, independently, configured to reduce meta linkages. Thus, in some instances, each of Ar.sup.L and Ar.sup.M is, independently, a bivalent linker formed by removing a hydrogen atom from opposite faces of an aryl group. Examples of such linkers include 1,4-benzenediyl (or 1,4-phenylene), 2,7-phenanthrylene (or 2,7-phenanthrenediyl), 1,5-naphthylene (or 1,5-napthalenediyl), etc. For example, the polymer can include a structure of Formula (I) but having Ar.sup.L as a R.sup.1-substituted 1,4-phenylene and Ar.sup.M as an R.sup.1-substituted 1,4-phenylene, an R.sup.3-substituted 1,4-phenylene, an R.sup.AF-substituted 1,4-phenylene, an R.sup.A-substituted 1,4-phenylene, or an R.sup.F-substituted 1,4-phenylene.
[0174] A polymer can include any useful number of structures of formula (I). In some embodiments, the polymer includes in structures, where in is an integer of from about 1 to 1000 (e.g., from about 1 to 500).
[0175] Functional groups R.sup.AF can be present on the same polymer or on the same segment of the polymer with any other different type of substitutions, e.g., reactive handle substitutions (e.g., R.sup.H), acidic substitutions (e.g., R.sup.S, R.sup.P, and/or R.sup.C, as well as combinations thereof) and R.sup.E substitutions. In particular embodiments, R.sup.A groups can be employed to install functional groups to promote binding to an anion, and R.sup.F groups can be employed to provide hydrophobic characteristics. In other embodiments, the use of acidic moieties and electron-withdrawing moieties could provide orthogonal chemistries to control and optimize performance (e.g., by employing acidic moieties to control ion conduction) and durability (e.g., by employing electron-withdrawing moieties to reduce oxidation). Further, the presence of a reactive handle R.sup.H allows the polymer to be further functionalized (e.g., with one or more functional groups R.sup.AF, R.sup.A, R.sup.F, R.sup.S, R.sup.P, R.sup.C, and/or R.sup.E, as well as any other groups described herein). In one instance, each pendent aryl group is substituted with an R.sup.AF (e.g., an R.sup.A and/or an R.sup.F), an R.sup.H, an R.sup.S, an R.sup.P, an R.sup.C, and/or an R.sup.E. Optionally, one or more backbone aryl groups can be further substituted with an R.sup.AF (e.g., an R.sup.A and/or an R.sup.F), an R.sup.H, an R.sup.S, an R.sup.P, an R.sup.C, and/or an R.sup.E.
[0176] As seen in
[0177] The aryl group Ar.sup.AF can be any useful aryl group (e.g., any herein, such as phenyl, benzyl, etc.) that is optionally substituted (e.g., any group herein described for an aryl group) and that also includes either a cationic moiety (e.g., any herein, such as an ammonium cation, a sulfonium cation, a phosphonium cation, an oxonium cation, a diazonium cation, or a halonium cation) and/or a halo (e.g., any herein, such as fluoro, chloro, bromo, or iodo). The alkyl group Ak.sup.AF can be any useful alkyl group (e.g., any herein, such as methyl, propyl, butyl, etc.) that is optionally substituted (e.g., any group herein described for an alkyl group) and that also includes either a cationic moiety (e.g., any herein, such as an ammonium cation, a sulfonium cation, a phosphonium cation, an oxonium cation, a diazonium cation, or a halonium cation) and/or a halo (e.g., any herein, such as fluoro, chloro, bromo, or iodo).
[0178] The R.sup.AF moiety can be present on any useful sites within a polymer. As seen in
[0179] An R.sup.AF moiety can either be a functional group including a cationic moiety (e.g., R.sup.A) or a functional group including a halo (e.g., R.sup.F) and a polymer can have any useful combination of R.sup.A and R.sup.F groups. As seen in
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Polymer Reagents
[0181] The present invention also includes reagents having any useful polymer segment described herein. For instance, the reagent can include a polymer segment disposed between two reactive end groups, where each end group can be the same or different. The polymer segment can be any described herein (e.g., a structure provided in formula (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ii), (Ij), (VI), (VIa), (VIb), (VIc), (VId), (VII), (VIII), (VIIIa), and (IX), as well as particular structures provided as structures (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), (IV-3), (IV-5), (IV-8), (IV-10), and (IV-11)). In addition, the polymer segment can include a second segment (e.g., Ar*), such as any described herein.
[0182] Optionally, a sublink L can be present between the polymer segment and a reactive end group. The sublink L can be composed of any useful linkage, such as any described herein (e.g., those described for linking segment L).
[0183] The reactive end group can be any useful group configured to react with a second reactive end group. In this way, ordered copolymer block structures can be synthesized by selectively placing reactive end groups on the ends of blocks or segments to form polymer reagents, and then reacting that polymer reagent to place the segments in an end-to-end fashion in the copolymer. A skilled artisan would understand how to place reactive end groups in a polymer reagent in order to form a copolymer with the desired configuration or order.
[0184] The reactive end group is usually placed on the ends of a first polymer reagent, as well as on the ends of the second polymer reagent. Then, a first reactive end group on the first polymer reagent reacts with the second reactive end group on a second polymer reagent. The first and second reactive end groups can be chosen from a pair of co-reactive groups. For example, such pairs of co-reactive groups include (i) a nucleophile for use with (ii) an electrophile; (i) an optionally substituted aryl group (e.g., having a C(O)R.sup.I group, where R.sup.I is an aryl group having one or more halo) for use with (ii) an optionally substituted aryl group (e.g., having a OR.sup.Pr group, where R.sup.Pr is H or an O-protecting group that can be deprotected prior to conducting a reaction); (i) an optionally substituted aryl group (e.g., having a C(O)R.sup.I group, where R.sup.I is an aryl group having one or more halo) for use with (ii) an optionally substituted alkoxy group (e.g., such as OR.sup.Pr, where R.sup.Pr is H or an O-protecting group that can be deprotected prior to conducting a reaction); (i) an optionally substituted aryl group for use with (ii) an optionally substituted alkoxy group (e.g., such as OR.sup.Pr, where R.sup.Pr is H or an O-protecting group that can be deprotected prior to conducting a reaction); (i) an optionally substituted alkynyl group for use with (ii) an optionally substituted azido group, which can participate in a Huisgen 1,3-dipolar cycloaddition reaction; as well as (i) an optionally substituted diene having a 4 electron system for use with (ii) an optionally substituted dienophile or an optionally substituted heterodienophile having a 2 electron system, which can participate in a Diels-Alder reaction. For the co-reactive groups above, reagent (i) reacts with reagent (ii) in each pair. In one instance, the reactive group is R.sup.H (e.g., any described herein).
[0185] An exemplary polymer reagent is provided as structure (VI) in
[0186] Further exemplary polymer reagents are provided as structure (VIa) to (VId) in
Copolymers
[0187] The present invention also includes copolymers. In one embodiment, the copolymer includes the structure of formula (VII), including salts thereof. As can be seen in
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[0189] Formulas (VII) and (VIII) also include additional groups, including a linking segment L and a second segment Ar* of n units. The linking segment L can be any useful linkage (e.g., any herein), including those to form a covalent bond between the two segments. In some embodiments, the linking segment includes those composed of structures, or a portion of such structures, in the first segment and/or the second segment. Exemplary linking segments L include a covalent bond, an optionally substituted alkylene, an optionally substituted heteroalkylene, an optionally substituted alkyleneoxy, an optionally substituted heteroalkyleneoxy, an optionally substituted arylene, an optionally substituted aryleneoxy, an Ar* unit, or a structure of formula (I).
