Block copolymers including poly(phenylene) and methods thereof

Abstract

The present invention relates to polymers and copolymer including a poly(phenylene) structure, as well as a long tether. In some embodiments, the long tether facilitates a reaction between the poly(phenylene) structure and another subunit of a second polymer. In some embodiments, the tether is flexible.

Claims

1. A composition comprising a structure having the formula (II): ##STR00008## or a salt thereof, wherein: 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.F, 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.F is an electron-withdrawing moiety; each Ar.sup.L and R.sup.M is, independently, a bivalent linker comprising optionally substituted arylene; each Ar.sup.P comprises an optionally substituted arylene or is a covalent bond; each q is, independently, an integer of from 1 to 5; m is an integer of from about 1 to 1000; each L.sup.1 is, independently, selected from the group consisting of: ##STR00009## or a salt thereof; each L.sup.2 is, independently, selected from the group consisting of: ##STR00010## ##STR00011## or a salt thereof; wherein each R.sup.T is, independently, H, halo, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 alkoxy, R.sup.S, R.sup.P, R.sup.C, or R.sup.F; wherein each t is, independently, an integer of from 1 to 4; wherein each L.sup.1a, L.sup.1b, L.sup.1c, L.sup.2a, L.sup.2b, and L.sup.2c is, independently, 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; wherein each of m1 and m2 is, independently, an integer of from 1 to 10; wherein Ar.sup.P comprises an optionally substituted arylene; and wherein at least one of L.sup.1a and/or L.sup.2a is not a covalent bond.

2. The composition of claim 1, wherein the composition comprises a structure having formula (IIa), or a salt thereof; and wherein each R.sup.2 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.F.

3. The composition of claim 1, wherein the composition comprises a structure having formula (IIIa): ##STR00012## or a salt thereof, wherein: each of R.sup.H1 and R.sup.H2 is, independently, a reactive end group.

4. The composition of claim 3, wherein each of R.sup.H1 or R.sup.H2 comprises an anion, an alkoxy, a hydroxyl, or an amino.

5. The composition of claim 3, wherein the composition comprises a structure having any one of formulas (IIIb) to (IIIj), (III-1), or (III-2), or a salt thereof.

6. A composition comprising a structure having the formula (IVa): ##STR00013## or a salt thereof, wherein: each R.sup.1 and R.sup.3 is, independently, H, halo, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sup.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.F, 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.F is an electron-withdrawing moiety; each Ar.sup.L and R.sup.M is, independently, a bivalent linker comprising optionally substituted arylene; each Ar.sup.P comprises an optionally substituted arylene or is a covalent bond; each Ar.sup.N comprises an optionally substituted arylene; each q is, independently, an integer of from 1 to 5; each m and n is, independently, an integer of from about 1 to 1000, each L.sup.1 is, independently, selected from the group consisting of: ##STR00014## or a salt thereof; each L.sup.2 is, independently, selected from the group consisting of: ##STR00015## or a salt thereof; wherein each R.sup.T is, independently, H, halo, optionally substituted C.sub.1-12 alkyl, optionally substituted C.sub.1-12 alkoxy, R.sup.S, R.sup.P, R.sup.C, or R.sup.F; wherein each t is, independently, an integer of from 1 to 4; wherein each L.sup.1a, L.sup.1b, L.sup.1c, L.sup.2a, L.sup.2b, L.sup.2c, and L.sup.3 is, independently, 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; wherein each of m1 and m2 is, independently, an integer of from 1 to 10; and wherein at least one of L.sup.1a and/or L.sup.2a is not a covalent bond.

7. The composition of claim 6, wherein Ar.sup.N is a hydrophobic segment.

8. The composition of claim 6, wherein Ar.sup.N comprises an optionally substituted phenylene, optionally substituted naphthylene, optionally substituted phenanthrylene, a sulfone subunit, an arylene sulfone subunit, an ether sulfone subunit, an arylene ether subunit, a perfluoroalkyl subunit, or a perfluoroalkoxy subunit.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows an exemplary schematic of a polymer structure as in formula (I) including a first linking segment L.sup.1, a polymeric segment (e.g., including a plurality of arylene (Ar) groups), and a second linking segment L.sup.2.

