Spirobisindane polymer with inherent microporosity and its manufacturing method

Abstract

The present invention describes intrinsically microporous spirobisindane polymers for use as separators in electrochemical cells.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 476,777, filed December 22, 2022, the entire contents of which are incorporated herein by reference for all purposes. The present invention describes intrinsically microporous spirobisindane polymers for use as separators in electrochemical cells. [Background technology]

[0002] Over the past few decades, lithium-ion batteries (Li-ion batteries) have emerged as the dominant high-energy chemistry due to their uniquely high energy density while maintaining high power output and cyclability at an acceptable price. However, the energy densities of currently commercially available Li-ion battery chemistries are approaching the theoretical limits of the technology. Meanwhile, the rapid trend toward electrification of the transportation and energy industries is driving demand for batteries with higher energy densities at lower unit costs. Batteries with improved capacity, longer cycle life, and higher stability are practically required. Replacing the graphite anode in Li-ion batteries with a lithium metal anode offers favorable conditions for significantly improving the energy density of lithium batteries. However, with repeated charge-discharge cycles, lithium metal batteries suffer from irreversible capacity loss caused by electrolyte depletion and lithium loss due to parasitic reactions between the highly reactive lithium metal anode and electrolyte components. This process contributes to localized inhomogeneities on the lithium anode surface, which further propagates into nonuniform coating and delamination, resulting in physically isolated "dead" lithium. Furthermore, non-uniform lithium film formation increases the risk of dendrite formation, which can lead to thermal runaway and catastrophic cell failure, posing a major obstacle to the commercialization of lithium metal batteries. Suppressing dendrite formation in lithium metal batteries is essential to enable their safe and stable use in commercial applications.

[0003] Battery separators are essential components of Li-ion batteries because they separate the electrodes, transport ions through large electrolyte-filled pores, and insulate electronic conductivity that would otherwise induce short circuits. Although the separator does not directly participate in the cell reaction, its physical properties play a key role in determining the battery's performance, including energy density, power density, and safety. Importantly, the mechanical integrity of the separator throughout the battery cell's lifetime is essential to preventing internal short circuits.

[0004] Currently, several porous membrane separator materials and composites are used in Li-ion batteries, including separators made from polyolefins such as polyethylene (PE), polypropylene (PP), and polypropylene-polyethylene-polypropylene (PP / PE / PP), as well as ceramic-coated separators comprising a PP, PE, or multilayer porous substrate coated on at least one side with a ceramic composite layer. As described in U.S. Pat. No. 6,432,583 (Celgard Inc.), the ceramic composite layer is intended to inhibit dendrite growth and prevent electronic short circuits. While ceramic-coated separators have been successfully used in Li-ion batteries to improve mechanical properties, their usefulness in lithium metal batteries is limited due to parasitic reactions induced at the anode by the binder material hosting the ceramic coating.

[0005] WO 2018 / 106957 (Sepion Technologies, Inc. et al.) describes the application of a porous polymer (10-40% porosity, 0.5-2.0 nm pores) as a template for delivering a solution-processed precursor of a solid halide-containing salt as a conformal coating between the Li metal surface and the separator surface, thereby enhancing the separator's wettability and increasing Li-ion concentration and mobility at the separator-anode interface. This document also describes an electrochemical cell including a separator with multiple layers, namely, a first polymer layer including planar species and linkers. The separator may also include a porous support made of PP or PE laminated to the first polymer layer. The separator may also include a second membrane layer laminated to the porous support, where the second layer includes a ceramic material.

[0006] Polymers of intrinsic microporosity (PIMs) have been investigated for use as selective battery membranes. PIMs consist of fused rings that provide rigidity and torsional sites that can be provided by spiro centers, bent or bridged ring moieties, or similar structural components that act as barriers to polymer chain conformational relaxation. PIMs have been reported and studied since 2006 because they form a continuous network of interconnected voids for use as gas separation membranes, hydrogen storage materials, adsorbents, and heterogeneous catalysts. The intrinsic microporosity of PIMs is defined as a continuous network of interconnected intermolecular voids that form as a direct result of the shape and rigidity of the polymeric components. In particular, Li et al. (Nano Lett. 2015, 15, 5724-5729) described the use of PIMs as a membrane platform for achieving high-flux ion-selective transport in nonaqueous electrolytes.

[0007] Due to its high reactivity, lithium metal forms a solid electrolyte interface (SEI) at the interface between the electrode and the adjacent electrolyte-filled separator. The composition and morphology of the SEI affect the performance of the electrochemical cell. On the one hand, the consumption of a portion of the lithium content inherent in the in situ SEI formation process reduces the coulombic efficiency of the electrochemical cell. On the other hand, an optimal SEI suppresses further decomposition of the electrolyte components, improves lithium ion transport at the electrode-separator interface, and enhances the cycling performance and life of the battery.

[0008] Artificial SEI layers have been investigated to limit the depletion process of lithium and electrolyte components at the surface of anode materials. One approach is based on the use of a PIM layer coated on a porous support. In particular, WO 2020 / 037246 A1 (The Regents of the University of California) describes microporous ladder polymers according to the formula -[A-AB-B]- containing amine-functionalized monomer segments, amidoxime-functionalized monomer segments, or a combination thereof. Such microporous polymers are used in separators that may include one or more support materials, such as glass fibers. Thin films of microporous polymers on porous supports, such as polyolefin battery separators (e.g., Celgard), are described in the examples. Chengyin Fu et al. (Nature Materials, April 2020) describe a lithium electrode laminated with a TBAF@PIM-1-coated polyolefin separator, i.e., a separator (Celgard 2325) coated with a microporous polymer host (e.g., PIM-1) combined with tetrabutylammonium fluoride (TBAF). The coated separator was then assembled into Li-Li or Li-NMC-622 cells with a carbonate electrolyte containing an ionizable lithium salt (e.g., LiPF6). This composite is said to act as a dendrite-suppressing solid ionic conductor (SIC) in lithium metal batteries. Summary of the Invention

[0009] In one embodiment, the present invention provides a polymer of Formula I, or a salt thereof: [ka] During the ceremony, R 1a and R 1b are each independently NR 1a1 R 1a2, a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Alternatively, R 1a1 and R 1a2 are joined together with the atom to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms which are independently N, O, or S; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 Haloalkoxy, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of the heterocycloalkyl and the heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R 1e substituted with a group; R 1d is C1-6 Alkyl or C 1-6 is hydroxyalkyl; Each R 1e independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 haloalkoxy, =CH2, =O, =NH, -CN, or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; R 3 is hydrogen, C 1-6 alkyl, or -CN; X is -N= or -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN, and The subscript n is an integer between 10 and 1000; where: R 2a and R 2b are each hydrogen, and R 3 is -CN, X is -C(CN)=, and R 1c When does not exist, R 1a and R 1b is other than pyrrolidine and morpholine, and R 2a and R 2b are each hydrogen, and R 3 is -CN, X is -C(CN)=, and R 1a and R 1b are each piperazine, R 1c is -C(O)OR 1d It's surprising.

[0010] In another embodiment, the present invention provides a compound of formula II: [ka] During the ceremony, R 1a and R 1b are each independently NR 1a1 R 1a2 , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Alternatively, R 1a1 and R 1a2 are joined together with the atom to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms which are independently N, O, or S; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 Haloalkoxy, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d)2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of the heterocycloalkyl and the heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R 1e substituted with a group; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; Each R 1e independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 haloalkoxy, =CH2, =O, =NH, -CN, or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; where: R 2a and R 2b are each hydrogen, and R 1c When does not exist, R 1a and R 1b is other than pyrrolidine and morpholine, and R 2a and R 2b are each hydrogen, and R 1a and R 1b are each piperazine, R 1c is -C(O)OR 1d It's surprising.

[0011] In another embodiment, the present invention provides a method for making a polymer of Formula I or a salt thereof: [ka] The method includes: (a) a compound of formula II: [ka] a non-nucleophilic base, a solvent, and a compound of formula III: [ka] forming a reaction mixture comprising: wherein, under conditions suitable to form said polymer of Formula I, the molar ratio of said compound of Formula II to said compound of Formula III is less than 1.1; During the ceremony, R 1a and R 1b are each independently NR 1a1 R 1a2 , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Alternatively, R 1a1 and R 1a2 are joined together with the atom to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms which are independently N, O, or S; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6Haloalkyl, C 1-6 Haloalkoxy, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of the heterocycloalkyl and the heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R 1e substituted with a group; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; Each R 1e independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 haloalkoxy, =CH2, =O, =NH, -CN, or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; R 3 is hydrogen, C 1-6 alkyl, or -CN; X is -N= or -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN; and n is an integer of 10 to 1000.

[0012] In another embodiment, the present invention provides an electrochemical cell comprising an anode, a cathode, a separator comprising a polymer of Formula I, and an electrolyte. DETAILED DESCRIPTION OF THE INVENTION

[0013] I. Definition The abbreviations used herein have their conventional meaning within the chemical and biological arts.

[0014] Where a substituent is designated by a conventional chemical formula written from left to right, that substituent is also intended to encompass the chemically identical substituent that would result if the structure were written from right to left; for example, -CHO- is equivalent to -OCH-.

[0015] "Alkyl" means an alkyl group having the indicated number of carbon atoms (i.e., C 1-6 means a straight or branched chain saturated aliphatic group of 1 to 6 carbons. 1-2 , C 1-3 , C 1-4 , C 1-5 , C 1-6 , C 1-7 , C 1-8 , C 1-9 , C 1-10 , C 2-3 , C 2-4 , C 2-5 , C 2-6 , C 3-4 , C 3-5 , C 3-6 , C 4-5 , C 4-6 , and C 5-6 It may contain any number of carbons, such as C 1-6 Alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, and the like.

[0016] "Alkenyl" means an alkyl group having at least two carbon atoms and at least one double bond, and having the number of carbon atoms indicated (i.e., C2-6 means a straight or branched chain hydrocarbon of 2 to 6 carbons. Alkenyl means a C2, C 2-3 , C 2-4 , C 2-5 , C 2-6 , C 2-7 , C 2-8 , C 2-9 , C 2-10 , C3, C 3-4 , C 3-5 , C 3-6 , C4, C 4-5 , C 4-6 , C5, C 5-6 The alkenyl group may contain any number of carbons, such as C, ... 2-4 Examples of alkenyl groups include, but are not limited to, vinyl (ethenyl), propenyl, isopropenyl, 1-butenyl, 2-butenyl, isobutenyl, or butadienyl.

[0017] "Alkynyl" refers to an alkyl group having at least two carbon atoms and at least one triple bond, and having the number of carbon atoms indicated (i.e., C 2-6 means a hydrocarbon of 2 to 6 carbons, either straight or branched. Alkynyl means a hydrocarbon of 2, C, C 2-3 , C 2-4 , C 2-5 , C 2-6 , C 2-7 , C 2-8 , C 2-9 , C 2-10 , C3, C 3-4 , C 3-5 , C 3-6 , C4, C 4-5 , C 4-6 , C5, C 5-6 C 2-4 Examples of alkynyl groups include, but are not limited to, acetylenyl, propynyl, 1-butynyl, 2-butynyl, isobutynyl, sec-butynyl, or butadiynyl.

[0018] "Hydroxyalkyl" or "alkylhydroxy" means an alkyl group as defined above, in which at least one of the hydrogen atoms is substituted with a hydroxy group. With respect to the alkyl group, the hydroxyalkyl group or the alkylhydroxy group may have any suitable number of carbon atoms, such as C 1-6 etc. Exemplary C 1-4 hydroxyalkyl groups include, but are not limited to, hydroxymethyl, hydroxyethyl (hydroxy at the 1- or 2-position), hydroxypropyl (hydroxy at the 1-, 2-, or 3-position), hydroxybutyl (hydroxy at the 1-, 2-, 3-, or 4-position), 1,2-dihydroxyethyl, and the like.

[0019] "Alkyl-alkoxy" or "alkoxyalkyl" means a group having an alkyl component and an alkoxy component, where in this case the alkyl component connects the alkoxy component at its point of attachment. The alkyl component is as defined above, provided that it is at least divalent, an alkylene, in order to connect to the alkoxy component and the point of attachment. The alkyl component may contain any number of carbons, such as C 0-6 C 1-2 C 1-3 C 1-4 C 1-5 C 1-6 C 2-3 C 2-4 C 2-5 C 2-6 C 3-4 C 3-5 C 3-6 C 4-5 C 4-6 and C 5-6 etc., and may contain any number of carbons. In some cases, the alkyl component may not be present. The alkoxy component is as defined above. Examples of alkyl-alkoxy groups include, but are not limited to, 2-ethoxy-ethyl and methoxymethyl.

[0020] "Halogen" means fluorine, chlorine, bromine, and iodine.

[0021] "Haloalkyl" means an alkyl as defined above in which some or all of the hydrogen atoms have been replaced with halogen atoms. With respect to alkyl groups, haloalkyl groups include those having C 1-6 It may have any suitable number of carbon atoms, such as 1,1,1-trifluoromethyl, 2,2,2-trifluoromethyl, etc. For example, haloalkyl includes trifluoromethyl, fluoromethyl, 2,2,2-trifluoroethyl, etc. In some cases, the term "perfluoro" can be used to define a compound or group in which all hydrogen atoms have been replaced with fluorine. For example, perfluoromethyl means 1,1,1-trifluoromethyl.

[0022] "Haloalkoxy" refers to an alkoxy group in which some or all of the hydrogen atoms are replaced with halogen atoms. With respect to alkyl groups, haloalkoxy groups include C 1-6 The alkoxy group may have any suitable number of carbon atoms, such as 1, 2, 3, or more. The alkoxy group may be substituted with one, two, three, or more halogens. When all hydrogens are replaced with halogens, such as fluorine, the compound is fully substituted, e.g., a perfluoro compound. Haloalkoxy includes, but is not limited to, trifluoromethoxy, 2,2,2-trifluoroethoxy, perfluoroethoxy, and the like.