[0190] The copolymer having formulas (VII) and (VIII) can have any useful second segment Ar*. In some embodiments, Ar* includes a structure of formula (I) (e.g., where each R.sup.3 is H, optionally substituted alkyl, or R.sup.E; or where the number of R.sup.S substituents in Ar* is less than the number of R.sup.S and/or R.sup.P substituents in the hydrophilic segment); a hydrophobic subunit; a sulfone subunit (e.g., a subunit including an SO.sub.2 group); an arylene sulfone subunit (e.g., (Ar).sub.aSO.sub.2(Ar).sub.b, where Ar is an optionally substituted arylene group, as defined herein, and each a and b is an integer of about 0 to 10 and at least one of a or b is 1 or more); an ether sulfone subunit (e.g., (X.sup.1).sub.aSO.sub.2(X.sup.2).sub.bO or X.sup.1OX.sup.2SO.sub.2, where each X.sup.1 and X.sup.2 is, independently, any useful group, such as optionally substituted arylene or optionally substituted alkylene, and each a and b is an integer of about 0 to 10 and at least one of a or b is 1 or more); an arylene ether subunit (e.g., (Ar).sub.aO(Ar).sub.b, where Ar is an optionally substituted arylene group, as defined herein, and each a and b is an integer of about 0 to 10 and at least one of a or b is 1 or more); an arylene ketone subunit (e.g., (Ar).sub.aC(O)(Ar).sub.b, where Ar is an optionally substituted arylene group, as defined herein, and each a and b is an integer of about 0 to 10 and at least one of a or b is 1 or more); a perfluoroalkyl subunit (e.g., (CF.sub.2).sub.f1, where f1 is an integer of 1 to about 16); or a perfluoroalkoxy subunit (e.g., O(CF.sub.2).sub.f1, (CF.sub.2).sub.f1O, O(CF.sub.2).sub.flCF(CF.sub.3)O(CF.sub.2).sub.f2, >CFO(CF.sub.2).sub.flCF(CF.sub.3)O(CF.sub.2).sub.f2, where each f1 and f2 is, independently, an integer of 1 to about 16).
[0191] In some embodiments, formulas (VII) and (VIII) include a second segment Ar* that is a hydrophobic segment. In some embodiments, the second segment Ar* is a hydrophobic segment having one or more electron-withdrawing moieties (e.g., R.sup.E) or one or more halo-containing functional groups (e.g., R.sup.F). In particular embodiments, each pendent aryl group in the polymer or a segment thereof is substituted with an R.sup.E substitution and/or an R.sup.F substitution, where each substitution may be the same or different. In other embodiments, both pendent and backbone aryl groups are each, independently, substituted with an R.sup.E substitution and/or an R.sup.F substitution.
[0192] In other embodiments, formulas (VII) and (VIII) include a second segment Ar* that is a hydrophilic segment. In some embodiments, the second segment Ar* is a hydrophilic segment that includes the two R.sup.1-substituted aryl groups and a bridging group Ar.sup.L. Thus, in some embodiments, at least one substituent in this hydrophilic segment (e.g., substituents R.sup.1, R.sup.2, or R.sup.3) is a hydrophilic moiety (e.g., an acidic moiety, such as any R.sup.A, R.sup.S, R.sup.P, and/or R.sup.C described herein or any moiety including a sulfonyl group or a phosphoryl group). In some embodiments, the hydrophilic segment includes one or more acidic moieties (e.g., R.sup.S, R.sup.P, and/or R.sup.C, as well as combinations thereof) on only the pendent aryl groups. Exemplary hydrophilic segments include those having R.sup.A-substituted pendent aryl groups, R.sup.S-substituted pendent aryl groups, R.sup.P-substituted pendent aryl groups, and R.sup.1-substituted backbone aryl groups.
[0193] A copolymer can include any useful number or ratio of first and second segments (e.g., hydrophilic and hydrophobic segments). In some embodiments, formulas (VII) and (VIII) include m number of first segments (e.g., hydrophilic segments) and n number of second segments (e.g., hydrophobic segments), where each of m and n is, independently, an integer of from about 1 to 1000. In other embodiments, the m (the number of first segments) is minimized in order to minimize swelling of the copolymer. For example, in some instances, m<n. In other instance, n is at least about 5 times greater than m (e.g., n is about 10 times greater than m, or n is about 20 times greater than m). In yet other instances, m is of from about 1 to 100, and n is of from about 5 to 500 (e.g., m is of from about 1 to 50, and n is of from about 5 to 500; m is of from about 1 to 50, and n is of from about 10 to 100; m is of from about 1 to 10, and n is of from about 5 to 500; m is of from about 1 to 20, and n is of from about 20 to 400; and m is of from about 1 to 10, and n is of from about 100 to 200). In some instances, m can be about 5.6 and n can be about 60.7 or 121.4. In other instances, m is of from about 1 to 20, and n is of from about 20 to 400.
[0194] For any polymer herein, including any copolymer herein, each and every R.sup.1 can be independently, R.sup.AF, R.sup.A, R.sup.F, R.sup.H, R.sup.S, R.sup.P, R.sup.C, and/or R.sup.E. For instance, in some embodiments, each aryl group in the polymer or a segment thereof is substituted with an R.sup.AF, an R.sup.A, an R.sup.F, an R.sup.H, an R.sup.S, an R.sup.P, and/or an R.sup.C substitution, where each substitution may be the same or different. Reactive handles R.sup.H can be present on the same polymer or on the same segment of the polymer with any other different type of substitutions, e.g., acidic substitutions (e.g., R.sup.S, R.sup.P, and/or R.sup.C, as well as combinations thereof) and R.sup.E substitutions, In particular, the use of acidic moieties and electron-withdrawing moieties could provide orthogonal chemistries to control and optimize performance (e.g., by employing acidic moieties to control ion conduction) and durability (e.g., by employing electron-withdrawing moieties to reduce oxidation). Further, the presence of a reactive handle R.sup.H allows the polymer to be further functionalized (e.g., with one or more functional groups R.sup.AF, R.sup.A, R.sup.F, R.sup.S, R.sup.P, R.sup.C, and/or R.sup.E). In one instance, each pendent aryl group is substituted with an R.sup.AF, an R.sup.A, an R.sup.F, an R.sup.H, an R.sup.S, an R.sup.P, an R.sup.C, and/or an R.sup.E. Optionally, one or more backbone aryl groups can be further substituted with an R.sup.AF, an R.sup.A, an R.sup.F, an R.sup.H, an R.sup.S, an R.sup.P, an R.sup.C, and/or an R.sup.E.
Functional Groups and Moieties
[0195] The present invention includes the use of functional groups and moieties, such as functional groups (e.g., R.sup.AF) including a cationic moiety (e.g., R.sup.A) or a halo (e.g., R.sup.F), reactive handles (e.g., R.sup.H), acidic moieties (e.g., R.sup.S, R.sup.P, or R.sup.C), electron-withdrawing moieties (e.g., R.sup.E), and other functional groups. Any number of these functional moieties can be present on the polymer (e.g., the polymer backbone aryl groups and/or pendent aryl groups).
[0196] Exemplary functional groups (e.g., R.sup.AF) including any useful group including a cationic moiety (e.g., an onium, such as any described herein) or a halo (e.g., any described herein). In some embodiments, the functional group R.sup.AF includes -L.sup.A-Ar.sup.AF or -L.sup.A-Ak.sup.AF, in which Ar.sup.AF is an optionally substituted aryl and in which Ak.sup.AF is an optionally substituted alkyl or optionally substituted heteroalkyl. In particular embodiments L.sup.A is any useful covalent bond or any useful linker (e.g., any described herein). In some embodiments, Ar.sup.AF or Ak.sup.AF is substituted with one or more substituents selected from the group of halo, cyano, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted nitroalkyl, and optionally substituted alkyl; and further includes a cationic moiety (e.g., an onium cation) or a halo (e.g., fluoro, or any described herein).
[0197] In some instances, the functional group R.sup.AF is a group including a linker R.sup.A and a functional moiety R.sup.AF1, R.sup.A1, or R.sup.F1. In particular embodiments, R.sup.AF1 is a cationic moiety or a halo. In some embodiments, R.sup.A1 is a cationic moiety or includes a cationic moiety (e.g., an ammonium cation, a sulfonium cation, a phosphonium cation, an oxonium cation, a diazonium cation, or a halonium cation). In other embodiments, R.sup.F1 is a halo or includes a halo.
[0198] In some embodiments, R.sup.A1 includes N.sup.+. In other embodiments, R.sup.A1 is N.sup.+R.sup.N1R.sup.N2R.sup.N3 or includes N.sup.+R.sup.N1R.sup.N2R.sup.N3, where each of R.sup.N1, R.sup.N2, and R.sup.N3 is, independently, H, optionally substituted alkyl, optionally substituted aryl, or optionally substituted alkaryl; or where R.sup.N1 and R.sup.N2, taken together with the nitrogen atom to which each are attached, form a heterocycle; or where R.sup.N1 and R.sup.N2, taken together, form an optionally substituted alkylene or heteroalkylene (e.g., as described herein). In some embodiments, each of R.sup.N1, R.sup.N2, and R.sup.N3 is, independently, H or optionally substituted C.sub.1-6 alkyl.