(2) FIG. 2A-2G shows exemplary schematics of (A) a polymer structure having an Ar.sup.P group, as in formula (Ia); (B) a polymer structure with a poly(phenylene) subunit, as in formula (Ib); (C) polymer structures with a covalent bond disposed between the polymeric segment and the linking segments, as in formula (Ic) or (Id); (D) a polymer structure having three arylene groups in the linking segment, as in formula (Ie); (E) another polymer structure having three arylene groups in the linking segment, as in formula (If); (F) yet another polymer structure having three arylene groups in the linking segment, as in formula (Ig); and (G) another polymer structure having three arylene groups in the linking segment, as in formula (Ih).

(3) FIG. 3A-3C shows (A) non-limiting exemplary structures (I-1) and (I-2) having a poly(phenylene) subunit; (B) non-limiting exemplary structures (I-3) and (I-4) having a sulfone linker and an oxy linker within the linking segment; and (C) non-limiting exemplary structures (I-5) and (I-6) having sulfonyl-based acidic moieties.

(4) FIG. 4A-4C shows (A) non-limiting polymer structures (II) and (IIa) having a first linking segment L.sup.1 and a second linking segment L.sup.2; (B) non-limiting linking segments (IIA-1) to (IIA-4) including R.sup.T-substituted arylene groups and linkers L.sup.1a, L.sup.1b, L.sup.1c; and (C) non-limiting linking segments (IIB-1) to (IIB-8) including the Ar.sup.P subunit, R.sup.T-substituted arylene groups and linkers L.sup.2a, L.sup.2b, L.sup.2c.

(5) FIG. 5 shows an exemplary schematic of a polymer structure as in formula (III) including a first reactive handle R.sup.H1, a first linking segment L.sup.1, a polymeric segment (e.g., including a plurality of arylene (Ar) groups), a second linking segment L.sup.2, and a second reactive handle R.sup.H2.

(6) FIG. 6 shows non-limiting polymer structures (IIIa) and (IIIb) having reactive handles.

(7) FIG. 7A-7I shows exemplary schematics of (A) a polymer structure having an Ar.sup.P group and reactive handles R.sup.H1, R.sup.H2, as in formula (IIIc); (B) a polymer structure with a poly(phenylene) subunit and reactive handles R.sup.H1, R.sup.H2, as in formula (IIId); (C) a polymer structure with a covalent bond disposed between the polymeric segment and the linking segments, as in formula (IIIe); (D) a polymer structure with a covalent bond disposed between the polymeric segment and the linking segments, as in formula (IIIf); (E) a polymer structure having three arylene groups in the linking segment, as in formula (IIIg); (F) another polymer structure having three arylene groups in the linking segment, as in formula (IIIh); (G) yet another polymer structure having three arylene groups in the linking segment, as in formula (IIIi); (H) another polymer structure having three arylene groups in the linking segment, as in formula (IIIj); and (I) non-limiting exemplary structure (III-1) having a poly(phenylene) subunit and a reactive handle including a hydroxyl group.

(8) FIG. 8 shows an exemplary schematic of a copolymer structure as in formula (IV) including a first linking segment L.sup.1, a first polymeric segment (e.g., including a plurality of arylene (Ar) groups), a second linking segment L.sup.2, a second polymeric segment (e.g., including an Ar.sup.N segment, such as a hydrophobic segment), and a third linking segment L.sup.3.

(9) FIG. 9A-9H shows exemplary schematics of (A) a copolymer structure having a first polymeric segment including a plurality of arylene groups and a second polymeric segment Ar.sup.N, as in formula (IVa); (B) a copolymer structure with a first polymeric segment and a second polymeric segments that both include a poly(phenylene) subunit, as in formula (IVb); (C) another copolymer structure with a first polymeric segment and a second polymeric segments that both include a poly(phenylene) subunit, as in formula (IVc); (D) a copolymer structure with a first polymeric segment that includes a poly(phenylene) subunit and a second polymeric segment that includes a plurality of arylene groups, as in formula (IVd); (E) another copolymer structure with a first polymeric segment that includes a poly(phenylene) subunit and a second polymeric segment that includes a plurality of arylene groups, as in formula (IVe); (F) yet another copolymer structure with a first polymeric segment that includes a poly(phenylene) subunit and a second polymeric segment that includes a plurality of arylene groups, as in formula (IVf); (G) non-limiting exemplary structures (IV-1) and (IV-2) having a poly(phenylene) segment and a poly(sulfone) segment; and (H) non-limiting exemplary structures (IV-3), (IV-4), and (IV-5) having a poly(phenylene) segment, a poly(phenylene) subunit, and a poly(sulfone) segment.