[0023] "Cycloalkyl" means a saturated or partially unsaturated, monocyclic, fused bicyclic, or bridged polycyclic ring assembly containing 3 to 12 ring atoms, or the number of atoms indicated. 3-6 , C 4-6 , C 5-6 , C 3-8 , C 4-8 , C 5-8 , C 6-8 , C 3-9 , C 3-10 , C 3-11 , and C 3-12The cycloalkyl group may contain any number of carbons, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Saturated monocyclic cycloalkyl rings include, for example, norbornane, [2.2.2]bicyclooctane, decahydronaphthalene, and adamantane. The cycloalkyl group may be partially unsaturated, having one or more double or triple bonds within the ring. Representative partially unsaturated cycloalkyl groups include, but are not limited to, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene (1,3- and 1,4-isomers), cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene (1,3-, 1,4-, and 1,5-isomers), norbornene, and norbornadiene. When the cycloalkyl is a saturated monocyclic C 3-8 When cycloalkyl, exemplary groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. 3-6 When cycloalkyl, exemplary groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Cycloalkyl groups can be substituted or unsubstituted.

[0024] "Cycloalkenyl" means a partially unsaturated, monocyclic, fused bicyclic, or bridged polycyclic ring assembly containing 5 to 12 ring atoms, or the number of atoms indicated. Cycloalkenyl is defined as C 5-6 , C 5-8 , or C 6-8Cycloalkenyl rings may contain any number of carbons, such as cyclopentene, cyclohexene, cyclohexadiene (1,3- and 1,4-isomers), cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene (1,3-, 1,4-, and 1,5-isomers), norbornene, and norbornadiene. Cycloalkenyl groups may be substituted or unsubstituted.

[0025] "Heterocycle" or "heterocycloalkyl" refers to a saturated or partially unsaturated ring system (heterocycloalkenyl) having 3 to 12 ring atoms and 1 to 4 heteroatoms, which are N, O, and S. The heteroatoms may be optionally oxidized, such as, but not limited to, -S(O)- and -S(O)-. Heterocycloalkyl groups may contain any number of ring atoms, such as 3 to 6, 4 to 6, 5 to 6, 3 to 8, 4 to 8, 5 to 8, 6 to 8, 3 to 9, 3 to 10, 3 to 11, or 3 to 12 ring atoms. Any suitable number of heteroatoms may be included in a heterocycloalkyl group, such as 1, 2, 3, or 4, or 1 to 2, 1 to 3, 1 to 4, 2 to 3, 2 to 4, or 3 to 4. Heterocycloalkyl groups may include groups such as aziridine, azetidine, pyrrolidine, piperidine, azepane, azocane, quinuclidine, pyrazolidine, imidazolidine, piperazine (1,2-, 1,3-, and 1,4-isomers), oxirane, oxetane, tetrahydrofuran, oxane (tetrahydropyran), oxepane, thiirane, thietane, thiolane (tetrahydrothiophene), thiane (tetrahydrothiopyran), oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiolane, morpholine, thiomorpholine, dioxane, or dithiane. Heterocycloalkyl groups may also be fused to aromatic or non-aromatic ring systems to form members including, but not limited to, indoline. Heterocycloalkyl groups may be unsubstituted or substituted. For example, heterocycloalkyl groups include, among others, C1-6 It may be substituted with alkyl or oxo (=O).

[0026] "Heterocycloalkenyl" refers to a partially unsaturated ring system having 3 to 12 ring atoms and 1 to 4 heteroatoms that are N, O, and S. Additional heteroatoms may also be useful, including, but not limited to, B, Al, Si, and P. The heteroatoms may also be oxidized, such as, but not limited to, -S(O)- and -S(O)2-. Heterocycloalkenyl groups may contain any number of ring atoms, such as 5 to 8 or 6 to 8. Any suitable number of heteroatoms may be included in a heterocycloalkyl group, such as 1, 2, 3, or 4, or 1 to 2, 1 to 3, 1 to 4, 2 to 3, 2 to 4, or 3 to 4. Heterocycloalkenyl groups can include groups such as 2,5-dihydro-1H-pyrrole, 1,2,3,6-tetrahydropyridine, 2,3,4,7-tetrahydro-1H-azepine, 2,7-dihydro-1H-azepine, etc. Heterocycloalkenyl groups can be unsubstituted or substituted.

[0027] "Heteroaryl" refers to a monocyclic or fused bicyclic or tricyclic aromatic ring assembly containing 5 to 16 ring atoms, wherein 1 to 5 of the ring atoms are heteroatoms such as N, O, or S. The heteroatoms may be optionally oxidized, including, but not limited to, N-oxide, -S(O)-, and -S(O)2-. One or more nitrogen atoms may be quaternized. A heteroaryl group may contain any number of ring atoms, such as 5 to 6, 5 to 8, 6 to 8, 5 to 9, 5 to 10, 5 to 11, or 5 to 12 ring atoms. A heteroaryl group may contain any suitable number of heteroatoms, such as 1, 2, 3, 4, or 5, or 1 to 2, 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, 2 to 5, 3 to 4, or 3 to 5. Heteroaryl groups can have 5 to 10 ring atoms and 1 to 4 heteroatoms, 5 to 8 ring atoms and 1 to 4 heteroatoms, or 5 to 8 ring atoms and 1 to 3 heteroatoms, or 5 to 6 ring atoms and 1 to 4 heteroatoms, or 5 to 6 ring atoms and 1 to 3 heteroatoms. Heteroaryl groups can include groups such as pyrrole, pyridine, imidazole, pyrazole, triazole, tetrazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole. Heteroaryl groups may also be fused to an aromatic ring system, such as a phenyl ring, to form members that include, but are not limited to, benzopyrroles such as indole and isoindole, benzopyridines such as quinoline and isoquinoline, benzopyrazine (quinoxaline), benzopyrimidine (quinazoline), benzopyridazines such as phthalazine and cinnoline, benzothiophene, and benzofuran. Other heteroaryl groups include heteroaryl rings linked by bonds, such as bipyridine.

[0028] The heteroaryl group may be linked through any position on the ring. For example, pyrrole includes 1-, 2-, and 3-pyrrole, pyridine includes 2-, 3-, and 4-pyridine, imidazole includes 1-, 2-, 4-, and 5-imidazole, pyrazole includes 1-, 3-, 4-, and 5-pyrazole, triazole includes 1-, 4-, and 5-triazole, tetrazole includes 1- and 5-tetrazole, pyrimidine includes 2-, 4-, 5-, and 6-pyrimidine, pyridazine includes 3- and 4-pyridazine, 1,2,3-triazine includes 4- and 5-triazine, 1,2,4-triazine includes 3-, 5-, and 6-triazine, 1,3,5-triazine includes 2-triazine, thiophene includes 2- and 3-thiophene, and furan includes 2-. and 3-furan, thiazole includes 2-, 4-, and 5-thiazole, isothiazole includes 3-, 4-, and 5-isothiazole, oxazole includes 2-, 4-, and 5-oxazole, isoxazole includes 3-, 4-, and 5-isoxazole, indole includes 1-, 2-, and 3-indole, isoindole includes 1- and 2-isoindole, quinoline includes 2-, 3-, and 4-quinoline, isoquinoline includes 1-, 3-, and 4-isoquinoline, quinazoline includes 2- and 4-quinoazoline, cinnoline includes 3- and 4-cinnoline, benzothiophene includes 2- and 3-benzothiophene, and benzofuran includes 2- and 3-benzofuran.

[0029] Some heteroaryl groups include those having 5 to 10 ring atoms and 1 to 3 ring atoms containing N, O, or S, such as pyrrole, pyridine, imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiophene, furan, thiazole, isothiazole, oxazole, isoxazole, indole, isoindole, quinoline, isoquinoline, quinoxaline, quinazoline, phthalazine, cinnoline, benzothiophene, and benzofuran. Other heteroaryl groups include those having 5 to 8 ring atoms and 1 to 3 heteroatoms, such as pyrrole, pyridine, imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole. Some other heteroaryl groups include those having 9 to 12 ring atoms and 1 to 3 heteroatoms, such as indole, isoindole, quinoline, isoquinoline, quinoxaline, quinazoline, phthalazine, cinnoline, benzothiophene, benzofuran, and bipyridine. Still other heteroaryl groups include those having 5 to 6 ring atoms and 1 to 2 ring atoms containing N, O, or S, such as pyrrole, pyridine, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole.

[0030] Some heteroaryl groups contain 5 to 10 ring atoms and only nitrogen heteroatoms, such as pyrrole, pyridine, imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), indole, isoindole, quinoline, isoquinoline, quinoxaline, quinazoline, phthalazine, and cinnoline. Other heteroaryl groups contain 5 to 10 ring atoms and only oxygen heteroatoms, such as furan and benzofuran. Some other heteroaryl groups contain 5 to 10 ring atoms and only sulfur heteroatoms, such as thiophene and benzothiophene. Still other heteroaryl groups contain 5 to 10 ring atoms and at least two heteroatoms, such as imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiazole, isothiazole, oxazole, isoxazole, quinoxaline, quinazoline, phthalazine, and cinnoline.

[0031] The term "salt" refers to an acid or base salt of the compound used in the method of the present invention. The salt of the basic compound of the present invention is a salt formed with an acid such as a mineral acid, an organic carboxylic acid, or an organic sulfonic acid. That is, examples of salts include, but are not limited to, halogen salts such as fluoride salts, chloride salts, bromide salts, and iodide salts; oxyanion salts such as chlorate salts, bromate salts, iodate salts, carbonate salts, nitrate salts, sulfate salts, or phosphate salts; carboxylate salts such as fumarate salts or acetate salts; and sulfonate salts such as trifluoromethylsulfonate salts.

[0032] Also included are base addition salts, such as sodium, potassium, calcium, ammonium, organic amino, or magnesium salts, or similar salts, when an acidic group is part of the structure. Examples of salts include salts of mineral acids (hydrochloric acid, hydrobromic acid, phosphoric acid, and the like), salts of organic acids (acetic acid, propionic acid, glutamic acid, citric acid, and the like), and salts of quaternary ammonium acids (methyl iodide, ethyl iodide, and the like).

[0033] "Sulfonate" means -S(O)3 - Examples of sulfonates include, but are not limited to, H3C-S(O)3 - , H3CCH2-S(O)3 - , or F3C-S(O)3 - Sulfonates are formed by a single bond -S(O)3 - The compound may include any chemical group attached to the compound.

[0034] "Forming a reaction mixture" refers to the process of contacting at least two different species such that they can mix and react together. However, it should be understood that the resulting reaction product may be produced directly from the reaction between the added reagents, or may be produced from an intermediate from one or more of the added reagents that can be produced in the reaction mixture.

[0035] "Non-nucleophilic base" refers to a base that is a moderate to strong base but is also a weak nucleophile. Representative non-nucleophilic bases include sodium carbonate, potassium carbonate, sodium tert-butoxide, potassium tert-butoxide, and nitrogen bases such as trimethylamine, diisopropylethylamine, N,N-diethylaniline, pyridine, 2,6-lutidine, 2,4,6-collidine, 4-dimethylaminopyridine, and quinuclidine.

[0036] "Solvent" refers to a substance, such as a liquid, capable of dissolving a solute. A solvent may be polar or nonpolar, protic or aprotic. Polar solvents typically have a dielectric constant greater than about 5 or a dipole moment less than about 1.0. Protic solvents are characterized by having a removable proton, such as a hydroxyl or carboxyl group. Aprotic solvents lack such groups. Representative polar protic solvents include alcohols (e.g., methanol, ethanol, propanol, isopropanol), acids (e.g., formic acid, acetic acid), and water. Representative polar aprotic solvents include dichloromethane, chloroform, tetrahydrofuran, diethyl ether, acetone, ethyl acetate, dimethylformamide, dimethylacetamide, acetonitrile, and dimethyl sulfoxide. Representative nonpolar solvents include alkanes (e.g., pentane, hexane), benzene, toluene, and 1,4-dioxane. Other solvents are also useful in the present invention.

[0037] "Electrode" means a conductive material in a circuit that is in contact with a non-metallic part of the circuit, such as the electrolyte. An electrode can be a positive electrode or cathode, which is the electrode where reduction occurs. An electrode can be a negative electrode or anode, which is the electrode where oxidation occurs.

[0038] "Anode" means the negative electrode, as described above.

[0039] "Cathode" means the positive electrode, as described above.

[0040] "Electrolyte" means a solution in an electrochemical cell that contains ions, such as metal ions and protons as well as anions, and that provides for ionic transfer between the positive and negative electrodes.

[0041] "Electrolyte solvent" means a molecule that solvates ions in a liquid electrolyte, such as a small organic carbonate or ethereal molecule, allowing the ions to diffuse through the electrolyte. The electrolyte solvent may be an ionic liquid or a gas at standard temperature and pressure.

[0042] "Separator" means an electrically insulating film between the positive and negative electrodes to prevent electrical shorting, i.e., to provide electronic insulation. The separator also allows ions to migrate between the positive and anode electrodes. The separator may comprise any suitable polymeric or inorganic material that is electrically insulating. The separator may comprise multiple layers, including one or more membrane layers, and a porous support material for the membrane layers.

[0043] "First polymer layer" means a layer of the separator that is permeable to a first species of electrolyte but substantially impermeable to liquid electrolyte. The membrane layer may be any suitable material capable of providing selective permeability, such as a composite of a microporous polymer and an inorganic material. "Substantially impermeable" means that less than 10% of the electrolyte solvent passes through the membrane layer, or less than 1%, or less than 0.1%, or less than 0.01%, or less than 0.001% of the liquid electrolyte passes through the membrane layer.

[0044] "Oxide" means a chemical compound that contains oxygen, such as a metal oxide or a molecular oxide.