[0199] In some embodiments, R.sup.AI includes S.sup.+. In other embodiments, R.sup.A1 is S.sup.+R.sup.S1R.sup.S2 or includes S.sup.+R.sup.S1R.sup.S2, where each of R.sup.S1 and R.sup.S2 is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkaryl, or optionally substituted alkenyl; or where R.sup.S1 and R.sup.S2, taken together with the sulky atom to which each are attached, form a heterocycle; or where R.sup.S1 and R.sup.S2, taken together, form an optionally substituted alkylene or heteroalkylene (e.g., as described herein). In some embodiments, each of R.sup.S1 and R.sup.S2 is, independently, H or optionally substituted C.sub.1-6 alkyl.
[0200] In some embodiments, R.sup.A1 includes P.sup.+. In other embodiments, R.sup.A1 is P.sup.+R.sup.P1R.sup.P2R.sup.P3 or includes P.sup.+R.sup.P1R.sup.P2R.sup.P3, where each of R.sup.P1, R.sup.P2, and R.sup.P3 is, independently, H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkaryl; or where two of R.sup.P1, R.sup.P2, and R.sup.P3, taken together, form an optionally substituted alkylene or heteroalkylene (e.g., as described herein). In some embodiments, each of R.sup.P1, R.sup.P2, and R.sup.P3 is, independently, H or optionally substituted C.sub.1-6 alkyl.
[0201] In some embodiments, R.sup.A1 includes O.sup.+. In other embodiments, R.sup.A1 is O.sup.+R.sup.O1R.sup.O2 or includes O.sup.+R.sup.O1R.sup.O2, where each of R.sup.O1 and R.sup.O2 is, independently, H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, or optionally substituted alkaryl; or where R.sup.O1 and R.sup.O2, taken together, form an optionally substituted alkylene or heteroalkylene (e.g., as described herein). In some embodiments, each of R.sup.O1 and R.sup.O2 is, independently, H or optionally substituted C.sub.1-6 alkyl.
[0202] In some embodiments, R.sup.A1 is N.sub.2.sup.+ or includes N.sub.2.sup.+.
[0203] In some embodiments, R.sup.A1 is X.sup.+ or includes X.sup.+, where X is halo as defined herein. Exemplary halonium groups include an iodonium group (e.g., I.sup.+), a bromonium group (e.g., Br.sup.+), a chloronium group (e.g., Cl.sup.+), or a fluoronium group (e.g., F.sup.+).
[0204] In some embodiments, R.sup.F1 is halo or includes halo (e.g., F, Cl, Br, or I).
[0205] As seen in
[0206] A polymer can include any useful combination of R.sup.AF groups, see, e.g.,
[0207] In any formula herein, the polymer includes a functional group in which the cationic moiety is distanced from the backbone. For instance, when R.sup.AF is L.sup.A-R.sup.AF1, in which L.sup.A is a linker and R.sup.AF1 is functional moiety including a cationic moiety, then L.sup.A is linker longer than three carbon atoms (e.g., an optionally substituted C.sub.4-18 alkylene). Without wishing to be limited by mechanism, under high temperatures (e.g., greater than about 80 C.), benzyl ammonium cations can degrade, and it has been postulated that the hydroxyl anions can nucleophilically attack the ammonium positive charge. Thus, a long alkyl tether can be employed to minimize such nucleophilic reactions, which may be explained by the increased steric bulk of the long alkyl chain that may wrap around the cation protecting it from nucleophilic attack.
[0208] Each R.sup.AF1 functional moiety can be a functional moiety including a cationic moiety (R.sup.A1) or a functional moiety including a halo (R.sup.F1). Each of R.sup.A1 and R.sup.F1 can be located at any useful position of the pendent or backbone aryl groups, see, e.g.,
[0209] Functional moieties R.sup.A1 and R.sup.F1 can be attached to the polymer in any useful manner, see, e.g.,
[0210] Polymers having reactive handles R.sup.H can be further reacted to provide functional moieties R.sup.AF on any useful polymer (e.g., a polymer having formula (I)). Exemplary reactive handles (e.g., R.sup.H) include any useful group, such as H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted heteroalkyl, halo, optionally substituted aryl, optionally substituted alkaryl, optionally substituted arylalkoxy, optionally substituted aryloxy, optionally substituted aryloxycarbonyl, optionally substituted aryloyl, optionally substituted arylcarbonylalkyl, optionally substituted arylsulfonyl, and optionally substituted arylsulfonylalkyl. In one instance, at least one R.sup.H includes an optionally substituted aryl group (e.g., an optionally substituted aryl group including a halo, a haloalkyl, a perfluoroalkyl, a hydroxyl, or an alkoxy group).
[0211] In some embodiments, the reactive handle R.sup.H includes -L.sup.H-Ar.sup.H or -L.sup.H-Ak.sup.H, in which Ar.sup.H is an optionally substituted aryl and in which Ak.sup.H is an optionally substituted alkyl or optionally substituted heteroalkyl. In particular embodiments L.sup.H is any useful covalent bond or any useful linker (e.g., any described herein). In some embodiments, Ar.sup.H or Ak.sup.H is substituted with one or more substituents selected from the group of halo, cyano, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted nitroalkyl, and optionally substituted alkyl.
[0212]
[0213] In some embodiments, the Ar.sup.H aryl-containing R.sup.H substituent is -L.sup.H-Ar.sup.H, in which Ar.sup.H is an R.sup.H1-substituted phenyl group. Furthermore, any number h of such R.sup.H substituents can be installed on each aryl group. R.sup.H1 can be any useful substituent, such as amino, amino, azido, nitro, nitroso, halo, as well as any described for an aryl group (e.g., substituents (1)-(47) as defined herein for aryl). As seen in
[0214] In other embodiments, the Ar.sup.H aryl-containing R.sup.H substituent is -L.sup.H-Ar.sup.H, in which L.sup.H is a sulfonyl group and in which Ar.sup.H is a halo-substituted phenyl group (e.g., pentafluorophenyl, tetrafluorophenyl, trifluorophenyl, difluorophenyl, or monofluorophenyl). As seen in
[0215] In yet other embodiments, the Ar.sup.H aryl-containing R.sup.H substituent is -L.sup.H-Ar.sup.H, in which L.sup.H is a carbonyl group and in which Ar.sup.H is a halo-substituted phenyl group (e.g., pentafluorophenyl, tetrafluorophenyl, trifluorophenyl, difluorophenyl, or monofluorophenyl). As seen in
[0216] As can also be seen in
[0217] In some embodiments, the Ak.sup.H alkyl-containing R.sup.H substituent is -L.sup.H-Ak.sup.H, in which Ak.sup.H is an R.sup.H1-substituted C.sub.1-alkyl group. Furthermore, any number h of such R.sup.H substituents can be installed on each aryl group, and any number h1 of CR.sup.H1R.sup.H1 groups can be present within the R.sup.H substituent, in which each R.sup.H1 can be the same or different. R.sup.H1 can be any useful substituent, such as amino, amido, azido, nitro, nitroso, halo, as well as any described for an aryl group (e.g., substituents (1)-(27) as defined herein for alkyl). As seen in
[0218] In other embodiments, the Ak.sup.H alkyl-containing R.sup.H substituent is -L.sub.H-Ak.sup.H, in which L.sup.H is a carbonyl group and in which Ak.sup.H is a halo-substituted alkyl group (e.g., perfluoroalkyl, (CF.sub.2).sub.h1F, (CH.sub.2).sub.h1F, or (CHF).sub.h1F, in which h1 is an integer of from about 1 to about 24). As seen in
[0219] Exemplary linkers (e.g., for L.sup.A or L.sup.H) include a covalent bond, carbonyl (C(O)), oxy (O), phosphonoyl phosphoryl (P(O)H), phosphoryl (P(O)<), sulfonyl (S(O).sub.2), sulfonyl (S(O)), sulfonamide (e.g., SO.sub.2NR.sup.L3 or NR.sup.L3SO.sub.2, where R.sup.L3 is H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkoxy, optionally substituted alkaryl, optionally substituted aryl, or halo), imino (NH), imine (e.g., CR.sup.L1N, where R.sup.L1 is H or optionally substituted alkyl), phosphine (e.g., PR.sup.L3 group, where R.sup.L3 is H or optionally substituted alkyl), nitrilo (e.g., NR.sup.L3, where R.sup.L3 is H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkoxy, optionally substituted alkaryl, optionally substituted aryl, or halo), optionally substituted C.sub.1-12 alkylene (e.g., (CR.sup.L1R.sup.L2).sub.La-, where each of R.sup.L1 and R.sup.L2 is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkoxy, optionally substituted alkaryl, optionally substituted aryl, or halo), optionally substituted C.sub.1-12 alkyleneoxy, optionally substituted C.sub.1-12 heteroalkylene (e.g., C(O)NR.sup.L3, NR.sup.L3C(O), (CR.sup.L1R.sup.L2).sub.LaC(O)NR.sup.L3, (CR.sup.L1R.sup.L2).sub.LaNR.sup.L3C(O), (CR.sup.L1R.sup.L2).sub.LaSO.sub.2NR.sup.L3, or SO.sub.2NR.sup.L3(CR.sup.L1R.sup.L2).sub.La, where each of R.sup.L1, R.sup.L2, and R.sup.L3 is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkoxy, optionally substituted alkaryl, optionally substituted aryl, or halo), optionally substituted C.sub.1-12 heteroalkyleneoxy, optionally substituted C.sub.4-18 arylene, or optionally substituted C.sub.4-18 aryleneoxy.