(10) FIG. 10 shows an exemplary reaction for forming a non-limiting poly(phenylene) compound (4).

(11) FIG. 11 shows an exemplary reaction for forming a non-limiting copolymer (6).

(12) FIG. 12A-12B shows (A) an exemplary schematic for a compound including a long tether (IA) and (B) a non-limiting exemplary structure (III-1).

(13) FIG. 13A-13C shows exemplary schematics for (A) a reaction to form an activated poly(phenylene) compound (V-i), (B) a further reaction to extend the linking segment for the compound (III-2), and (C) a polymerization reaction to form a copolymer (IV-6).

(14) FIG. 14 shows an exemplary schematic for a reaction to functionalize a copolymer (IV-6) to form a functionalized copolymer including a plurality of acidic moieties (IV-7).

DETAILED DESCRIPTION OF THE INVENTION

(15) The present invention relates to polymer structures having a long tether (e.g., an extended linking segment). In particular embodiments, these long tethers allow for a reaction between a first polymeric segment at reduced reaction temperatures, thereby reducing the potential for forming a solid. Structures for such polymers, as well as methods for making and using such polymers are described herein.

(16) Polymer, Including Copolymers

(17) The present invention encompasses polymers, including copolymers. Exemplary polymer include any described herein, such as non-limiting generic structure provided in formulas (I), (IA), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (II), (IIa), (III), (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IV), (IVa), (IVb), (IVc), (IVd), (IVe), and (IVf), as well as particular structures (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (III-1), (III-2), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), and (IV-7), including salts thereof. Any of the polymers can include a linking segment provided in formulas (IIA-1), (IIA-2), (IIA-3), (IIA-4), (IIB-1), (IIB-2), (IIB-3), (IIB-4), (IIB-5), (IIB-6), (IIB-7), and (IIB-8), including salts thereof.

(18) Of these, formulas (IV), (IVa), (IVb), (IVc), (IVd), (IVe), and (IVf) are considered to be copolymers. In particular embodiments, the copolymer of the invention includes at least one hydrophilic segment, at least one hydrophobic segment, and at least one linking segment connecting at least one hydrophilic segment with at least one hydrophobic segment.

(19) In one embodiment, a polymer includes the structure of formula (I), including salts thereof. As can be seen in FIG. 1, formula (I) is a generic structure encompassing other structures (e.g., formula (Ia)).

(20) Furthermore, formula (Ia) includes a polymeric segment disposed between two linking segments. The polymeric segment can include any useful backbone structure. For instance, in formula (Ia), the backbone includes three groups, i.e., two R.sup.1-substituted aryl groups and a bridging group Ar.sup.L. The polymer can include any useful type of backbone substituents (e.g., backbone substituents R.sup.1), as well as any useful number of such substituents on each group (e.g., q substituents, where q can be 1, 2, 3, 4, or 5). For any structure described herein, each R.sup.1 is, independently, 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.S, R.sup.P, R.sup.C, or R.sup.F.

(21) Each linking segment can include a linker (e.g., L.sup.1a or L.sup.2a) and an optionally substituted arylene (e.g., R.sup.T-substituted arylene). Each linking segment can include any number of linkers and arylene groups (e.g., any m1 or m2 number of linkers and arylene groups, in which m1 and m2 is, independently, an integer of from 1 to 10). Each R.sup.T can be any useful substituent, such as any described herein.

(22) The linking segment can have any useful number of arylene groups. As seen in FIG. 2C, the linking segment can have any useful arrangement of linkers L.sup.1a, L.sup.2b and R.sup.T-substituted arylene groups. In other embodiments, the linking segment can include three arylene groups, as in formulas (Ie) to (Ih) in FIG. 2D-2G. Additional linking segments are provided in formulas (IIA-1) to (IIA-4) and (IIB-1) to (IIB-8) in FIG. 4A-4C. In particular embodiments, each linker in the linking segment is not a covalent bond (e.g., each linking segment is, independently, carbonyl, oxy, thio, azo, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, nitrilo, optionally substituted C.sup.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).