[0045] "Pore size" or "pore diameter" refers to the average diameter of the interstitial space not occupied by the pore-forming material. This includes, but is not limited to, the space remaining between polymer chains due to inefficient packing, the space remaining between organic linkers and metal ions in metal-organic frameworks, the space between layers and within the pores of layered two-dimensional materials, and the space left in amorphous or semicrystalline carbon due to misaligned covalent bonds. Pore size may also change when wetted with an electrolyte, or the pore size may remain the same.

[0046] "Surface area" refers to the surface area of ​​a porous material as measured by various methods, such as the nitrogen adsorption BET method.

[0047] By "microporous polymer" is meant an amorphous glassy polymer having interconnected pores with an average diameter of less than 10 nm, or less than 5, 4, 3, 2 nm, or less than 1 nm.

[0048] By "microporous" is meant a layer of membrane with pores of 2 nm or less in size.

[0049] "Intrinsic microporosity" means a polymer that provides a continuous network of interconnected intermolecular voids (suitably 4 nm or less in size) formed as a direct result of the shape and rigidity of at least a portion of the polymer's component monomers. As will be understood by those skilled in the art, intrinsic microporosity arises due to the structure of the monomers used to form the polymer and, as the term suggests, is an inherent property of polymers formed from such monomers.

[0050] It is understood that the network polymers disclosed herein have certain properties (i.e., inherent microporosity). Disclosed herein are certain structural requirements for the monomers used to provide the polymers that perform the disclosed functions; it is understood that there are various structures that can perform the same functions related to the disclosed monomer structures, and that these structures typically achieve the same results.

[0051] "Molecular weight" means the molecular weight of a polymer as determined by size exclusion chromatography (SEC), laser light scattering, MALDI-TOF, or other methods. Molecular weight may be measured by weight average or number average. "Number average molecular weight" (M N "Weight average molecular weight" (M) means the mole fraction of molecules in a polymer sample, i.e., the total weight of the polymer divided by the total number of molecules, or the arithmetic mean. W ) refers to the weight fraction of molecules in a polymer sample, with emphasis on the weight of individual molecules, and therefore M W is M N Greater than M W / M NThe polydispersity index, which is the ratio of

[0052] "Metal" refers to an element of the periodic table that is metallic and can be neutral, negatively, or positively charged as a result of having more or fewer electrons in its valence shell than would be present in a neutral metallic element. Metals useful in the present invention include alkali metals, alkaline earth metals, transition metals, and post-transition metals. Alkali metals include Li, Na, K, Rb, and Cs. Alkaline earth metals include Be, Mg, Ca, Sr, and Ba. Transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and Ac. Post-transition metals include Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, and Po. Rare earth metals include Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Those skilled in the art will appreciate that each of the above metals can have several different oxidation states, all of which are useful in the present invention. In some cases, the most stable oxidation state will be formed, but other oxidation states are also useful in the present invention.

[0053] By "porous support" is meant any suitable material that is capable of supporting the membrane layers of the present invention and that is permeable to the electrolyte.

[0054] "Laminated" refers to the deposition of one layer onto another, such as a microporous polymer layer or a first polymer layer onto a porous support.

[0055] II. Spirobisindane Polymers The present invention provides a polymer of Formula I or a salt thereof. In some embodiments, the present invention provides a polymer of Formula I or a salt thereof: [ka] During the ceremony, R 1a and R 1b are each independently NR 1a1 R 1a2 , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Alternatively, R 1a1 and R 1a2 are joined together with the atom to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms which are independently N, O, or S; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 Haloalkoxy, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d)2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of the heterocycloalkyl and the heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R 1e substituted with a group; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; Each R 1e independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 haloalkoxy, =CH2, =O, =NH, -CN, or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; R 3 is hydrogen, C 1-6 alkyl, or -CN; X is -N= or -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN; and The subscript n is an integer between 10 and 1000; where: R 2a and R 2b are each hydrogen, and R 3 is -CN, X is -C(CN)=, and R 1c When does not exist, R 1a and R 1b is other than pyrrolidine and morpholine, and R 2a and R 2b are each hydrogen, and R3 is -CN, X is -C(CN)=, and R 1a and R 1b are each piperazine, R 1c is -C(O)OR 1d It's surprising.

[0056] In some embodiments, the present invention provides a polymer of Formula I, or a salt thereof: [ka] During the ceremony, R 1a and R 1b are each independently a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R 1c substituted with a group; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; R 2a and R 2b are each independently hydrogen or C 1-6is alkyl; R 3 is hydrogen, C 1-6 alkyl, or -CN; X is -N= or -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN; and The subscript n is an integer between 10 and 1000; where: R 2a and R 2b are each hydrogen, and R 3 is -CN, X is -C(CN)=, and R 1c When does not exist, R 1a and R 1b is other than pyrrolidine and morpholine, and R 2a and R 2b are each hydrogen, and R 3 is -CN, X is -C(CN)=, and R 1a and R 1b are each piperazine, R 1c is -C(O)OR 1d It's surprising.

[0057] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently a 5- to 10-membered heterocycloalkyl having 2 to 4 heteroatoms which are each independently N or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms which are each independently N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R 1c is substituted with a group; and Each R 1c But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d, -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; It is a polymer.

[0058] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently a 5-10 membered heterocycloalkyl having 1-4 heteroatoms which are each independently N, O, or S, and each of said heterocycloalkyls is independently selected from 0, 1, 2, or 3 R 1c is substituted with a group; and Each R 1c But independently, C 1-6 Alkyl, =O, -S(O)2-C 1-6 alkyl, or a 3- to 6-membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; It is a polymer.

[0059] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms which are each independently N, O, or S, and the heterocycloalkyl is selected from 0, 1, 2, or 3 R 1c is substituted with a group; and Each R 1c But independently, C 1-6 Alkyl, =O, -S(O)2-C 1-6 alkyl, or a 3- to 6-membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; It is a polymer.

[0060] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently a 5- to 6-membered heterocycloalkyl having 1 to 3 heteroatoms which are each independently N, O, or S, and each of said heterocycloalkyls is independently selected from 0, 1, 2, or 3 R 1c is substituted with a group; and Each R 1c But independently, C 1-3 Alkyl, =O, -S(O)2-C 1-3 alkyl, or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; It is a polymer.

[0061] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each a 5- to 6-membered heterocycloalkyl having 1 to 3 heteroatoms, each independently N, O, or S, and the heterocycloalkyl is selected from 0, 1, 2, or 3 R 1c is substituted with a group; and Each R 1c But independently, C 1-3 Alkyl, =O, -S(O)2-C 1-3 alkyl, or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; It is a polymer.

[0062] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each a 5- to 6-membered heterocycloalkyl having 2 to 3 heteroatoms each independently being N or S, and the heterocycloalkyl is 1c is substituted with a group; and Each R 1cBut independently, C 1-3 Alkyl, =O, -S(O)2-C 1-3 alkyl, or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; It is a polymer.

[0063] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently pyrrolidine, piperidine, diazinane, triazinane, morpholine, or thiomorpholine; and each independently 0, 1, 2, or 3 R 1c is substituted with a group; and Each R 1c are independently methyl, =O, -SO2-C 1-3 alkyl, tetrahydropyran, pyrrolidine, piperidine, diazinan, thiolane, thiane, or morpholine; It is a polymer.

[0064] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each pyrrolidine, piperidine, diazinane, triazinane, morpholine, or thiomorpholine, and each independently contain 0, 1, 2, or 3 R 1c is substituted with a group; and Each R 1c are independently methyl, =O, -SO2-C 1-3 alkyl, tetrahydropyran, pyrrolidine, piperidine, diazinan, thiolane, thiane, or morpholine; It is a polymer.

[0065] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b is a polymer, wherein each independently is: [ka]

[0066] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b is a polymer, wherein each independently is: [ka]

[0067] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b However, each independently, NR 1a1 R 1a2 and R 1a1 and R 1a2 However, each independently, C 1-3 Alkyl, C 2-4 Alkenyl, or C 2-4 In some embodiments, the polymer of Formula I or a salt thereof is a polymer having an R 1a and R 1b However, each independently, NR 1a1 R 1a2 and R 1a1 and R 1a2 However, each independently, C 1-3 Alkyl or C 2-4 In some embodiments, the polymer of Formula I or a salt thereof is a polymer having an R 1a and R 1b However, each independently, NR 1a1 R 1a2 and R 1a1 and R 1a2 are each independently methyl, ethyl, propyl, isopropyl, ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, isobutenyl, ethynyl, 1-propynyl, 2-propynyl, isopropynyl, 1-butynyl, 2-butynyl, and 3-butynyl. 1a and R 1b However, each independently, NR 1a1 R 1a2 and R 1a1and R 1a2 are each independently methyl, ethyl, propyl, isopropyl, ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, or isobutenyl.

[0068] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b is a polymer, wherein each independently is: [ka]

[0069] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b is a polymer, wherein each independently is: [ka]

[0070] In some embodiments, the polymer of Formula I or a salt thereof is R 2a and R 2b are each hydrogen atoms.

[0071] In some embodiments, the polymer of Formula I or a salt thereof is R 3 But hydrogen, C 1-3 In some embodiments, the polymer of Formula I or a salt thereof is a polymer in which R 3 is a polymer where

[0072] In some embodiments, the polymer of Formula I or a salt thereof is a polymer where X is -N=. In some embodiments, the polymer of Formula I or a salt thereof is a polymer where X is -C(R 4 ) and R 4 But hydrogen, C 1-6 alkyl, or -CN.

[0073] In some embodiments, the polymer of Formula I or a salt thereof is R 4 is a polymer where

[0074] In some embodiments, the polymer of Formula I or a salt thereof is selected from the group consisting of tetrafluoroborate, bis(oxalato)borate, difluoro(oxalato)borate, trifluorocyanoborate, cyanotris(2,2,2-trifluoroethyl)borate, carbonate, bicarbonate, carboxylate, acetate, trifluoroacetate, dicarboxylate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, thiocyanate, nitrite, nitrate, hexafluorosilicate, phosphite, phosphate, difluorophosphate, hexafluorophosphate, hydrogenphosphate, dihydrogenphosphate , tetrafluorooxalate phosphate, difluoro(bisoxalate)phosphate, phosphonate, sulfite, bisulfite, sulfate, bisulfate, thiosulfate, sulfonate, trifluoromethanesulfonate, p-toluenesulfonate, halide, hypochlorite, chlorite, chlorate, perchlorate, bromate, iodate, chromate, dichromate, or permanganate. In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein the salt is composed of an anion that is a sulfonate. In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein the salt is composed of the following anion: [ka]

[0075] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein the salt is composed of a cation: [ka]

[0076] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b However, each independently, NR 1a1 R 1a2 , a 5- to 10-membered heterocycloalkyl having 2 to 4 heteroatoms, each independently being N or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Each R 1c But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; X is -N= or -C(R 4 )=; and R 4 But hydrogen, C 1-6 alkyl, or -CN; where: When X is -C(CN)=, R 1a and R 1b are each other than morpholine, It is a polymer.

[0077] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently a 5- to 10-membered heterocycloalkyl having 2 to 4 heteroatoms, each independently being N or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R 1c substituted with a group; Each R 1c But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; X is -N= or -C(R 4 )=; and R 4 But hydrogen, C 1-6 alkyl, or -CN; It is a polymer.

[0078] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R 1c substituted with a group; Each R 1c But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d ) 2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; and X is -N=; It is a polymer.

[0079] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b However, each independently, NR 1a1 R 1a2 , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Each R 1c But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; X is -C(R 4 )=; and R 4 But hydrogen, C 1-6 alkyl, or -CN; where: When X is -C(CN)=, R 1a and R 1b are each other than morpholine, It is a polymer.

[0080] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R 1csubstituted with a group; Each R 1c But independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; X is -C(R 4 )=; and R 4 But hydrogen, C 1-6 alkyl, or -CN; It is a polymer.

[0081] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b However, each independently, NR 1a1 R 1a2 , a 5-6 membered heterocycloalkyl having 1-3 heteroatoms, each independently being N, O, or S, and each of said heterocycloalkyls independently being 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 But independently, C 1-3 Alkyl or C 2-4 is alkenyl; Each R 1c But independently, C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 -), or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; R 2a and R 2b are each hydrogen; R 3 is -CN; and X is -N= or -C(CN)=; where: When X is -C(CN)=, R 1a and R 1b are each other than morpholine, It is a polymer.

[0082] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently a 5- to 6-membered heterocycloalkyl having 1 to 3 heteroatoms which are each independently N, O, or S, and each of said heterocycloalkyls is independently selected from 0, 1, 2, or 3 R 1c substituted with a group; Each R 1c But independently, C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ), or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; R 2a and R 2b are each hydrogen; R 3 is -CN; and X is -N= or -C(CN)=; where: When X is -C(CN)=, R 1a and R 1b are each other than morpholine, It is a polymer.

[0083] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R1b are each independently a 5- to 6-membered heterocycloalkyl having 1 to 3 heteroatoms which are each independently N, O, or S, and each of said heterocycloalkyls is independently selected from 0, 1, 2, or 3 R 1c substituted with a group; Each R 1c But independently, C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ), or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; R 2a and R 2b are each hydrogen; R 3 is -CN; and X is -N=; It is a polymer.

[0084] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently: [ka] R 2a and R 2b are each hydrogen; R 3 is -CN; and X is -N= or -C(CN)=; where: When X is -C(CN)=, R 1a and R 1b are each other than morpholine, It is a polymer.

[0085] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are each independently: [ka] R 2a and R 2b are each hydrogen; R 3 is -CN; and X is -C(CN)=; It is a polymer.

[0086] In some embodiments, the polymer of Formula I or a salt thereof is R 1a and R 1b are respectively: [ka] R 2a and R 2b are each hydrogen; R 3 is -CN; and X is -N= or -C(CN)=; where: When X is -C(CN)=, R 1a and R 1b are each other than morpholine, It is a polymer.