[0220] Further exemplary reactive handles R.sup.H include C(O)Ar.sup.H, in which Ar.sup.H is an optionally substituted aryl (e.g., optionally substituted phenyl with one or more optional substituents selected from the group of halo, haloalkyl, nitro, nitroso, alkoxy, etc.). In another instance, R.sup.H includes C(O)-Ph, in which Ph is substituted with h1 number of R.sup.H1, where R.sup.H1 is selected from the group of halo, haloalkyl, nitro, nitroso, alkoxy, etc., and where h1 is an integer of from 1 to 5).
[0221]
[0222] Any useful number of aryl groups in the polymer can include R.sup.H. For instance, as seen in
[0223] The polymer structure can include any useful combination of substitutions, including one or more R.sup.H substituents in combination with one or more R.sup.1 and/or R.sup.3 substituents. For instance, as seen in
[0224] In one instance, the number h of R.sup.H substituent(s) is of from 0 to 5 for each aryl group (e.g., from 0 to 4, 0 to 3, 0 to 2, 0 to 1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, or 2 to 3). In some embodiments, each aryl group includes one or more R.sup.H. In other embodiments, one aryl group includes one or more R.sup.H. In other embodiments, each pendent aryl group includes one or more R.sup.H. In yet other embodiments, one to three pendent aryl groups includes one or more R.sup.H. In other embodiments, each backbone aryl group or Ar.sup.L aryl group includes one or more R.sup.H. In some embodiments, one backbone aryl group includes one or more R.sup.H. In particular embodiments, each h for each aryl group is the same or different.
[0225] In another instance, each backbone aryl group or Ar.sup.L aryl group includes one or more R.sup.1. In particular embodiments, each q for each aryl group is the same or different. In yet another instance, the number q of R.sup.3 substituent(s) is of from 0 to 5 for each aryl group (e.g., from 0 to 1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, or 2 to 3). in some embodiments, each pendent aryl group includes one or more R.sup.3.
[0226] Any useful R.sup.H substituents can be present on any number of aryl groups (e.g., some of the pendent aryl groups, such as of from about 1 to about 3 pendent aryl groups). For instance,
[0227] Other exemplary reactive handles R.sup.H include SO.sub.2Ar.sup.H, in which Ar.sup.H is an optionally substituted aryl (e.g., optionally substituted phenyl with one or more optional substituents selected from the group of halo, haloalkyl, nitro, nitroso, alkoxy, etc.). In another instance, R.sup.H includes SO.sub.2-Ph, in which Ph is substituted with h1 number of R.sup.H1, where R.sup.H1 is selected from the group of halo, haloalkyl, nitro, nitroso, alkoxy, etc., and where h1 is an integer of from 1 to 5).
[0228] Exemplary acidic moieties (e.g., R.sup.S) include any group having one or more sulfonyl groups, such as sulfo (e.g., SO.sub.2OH), alkylsulfonyl (e.g., SO.sub.2R.sup.S1, where R.sup.S1 is optionally substituted C.sub.1-12 alkyl), alkylsulfonylalkyl (e.g., R.sup.SASO.sub.2R.sup.S1, where each of R.sup.S1 is optionally substituted C.sub.1-12 alkylene or optionally substituted heteroalkylene and R.sup.S1 is optionally substituted C.sub.1-12 alkyl), arylsulfonyl (e.g., SO.sub.2R.sup.Ar, where R.sup.Ar is optionally substituted C.sub.4-18 aryl), arylsulfonylalkyl (e.g., R.sup.SASO.sub.2R.sup.Ar, where R.sup.SA is independently, optionally substituted C.sub.1-12 alkyl or alkylene and R.sup.Ar is optionally substituted C.sub.4-18 aryl), sulfonamoyl (e.g., SO.sub.2NR.sup.N1R.sup.N2), sulfoamino (e.g., N(R.sup.N1)SO.sub.2R.sup.S3), aminosulfonyl (e.g., SO.sub.2NR.sup.N1R.sup.S2), or sulfonyl imide (e.g., SO.sub.2NR.sup.N1SO.sub.2R.sup.S3), where each of R.sup.N1 and R.sup.N2 is, independently, H, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as perfluoroalkyl), optionally substituted C.sub.4-18 aryl, or optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl; R.sup.S2 is H, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as perfluoroalkyl), hydroxyl, optionally substituted C.sub.1-12 alkylsulfonyl, optionally substituted C.sub.4-18 aryl, or optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl; and R.sup.S3 is H, hydroxyl, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as perfluoroalkyl), optionally substituted C.sub.4-18 aryl, or optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl.
[0229] In any of these moieties, each R.sup.S1 and R.sup.S3 is, independently, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as C.sub.1-12 perfluoroalkyl), optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H; each R.sup.S2 is independently, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as perfluoroalkyl), optionally substituted C.sub.1-12 alkylsulfonyl, optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H; each R.sup.Ar is, independently, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, or optionally substituted C.sub.4-18 aryloxy; each of R.sup.SA is, independently, oxy, optionally substituted C.sub.1-12 alkylene, or optionally substituted heteroalkylene; and each of R.sup.N1 and R.sup.N2 is, independently, H, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as perfluoroalkyl), optionally substituted C.sub.4-18 aryl, or optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl.
[0230] Other exemplary acidic moieties (e.g., R.sup.P) include any group having one or more phosphoryl groups, such as phosphono (e.g., P(O)(OH).sub.2), phosphoric ester (e.g., OPO(OH).sub.2 or OP(O)<R.sup.P1R.sup.P2 or OP(O)<R.sup.ArR.sup.P2 or OP(O)<R.sup.ArR.sup.Ar, where each R.sup.Ar is the same or different), alkylphosphoryl (e.g., P(O)<R.sup.P1R.sup.P2, where R.sup.P1 is optionally substituted C.sub.1-12 alkyl or optionally substituted C.sub.1-12 alkoxy; and R.sup.P2 is optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H), substituted phosphonoyl (e.g., P(O)HR.sup.P1, where R.sup.P1 is optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H), alkylphosphorylalkyl (e.g., R.sup.PAP(O)<R.sup.P1R.sup.P2, where R.sup.PA is optionally substituted C.sub.1-12 alkylene or optionally substituted heteroalkylene; and each of R.sup.P1 and R.sup.P2 is, independently, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H), arylphosphoryl (e.g., P(O)<R.sup.ArR.sup.P2 or P(O)<R.sup.ArR.sup.Ar, where each R.sup.Ar is, independently, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, or optionally substituted C.sub.4-18 aryloxy; and R.sup.P2 is optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H), or arylphosphorylalkyl (e.g., R.sup.PAP(O)<R.sup.ArR.sup.P2 or R.sup.PAP(O)<R.sup.ArR.sup.Ar, where R.sup.PA is, independently, optionally substituted C.sub.1-12 alkylene or optionally substituted heteroalkylene; each R.sup.Ar is, independently, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, or optionally substituted C.sub.4-18 aryloxy; and R.sup.P2 is optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H), where each of these groups can be optionally substituted (e.g., with one or more substituents described for alkyl, as defined herein).