(23) Subunit Ar.sup.P can be disposed between a polymeric segment and a linking segment. In particular embodiments, Ar.sup.P can include one or more optionally substituted arylene groups. Alternatively, Ar.sup.P is a covalent bond. In one non-limiting instance, Ar.sup.P includes a poly(phenylene) segment. In another instance, Ar.sup.P includes a structure having formula (IB):

(24) ##STR00005##
or a salt thereof. In some embodiments, p1 is an integer of from about 1 to 10. In other embodiments, each of R.sup.1, R.sup.3, Ar.sup.L, Ar.sup.M, and q is, independently, any described herein. In yet other embodiments, Ar.sup.L includes a R.sup.1-substituted 1,4-phenylene, and Ar.sup.M includes an R.sup.2-substituted 1,4-phenylene. In other embodiments, the subunit can include an optionally substituted poly(phenylene) group, as in formula (Ib) in FIG. 2B.

(25) Within the polymeric segment, 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.S substituent(s), R.sup.P substituent(s), R.sup.C substituent(s), R.sup.F 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. Examples of Ar.sup.L and Ar.sup.M 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 (IIa) having Ar.sup.L as a R.sup.1-substituted 1,4-phenylene and Ar.sup.M as an R.sup.2-substituted 1,4-phenylene.

(26) The polymeric segment can also include any useful type of pendent substituents (e.g., pendent substituents R.sup.3), as well as any useful number of such substituents on each aryl group (e.g., q substituents, where q can be 1, 2, 3, 4, or 5). For any structure described herein, each R.sup.3 is, independently, 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.3 is, independently, R.sup.S, R.sup.P, R.sup.C, or R.sup.F. In some embodiments, fully substituted pendent groups (e.g., R.sup.3 is not H) can provide polymers with enhanced proton conduction and durability characteristics.

(27) A polymer can include any useful number of structures of formula (Ia). In some embodiments, the polymer includes m structures, where m is an integer of from about 1 to 1000 (e.g., from 1 to 500).

(28) The present invention also includes copolymers. In one embodiment, the copolymer includes the structure of formula (IV), including salts thereof. As can be seen in FIG. 8, formula (IV) is a generic structure encompassing other structures (e.g., formula (IVa)). Similar to formula (Ia) described above, the copolymer structure of formula (IVa) includes R.sup.1-substituted aryl groups, bridging group Ar.sup.L, connecting group Ar.sup.M, pendent substituents R.sup.3, and m units. Thus, the description for these substituents provided for formula (Ia) applies equally to formula (IVa). In some embodiments, each of Ar.sup.L and Ar.sup.N is, independently, an optionally substituted phenylene. In other embodiments, each of Ar.sup.L and Ar.sup.N is, independently, an optionally substituted 1,4-phenylene.

(29) Formula (IVa) includes various groups present in formula (Ia) or (II), including a first linking segment L.sup.1, a second linking segment L.sup.2, a first polymeric segment, and a subunit Are. Formula (IVa) can include additional groups, such as a third linking segment L.sup.3 and a second polymeric segment Ar.sup.N of n units. The linking segment L.sup.3 can be any useful linkage to form a covalent bond between the two segments (e.g., any linking segment described herein). Exemplary linking segments L.sup.3 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.sup.N unit, or a structure of formula (Ia) or (II), or a portion thereof (e.g., the polymeric segment of formula (Ia) or (II)).

(30) The copolymer can have any useful polymeric segment Ar.sup.N. In some embodiments, Ar.sup.N includes a structure of formula (Ia) or a portion of the structure of formula (Ia), such as a polymeric segment of formula (Ia) (e.g., where each R.sup.3 is H, optionally substituted alkyl, R.sup.S, R.sup.P, R.sup.C, or R.sup.F; or where the number of R.sup.S substituents in Ar.sup.N is less than the number of R.sup.S and/or R.sup.P substituents in the hydrophilic segment); 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.f1CF(CF.sub.2).sub.f2, or >CFO(CF.sub.2).sub.f1CF(CF.sub.2).sub.f2, where each f1 and f2 is, independently, an integer of 1 to about 16).