[0087] In some embodiments, the polymer of Formula I or a salt thereof is a polymer: [ka] [ka]

[0088] In some embodiments, the polymer of Formula I or a salt thereof is a polymer: [ka]

[0089] In some embodiments, the polymer of Formula I or a salt thereof is a polymer: [ka] [ka]

[0090] The polymers of the present invention can be prepared from a variety of monomers. In some embodiments, the present invention provides compounds of Formula II: [ka] During the ceremony, R 1a and R 1b are each independently NR 1a1 R 1a2 , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Alternatively, R 1a1 and R 1a2 are joined together with the atom to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms which are independently N, O, or S; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6Haloalkoxy, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of the heterocycloalkyl and the heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R 1e substituted with a group; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; Each R 1e independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 haloalkoxy, =CH2, =O, =NH, -CN, or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; where: R 2a and R 2b are each hydrogen, and R 1c When does not exist, R 1a and R 1b is other than pyrrolidine and morpholine, and R 2a and R 2b are each hydrogen, and R 1a and R 1b are each piperazine, R 1c is -C(O)OR 1dIt's surprising.

[0091] In some embodiments, the present invention provides a compound of formula II: [ka] During the ceremony, R 1a and R 1b are each independently a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R 1c substituted with a group; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; where: R 2a and R 2b are each hydrogen, and R 1c When does not exist, R 1aand R 1b is other than pyrrolidine and morpholine, and R 2a and R 2b are each hydrogen, and R 1a and R 1b are each piperazine, R 1c is -C(O)OR 1d It's surprising.

[0092] R in Formula II 1a , R 1b , R 1c , R 1d , R 2a , and R 2b Each embodiment of can be defined as described above for the polymer of Formula I.

[0093] In some embodiments, the compound of formula II is: [ka]

[0094] In some embodiments, the compound of formula II is: [ka]

[0095] III. Preparation of spirobisindane polymers The compounds of the present invention can be prepared by a variety of methods. In some embodiments, the present invention provides a method for preparing a polymer of Formula I or a salt thereof, comprising: [ka] A method is provided that includes: (a) a compound of formula II: [ka] a non-nucleophilic base, a solvent, and a compound of formula III: [ka] forming a reaction mixture comprising: wherein, under conditions suitable to form said polymer of Formula I, the molar ratio of said compound of Formula II to said compound of Formula III is less than 1.1; During the ceremony, R 1a and R 1b are each independently NR 1a1 R 1a2 , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R 1c substituted with a group; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, or C 5-8 is cycloalkenyl; Alternatively, R 1a1 and R 1a2 are joined together with the atom to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms which are independently N, O, or S; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 Haloalkoxy, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d)2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of the heterocycloalkyl and the heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R 1e substituted with a group; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; Each R 1e independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Haloalkyl, C 1-6 haloalkoxy, =CH2, =O, =NH, -CN, or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; R 3 is hydrogen, C 1-6 alkyl, or -CN; X is -N= or -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN; and n is an integer of 10 to 1000.

[0096] In some embodiments, the present invention provides a method for preparing a polymer of Formula I or a salt thereof: [ka] A method is provided that includes: (a) a compound of formula II: [ka] a non-nucleophilic base, a solvent, and a compound of formula III: [ka] forming a reaction mixture comprising: wherein, under conditions suitable to form said polymer of Formula I, the molar ratio of said compound of Formula II to said compound of Formula III is less than 1.0; During the ceremony, R 1a and R 1b are each independently a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R 1c substituted with a group; Each R 1c independently, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, halogen, C 1-6 Haloalkyl, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1d , -C(O)OR 1d , -S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - ), -O(P=O)(OR 1d )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; R 1d is C 1-6 Alkyl or C 1-6 is hydroxyalkyl; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; R 3 is hydrogen, C 1-6alkyl, or -CN; X is -N= or -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN; and n is an integer of 10 to 1000.

[0097] The method of the present invention is capable of preparing polymers of Formula I described herein.

[0098] The non-nucleophilic base may be any suitable non-nucleophilic base. In some embodiments, the method for making a polymer of Formula I or a salt thereof is a method in which the non-nucleophilic base is an inorganic base. In some embodiments, the method for making a polymer of Formula I or a salt thereof is a method in which the non-nucleophilic base is sodium carbonate, potassium carbonate, rubidium carbonate, or cesium carbonate.

[0099] The non-nucleophilic base may also be a non-nucleophilic amine base. Representative non-nucleophilic amine bases include, but are not limited to, trimethylamine, triethylamine, diisopropylethylamine (DIPEA or Hunig's base), 1,8-diazabicycloundec-7-ene (DBU), 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), 2,6-di-tert-butylpyridine, quinuclidine, and lutidine.

[0100] The reaction mixture may contain any suitable solvent. For example, the solvent may be a polar solvent, a non-polar solvent, a protic solvent, an aprotic solvent, or a combination thereof. In some embodiments, the method for producing a polymer of Formula I or a salt thereof is a method in which the solvent is a polar solvent. In some embodiments, the method for producing a polymer of Formula I or a salt thereof is a method in which the solvent is a polar aprotic solvent. In some embodiments, the method for producing a polymer of Formula I or a salt thereof is a method in which the solvent is ethyl acetate, acetonitrile, dimethylformamide, dimethylacetamide, or dimethylsulfoxide.

[0101] The molar ratio of the compound of Formula II to the compound of Formula III can be any suitable ratio. For example, the molar ratio of the compound of Formula II to the compound of Formula III can be 0.9 to 1.1, 0.95 to 1.05, 0.96 to 1.04, or 0.97 to 1.03. Other examples of the molar ratio of the compound of Formula II to the compound of Formula III can be about 1.1, 1.09, 1.08, 1.07, 1.06, 1.05, 1.04, 1.03, 1.02, 1.01, 1.0, 0.99, 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, or about 0.90.

[0102] The molar ratio of the compound of Formula II to the compound of Formula III may be any suitable ratio less than 1.0. For example, the molar ratio of the compound of Formula II to the compound of Formula III may be less than 1.0, or may be 0.9 to 0.99, 0.95 to 0.99, 0.96 to 0.99, 0.97 to 0.99, or 0.98 to 0.99. Other examples of the molar ratio of the compound of Formula II to the compound of Formula III may be about 0.99, 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, or about 0.90. In some embodiments, the method for producing a polymer of Formula I or a salt thereof is a method in which the molar ratio of the compound of Formula II to the compound of Formula III is less than 1.0. In some embodiments, the method for producing a polymer of Formula I or a salt thereof is a method in which the molar ratio of the compound of Formula II to the compound of Formula III is 0.95 to 0.99. In some embodiments, the method for preparing the polymer of Formula I or a salt thereof is a method in which the molar ratio of the compound of Formula II to the compound of Formula III is from 0.98 to 0.99.

[0103] The molar ratio of the compound of Formula II to the compound of Formula III may be any suitable ratio greater than 1.0. For example, the molar ratio of the compound of Formula II to the compound of Formula III may be greater than 1.0, or may be 1.01 to 1.1, 1.01 to 1.05, 1.01 to 1.04, 1.01 to 1.03, or 1.01 to 1.02. Other examples of the molar ratio of the compound of Formula II to the compound of Formula III may be about 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, or about 1.1. In some embodiments, the method for producing a polymer of Formula I or a salt thereof is a method in which the molar ratio of the compound of Formula II to the compound of Formula III is 1.01 to 1.05. In some embodiments, the method for producing a polymer of Formula I or a salt thereof is a method in which the molar ratio of the compound of Formula II to the compound of Formula III is 1.01 to 1.03. In some embodiments, the method for preparing the polymer of Formula I or a salt thereof is a method in which the molar ratio of the compound of Formula II to the compound of Formula III is from 1.01 to 1.02.

[0104] In some embodiments, the present invention provides a method for making a polymer of Formula I or a salt thereof, comprising: (a) a compound of formula II: [ka] a non-nucleophilic base, a solvent, and a compound of formula III: [ka] forming a reaction mixture comprising: wherein the molar ratio of the compound of formula II to the compound of formula III is from 1.0 to 1.1 under conditions suitable for forming the polymer of formula I; During the ceremony, R 1a and R 1b are each independently NR 1a1 R 1a2 and; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6Alkenyl, or C 5-8 is cycloalkenyl; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; R 3 is hydrogen, C 1-6 alkyl, or -CN; X is -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN, and n is an integer of 10 to 1000.

[0105] In some embodiments, the present invention provides a method for preparing a polymer of Formula I, or a salt thereof, wherein: R 1a and R 1b are each independently NR 1a1 R 1a2 and; Each R 1a1 and R 1a2 independently, C 1-6 Alkyl, C 2-6 Alkenyl, or C 5-8 is cycloalkenyl; R 2a and R 2b are each independently hydrogen or C 1-6 is alkyl; R 3 is hydrogen, C 1-6 alkyl, or -CN; X is -C(R 4 )=and; R 4 is hydrogen, C 1-6 alkyl, or -CN; and n is an integer of 10 to 1000.

[0106] In some embodiments, the method of making a polymer of Formula I or a salt thereof is a method in which a compound of Formula II is: [ka]

[0107] Other embodiments of Formula II that are useful in the process for making the polymers of Formula I are described herein.

[0108] In some embodiments, the method of making a polymer of Formula I or a salt thereof is a method in which a compound of Formula III is: [ka]

[0109] In some embodiments, the method of making a polymer of Formula I or a salt thereof is a method in which a compound of Formula III is: [ka]

[0110] In some embodiments, the method of making a polymer of Formula I or a salt thereof is a method in which a compound of Formula III is: [ka]

[0111] In some embodiments, a method for preparing a polymer of Formula I or a salt thereof includes: (a) a compound of formula II: [ka] potassium carbonate, dimethylformamide, and a compound of formula III having the following structure: [ka] forming a reaction mixture comprising: wherein the molar ratio of the compound of formula II to the compound of formula III is from 0.98 to 0.99 under conditions suitable for forming the polymer of formula I; During the ceremony, R 1a and R1b are each independently a 5- to 6-membered heterocycloalkyl having 1 to 3 heteroatoms, each independently N, O, or S, or a 5- to 6-membered heteroaryl having 1 to 3 heteroatoms, each independently N, O, or S; Each R 1c But independently, C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ), -SO2-C 1-3 alkyl, or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; R 2a and R 2b are each hydrogen; R 3 is -CN; X is -N= or -C(R 4 )=and; R 4 is -CN; and The subscript n is an integer from 10 to 1000.

[0112] In some embodiments, a method for preparing a polymer of Formula I or a salt thereof includes: (a) a compound of formula II: [ka] potassium carbonate, dimethylformamide, and a compound of formula III having the following structure: [ka] forming a reaction mixture comprising: wherein the molar ratio of the compound of formula II to the compound of formula III is from 1.01 to 1.03 under conditions suitable for forming the polymer of formula I; During the ceremony, R 1a and R 1b However, each independently, NR 1a1 R 1a2 and; Each R 1a1and R 1a2 But independently, C 1-3 Alkyl or C 2-4 is alkenyl; R 2a and R 2b are each hydrogen; R 3 is -CN; X is -C(CN)=; and The subscript n is an integer from 10 to 1000.

[0113] In some embodiments, the method for preparing a polymer of Formula I or a salt thereof comprises: R 1a and R 1b However, each independently, NR 1a1 R 1a2 and; Each R 1a1 and R 1a2 But independently, C 1-3 Alkyl or C 2-4 is alkenyl; R 2a and R 2b are each hydrogen; R 3 is -CN; X is -C(CN)=; and The subscript n is an integer between 10 and 1000; It is a method.

[0114] Each step of the process of the present invention may be carried out for any suitable reaction time. For example, the reaction time may be several minutes, several hours, or several days. In some embodiments, the reaction time may be several hours, such as at least 8 hours. In some embodiments, the reaction time may be several hours, such as at least overnight. In some embodiments, the reaction time may be several days. In some embodiments, the reaction time may be at least 2 hours. In some embodiments, the reaction time may be at least 8 hours. In some embodiments, the reaction time may be at least several days. In some embodiments, the reaction time may be about 2 hours, or about 4 hours, or about 6 hours, or about 8 hours, or about 10 hours, or about 12 hours, or about 14 hours, or about 16 hours, or about 18 hours, or about 20 hours, or about 22 hours, or about 24 hours. In some embodiments, the reaction time may be about 1 day, or about 2 days, or about 3 days, or about 4 days, or about 5 days, or about 6 days, or about 1 week, or more than about 1 week.

[0115] Each step of the process of the present invention may be carried out at any suitable reaction temperature. Typical temperatures include, but are not limited to, below room temperature, room temperature, or above room temperature. Other temperatures useful in the process of the present invention include about -40°C to about 65°C, or about room temperature to about 40°C, or about 40°C to about 65°C, or about 40°C to about 60°C. In some embodiments, the reaction mixture may be at a temperature of about room temperature, or about 15°C, or about 20°C, or about 25°C, or about 30°C, or about 35°C, or about 40°C, or about 45°C, or about 50°C, or about 55°C, or about 60°C, or about 65°C.

[0116] IV. Electrochemical Cell In some embodiments, the present invention provides an electrochemical cell comprising an anode, a cathode, a separator comprising a polymer of Formula I, and an electrolyte.

[0117] The separator may comprise the polymer of the present invention alone or in combination with other components. In some embodiments, the present invention provides a coated separator comprising: a porous support having a first surface and an opposite second surface; and a microporous polymer layer comprising a first polymer of intrinsic microporosity (PIM); Here, the microporous polymer layer covers the first surface of the porous support.

[0118] In some embodiments, the coated separator also includes a first polymer layer between the microporous polymer layer and the first surface of the porous support. In some embodiments, the present invention provides a multi-layer coated separator comprising: a porous support having a first surface and an opposite second surface; a first polymer layer; and a microporous polymer layer comprising a first polymer of intrinsic microporosity (PIM); wherein the first polymer layer covers a first surface of the porous support; and The microporous polymer layer covers the first polymer layer.