[0231] In any of these moieties, each of R.sup.P1 and R.sup.P2 is, independently, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as C.sub.1-12 perfluoroalkyl), optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H; each of R.sup.Ar is, independently, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, or optionally substituted C.sub.4-18 aryloxy; and each R.sup.PA is, independently, oxy, optionally substituted C.sub.1-12 alkylene, or optionally substituted heteroalkylene.
[0232] Yet other exemplary acidic moieties (e.g., R.sup.C) include any group having a carbonyl group, such as carboxyl (e.g., CO.sub.2H), C(O)R.sup.C1, or R.sup.CAC(O)R.sup.C1 (e.g., where each R.sup.C1 is, independently, optionally substituted C.sub.1-12 alkyl (e.g., haloalkyl, such as C.sub.1-12 perfluoroalkyl), optionally substituted C.sub.1-12 alkoxy, optionally substituted C.sub.4-18 aryl, optionally substituted C.sub.1-12 alk-C.sub.4-18 aryl, optionally substituted C.sub.4-18 aryloxy, hydroxyl, or H; and each R.sup.CA is, independently, oxy, optionally substituted C.sub.1-12 alkylene, or optionally substituted heteroalkylene).
[0233] Exemplary electron-withdrawing moieties (e.g., R.sup.E) include optionally substituted C.sub.7-11 aryloyl, optionally substituted C.sub.6-18 aryl, carboxyaldehyde, optionally substituted C.sub.2-7 alkanoyl, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 haloalkyl, optionally substituted C.sub.2-7 alkoxycarbonyl, nitro, nitroso, cyano, sulfa carboxyl, and quaternary ammonium (e.g., N.sup.+R.sup.N1R.sup.N2R.sup.N3, where each of R.sup.N1, R.sup.N2, and R.sup.N3 is, independently, optionally substituted alkyl, optionally substituted alkaryl, or optionally substituted aryl, or two of R.sup.N1, R.sup.N2, and R.sup.N3, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein). In another embodiment, R.sup.E includes or is substituted by a C.sub.1-12 perfluoroalkyl group. In yet another embodiment, R.sup.E is a C.sub.1-12 perfluoroalkyl group.
[0234] One or more functional groups can be appended to a reactive handle R.sup.H. Exemplary functional groups include any useful group, such as halo, nitro, nitroso, cyano, amino, amido, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 haloalkyl, optionally substituted C.sub.1-12 perfluoroalkyl, optionally substituted C.sub.1-12 heteroalkyl, optionally substituted C.sub.1-12 alkoxy, optionally substituted aryl, optionally substituted alkaryl, optionally substituted arylalkoxy, optionally substituted aryloxy, optionally substituted aryloxycarbonyl, optionally substituted aryloyl, optionally substituted arylsulfonyl, and optionally substituted arylsulfonylalkyl, in addition to any that provides an R.sup.AF (e.g., as defined herein).
[0235] The functional moieties including a cationic moiety, functional moieties including a halo, reactive handles, acidic moieties, electron-withdrawing moieties, and/or functional groups can be substituted or unsubstituted. For example, these groups can be substituted with one or more substitution groups, as described herein for alkyl and/or aryl.
Aryl groups
[0236] The aryl groups herein can have any useful configuration, structure, and substitutions. Exemplary aryl groups (e.g., including arylene groups, such as for Ar.sup.L, Ar.sup.M, and Ar*) include the following groups, which may be optionally substituted:
##STR00004## ##STR00005##
where each of Z, Z.sup.1, Z.sup.2, and Z.sup.3 is, independently, O, S, SO.sub.2, optionally substituted alkylene, optionally substituted C.sub.1-12 alkyleneoxy, optionally substituted C.sub.1-12 heteroalkylene, optionally substituted C.sub.1-12 heteroalkyleneoxy, CF.sub.2, CH.sub.2, OCF.sub.2, perfluoroalkylene, perfluoroalkyleneoxy, Si(R.sup.i).sub.2, P(O)(R.sup.i), PR.sup.i, C(O), C(CF.sub.3).sub.2, C(CH.sub.3).sub.2, or CCF.sub.3Ph-, and where R.sup.i is H, optionally substituted alkyl, or optionally substituted a methyl, ethyl, isopropyl, t-butyl, or phenyl).
Polymer Salts and Forms Thereof Including a Counter Ion
[0237] The present invention includes a salt or a form thereof including a counter ion of any polymer described herein, e.g., a salt or a form thereof including a counter ion of any one of formulas (I), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (VI), (VIa), (VIb), (VIc), (VId), (VII), (VIII), (VIIIa), and (IX), as well as particular structures provided as structures (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), (IV-3), (IV-5), (IV-8), (IV-10), and (IV-11). In particular embodiments, the salt is a sodium salt. In other embodiments, the counter ion is an anion (e.g., a chloride anion or a hydroxide anion).
Polymeric Starting Material
[0238] Polymers having formula (II) can be employed as a starting material, in which reactive handles R.sup.H can be further reacted to provide functional moieties R.sup.AF on polymer having formula (I). As can be seen in
[0239] The polymer (e.g., of formula (II) or (V)) can include any useful type of pendent substituents (e.g., pendent substituents R.sup.H and/or R.sup.3), any useful number of such substituents on each aryl group (e.g., h substituents for R.sup.H and/or q substituents for R.sup.3, where each of h and q is, independently, 0, 1, 2, 3, 4, or 5, and/or where at least one h is not 0), any useful backbone structure (e.g., two R.sup.1-substituted aryl groups and a bridging group Ar.sup.L optionally including a reactive handle R.sup.H), any useful type of backbone substituents (e.g., backbone substituents R.sup.1 or R.sup.H disposed on a backbone aryl group), and any useful number of such substituents on each group (e.g., h substituents for R.sup.H and/or q substituents for R.sup.1, where each of h and q is, independently, 0, 1, 2, 3, 4, or 5, and/or where at least one h is not 0). Each of bridging group Ar.sup.L and connecting group Ar.sup.Mcan be any useful bivalent linker (e.g., any described herein). In particular embodiments, each of Ar.sup.L and Ar.sup.M is, independently, includes an optionally substituted arylene group. Furthermore, a polymer can include any useful number of structures of formula (I). In some embodiments, the polymer includes In structures, where m is an integer of from about 1 to 1000 (e.g., from about 1 to 500).
[0240] For any structure described herein, each R.sup.1 or R.sup.3 is, independently, a reactive handle R.sup.H, an acidic moiety (e.g., R.sup.S, R.sup.P, R.sup.C, or any described herein), an electron-withdrawing moiety (e.g., R.sup.F or any described herein), or an inert substituent (e.g., H, halo, optionally substituted alkyl, optionally substituted alkoxy, etc.). In some embodiments, each and every R.sup.1 is, independently, R.sup.H, R.sup.S, R.sup.P, R.sup.C, or R.sup.E. In other embodiments, each and every R.sup.3 is, independently, R.sup.H, R.sup.S, R.sup.P, R.sup.C, or R.sup.E.
[0241] As seen in
[0242] As seen in
[0243] Any polymer including an R.sup.H functional moiety can be employed as a starting material (e.g., any described herein, such as in
Methods of Making Polymer Structures
[0244] The polymers of the invention can be synthesized using any useful scheme. The following synthetic schemes are provided as non-limiting examples.
[0245]
[0246] In
[0247]
[0248] A functionalized polymer can be further reacted in any useful manner to provide a cationic, hydrophobic polymer (e.g., as a film). For instance,
[0249] A functional group present on a polymer can be further reacted in any useful manner. In one instance, the linker includes an oxo group, which can be reduced with any useful reducing agent. As seen in
##STR00006##
[0250] As shown in Scheme I, the polymer of formula (IXa) can be formed by reacting a polymer of formula (IIi) having reactive handles, in which polymer (IIi) in turn can be formed by performing a Diels-Alder reaction to form the pendent and backbone aryl groups, and then performing a first substitution reaction to introduce R.sup.H to the parent structure. These steps are described in more detail below.