(31) The copolymer can have any useful combination of first and second polymeric segments. The first polymeric segment can include a poly(phenylene) group (e.g., optionally substituted with one or more R.sup.S, R.sup.P, and/or R.sup.C). The second polymeric segment can include a poly(phenylene) group (e.g., optionally substituted with one or more R.sup.F) (e.g., as in formula (IVb) in FIG. 9B or in formula (IVc) in FIG. 9C). Alternatively, the second polymeric segment can include a poly(aryl) group (e.g., R.sup.n-substituted arylene groups) having linkers L.sup.N1, L.sup.N2, or L.sup.N3 (e.g., as in formula (IVd) to (IVf) in FIG. 9D-9F). In some embodiments, R.sup.n is H, halo, C.sub.1-12 alkyl, or R.sup.F.

(32) In some embodiments, formula (IVa) includes a first polymeric segment that is hydrophilic and a second polymeric segment Ar.sup.N that is a hydrophobic segment. In other embodiments, the hydrophilic segment 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.S, R.sup.P, and/or R.sup.C described herein or any moiety including a sulfonyl group or a phosphoryl group).

(33) A copolymer can include any useful number or ratio of hydrophilic and hydrophobic segments. In some embodiments, formula (IVa) includes m number of hydrophilic segments and n number of hydrophobic segments, where each of m and n is, independently, an integer of from about 1 to 500. In other embodiments, the m (the number of hydrophilic 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).

(34) For any polymer herein, including any copolymer herein, each and every R.sup.1 can be independently, R.sup.S, R.sup.P, R.sup.C, and/or R.sup.F. For instance, in some embodiments, each aryl group in the polymer or a segment thereof is substituted with an R.sup.S, an R.sup.P, and/or an R.sup.C substitution, where each substitution may be the same or different. In some embodiments, each aryl group in the first polymeric segment is substituted with an R.sup.S (e.g., an acidic moiety including a sulfonyl group). In other embodiments, the hydrophilic segment of the copolymer is composed of a structure in which each aryl group is substituted with an R.sup.S, an R.sup.P, and/or an R.sup.C substitution, where each substitution may be the same or different.

(35) As can be seen, the copolymers include a linking segment L.sup.2. The linking segment can be any useful linkage (e.g., any herein), including those composed of structures, or a portion of such structures, in the hydrophilic segment and/or the hydrophobic segment. In other embodiments, the linking segment L.sup.2 is composed of three substructures: (i) a substituted polyphenylene structure of the hydrophilic segment; (ii) a reactive group, which includes an optionally substituted arylene ketone (i.e., -Ph-C(O)-Ph, in which Ph is an optionally substituted phenylene group) and (ii) an arylene sulfone structure of the hydrophobic segment.

(36) In particular embodiments, the copolymer is composed of a hydrophilic segment (e.g., including one or more R.sup.S substitutions, where each R.sup.S can be the same or different) and a hydrophobic segment (e.g., including one or more R.sup.F substitutions, where each R.sup.F can be the same or different).

(37) In some embodiments, the copolymer includes a hydrophilic first polymeric segment having 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.S-substituted pendent aryl groups, R.sup.P-substituted pendent aryl groups, and R.sup.1-substituted backbone aryl groups.

(38) Both acidic substitutions (e.g., R.sup.S, R.sup.P, and/or R.sup.C, as well as combinations thereof) and R.sup.F substitutions can be present on the same polymer or on the same segment of the polymer. 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). In some embodiments, each pendent aryl group is substituted with an R, an R.sup.S, an R.sup.P, and/or an R.sup.C. Optionally, one or more backbone aryl groups can be further substituted with an R.sup.F, an R.sup.S, an R.sup.P, and/or an R.sup.C.

(39) Polymer Reagents

(40) The present invention also includes reagents having any useful polymer segment (e.g., hydrophilic segment or hydrophobic 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. Exemplary polymer reagents including those having a structure provided in formulas (III), (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), and (IIIj). In addition, the polymer segment can include a second polymeric segment (e.g., Ar.sup.N), such as any described herein.

(41) Optionally, a linking segment L.sup.2 can be present between the polymer segment and a reactive end group. The linking segment L.sup.2 can be composed of any useful linkage, such as any described herein (e.g., those described for linking segment L.sup.1).