[0119] porous support In some embodiments, the pore size of the porous support is about 0.01 micrometers to 5 micrometers, or more specifically, about 0.02 micrometers to 0.5 micrometers. The porosity of the porous support can be about 20% to 85%, or more specifically, about 30% to 60%. Those skilled in the art will understand that pore size can be affected by the composition of the electrolyte provided within the separator pores. For example, some components of the separator (e.g., the porous support or the first polymer layer) may swell upon contact with a portion of the electrolyte material, changing the pore size. Unless otherwise specified, pore size and other similar parameters refer to the separator components prior to contact with the electrolyte.

[0120] Larger pore sizes allow for the use of porous supports that are significantly thicker than the first polymer layer without significantly compromising the overall permeability of the separator to the first species. In some embodiments, the thickness of the porous support is about 5 micrometers to 500 micrometers, or in more specific embodiments, about 5 micrometers to 50 micrometers, or more specifically, about 10 micrometers to 30 micrometers. In the same or other embodiments, the thickness of the porous support may be about 1 to 50 times thicker, or more specifically, about 5 to 25 times thicker, than the thickness of the first polymer layer.

[0121] Some examples of materials suitable for the porous support include, but are not limited to, poly(ethylene-co-tetrafluoroethylene (PETFE)) and poly(ethylenechloro-co-trifluoroethylene) fluoropolymer fibers (e.g., woven fabrics thereof, used alone or laminated with fluoropolymer microporous films), polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polystyrene, polyarylethersulfone, polyvinyl chloride, polypropylene, polyethylene (including LDPE, LLDPE, HDPE, and ultra-high molecular weight polyethylene), polyamide, polyimide, polyethylene terephthalate ... Porous supports include nonwoven glass, glass fiber materials, ceramics, metal oxides, composites of organic and inorganic species, and polypropylene membranes. Porous supports may also be supplied with an additional coating of a second suitable material, including, but not limited to, PTFV, PVDF, and PETFE. These examples of porous supports are available from Celanese, Charlotte, NC, USA, under the name CELGARD. Plastic Company, Inc.; Asahi Kasei Corporation, Tokyo, Japan; Tonen, Tokyo, Japan; Ube Industries, Tokyo, Japan; Nitto Denko Corporation, Osaka, Japan; Nippon Advanced Paper Industries Co., Ltd., Kochi, Japan; Entek, Lebanon, Oregon, USA; SK Innovation, Jongro-Gu, Korea; Sumitomo Corporation, Tokyo, Japan; Toray Industries, Inc., Tokyo, Japan; DuPont USA, Wilmington, DE, USA; W-Scope, Japan; and Parker Hannifin Filtration Group, Carson, CA, USA.

[0122] In some embodiments, the coated separator is a separator in which the porous support comprises polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), poly(vinyl chloride) (PVC), poly(vinylidene difluoride) (PVDF), cellulose, ceramic, or a combination thereof. In some embodiments, the coated separator is a separator in which the porous support comprises polyethylene.

[0123] The porous support may have a thickness of about 3 micrometers to 200 micrometers, or about 5 micrometers to 100 micrometers, or about 10 micrometers to 50 micrometers, or about 9 micrometers to 25 micrometers, or about 10 micrometers to 20 micrometers, or more specifically about 15 micrometers to 30 micrometers. The porous support may have a thickness of about 5 micrometers, or about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 micrometers.

[0124] First Polymer Layer The selective blocking properties of one or more polymer layers used in the separator derive from the composition or specific pore structure of those layers. For purposes of this disclosure, the term "blocking" means screening, selecting, or excluding. In some embodiments, the pore structure of the polymer layer appears as a network of interconnected pores with small pore sizes, narrow pore size distribution, high surface area, and high porosity, as further described below. In some embodiments, the pore structure of the polymer layer appears as an array of channels with small pore sizes, narrow pore size distribution, high surface area, and high porosity, as further described below. In addition to these blocking properties, the first polymer layer possesses various other properties that make it suitable for electrochemical cell applications, such as chemical and electrochemical stability, wettability, thickness, thermal stability, and the like.

[0125] The blocking mechanism is based on chemical exclusion (non-wetting) or size exclusion, which occurs on the nanometer to subnanometer scale when tortuous ion-permeable pathways are established in the polymer layer. For example, a polymer layer may allow Li ions (or other similar species discussed below) to pass through while blocking larger electrolyte solvents or the like. Membranes can be formed from ladder polymers with angular spiro centers and either no rotatable bonds in the polymer backbone or bonds in the backbone with restricted bond rotation. These properties result in inefficient solid packing, with porosity of approximately 10% to 40% of the bulk powder, or more specifically, approximately 20% to 30%. The pores can then be filled with inorganic components to result in a non-porous or partially porous polymer layer.

[0126] The first polymer layer may comprise any suitable polymer. In some embodiments, the multilayer coated separator is a separator in which the first polymer layer is substantially insoluble in carbonate electrolyte. Exemplary carbonate electrolytes are described herein. For example, the first polymer layer may be greater than 50% insoluble in carbonate electrolyte, or greater than 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99% insoluble in carbonate electrolyte.

[0127] The first polymer layer may comprise one or more different polymer layers, for example, the first polymer layer may comprise a first polymer layer, a second polymer layer, or an additional polymer layer. In some embodiments, the multilayer coated separator is a separator in which a first polymer layer comprises polyacrylonitrile, poly(acrylonitrile-methyl acrylate), poly(acrylonitrile-co-methacrylic acid), poly(acrylonitrile-acrylic acid), poly(acrylonitrile-itaconic acid), poly(acrylonitrile-methyl methacrylate), poly(acrylonitrile-itaconic acid-methyl acrylate), poly(acrylonitrile-methacrylic acid-methyl acrylate), poly(acrylonitrile-vinylpyridine), poly(acrylonitrile-vinyl chloride), poly(acrylonitrile-vinyl acetate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), a second polymer of intrinsic microporosity different from the first polymer of intrinsic microporosity, or a combination thereof. In some embodiments, the multilayer coated separator is a separator in which a first polymer layer comprises poly(acrylonitrile-co-methyl acrylate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), a second polymer of intrinsic microporosity different from the first polymer of intrinsic microporosity, or a combination thereof.

[0128] PIM polymer layer Intrinsically microporous polymers useful in the electrochemical devices of the present invention include those described in U.S. Pat. Nos. 10,710,065 and 11,394,082, U.S. Patent Application Publication Nos. 2021 / 0309802 and 2019 / 0326578, each of which is incorporated herein by reference in its entirety.

[0129] High free volume and microporosity are required to achieve the extremely high ionic transport required for fast charging and high-power applications. Polymers that exhibit these properties are known as high-free-volume polymers. These highly permeable polymers have been primarily applied in gas separation. Some examples include certain substituted polyacetylenes (e.g., PTMSP), some perfluoropolymers (e.g., Teflon® AF), certain poly(norbornenes), intrinsically microporous polymers, and some polyimides. Their microporosity has been demonstrated by molecular modeling and positron lifetime spectroscopy (PALS). Highly permeable polyacetylenes have bulky side groups that inhibit conformational changes and force the backbone into a twisted shape. These rigid polymers lack proper packing in the solid state, resulting in high free volume. The free volume distribution consists of discrete elements, as in the case of glassy polymers, as well as continuous microvoids. In the case of Teflon® perfluoropolymer, its high free volume is due to the high barrier to rotation between adjacent dioxolane rings, combined with the weak interchain interactions known for fluoropolymers, resulting in low packing density and therefore high permeability. In the case of poly(norbornene) and PTMSP, the presence of bulky trimethylsilyl groups on the rings severely limits the polymer's freedom to undergo conformational changes. In inherently microporous polymers (PIMs), molecular linkers containing twist points are held in a non-coplanar orientation by rigid molecules, preventing the resulting polymer from packing closely and ensuring high microporosity. The PIM concept has been reported for polymides [PM Budd and NB McKewon, "Highly permeable polymers for gas separation membranes," Polymer Chemistry, 1, 63-68, 2010].

[0130] Depending on the monomer selection, there are two different types of PIMs: i) non-network (linear) polymers, which can be soluble in organic solvents, and ii) network polymers, which are generally insoluble. PIMs have an internal molecular free volume (IMFV), which is a measure of the concave area and is defined by Swager as the difference in the volume of a concave unit compared to the non-convex area [TM Long and TM Swager, "Minimization of Free Volume: Alignment of Triptycenes in Liquid Crystals and Stretched Polymers," Adv. Mater., 13, 8, 601-604, 2001]. While the inherent microporosity of linear PIMs is believed to originate from the non-penetrating concave areas provided by their twisted structure, it has also been proposed that the microporosity of network PIMs originates from the concave areas associated with the macrocycles. While single bond rotation must be avoided in non-network PIMs, single bonds can exist in network PIMs without losing microporosity because branching and crosslinking are believed to prevent structural rearrangements that could result in loss of microporosity (McKeown, 2010). Network PIMs have generally been observed to have greater microporosity than non-network PIMs due to their macrocyclization [NB McKewon, PM Budd, "Explotation of Intrinsic Microporosity in Polymer-Based Materials," Macromolecules, 43, 5163-5176, 2010]. However, prior art network PIMs are not soluble and can only be incorporated into membranes when mixed as fillers with microporous soluble materials, including soluble PIMs or other soluble polymers. Non-network PIMs strictly require the absence of single bonds in the polymer backbone to prevent freedom of rotation and thereby create intrinsic microporosity. A highly rigid and twisted molecular structure is required, which leads to an awkward polymer shape that cannot efficiently fill space.Molecules with awkward shapes present packing problems due to their cavities. However, for non-network PIMs to be microporous, cavities must be sufficiently interconnected (i.e., intrinsic microporosity) for transport to occur with minimal energy [Macromolecules, 43, 5163-5176, 2010]. Non-network PIMs can be soluble, making them suitable for use in casting membranes by phase inversion or coating support membranes to create thin-film composites. However, their solubility in various solvents limits their application in organic solvent nanofiltration [Ulbricht M, Advanced functional polymer membranes. Single Chain Polymers, 47, 2217-2262, 2006].

[0131] U.S. Patent No. 7,690,514 B2 describes intrinsically microporous materials comprising organic polymers composed of first generally planar species linked by linkers with twist points, whereby two adjacent first planar species connected by the linkers are held in a non-coplanar orientation. Preferred twist points are spiro groups, bridging ring moieties, and sterically congested bonds with restricted rotation. These non-network PIMs can be soluble in common organic solvents and thus can be cast into films or coated onto other support membranes to produce thin-film composites.

[0132] PIM-1 (soluble PIM) membranes exhibit selectivity exceeding the 1991 Robeson upper limit for gas combinations such as CO2 / CH4 and O2 / N2, and exhibit gas permeabilities surpassed only by very high free volume polymers such as Teflon® AF2400 and PTMSP. Studies have shown that methanol treatment improves permeability by helping to flush out residual casting solvent and allowing chain relaxation [PM Budd and NB McKewon, D Fritsch, "Polymers of Intrinsic Microporosity (PIMs): High free volume polymers for membrane applications," Macromol Symp, 245-246, 403-405, 2006].

[0133] Ghanem et al. prepared various polyimides with properties similar to microporous polymers (PIMs). Gas permeation experiments of these PIM-polyimides showed that they were among the most permeable of all polyimides and had selectivities approaching the upper limit for several important gas combinations [BG Ghanem, NB McKeown, PM Budd, NM Al-Harbi, D Fritsch, K Heinrich, L Starannikova, A Tokarev, and Y Yampolskii, "Synthesis, characterization, and gas permeation properties of a novel group of polymers with intrinsic microporosity: PIM-polyimides," Macromolecules, 42, 7781-7888, 2009].

[0134] US Pat. No. 7,410,525 B1 describes polymer / polymer mixed matrix membranes incorporating intrinsically microporous soluble polymers as microporous fillers for use in gas separation applications.

[0135] WO 2005 / 113121 (PCT / GB2005 / 002028) describes the formation of thin film composite membranes from PIM by coating a solution of PIM in an organic solvent onto a support membrane, followed by optional crosslinking of the PIM film to increase its stability in organic solvents.

[0136] With the aim of improving the gas transport properties of soluble PIM membranes, U.S. Pat. No. 7,758,751 B1 describes high-performance UV-exposed membranes from polymers of intrinsic microporosity (PIM) and their use in both gas separations and liquid separations involving organic solvents, such as olefin / paraffin, deep desulfurization of gasoline and diesel fuels, and ethanol / water separation.

[0137] In some embodiments, the microporous polymer layer comprises a polymer having a chain composed of interconnected repeating units. Each unit may comprise a first generally planar species having at least one aromatic ring and further comprising a spiro group, a bridged ring moiety, or a rigid linker having a sterically congested single covalently bonded torsion site. The rigid linker restricts rotation of the first planar species in a non-coplanar orientation. In some embodiments, at least 50 mol% (or 70 mol%, 80 mol%, or even 90 mol%) of the first planar species in the chain are connected to up to two other planar species by rigid linkers and are free of cross-linked covalent three-dimensional structures. Thus, the polymer may comprise a rigid linker having a torsion site. Because these polymer chains do not pack together due to their rigid torsional structure, the microporous polymer layer possesses inherent microporosity, and in some cases nanoporosity. Thus, this combination of unpacked and uncross-linked polymer chains spans three dimensions. This may be considered a non-network polymer. Cross-linked polymers are also within the scope.

[0138] In some embodiments, the surface area of ​​the PIM polymer layer (as measured by nitrogen adsorption or related techniques of the dry powder before membrane processing) prior to loading with the inorganic component is at least 200 m 2 / g or at least 500m 2 / g, and 200m 2 / g~2200m 2 / g, or more specifically 600m 2 / g~900m 2 / g. A typical method for measuring surface area is the nitrogen adsorption BET method. Surface area is directly related to porosity and is essential for efficient transport of supporting electrolyte between the electrodes and high power cell operation. Typical porosities are in the range of 20% to 70%, or more specifically, 30% to 60%. The surface area of ​​a PIM polymer layer is measured in 100 m 2 / g~3000m 2 / g, and 100m 2 / g, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, or 3000m 2 In some embodiments, the coated separator has a microporous polymer layer having a porosity of 100 m / g as measured by nitrogen adsorption BET. 2 / g~3000m 2 / g of surface area.