[0251] First, a Diels-Alder reaction can be performed with an optionally substituted diene, such as a 1,4-bis-(2,4,5-triphenylcyclopentadienone)arylene reagent (1), with an optionally substituted dienophile, such as a diethynylarylene reagent (2). This reaction provides a Diels-Alder poly(phenylene) polymer (DAPP) (3). As can be seen, in this step, the number of subunits m is controlled by the stoichiometry of reagents (1) and (2).
[0252] Second, a substitution reaction is performed with reagent R.sup.HX with the DAPP product (3) to provide a substituted polymer (IIi), where X is any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate) and R.sup.H is any described herein (e.g., R.sup.H can be -L.sup.H-Ar.sup.H or L.sup.H-Ak.sup.H).
[0253] The concentration of R.sup.HX can be controlled to provide the desired extent of substitution on the DAPP pendent and/or backbone aryl groups. As can be seen, the number of R.sup.H substituents h on each aryl group can be controlled by the stoichiometry of reagent R.sup.HX and (DAPP) (3). In one instance, concentration can be controlled in order to install R.sup.H substituents on readily accessible pendent aryl groups. The reaction can be conducted until completion in order to access the backbone aryl groups, which are sterically more difficult to functionalize.
[0254] Optionally, the substitution reaction with reagent R.sup.HX is performed in the presence of a metal salt and/or in the presence of an acid. Exemplary metal salts include M[O(SO.sub.2R.sup.MF)], M[N(SO.sub.2R.sup.MF).sub.2], or M[C(SO.sub.2R.sup.MF).sub.3], where R.sup.MF is optionally substituted alkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted haloalkyl, or perfluoroalkyl, and where M is Ag, Al, Ba, Bi, Ca, Cu, In, Re, Sc, Sn, Ti, Y, Yb, or Zn. Particular embodiments of metal salts include M[OTf].sub.mf, where mf is an integer from 1 to 3 and where M is Ag, Al, Ba, Bi, Ca, Cu, In, Sc, Y, or Yb; as well as M[NTf.sub.2].sub.mf, where mf is an integer from 1 to 3 and where M is Ag, Al, Sn, Ti, Yb, or Zn.
[0255] Exemplary acids include a Lewis acid or a Bronsted acid that acts as a catalyst, such as, e.g., HO(SO.sub.2R.sup.AF), HO(SO.sub.2R.sup.Ar), HO(SO.sub.2F), HO(SO.sub.2R.sup.Ar), and HO(C(O)R.sup.AF), where R.sup.AF is optionally substituted alkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted haloalkyl, or perfluoroalkyl, and where R.sup.Ar is optionally substituted aryl or optionally substituted alkaryl. Particular embodiments of acids include HO(SO.sub.2CF.sub.3), HO(SO.sub.2F), H.sub.2SO.sub.4, HO(SO.sub.2(p-CH.sub.3)Ph), or HO(COCF.sub.3).
[0256] Third, a substitution reaction is performed to react a reactive handle R.sup.H in the presence of a functional agent R.sup.AF*X, thereby providing a functional group R.sup.AF. As seen in formula (IXa), R.sup.AF is formed by a reacted R.sup.H group (indicated by R.sup.H*) that is appended by a reacted functional moiety R.sup.AF*. In one non-limiting example, the reactive group R.sup.H can be a -Ph-CH.sub.2Cl group that is reacted with an amine NR.sup.N1R.sup.N2R.sup.N3 (e.g., where each of R.sup.N1 and R.sup.N2 and R.sup.N3 is, independently, H or optionally substituted alkyl, or R.sup.N1 and R.sup.N2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein), thereby providing an R.sup.AF moiety of -Ph-CH.sub.2NR.sup.N1R.sup.N2R.sup.N3, in which reacted R.sup.H* is -Ph-CH.sub.2 and reacted R.sup.AF* is NR.sup.N1R.sup.N2R.sup.N3.
##STR00007## ##STR00008##
[0257] As shown in Scheme II, the polymer of formula (II) can be formed by performing a Diels-Alder reaction to form the pendent and backbone aryl groups, performing a first substitution reaction to introduce R.sup.3 to the parent structure, performing a second substitution reaction to introduce R.sup.1, and performing a final substitution reaction to introduce R.sup.H. Polymer (II), in turn, can be reacted (e.g., by way of a substitution or replacement reaction) with a functional agent to provide a polymer of formula (I). The four steps to provide formula (II) are described in more detail below.
[0258] Similar to Scheme I, the first step in Scheme II includes a Diels-Alder reaction that is performed with an optionally substituted diene, such as a 1,4-bis-(2,4,5-triphenyl cyclopentadienone)arylene reagent (1), in the presence of an optionally substituted dienophile, such as a diethynylarylene reagent (2). This reaction provides a Diels-Alder poly(phenylene) polymer (DAPP) (3).
[0259] The second step includes an initial substitution reaction, which is performed with reagent R.sup.3X in the presence of the DAPP product (3), thereby providing a substituted polymer (4). For reagent R.sup.3X, X is any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate) and R.sup.3 is any described herein.
[0260] The third step includes a second substitution reaction, which is performed with reagent R.sup.1X in the presence of the substituted polymer (4) to provide the desired polymer of formula (I). For reagent R.sup.1X, X is any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate), and R.sup.1 is any described herein.
[0261] Finally, the fourth step includes a third substitution reaction, which is performed with reagent R.sup.HX in the presence of the DAPP product (3) to provide a substituted polymer (II). For reagent R.sup.HX, X is any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate), and R.sup.H is any described herein (e.g., R.sup.H can be -L.sup.H-Ar.sup.H or -L.sup.H-Ak.sup.H).
[0262] The three substitution steps (i.e., the second, third, and fourth steps) can be performed in any order to obtain the desired substitution pattern. Of course, if R.sup.3 and R.sup.1 are the same substituents, then only one of the substitution reaction steps can be conducted. Alternatively, one or more steps may be required to install R.sup.1 or R.sup.3 on the parent molecule. For instance, when R.sup.1 or R.sup.3 is SO.sub.2NR.sup.N1R.sup.S2, multiple steps may be required to first install the SO.sub.2 functional group on the parent molecule. Then, this functional group may be activated (e.g., by forming a sulfonyl halide, such as sulfonyl chloride) and reacted with an amine (e.g., NHR.sup.N1R.sup.S2).
[0263] In another instance, an additional step may be required to install the functional group. For example, when R.sup.1 or R.sup.3 includes two sulfonyl groups, such as in SO.sub.2NR.sup.N1SO.sub.2R.sup.S2, then then sulfonyl groups can be attached sequentially. In one example, the method includes installing the first SO.sub.2 functional group on the parent molecule and then reacted with a primary amine, such as NH.sub.2R.sup.N1, thereby providing a parent molecule having a SO.sub.2NHR.sup.N1 sulfonamide group. This sulfonamide can then be reacted with an activated sulfonyl agent, e.g., a ClSO.sub.2R.sup.S2 agent, where R.sup.S2 is an optionally substituted C.sub.1-12 alkyl, thereby providing an R.sup.S moiety of SO.sub.2NR.sup.N1SO.sub.2R.sup.S2 on the polymer.
[0264] In yet another instance, when R.sup.1 or R.sup.3 is R.sup.PAP(O)<(R.sup.P1R.sup.P2, multiple steps may be required to first install the R.sup.PA alkylene or heteroalkylene on the parent molecule, and then to later install the P(O)<R.sup.P1R.sup.P2 group on the alkylene or heteroalkylene molecule. Furthermore, if R.sup.P1 or R.sup.P2 is an alkoxy or aryloxy group, then additional step may be required to modify a hydroxyl group attached to the phosphorous atom with an alkoxy or aryloxy group. A skilled artisan would understand that additional modifications or step can be employed to arrive at the desired structure.