(42) 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 reagents 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.

(43) 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 the 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 group, where R 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.

(44) Exemplary polymer reagents are provided as structures (IIIa) and (IIIb) in FIG. 6. As can be seen, polymer reagent (IIIa) and (IIIb) includes a two reactive end groups R.sup.H1 and R.sup.H2 with a polymeric segment (in brackets) placed between the reactive end groups. For this exemplary reagent, the subunit Ar.sup.P and linking segments L.sup.1 and L.sup.2 are located between the polymer segmentic and one of the reactive end groups. For reagent (IIIa), the polymeric segment is similar to that of formula (Ia), but any formula or structure herein can be employed for this polymer segment.

(45) Any useful linking segments can be employed. As seen in FIG. 7A-7H, any useful combination and configuration of linkers (e.g., L.sup.1a, L.sup.1b, L.sup.1c, L.sup.2a, L.sup.2b, and L.sup.2c) and R.sup.T-substituted arylene groups.

(46) Functional Moieties

(47) The present invention includes the use of functional moieties, such as acidic moieties and electron-withdrawing moieties. 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.SA 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.2-R.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.

(48) 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.

(49) 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.1 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).

(50) In any of these moieties, each of R.sup.1 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.

(51) 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).

(52) Exemplary electron-withdrawing moieties (e.g., R.sup.F) 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, cyano, sulfo, 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.F includes or is substituted by a C.sub.1-12 perfluoroalkyl group. In yet another embodiment, R.sup.F is a C.sub.1-12 perfluoroalkyl group.

(53) The acidic moieties and electron-withdrawing moieties 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.

(54) Aryl Groups

(55) The aryl groups herein can have any useful configuration, structure, and substitutions.

(56) Exemplary aryl groups (e.g., including arylene groups, such as for Ar.sup.L, Ar.sup.M, Ar.sup.P, and Ar.sup.N) include the following groups, which may be optionally substituted:

(57) ##STR00006## ##STR00007##
where each of Z, Z.sup.1, Z.sup.2, and Z.sup.3 is, independently, O, S, SO.sub.2, 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, 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 aryl (e.g., methyl, ethyl, isopropyl, t-butyl, or phenyl).

(58) Polymer Salts

(59) The present invention includes a salt of any polymer described herein, e.g., a salt of any one of formulas (I), (IA), (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (II), (IIa), (III), (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), (IV), (IVa), (IVb), (IVc), (IVd), (IVe), and (IVf), as well as particular structures (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (III-1), (III-2), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), and (IV-7). In particular embodiments, the salt is a sodium salt. In other embodiments, the salt is a hydroxide salt.

(60) Methods of Making Polymer Structures

(61) The polymers of the invention can be synthesized using any useful scheme. Polymers having poly(phenylene) structures can be formed by performing a Diels-Alder reaction to form the pendent and backbone aryl groups, and then performing one or more substitution reactions to introduce R.sup.3 and/or R.sup.1 to the parent structure.

(62) Additional functional groups can be instilled in any useful manner. 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).

(63) In another instance, an additional step may be required to install the R.sup.S2 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.2-R.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.2-R.sup.S2 on the polymer.

(64) 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.

(65) 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.

(66) Any reactions herein can be conducted with any useful reagent, solvent, or conditions. Exemplary reagents include 1,4-bis-(2,4,5-triphenylcyclopentadienone)benzene and a 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.

(67) Additional details on synthesis are described in Fujimoto C H et al., lonomeric 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, and 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, as well as U.S. Pat. Nos. 8,110,636 and 7,301,002, each of which is incorporated herein by reference in its entirety.

(68) Uses

(69) 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. 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 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.

EXAMPLE

Example 1: Block Copolymer Electrolyte Membranes

(70) Described herein are design strategies to provide high performance, low cost, and durable membranes based on poly(phenylene) polymeric segments. An exemplary poly(phenylene) segment is provided in FIG. 10, in which the tetracyclone monomer (1) and di(ethynyl) benzene monomer (2) are added at a specific mole ratio. This mole ratio, in turn, determines the repeat unit length (m), and the 4-ethynyl anisole (3) is added as the end cap. The methoxy group is then removed via BBr3, to generate the active phenol polymer segment (4).