[0139] In some embodiments, the coated separator is a separator in which the average pore size of the microporous polymer layer before filling with the inorganic component is less than 100 nm, or about 0.1 nm to about 20 nm, or about 0.1 nm to about 10 nm, or about 0.1 nm to about 5 nm, or about 0.1 nm to about 2 nm, or about 0.1 nm to about 1 nm. For example, the average pore size of the microporous polymer layer can be less than about 10 nm, or less than about 9, 8, 7, 6, 5, 4, 3, 2, or 1 nm. For example, the average pore size of the microporous polymer layer can be about 10 nm, or about 9, 8, 7, 6, 5, 4, 3, 2, or 1 nm. This pore size ensures that certain substances (e.g., substances having a unit size larger than the pore size) are blocked by the microporous polymer layer, while other substances (e.g., substances having a smaller unit size) can pass through. In some embodiments, the coated separator is a separator in which the microporous polymer layer has an average pore size of 0.1 nm to 10 nm. In some embodiments, the coated separator is a separator in which the microporous polymer layer has an average pore size of 0.1 nm to 2 nm. In some embodiments, the coated separator is a separator in which the microporous polymer layer has an average pore size of 0.1 nm to 1 nm.

[0140] In some embodiments, the coated separator has a microporous polymer layer having a number average molecular weight (Mn) of 1×10 3 ~2000×10 3 kg / mol (kDa), or more specifically, 15 x 10 3 ~500×10 3 kg / mol (kDa), or 20 x 10 3 ~200×10 3 The number average molecular weight of a polymer is kg / mol (kDa), which is the separator. The higher the number average molecular weight, the better the mechanical properties of the resulting membrane.

[0141] In some embodiments, the coated separator has a microporous polymer layer having a weight average molecular weight (Mw) of 1×10 3 ~2000×10 3 kg / mol (kDa), or more specifically, 15 x 10 3 ~500×103 kg / mol (kDa), or 20 x 10 3 ~200×10 3 The number average molecular weight of a polymer is kg / mol (kDa), which is the separator. The higher the number average molecular weight, the better the mechanical properties of the resulting membrane.

[0142] The microporous polymer layer may be a film cast, sprayed, or coated from solution (e.g., onto a porous support), a composite composed of multiple individual membrane layers, a free-standing film, or a supported film (e.g., by a porous support).

[0143] In some embodiments, the coated separator is one in which the microporous polymer layer has a thickness of about 5 nanometers to 20 micrometers, or about 100 nanometers to 10 micrometers, or more specifically about 500 nanometers to 5 micrometers.

[0144] The microporosity of the polymer layer is due to its high surface area (approximately 680–850 m), determined using nitrogen adsorption measurements (BET calculations). 2 / g). Cyano and methyl groups may be present as desired; they may be omitted or replaced by other simple substituents. Each phenyl group may contain one or more substituents. In addition, the nature and arrangement of the substituents on the spiro-indane moiety may be selected to provide any desired configuration around the carbon atom common to both five-membered rings.

[0145] electrolyte The electrochemical cells of the present invention also include an electrolyte, which can have a variety of components, such as an alkyl carbonate, a fluorinated carbonate, a diisocyanate, a lithium salt, or a combination thereof.

[0146] Representative alkyl carbonates of the electrolyte include, but are not limited to, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, n-propyl propionate, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, or propylene carbonate. In some embodiments, the alkyl carbonate is dimethyl carbonate.

[0147] Representative fluorinated carbonates for the electrolyte include, but are not limited to, fluoroethylene carbonate, CH3OC(O)OCH2CF3, CH3OC(O)OCH2CF2CHF2, CH3OC(O)OCH2CF2CHF2, CF3CH2OC(O)OCH2CF3, CH3OC(O)OCH2CF2CF2CF3, CH3CH2OC(O)OCH2CF2CF3, CH3CH2OC(O)OCH2CF2CHF2, or CH3OC(O)OCH2CF2CF2CF3.

[0148] Representative diisocyanates for the electrolyte include, but are not limited to, tolylene-2,4-diisocyanate or tolylene-2,6-diisocyanate.

[0149] The lithium salt of the electrolyte composition of the present invention may be any suitable lithium salt. For example, suitable lithium salts include, but are not limited to, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof. In some embodiments, the lithium salt may be lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof.

[0150] In some embodiments, the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSi), lithium hexafluorophosphate, or a combination thereof. In some embodiments, the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSi).

[0151] The first lithium salt may be present in the electrolyte composition in any suitable amount. For example, the first lithium salt may be present in the electrolyte composition in an amount of 0.1-20 mol%, 0.1-20 mol%, 1-20 mol%, 5-20 mol%, 5-15 mol%, 8-12 mol%, or 9-11 mol%. Representative amounts of the first lithium salt in the electrolyte composition of the present invention include, but are not limited to, about 5 mol%, or about 6, 7, 8, 9, 10, 11, 12, 13, 14, or about 15 mol%.

[0152] The electrolyte can include one or more lithium salts. For example, the electrolyte can include one, two, three, four, or more different lithium salts, as defined above. In some embodiments, the electrolyte includes a single lithium salt. In some embodiments, the electrolyte includes two different lithium salts. In some embodiments, the electrolyte includes three different lithium salts.

[0153] The electrolyte can include a second lithium salt that is different from the first lithium salt. In some embodiments, the electrolyte includes a second lithium salt that is different from the first lithium salt.

[0154] In some embodiments, the electrolyte includes a second lithium solvent that can be lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or a combination thereof. In some embodiments, the electrolyte includes a second lithium salt that can be lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, or a combination thereof. In some embodiments, the electrolyte includes a second lithium salt that can be lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium. In some embodiments, the electrolyte includes a second lithium salt that can be lithium difluoro(oxalato)borate. In some embodiments, the electrolyte includes a second lithium salt that can be lithium nitrate.

[0155] The second lithium salt may be present in the electrolyte composition in any suitable amount. For example, the second lithium salt may be present in the electrolyte composition in an amount of 0.1-10 mol%, 0.1-5 mol%, 0.5-5 mol%, 0.5-4 mol%, 0.5-3.5 mol%, 1-3 mol%, 1.0-2.5 mol%, or 1.5-2.5 mol%. Representative amounts of the second lithium salt in the electrolyte composition of the present invention include, but are not limited to, about 1.5 mol%, or about 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or about 2.5 mol%.

[0156] In some embodiments, the electrolyte comprises a second lithium salt that can be present in the electrolyte in an amount of 0.1 to 5 mol %. In some embodiments, the electrolyte comprises a second lithium salt that can be present in the electrolyte in an amount of 0.5 to 3.5 mol %. In some embodiments, the electrolyte comprises a second lithium salt that can be present in the electrolyte in an amount of 1 to 3 mol %. In some embodiments, the electrolyte comprises a second lithium salt that can be present in the electrolyte in an amount of 1.5 to 2.5 mol %. [Example]

[0157] V. Working Examples Molecular weight information for PIM-13 and novel PIM examples was determined using a Waters Acquity advanced Polymer Chromatography system equipped with a refractive index detector and chloroform as the mobile phase. Relative molecular weights were determined using a calibration curve constructed from polystyrene standards ranging in molecular weight from 0.266 to 1760 kg / mol (kDa).

[0158] Example 1: Synthesis of PIM-1-Py(a1) [ka] A 500 mL two-neck round-bottom flask equipped with a vacuum adapter, septum, and stir bar was charged with 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (4.83 g, 14.2 mmol, 1 equiv.) and tetrafluorocyanopyridine (2.50 g, 14.2 mmol, 1 equiv.). The flask was then purged with argon by three cycles of evacuation and refilling. Dry N,N-dimethylformamide (150 mL) was then added, and the reaction mixture was purged with argon for 30 minutes. The reaction mixture was then heated to 65 °C, and anhydrous potassium carbonate (8.00 g, 57.94 mmol, 4.08 equiv.), which had previously been dried under vacuum at 150 °C and ground with a mortar and pestle, was added. The reaction mixture was stirred at 65°C for 18 hours, then precipitated into water (500 mL) and washed with additional water (2 x 100 mL) and ethanol (2 x 100 mL). The resulting solid was dried under vacuum and subsequently dissolved in tetrahydrofuran (THF) at 50 mg / mL. This solution was precipitated into ethanol, and the precipitated polymer was isolated by vacuum filtration and dried under vacuum to give PIM-13 (a1, 5.33 g, 86% yield, Mw = 51.5 kg / mol (kDa)) as a light yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ6.76(1H,d),6.39(1H,D),2.23(2H,d),1.33(6H,d)

[0159] Example 2: Preparation of PIM-13(b2) Synthesis of SBI-morpholine (b1) : [ka] To a 1 L two-neck round-bottom flask equipped with a reflux condenser was added paraformaldehyde (4.41 g, 147 mmol, 2.5 equiv.), morpholine (12.65 mL, 147 mmol, 2.5 equiv.), and ethanol (300 mL). The reaction mixture was purged with argon for 25 minutes and then heated to reflux for 1 hour. After heating for 1 hour, 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (20 g, 58.8 mmol, 1 equiv.) was added, and the reaction mixture was stirred at reflux under argon for 24 hours, after which a white precipitate was observed. The reaction mixture was then cooled to room temperature, poured into heptane (700 mL), and cooled to 0 °C. The reaction mixture was then filtered, washed with heptane (2×50 mL), and dried under vacuum to give SBI-morpholine (5.22 g, 16.5% yield). 1 H-NMR(400MHz,DMSO-d6,δ):δ11.01(s,2H),8.41(s,2H),6.52(s,2H),3.52 (s,8H),3.07(dd,4H),2.25(s,8H),2.17(dd,4H),1.32(s,6H),1.20(s,6H)

[0160] Synthesis of PIM-13(b2) [ka] A 500 mL two-neck round-bottom flask equipped with a vacuum adapter, septum, and stir bar was charged with SBI-morpholine (12.50 g, 23.2 mmol, 0.98 equiv.) and tetrafluoroterephthalonitrile (4.74 g, 23.68 mmol, 1 equiv.). The flask was then purged with argon by three cycles of evacuation and refilling. Dry N,N-dimethylformamide (250 mL) was then added, and the reaction mixture was purged with argon for 30 minutes. The reaction mixture was then heated to 65 °C, and anhydrous potassium carbonate (13.35 g, 96.61 mmol, 4.08 equiv.), which had previously been dried under vacuum at 150 °C and ground with a mortar and pestle, was added. The reaction mixture was stirred at 65 °C for 18 hours, then precipitated into water (500 mL), followed by washing with additional water (2 × 50 mL) and ethanol (2 × 50 mL). The resulting solid was dried under vacuum and then dissolved in THF at 50 mg / mL. This solution was precipitated in ethanol (500 mL). The precipitated polymer was isolated by vacuum filtration and dried under vacuum to give PIM-13 (b2, 12.2 g, 81.5% yield, Mw = 80 kg / mol (kDa)) as a light yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ6.81(1H,s),3.54(4H,s,br),3.0(3H,m,br),2.24(5H,s,br),1.36(6H,d)

[0161] Decreasing this mole fraction from 1 to 0.98 increases the proportion of high molecular weight fragments in the polymer, as evidenced by the increase in Mw and Mz with this change. [Table 1] [Table 2]

[0162] Example 3: Synthesis of PIM-13-Py (b3) [ka] To a dry 250 mL two-neck round-bottom flask was added SBI-morpholine (1, 5.81 g, 10.79 mmol, 1.0 equiv.), tetrafluorocyanopyridine (1.90 g, 10.79 mmol, 1 equiv.), and anhydrous dimethylformamide (114 mL). The reaction mixture was purged with argon for 25 minutes and then heated to 65 °C. After reaching 65 °C, anhydrous potassium carbonate (6.08 g, 44.03 mmol, 4.08 equiv.), which had been previously dried under vacuum at 150 °C and ground with a mortar and pestle, was added. The reaction mixture was then stirred under argon at 65 °C for 18 hours, after which it was precipitated into water (500 mL) and subsequently washed with additional water (2 × 50 mL) and ethanol (2 × 50 mL). The resulting solid was dried under vacuum and then dissolved in THF at 50 mg / mL. The solution was precipitated in ethanol (500 mL), and the precipitated polymer was isolated by vacuum filtration and dried in vacuo to give bright yellow PIM-13-Py (Mw=61 kDa). 1 H-NMR(400MHz,CDCl3,δ):δ6.74(2H,m),2.5(24H,m),1.65(6H,s),1.42(6H,s)

[0163] Example 4: Synthesis of PIM-13S(c2) Synthesis of SBI-thiomorpholine (c1) [ka] To a 1 L two-neck round-bottom flask equipped with a reflux condenser was added paraformaldehyde (4.41 g, 147 mmol, 2.5 equiv.), thiomorpholine (14.71 mL, 147 mmol, 2.5 equiv.), and ethanol (300 mL). The reaction mixture was purged with argon for 25 minutes and then heated to reflux for 1 hour. After heating for 1 hour, 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (20 g, 58.8 mmol, 1 equiv.) was added, and the reaction mixture was stirred at reflux under argon for 24 hours, after which a white precipitate was observed. The reaction mixture was then cooled to room temperature, poured into heptane (700 mL), and cooled to 0 °C. The reaction mixture was then filtered, washed with heptane (2×50 mL), and dried under vacuum to give SBI-thiomorpholine (5.23 g, 15.6% yield). 1 H-NMR(400MHz,DMSO-d6,δ):δ10.98(s,2H),8.36(s,2H),6.52(s,2H),3.09(dd,4H),2.52(m,16H),2.15(dd,4H),1.30(s,6H),1.20(s,6H)