[0265] Exemplary R.sup.1X and R.sup.3X reagents include HSO.sub.3Cl, H.sub.2SO.sub.4, PCl.sub.3, POCl.sub.3, H.sub.3PO.sub.4, SO.sub.3, fuming sulfuric acid, thionyl chloride, trimethylsilyl chlorosulfonate, dialkyl phosphites (e.g., diethyl phosphate with an optional catalyst, such as a Pd(0) catalyst), phosphines (e.g., tertiary phosphines), phosphoric acids (e.g., hypophosphorous acids, phosphonic acids, phosphinic acids, etc.), aryl halide (e.g., RX, where R is an optionally substituted aryl group, as defined herein, and X is halo), aryl halide (e.g., RX, where R is an optionally substituted aryloyl group, as defined herein, and X is halo, such as trifluorobenzoyl chloride), protein kinase (e.g., to install a phosphoryl group), phosphonoxyphenols, as well as mixtures thereof.
##STR00009## ##STR00010##
[0266] As discussed herein, the substitution steps can be performed in any useful order. In one non-limiting instance, the reaction scheme includes introducing one or more reactive handles R.sup.H, and then introducing other substitution groups (e.g., R.sup.1 and/or R.sup.3). As shown in Scheme III, the polymer of formula (II) can be formed by performing a Diels-Alder reaction to form the pendent and backbone aryl groups, performing a first substitution reaction to introduce R.sup.H, performing a second substitution reaction to introduce R.sup.3 to the parent structure, and performing a final substitution reaction to introduce R.sup.1. In one instance, the substitution steps including R.sup.3 and R.sup.1 can be conducted in the opposite order. These four steps are described in more detail below.
[0267] Similar to Schemes I and II, the first step in Scheme III includes a Diels-Alder reaction that is performed with an optionally substituted diene, such as a 1,4-bis-(2,4,5-triphenyl cyclopentadienone)arylene reagent (1), in the presence of an optionally substituted dienophile, such as a diethynylarylene reagent (2). This reaction provides a Diels-Alder poly(phenylene) polymer (DAPP) (3).
[0268] The second step includes a first substitution reaction, which is performed with reagent R.sup.HX in the presence of the DAPP product (3) to provide a R.sup.H-substituted polymer (5). For reagent R.sup.HX, X is any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate), and R.sup.H is any described herein (e.g., R.sup.H can be -L.sup.H-Ar.sup.H or -L.sup.H-Ak.sup.H).
[0269] The third step includes a second substitution reaction, which is performed with reagent R.sup.3X in the presence of the R.sup.H-substituted polymer (5), thereby providing a R.sup.H-, R.sup.3-substituted polymer (6). For reagent R.sup.3X, X is any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate) and R.sup.3 is any described herein.
[0270] Finally, the fourth step includes a third substitution reaction, which is performed with reagent R.sup.1X in the presence of the R.sup.H-, R.sup.3-substituted polymer (6) to provide the desired polymer of formula (II). For reagent R.sup.1X, X is any useful leaving group (e.g., halo, hydroxyl, or sulfonate, such as mesylate, tosylate, or triflate), and R.sup.1 is any described herein.
##STR00011## ##STR00012##
[0271] As shown in Scheme IV, the polymer reagent of formula (12) can be formed by performing a Diels-Alder reaction to form the pendent and backbone aryl groups and to install reactive end groups R.sup.L. Then, substitution reactions can be performed in order to introduce R.sup.3, R.sup.1, and/or R.sup.H. These three steps are described in more detail below.
[0272] Similar to that of Scheme I, the first segment is formed by performing a Diels-Alder reaction with a 1,4-bis-(2,4,5-triphenylcyclopentadienone)arylene reagent (1) and a diethynylarylene reagent (2).
[0273] To further install reactive end groups, the Diels-Alder reaction is also performed in the presence of a monoethynylarylene reagent (7). As can be seen, because reagent (2) includes two dienophile groups (i.e., two ethynyl groups), this reagent can react with two diene molecules (1), where the product of this reaction can further propagate the polymerization reaction. In contrast, reagent (7) includes only one dienophile group, and therefore terminates the polymerization reaction and provides a polymer reagent (8) having a terminal reactive end group R.sup.L. Additional methods for installing reactive end groups are described in U.S. Pat. No. 8,110,636, which is incorporated herein by reference in its entirety.
[0274] Then, substitution reaction(s) can be performed. In Scheme IV, the substitution reactions are provided as three steps performed first with reagent R.sup.3X (e.g., as described herein) in the presence of an unsubstituted polymer (8) to form a further polymer (9), then with reagent R.sup.1X (e.g., as described herein) to form a further polymer (10), and finally with reagent R.sup.HX (e.g., as described herein) to form polymer reagent (12). If R.sup.3 and R.sup.1 are the same substituents, then a single substitution reaction step can be conducted. If R.sup.3 and R.sup.1 are different, then these substituents can be added in any desired order. A skilled artisan would understand that other modifications could be made to form the desired polymer reagent (12). In exemplary Scheme IV, Ar.sup.L in formula (12) is Ar.sup.L(R.sub.1).sub.q, which is a non-limiting embodiment.
[0275] Methods of making the polymer also include preparing an initial polymer having one or more R.sup.1 and/or R.sup.3 substituents, and then installing one or more R.sup.H on one or more pendent and/or backbone aryl groups. As seen in
[0276] In another instance, a precursor of the polymer herein (e.g., a polymer having a structure of formula (I)) is prepared as a membrane, and further functionalization is conducted to include one or more R.sup.H, R.sup.1, and/or R.sup.3 substituents by reacting the membrane with one or more reagents to install such substituents.
[0277] Any reactions herein can be conducted with any useful reagent, solvent, or conditions. An example of reagent (1) includes 1,4-bis-(2,4,5-triphenylcyclopentadienone)benzene, and an example of reagent (2) includes diethynylbenzene reagent. Exemplary solvents useful for Diels-Alder and substitution reactions include an ether (e.g., diphenyl ether), methylene chloride, dichloroethane, etc. Salts of any polymers can be obtained by reacting any product with a suitable acid or base to obtain the desired acid or base addition salt. Furthermore, additional reaction steps can be conducted to further purify, test, or use any polymer herein.
[0278] Additional details on synthesis are described in Fujimoto C H et at, Ionomeric poly(phenylene) prepared by Diels-Alder polymerization: Synthesis and physical properties of a novel polyelectrolyte, Macromolecules 2005; 38:5010-6, Lim Y et al., Synthesis and properties of sulfonated poly(phenylene sulfone)s without ether linkage by Diels-Alder reaction for PEMFC application, Electrochim. Acta 2014; 119:16-23, Hibbs M R et al., Synthesis and characterization of poly(phenylene)-based anion exchange membranes for alkaline fuel cells, Macromolecules 2009; 42:8316-21, Jakoby K et al., Palladium-catalyzed phosphonation of polyphenylsulfone,Macromol. Chem. Phys. 2003; 204:61-7, Parcero E et al., Phosphonated and sulfonated polyphenylsulfone membranes for fuel cell application, J Membr. Sci. 2006; 285:206-13, Poppe D et al., Carboxylated and sulfonated poly(arylene-co-arylene sulfone)s: thermostable polyelectrolytes for fuel cell applications, Macromolecules 2002; 35:7936-41, Akiko O et al., Electrophilic aromatic aroylation with CF.sub.3-bearing arenecarboxylic acid derivatives: Reaction behavior and acidic mediator dependence, Synth. Commun. 2007; 37:2701-15, Jang D O et al., Highly selective catalytic Friedel-Crafts acylation and sulfonylation of activated aromatic compounds using indium metal, Tetrahedron Lett. 2006; 47:6063-6, Skalski T J G et al., Structurally-defined, sulfo-phenylated, oligophenylenes and polyphenylenes, J Am. Chem. Soc. 2015; 137(38):12223-6, Kobayashi S et al., Catalytic Friedel-Crafts acylation of benzene, chlorobenzene, and fluorobenzene using a novel catalyst system, hafnium triflate and trifluoromethanesulfonic acid, Tetrahedron Lett. 1998; 39:4697-700, Noji M et al., Secondary benzylation using benzyl alcohols catalyzed by lanthanoid, scandium, and hafnium triflate, J. Org. Chem. 2003; 68:9340-7, Singh R P et al., An efficient method for aromatic Friedel-Crafts alkylation, acylation, benzoylation, and sulfonylation reactions, Tetrahedron 2001; 57:241-7, Ellenberger F et al., Trifluoromethanesulfonic-carboxylic anhydrides, highly active acylation agents, Angew. Chem. Int'l Ed 1972; 11(4):299-300, Effenberger F et al., Catalytic Friedel-Crafts acylation of aromatic compounds, Angew. Chem. Int'l Ed, 1972; 11(4):300-1, and Rakira P E, Triflic acid and its derivatives: a family of useful reagents for synthesis, Chem. Today 2004 May/April:48-50, as well as U.S. Pat. Nos. 8,809,483, 8,110,636 and 7,301,002, each of which is incorporated herein by reference in its entirety.