(71) Activate polymer segments can then be reacted with a further polymeric subunit, thereby providing a copolymer. FIG. 11 shows an exemplary hydroxyl end-capped Diels Alder poly(phenylene) oligomer (4) that is then reacted with the para fluorine group of an end-capped decafluorobiphenyl poly(sulfone) oligomer (5). In this manner, the copolymer (6) includes a poly(phenylene) segment and a poly(sulfone) segment.

(72) Coupling of the two polymeric segments can be sensitive to reaction temperature and to the rate of temperature increase. In one instance, the coupling reaction in FIG. 11 could result in an unprocessable solid if the reaction was heated too quickly to 65 C. Without wishing to be limited by mechanism, the hydroxyl end-capped poly(phenylene) oligomer (4) is sterically hindered (due to the nearby pendent phenyl groups), and use of high temperatures (e.g., at or above 65 C.) are required to promote polymerization but can result in undesired gelation. In part, at this elevated reaction temperature, activated para fluorine groups in decafluorobiphenyl oligomer facilitate copolymerization between the poly(phenylene) segment and the poly(sulfone) segment, but ortho fluorine groups in the decafluorobiphenyl oligomer can also undergo substitution reactions that can lead to cross-linked gels.

(73) Thus, due to the close proximity of the nucleophilic hydroxyl group and the bulky poly(phenylene) repeat group (compound (4) in FIG. 12A), higher temperatures are generally required to couple with decafluorobiphenyl end-capped poly(sulfone), which can easily lead to gel formation. Herein, we describe the use of a long tether to lengthen the distance of the reactive handle R.sup.H1 or R.sup.H2 (e.g., a hydroxyl group) from the poly(phenylene) repeat unit (FIG. 12A). By employing this long tether, the compound (IA) should have an increased nucleophilic character, and reaction of this compound could allow for use of lower temperatures during polymer coupling. FIG. 12B shows an exemplary compound (III-1) including this long tether.

(74) FIG. 13A-13B provides an exemplary synthetic route to provide a non-limiting, long tethered poly(phenylene) oligomer. As in the reaction including a methoxy-end capped poly(phenylene) oligomer in FIG. 10, the tetracyclone monomer (1) and 2-fluoro, 1,4-bis(ethynyl) benzene monomer (2) are added at a specific mole ratio. The backbone fluorine is used as a reference so through .sup.19F-NMR it is possible to determine the value of m, however it is not vital to incorporate the backbone fluorine. Instead of adding 4-methoxy anisole as an end cap, 4-fluorophenyl,4-ethynyl benzene sulfone (3) is employed as the end cap in FIG. 13A to provide compound (V-1).

(75) FIG. 13B provides the next step to attach a further phenyl group, followed by generation of the reactive hydroxyl group through BBr.sub.3 to provide compound (III-2). As can be seen, compound (III-2) includes three phenyl groups in the linking segment, as well as a sulfone and an oxy between phenyl groups to provide a flexible linker.

(76) FIG. 13C provides a copolymer (IV-6) formed by reacting the long tethered oligomer. The long tethered poly(phenylene) oligomer (III-2) can be reacted with decafluorobiphenyl end-capped poly(sulfone) (5) at low temperatures between 40 C. to 50 C. Moreover, at these reaction temperatures, a gel or an insoluble solid was not observed.

(77) In non-limiting embodiments, the copolymer can be further reacted or functionalized. In one instance, the resultant block copolymers are further functionalized by sulfonating with sulfuric acid. The block copolymer (e.g., in powder form or film form) can be sulfonated in neat sulfuric acid. By sulfonating at temperatures near 50 C. for a few days (e.g., three to four days), the entire poly(phenylene) segment (pendent and/or backbone) (IV-6) can be sulfonated to provide high concentrations of acid moieties in the hydrophilic domain of the copolymer (IV-7) (FIG. 14). In one instance, if the poly(sulfone) segment is strongly electron-withdrawing, then this unit would have reduced reactivity towards sulfuric acid. These sulfonated block co-polymers have use in various electrochemical devices as separator membranes and is a strong candidate to replace Nafion.

OTHER EMBODIMENTS

(78) 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.

(79) 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.

(80) Other embodiments are within the claims.