[0164] Synthesis of PIM-13S(c2) [ka] To a dry 250 mL two-neck round-bottom flask was added SBI-thiomorpholine (3, 3.71 g, 6.49 mmol, 0.99 equiv.), tetrafluoroterephthalonitrile (1.31 g, 6.56 mmol, 1 equiv.), and anhydrous dimethylformamide (65 mL). The reaction mixture was purged with argon for 25 minutes and then heated to 65 °C. After reaching 65 °C, anhydrous potassium carbonate (3.70 g, 26.75 mmol, 4.08 equiv.), which had been previously dried under vacuum at 150 °C and ground with a mortar and pestle, was added. The reaction mixture was then stirred under argon at 65 °C for 18 hours, after which it was precipitated into water (500 mL) and subsequently washed with additional water (2 × 50 mL) and ethanol (2 × 50 mL). The resulting solid was dried under vacuum, dissolved in THF at 50 mg / mL, and precipitated into ethanol (500 mL). The precipitated polymer was isolated by vacuum filtration and dried in vacuo to give bright yellow PIM-13S (4.19 g, 94% yield, Mw=78 kDa). 1 H-NMR(400MHz,CDCl3,δ):δ6.82(s,2H),3.07(d,4H),2.48(m,16H),1.41(s,6H),1.32(s,6H) [Table 3]

[0165] Example 5: PIM-13SO 0.5 Synthesis of (c3) [ka] To a 100 mL round-bottom flask was added PIM-13S (b2, 1000 mg, 1.45 mmol) dissolved in chloroform (20 mL). The reaction mixture was then cooled to 0° C. in an ice bath, and a solution of meta-chloroperoxybenzoic acid (77%, 324 mg, 1.45 mmol, 1 equiv.) in chloroform (10 mL) was added dropwise. The reaction mixture was then removed from the ice bath and stirred at room temperature for 2 hours before being precipitated in ethanol (300 mL). The resulting yellow solid was isolated by filtration and then stirred in concentrated ammonia solution (100 mL) for 1 hour. The solid was then collected by filtration, washed with water (100 mL) and ethanol (100 mL), and dried under vacuum to give PIM-13S. 0.5 was obtained as a light yellow powder. 1 H-NMR(400MHz,CDCl3,δ):δ6.85(2H,m),2.75(24H,m,broad),1.41(6H,s),1.32(6H,s)

[0166] Example 6: PIM-13SO 1 Synthesis of (c4) [ka] To a 100 mL round-bottom flask was added PIM-13S (b2, 1000 mg, 1.45 mmol) dissolved in chloroform (20 mL). The reaction mixture was then cooled to 0 °C in an ice bath, and a solution of meta-chloroperoxybenzoic acid (77%, 649 mg, 2.89 mmol, 2 equiv.) in chloroform (10 mL) was added dropwise. The reaction mixture was then removed from the ice bath and stirred at room temperature for 2 h before being precipitated in ethanol (300 mL). The resulting yellow solid was isolated by filtration and then stirred in concentrated ammonia solution (100 mL) for 1 h. The solid was then collected by filtration, washed with water (100 mL) and ethanol (100 mL), and dried under vacuum to give PIM-13SO1 as a light yellow powder. 1 H-NMR(400MHz,CDCl3,δ):δ6.85(2H,m),2.75(24H,m,broad),1.41(6H,s),1.32(6H,s)

[0167] Example 7: PIM-13SO 1.5 Synthesis of (c5) [ka] To a 100 mL round-bottom flask was added PIM-13S (b2, 1000 mg, 1.45 mmol) dissolved in chloroform (20 mL). The reaction mixture was then cooled to 0 °C in an ice bath, and a solution of meta-chloroperoxybenzoic acid (77% purity, 973 mg, 4.34 mmol, 3 equiv.) in chloroform (10 mL) was added dropwise. The reaction mixture was then removed from the ice bath and stirred at room temperature for 2 hours, after which it was precipitated in ethanol (300 mL). The resulting yellow solid was isolated by filtration and then stirred in concentrated ammonia solution (100 mL) for 1 hour. The solid was then collected by filtration, washed with water (100 mL) and ethanol (100 mL), and dried under vacuum to give PIM-13S. 1.5 was obtained as a light yellow powder. 1 H-NMR(400MHz,CDCl3,δ):δ6.85(2H,broad),2.75(24H,m,broad),1.41(6H,broad),1.32(6H,broad)

[0168] Example 8: Synthesis of PIM-13S-Py(c6) [ka] To a dry 250 mL two-neck round-bottom flask was added SBI-thiomorpholine (3, 6.35 g, 11.13 mmol, 0.98 equiv.), tetrafluorocyanopyridine (2.00 g, 11.36 mmol, 1 equiv.), and anhydrous dimethylformamide (120 mL). The reaction mixture was purged with argon for 25 minutes and then heated to 65 °C. After reaching 65 °C, anhydrous potassium carbonate (6.40 g, 46.34 mmol, 4.08 equiv.), which had been previously dried under vacuum at 150 °C and ground with a mortar and pestle, was added. The reaction mixture was then stirred under argon at 65 °C for 18 hours, after which it was precipitated into water (500 mL) and subsequently washed with additional water (2 × 50 mL) and ethanol (2 × 50 mL). The resulting solid was dried under vacuum and then dissolved in THF at 50 mg / mL. This solution was precipitated into ethanol (500 mL), and the precipitated polymer was isolated by vacuum filtration and dried in vacuo to give bright yellow PIM-13S-Py (7.09 g, 94% yield, Mw=53 kDa). 1 H-NMR(400MHz,CDCl3,δ):δ6.74(m,2H),3.07(d,4H),2.47(m,16H),1.39(s,6H),1.31(s,6H)

[0169] Example 9: Synthesis of PIM-4-morpholinopiperidine (e2) Synthesis of SBI-4-morpholinopiperidine (e1) [ka] The compounds can be prepared by methods known in the art.

[0170] Synthesis of PIM-4-morpholinopiperidine (e2) [ka] Polymer PIM-4-morpholinopiperidine can be prepared by the methods described herein.

[0171] Example 10: PIM-Piperazine-MeSO 2 Synthesis of (f2) SBI-Piperazine-MeSO 2 Synthesis of (f1) [ka] Paraformaldehyde (1.10 g, 36.7 mmol, 2.5 equiv.), piperazine methyl sulfate (6.03 g, 36.7 mmol, 2.5 equiv.), and ethanol (75 mL) were added to a 250 L, two-necked round-bottom flask equipped with a reflux condenser. The reaction mixture was purged with argon for 25 minutes and then heated to reflux for 1 hour. After heating for 1 hour, 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (5 g, 14.7 mmol, 1 equiv.) was added, and the reaction mixture was stirred at reflux under argon for 24 hours, after which a white precipitate was observed. The reaction mixture was then cooled to room temperature, the solvent was removed on a rotary evaporator, and the resulting solid was purified using column chromatography on a silica column with a mixed mobile phase of ethyl acetate and hexane and dried in vacuo to give SBI-piperazine-MeSO2 (1.29 g, 12.6% yield). 1 H-NMR(400MHz,DMSO-d6,δ):δ10.52(2H,s),8.31(2H,s),6.53(2H,s),3.12(12H,m),2.25(12H,m),1.32(6H,s),1.18(6H,s)

[0172] PIM-Piperazine-MeSO 2 Synthesis of (f2) [ka] The polymer PIM-piperazine-MeSO2 can be prepared by the methods described herein.

[0173] Example 11: Additional Polymers The following polymers can be prepared by the methods described herein. [ka]

[0174] Example 12: Synthesis of PIM-diallylamine Synthesis of SBI-diallylamine (g1) [ka] A 2 L, two-necked round-bottom flask equipped with a reflux condenser and septum was charged with paraformaldehyde (14.7 g, 490 mmol, 2.5 equiv.), toluene (1000 mL), and diallylamine (47.6 g, 490 mmol, 2.5 equiv.). The mixture was then heated at reflux under nitrogen until homogeneous (approximately 30 min). Subsequently, 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (66.7 g, 196 mmol, 1 equiv.) was added, and the reaction mixture was stirred at reflux for 4 h. The reaction mixture was then cooled to room temperature, the solvent was removed on a rotary evaporator, and the resulting solid was recrystallized from isopropanol to give SBI-diallylamine (59.8 g, 54.6%) as a white crystalline solid. 1 H-NMR(400MHz,DMSO-d6,δ):δ11.51(1H,s),8.31(1H,s),6.50(1H,s),5.64(2H,m),5.10(4H,dd),3.1 9(1H,d),3.09(1H,d),2.93(2H,dd),2.82(2H,dd),2.17(1H,d),2.08(1H,d),1.30(3H,s),1.19(3H,s)

[0175] Synthesis of PIM-diallylamine (g2) [ka] To a 500 mL round-bottom flask was added tetrafluoroterephthalonitrile (3.00 g, 15 mmol, 1 equiv.), SBI-diallylamine (8.55 g, 15.3 mmol, 1.02 equiv.), and anhydrous N,N-dimethylformamide (160 mL). The reaction mixture was then heated to 65° C. under nitrogen, and potassium carbonate (8.46 g, 61.2 mmol, 4.08 equiv.) was added. The reaction mixture was further stirred at 65° C. for 16 hours, then cooled to room temperature, precipitated into deionized water (700 mL), and the resulting solid was filtered. The solid was further washed with additional water (200 mL) and ethanol (200 mL), followed by drying under vacuum. This crude solid was then stirred as a 25 mg / mL mixture in 1:1 methyl ethyl ketone / ethanol (v / v) for 16 hours and filtered to give PIM-diallylamine (8.31 g, 81.6%) as a light yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ6.83(1H,s),5.51(2H,s),4.98(4H,s),3.24(2H,d),2.76(5H,m),2.19(1H,s),1.38(3H,s),1.34(3H,s)

[0176] Example 13: Synthesis of PIM-allylmethylamine Synthesis of SBI-allylmethylamine (h1) [ka] A 500 mL two-neck round-bottom flask equipped with a reflux condenser and septum was charged with paraformaldehyde (2.20 g, 73.4 mmol, 2.5 equiv.), toluene (150 mL), and allylmethylamine (5.22 g, 73.4 mmol, 2.5 equiv.). The mixture was then heated at reflux under nitrogen until homogeneous (approximately 30 min). Subsequently, 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (10.0 g, 29.4 mmol, 1 equiv.) was added, and the reaction mixture was stirred at reflux for 4 h. The reaction mixture was then cooled to room temperature, the solvent was removed on a rotary evaporator, and the resulting solid was recrystallized from isopropanol to give SBI-methylallylamine (14.9 g, 46.5%) as a white crystalline solid.1 H-NMR(400MHz,DMSO-d6,δ):δ11.51(1H,s),8.26(1H,s),6.50(1H,s),5.66(1H,m),5.11(1H,dd),5.12(1H,d),3.1 3(1H,d),3.04(1H,d),2.88(1H,dd),2.82(1H,dd),2.18(1H,d),2.11(1H,d),1.99(3H,s),1.30(3H,s),1.20(3H,s)

[0177] Synthesis of PIM-allylmethylamine (h2) [ka] A 20 mL scintillation vial was charged with tetrafluoroterephthalonitrile (300 mg, 1.5 mmol, 1 equiv.), SBI-allylmethylamine (745 mg, 1.47 mmol, 0.98 equiv.), and anhydrous N,N-dimethylformamide (16 mL). The vial was then capped and heated to 65 °C, and anhydrous potassium carbonate (846 mg, 6.12 mmol, 4.08 equiv.) was added. After stirring at 65 °C for 16 h, the reaction mixture was precipitated into deionized water (125 mL), and the resulting solid was filtered and washed with water (100 mL) and ethanol (100 mL). This crude product was then stirred for 16 h as a 25 mg / mL suspension in 1:1 methyl ethyl ketone / ethanol (v / v), filtered, and dried under vacuum to give PIM-allylmethylamine (784 mg, 85%) as a light yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ6.81(1H,s),5.61(1H,s),5.06(1H,s),4.98(1H,s ),3.09(2H,d),2.77(2H,d),2.00(2H,d)1.87(3H,s),1.07(3H,s),1.06(3H,s)

[0178] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be understood by those skilled in the art that certain changes and modifications may be practiced within the scope of the appended claims. Additionally, each reference cited herein is incorporated by reference in its entirety to the same extent as if each reference were individually incorporated by reference. In the event of a conflict between this application and a reference cited herein, the present application shall control.