Uses
[0279] The polymers of the invention can be used in a variety of electrochemical applications. For instance, any polymer herein can be prepared as a membrane (e.g., by casting), and the membrane (e.g., a proton exchange membrane) can be incorporated into any device. In another instance, a precursor of the polymer herein (e.g., a polymer having a structure of formula (I)) is prepared as a membrane (e.g., an anion exchange membrane), and further functionalization is conducted to include one or more R.sup.AF (e.g., R.sup.A and/or R.sup.F), R.sup.H, R.sup.1, and/or R.sup.3 substituents by reacting the membrane with one or more reagents to install such substituents.
[0280] Exemplary devices include fuel cells (e.g., automotive fuel cells, hydrogen fuel cells, or direct methanol fuel cells), flow batteries (e.g., redox flow batteries, such as vanadium redox flow batteries), electrolyzers, electrochemical hydrogen production devices, etc. The membranes can be used for any use, such as a proton exchange membrane, an anion exchange membrane, an ion exchange resin, a polymer separator, etc. In addition, the membranes can be in any useful form, such as a hydrogel. Membranes formed from the polymers herein can, in some instances, display enhanced properties, such as enhanced ion exchange capacity, decreased water uptake, and/or enhanced durability (e.g., as determined by stress-strain measurements). Methods of forming and testing membranes are described in Fujimoto C H et al., Macromolecules 2005; 38:5010-6, Lim Y et al., Electrochim. Acta 2014; 119:16-23, Sun C-N et al., Evaluation of Diels-Alder poly(phenylene) anion exchange membranes in all-vanadium redox flow batteries, Electrochem. Commun. 2014; 43:63-6, Merle G et al., Anion exchange membranes for alkaline fuel cells: A review, J. Membrane Sci. 2011; 377:1-35, Stanis R J et al., Evaluation of hydrogen and methanol fuel cell performance of sulfonated Diels Alder poly(phenylene) membranes, J. Power Sci. 2010; 195:104-10, and Fujimoto C et al., Vanadium redox flow battery efficiency and durability studies of sulfonated Diels Alder poly(phenylene)s, Electrochem. Commun. 2012; 20:48-51, as well as U.S. Pat. Nos. 8,809,483, 8,110,636, and 7,888,397, each of which is incorporated herein by reference in its entirety.
EXAMPLES
Example 1
Fluorine-Containing Anion Exchange Membranes
[0281] Anionic exchange membranes generally employ materials having a cationic charge in order to bind to anions, However, one recent hurdle in use of such anion exchange membranes in fuel cells has been the high water affinity of these materials due to the cationic charge. High water affinity results in poor fuel cell performance at high current density since the water created in the fuel cell is not rejected, and then blocks incoming hydrogen and air from reaching the catalytic sites. This results in flooding. We proposed using halo groups (e.g., fluoro) within the anion exchange polymer structure, which should improve the hydrophobic properties and resist flooding problems. One synthesis issue is that fluorine incorporation is typically difficult and require multi-step reactions.
[0282] Provided herein are compositions and methods including such halo-containing polymers that also include a cationic moiety, thereby enabling its use as an anion exchange membrane. We discuss methods to attach both fluorine and benzyl halide groups onto the Diels-Alder backbone. In
[0283] As seen in
[0284] Furthermore, any other useful synthetic steps can be employed to modify any portion of the polymer. In one non-limiting instance, a ketone functional group can be sensitive to attach by a nucleophile (e.g., a hydroxide anion), and such a ketone group can be removed from the linker in any useful manner. In one instance, the ketone functional group is reduced prior to attaching the ammonium cation (
[0285] Any useful reagents can be employed. For instance, for the reduction of ketone groups, refluxing in 1,2 dichloroethane (DCE) with triethyl silane and trifluoroacetic acid is sufficiently gentle enough to minimize side reactions with the benzyl chloride groups. After reduction of the ketone, the resultant polymer can either be cast as a film or dissolved in a solvent (e.g., THF) to react with an amine (e.g., a trialkyl amine, such as NMe.sub.3) to form the ammonium cation.
[0286] A lengthy linker between the pendent aryl group and the cationic moiety can also be incorporated by first attaching an alkyl chloride group in the optional presence of a Lewis acid catalyst (e.g., a 6-bromohexanoyl chloride in the presence of aluminum trichloride), then attachment of a halo-containing aryl group in the presence of an acid catalyst (e.g., a trifluorobenzoyl chloride with triflic acid), followed by ketone reduction, and then reaction with an amine to provide a cationic moiety (e.g., reaction with a trialkyl amine, such as NMe.sub.3). An exemplary polymer (IV-11) provided by such a synthetic scheme is provided in
Example 2
Testing of Anion Exchange Membranes
[0287] Anion exchange membranes have been developed using poly(phenylene) polymers formed by a Diels-Alder reaction (Diels-Alder polyphenylene polymers, DAPPs). In particular, such a synthesis allows for use of poly(phenylene) polymers as the backbone scaffold.
Example 3
Functionalization of Diels-Alder Polyphenylene Polymers
[0288] Friedel-Crafts acylation reactions can be employed to functionalize Diels-Alder polyphenylene polymers (see, e.g., U.S. Pat. No. 8,809,483). Such functionalized polymers can be further reacted to provide any useful polymer (e.g., a polymer having formula (I)). As seen in
[0289] When this Friedel-Crafts acylation approach was used to attach aryl acyl chlorides (e.g., benzoyl chloride), an insoluble product was obtained, which could not be processed further (
[0290] There are numerous differences between an alkyl acylation reaction (e.g., as in
[0291] New strategies were required to effectively attach aryl-based functional groups on DAPP backbone and/or pendent groups. In particular, these developments included use of a metal salt to promote aryl acylation. Effenberger published work discussing non-metal catalyzed, Friedel Crafts acylation employing silver triflate (see Effenberger F et al., Trifluoromethanesulfonic-carboxylic anhydrides, highly active acylation agents, Angew. Chem. Int'l Ed. 1972; 11(4):299-300). Without wishing to be limited by mechanism, a reaction between silver triflate and benzoyl chloride generally generates a trifluoromethanesulfonic-carboxylic anhydride and silver chloride (
[0292] We have applied this chemistry onto a Diels-Alder polyphenylene (DAPP) by reacting a F-labeled DAPP with 4-fluorobenzoyl chloride in the presence of sliver triflate (
[0293] The synthetic protocol is provided in
[0294] The resultant product was dissolved in D-chloroform for 19F-NMR analysis to determine fluorine quantitative incorporation (
[0295] The aryl fluorine group can serve as a reactive handle, which can be further reacted with other functional groups. In particular, the functional versatility of attaching the 4-fluorobenzoyl group is the lability of aryl halides in the presence of a strong electron withdrawing group towards nucleophilic aromatic substitution (SnAr2). As seen in
Example 4
Acylation Using an Arylsulfonyl Reagent
[0296]
[0297] The reactive handle R.sup.H can be installed in any useful manner. In one instance, R.sup.H can be reacted with the F-labeled DAPP in the presence of a metal salt, e.g., M(OTf), a metal triflate salt. The metal triflate can promote the Friedel Crafts aryl acylation reaction, thereby providing an exemplary DAPP polymer (II-15) having one or more R.sup.H groups appended to the pendent aryl groups and/or the backbone aryl groups of the DAPP polymer.
Example 5
Synthesis of the Fluorinated Diels-Alder Poly(phenylene) F-DAPP (3*)
[0298]
Example 6
Acylation of Diels-Alder Poly(phenylene) Backbone With Silver Triflate
[0299]
Other embodiments
[0300] All publications, patents, and patent applications mentioned in this specification are incorporated herein by reference to the same extent as if each independent publication or patent application was specifically and individually indicated to be incorporated by reference.
[0301] While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure that come within known or customary practice within the art to which the invention pertains and may be applied to the essential features hereinbefore set forth, and follows in the scope of the claims.
[0302] Other embodiments are within the claims.