Claims

1. A polymer of Formula I or a salt thereof: 【Chemistry 1】 During the ceremony, R １ａ and R １ｂ are each independently NR １ａ１ R １ａ２ , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R １ｃ substituted with a group; Each R １ａ１ and R １ａ２ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, or C ５－８ is cycloalkenyl; Or, R １ａ１ and R １ａ２ are joined together with the atoms to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms, independently N, O, or S; Each R １ｃ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, C １－６ Hydroxyalkyl, C １－６ Alkoxy, C ２－６ Alkoxyalkyl, halogen, C １－６ Haloalkyl, C １－６ Haloalkoxy, ═O, ═NH, —CN, —NO ２ , -C(O)H, -C(O)R １ｄ , -C(O)OR １ｄ , -S(O) ２ -C １－６ Alkyl, —C １－６ Alkyl-(SO ３ － ), -O(P=O)(OR １ｄ ) ２ , a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of said heterocycloalkyl and said heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R １ｅ substituted with a group; R １ｄ is C １－６ Alkyl or C １－６ is hydroxyalkyl; Each R １ｅ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, C １－６ Hydroxyalkyl, C １－６ Alkoxy, C ２－６ Alkoxyalkyl, halogen, C １－６ Haloalkyl, C １－６ Haloalkoxy, =CH ２ , ═O, ═NH, —CN, or —NO ２ and R ２ａ and R ２ｂ are each independently hydrogen or C １－６ is alkyl; R ３ is hydrogen, C １－６ alkyl, or —CN; X is -N= or -C(R ４ ) = and R ４ is hydrogen, C １－６ alkyl, or —CN; and The subscript n is an integer from 10 to 1000; where: R ２ａ and R ２ｂ are each hydrogen, and R ３ is -CN, X is -C(CN)=, and R １ｃ When does not exist, R １ａ and R １ｂ is other than pyrrolidine and morpholine, and R ２ａ and R ２ｂ are each hydrogen, and R ３ is -CN, X is -C(CN)=, and R １ａ and R １ｂ are each piperazine, R １ｃ is -C(O)OR １ｄ Other than that, A polymer of Formula I or a salt thereof:

2. R １ａ and R １ｂ are each independently a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S, and the heterocycloalkyl and the heteroaryl are each independently selected from 0, 1, 2, or 3 R １ｃ substituted with a group; Each R １ｃ But independently, C １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, halogen, C １－６ Haloalkyl, ═O, ═NH, —CN, —NO ２ , -C(O)H, -C(O)R １ｄ , -C(O)OR １ｄ , -S(O) ２ -C １－６ Alkyl, —C １－６ Alkyl-(SO ３ － ), -O(P=O)(OR １ｄ ) ２ , a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently N, O, or S; R １ｄ But C １－６ Alkyl or C １－６ is hydroxyalkyl; R ２ａ and R ２ｂ are each independently hydrogen or C １－６ is alkyl; R ３ But hydrogen, C １－６ alkyl, or —CN; X is -N= or -C(R ４ ) = and R ４ But hydrogen, C １－６ alkyl, or —CN; and The subscript n is an integer from 10 to 1000; where: R ２ａ and R ２ｂ are each hydrogen, and R ３ is -CN, X is -C(CN)=, and R １ｃ When does not exist, R １ａ and R １ｂ is other than pyrrolidine and morpholine, and R ２ａ and R ２ｂ are each hydrogen, and R ３ is -CN, X is -C(CN)=, and R １ａ and R １ｂ are each piperazine, R １ｃ is -C(O)OR １ｄ Other than that, The polymer or salt thereof according to claim 1 .

3. R １ａ and R １ｂ are each independently a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms which are each independently N, O, or S, and each of said heterocycloalkyls independently has 0, 1, 2, or 3 R １ｃ is substituted with a group; and Each R １ｃ But independently, C １－６ Alkyl, ═O, —S(O) ２ -C １－６ alkyl, or a 3- to 6-membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; The polymer or salt thereof according to claim 1 .

4. R １ａ and R １ｂ are each independently a 5- to 6-membered heterocycloalkyl having 1 to 3 heteroatoms which are each independently N, O, or S, and each of said heterocycloalkyls is independently selected from 0, 1, 2, or 3 R １ｃ is substituted with a group; and Each R １ｃ But independently, C １－３ Alkyl, ═O, —S(O) ２ -C １－３ alkyl, or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; The polymer or salt thereof according to any one of claims 1 to 3.

5. R １ａ and R １ｂ are each independently pyrrolidine, piperidine, diazinane, triazinane, morpholine, or thiomorpholine; and each independently 0, 1, 2, or 3 R １ｃ is substituted with a group; and Each R １ｃ are independently methyl, ═O, —S(O) ２ -C １－３ alkyl, tetrahydropyran, pyrrolidine, piperidine, diazinan, thiolane, thiane, or morpholine; The polymer or salt thereof according to any one of claims 1 to 4.

6. R １ａ and R １ｂ are each independently the following: 【Chemistry 2】

7. R １ａ and R １ｂ are each independently NR １ａ１ R １ａ２ and Each R １ａ１ and R １ａ２ But independently, C １－３ Alkyl or C ２－４ is alkenyl, The polymer or salt thereof according to claim 1 .

8. R １ａ and R １ｂ are each independently NR １ａ１ R １ａ２ and Each R １ａ１ and R １ａ２ are independently methyl, ethyl, propyl, isopropyl, ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, or isobutenyl; The polymer or salt thereof according to claim 7 .

9. R １ａ and R １ｂ are each independently the following: 【Transformation 3】

10. R ２ａ and R ２ｂ and each represent hydrogen. The polymer or salt thereof according to any one of claims 1 to 9.

11. R ３ But hydrogen, C １－３ The polymer or salt thereof according to any one of claims 1 to 10, wherein the aryl group is alkyl, or -CN.

12. R ３ The polymer or salt thereof according to any one of claims 1 to 11, wherein is -CN.

13. The polymer or salt thereof according to any one of claims 1 to 12, wherein X is -N=.

14. X is -C(R ４ ) and R ４ But hydrogen, C １－６ alkyl, or —CN; The polymer or salt thereof according to any one of claims 1 to 13.

15. R ４ The polymer or salt thereof according to any one of claims 1 to 14, wherein is -CN.

16. 16. The polymer or salt thereof according to any one of claims 1 to 15, wherein the salt is composed of the following anion: Tetrafluoroborate, bis(oxalate)borate, difluoro(oxalate)borate, trifluorocyanoborate, cyanotris(2,2,2-trifluoroethyl)borate, carbonate, bicarbonate, carboxylate, acetate, trifluoroacetate, dicarboxylate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, thiocyanate, nitrite, nitrate, hexafluorosilicate, phosphite, phosphate, difluorophosphate , hexafluorophosphate, hydrogen phosphate, dihydrogen phosphate, tetrafluorooxalate phosphate, difluoro(bisoxalate)phosphate, phosphonate, sulfite, bisulfite, sulfate, bisulfate, thiosulfate, sulfonate, trifluoromethanesulfonate, p-toluenesulfonate, halide, hypochlorite, chlorite, chlorate, perchlorate, bromate, iodate, chromate, dichromate, or permanganate.

17. R １ａ and R １ｂ are each independently: 【Chemistry 4】 R ２ａ and R ２ｂ are each hydrogen; R ３ is —CN; and X is -N= or -C(CN)=; Here, when X is -C(CN)=, R １ａ and R １ｂ are each other than morpholine, The polymer or salt thereof according to any one of claims 1 to 16.

18. The polymer or salt thereof according to any one of claims 1 to 17, wherein the polymer is: 【Chemistry 5-1】 【Chemistry 5-2】

19. The polymer or salt thereof according to any one of claims 1 to 18, wherein the polymer is: 【Chemistry 6-1】 【Chemistry 6-2】

20. A compound of formula II: 【Transformation 7】 During the ceremony, R １ａ and R １ｂ are each independently NR １ａ１ R １ａ２ , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R １ｃ substituted with a group; Each R １ａ１ and R １ａ２ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, or C ５－８ is cycloalkenyl; Or, R １ａ１ and R １ａ２ are joined together with the atoms to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms, independently N, O, or S; Each R １ｃ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, C １－６ Hydroxyalkyl, C １－６ Alkoxy, C ２－６ Alkoxyalkyl, halogen, C １－６ Haloalkyl, C １－６ Haloalkoxy, ═O, ═NH, —CN, —NO ２ , -C(O)H, -C(O)R １ｄ , -C(O)OR １ｄ , -S(O) ２ -C １－６ Alkyl, —C １－６ Alkyl-(SO ３ － ), -O(P=O)(OR １ｄ ) ２ , a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of said heterocycloalkyl and said heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R １ｅ substituted with a group; R １ｄ is C １－６ Alkyl or C １－６ is hydroxyalkyl; Each R １ｅ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, C １－６ Hydroxyalkyl, C １－６ Alkoxy, C ２－６ Alkoxyalkyl, halogen, C １－６ Haloalkyl, C １－６ Haloalkoxy, =CH ２ , ═O, ═NH, —CN, or —NO ２ and R ２ａ and R ２ｂ are each independently hydrogen or C １－６ is alkyl; where: R ２ａ and R ２ｂ are each hydrogen, and R １ｃ When does not exist, R １ａ and R １ｂ is other than pyrrolidine and morpholine, and R ２ａ and R ２ｂ are each hydrogen, and R １ａ and R １ｂ are each piperazine, R １ｃ is -C(O)OR １ｄ Other than that, A compound of formula II.

21. 21. The compound of claim 20, which is the following compound: 【Transformation 8】

22. 1. A method for preparing a polymer of Formula I or a salt thereof, comprising: 【Chemistry 9】 Manufacturing methods including: (a) a compound of formula II: 【Chemistry 10】 a non-nucleophilic base, a solvent, and a compound of formula III: 【Chemistry 11】 forming a reaction mixture comprising: wherein the molar ratio of said compound of Formula II to said compound of Formula III is less than 1.1 under conditions suitable for forming said compound of Formula I; During the ceremony, R １ａ and R １ｂ are each independently NR １ａ１ R １ａ２ , a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein the heterocycloalkyl and the heteroaryl each independently contain 0, 1, 2, or 3 R １ｃ substituted with a group; Each R １ａ１ and R １ａ２ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, or C ５－８ is cycloalkenyl; Or, R １ａ１ and R １ａ２ are joined together with the atoms to which they are attached to form a 5-8 membered heterocycloalkenyl ring having 0 or 1 additional heteroatoms, independently N, O, or S; Each R １ｃ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, C １－６ Hydroxyalkyl, C １－６ Alkoxy, C ２－６ Alkoxyalkyl, halogen, C １－６ Haloalkyl, C １－６ Haloalkoxy, ═O, ═NH, —CN, —NO ２ , -C(O)H, -C(O)R １ｄ , -C(O)OR １ｄ , -S(O) ２ -C １－６ Alkyl, —C １－６ Alkyl-(SO ３ － ), -O(P=O)(OR １ｄ ) ２ , a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms, each independently being N, O, or S, or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms, each independently being N, O, or S, wherein each of said heterocycloalkyl and said heteroaryl independently has 0, 1, 2, 3, 4, 5, or 6 R １ｅ substituted with a group; R １ｄ is C １－６ Alkyl or C １－６ is hydroxyalkyl; Each R １ｅ are independently １－６ Alkyl, C ２－６ Alkenyl, C ２－６ Alkynyl, C １－６ Hydroxyalkyl, C １－６ Alkoxy, C ２－６ Alkoxyalkyl, halogen, C １－６ Haloalkyl, C １－６ Haloalkoxy, =CH ２ , ═O, ═NH, —CN, or —NO ２ and R ２ａ and R ２ｂ are each independently hydrogen or C １－６ is alkyl; R ３ is hydrogen, C １－６ alkyl, or —CN; X is -N= or -C(R ４ ) = and R ４ is hydrogen, C １－６ alkyl, or —CN; and The subscript n is an integer between 10 and 1000.

23. 23. The method of claim 22, wherein the non-nucleophilic base is sodium carbonate, potassium carbonate, rubidium carbonate, or cesium carbonate.

24. 24. The method of claim 22 or 23, wherein the solvent is ethyl acetate, acetonitrile, dimethylformamide, dimethylacetamide, or dimethylsulfoxide.

25. 25. The method of any one of claims 22 to 24, wherein the molar ratio of the compound of formula II to the compound of formula III is less than 1.

0.

26. 26. The method of any one of claims 22 to 25, wherein the molar ratio of the compound of formula II to the compound of formula III is from 0.95 to 0.

99.

27. 25. The method of any one of claims 22 to 24, wherein the molar ratio of the compound of formula II to the compound of formula III is from 1.01 to 1.

05.

28. In the compound of formula II, R １ａ and R １ｂ are each independently NR １ａ１ R １ａ２ and Each R １ａ１ and R １ａ２ But independently, C １－６ Alkyl, C ２－６ Alkenyl, or C ５－８ is cycloalkenyl; R ２ａ and R ２ｂ are each independently hydrogen or C １－６ is alkyl; R ３ But hydrogen, C １－６ alkyl, or —CN; X is -C(R ４ ) = and R ４ But hydrogen, C １－６ alkyl, or —CN; and n is an integer from 10 to 1000; 28. The method of claim 27.

29. The method of any one of claims 22 to 28, wherein the compound of formula II is: 【Chemistry 12】

30. The method of any one of claims 22 to 29, wherein the compound of formula III is: 【Chemistry 13】

31. The method of any one of claims 22 to 30, comprising: (a) the compound of formula II: 【Chemistry 14】 potassium carbonate, dimethylformamide, and the compound of formula III having the following structure: 【Chemistry 15】 forming the reaction mixture comprising: wherein the molar ratio of the compound of formula II to the compound of formula III is 0.98 to 0.99 under conditions suitable to form the compound of formula I; During the ceremony, R １ａ and R １ｂ are each independently a 5-6 membered heterocycloalkyl having 1-3 heteroatoms which are each independently N, O, or S, or a 5-6 membered heteroaryl having 1-3 heteroatoms which are each independently N, O, or S; Each R １ｃ But independently, C １－３ Alkyl, ═O, —C １－３ Alkyl-(SO ３ － ), -SO ２ -C １－３ alkyl, or a 5-6 membered heterocycloalkyl having 1-2 heteroatoms, each independently N, O, or S; R ２ａ and R ２ｂ are each hydrogen; R ３ is —CN; X is -N= or -C(R ４ ) = and R ４ is —CN; and The subscript n is an integer from 10 to 1000.

32. The method of any one of claims 22 to 30, comprising: (a) the compound of formula II: 【Chemistry 16】 potassium carbonate, dimethylformamide, and the compound of formula III having the following structure: 【Chemistry 17】 forming the reaction mixture comprising: wherein the molar ratio of the compound of formula II to the compound of formula III is from 1.01 to 1.03 under conditions suitable to form the compound of formula I; During the ceremony, R １ａ and R １ｂ are each independently NR １ａ１ R １ａ２ and Each R １ａ１ and R １ａ２ But independently, C １－３ Alkyl or C ２－４ alkenyl; R ２ａ and R ２ｂ are each hydrogen; R ３ is —CN; X is -C(CN)=; and The subscript n is an integer from 10 to 1000.

33. An electrochemical cell comprising: anode; cathode; A separator comprising the polymer of any one of claims 1 to 19; and Electrolytes.

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