Spirobisindane polymer with inherent microporosity and preparation method thereof

Abstract

Spirobisindane polymers having intrinsic microporosity are described for use as separators in electrochemical cells.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 476,777, filed on December 22, 2022, which is incorporated herein in its entirety for all purposes. Background Art

[0003] 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 and cycling capabilities at an affordable price. However, the energy density of current commercial Li-ion battery chemistries is approaching the theoretical limit of the technology, and with the rapid electrification trend targeting the transportation and energy sectors, the demand for higher energy density batteries at a lower unit cost is growing. There is a clear need for batteries with improved capacity, long cycle life, and high stability. Replacing graphite anodes in Li-ion batteries with lithium metal anodes offers the potential to significantly increase the energy density of Li-ion batteries. However, after repeated charge-discharge cycling, Li-metal batteries suffer irreversible capacity loss due to electrolyte depletion and lithium inventory loss due to parasitic reactions between the highly reactive Li-metal anode and electrolyte components. This process creates localized inhomogeneities on the Li-anode surface, further exacerbating uneven plating and stripping and leading to the appearance of physically isolated "dead" lithium. Furthermore, uneven Li plating increases the risk of dendrite formation, which can cause thermal runaway and catastrophic battery failure, posing a significant obstacle to the commercialization of Li-metal batteries. Slowing down the formation of dendrites in lithium metal batteries is crucial for their safe and stable use in commercial applications.

[0004] The battery separator is a critical component of Li-ion batteries because it separates the electrodes, provides ion transport through large pores filled with electrolyte, and prevents electronic conduction that would otherwise cause short circuits. Although the separator does not directly participate in the battery reaction, its physical properties play an important role in determining battery performance, including energy density, power density, and safety. Importantly, the mechanical integrity of the separator is crucial to preventing internal short circuits throughout the battery cell's life.

[0005] Currently, a variety of porous membrane separator materials and composites are used in Li-ion batteries, including separators made of polyolefins, such as polyethylene (PE), polypropylene (PP), and polypropylene-polyethylene-polypropylene (PP / PE / PP), as well as ceramic-coated separators (including PP, PE, or a multilayer porous substrate coated with a ceramic composite layer on at least one side). As described in U.S. Patent 6,432,583 (Celgard Inc.), the ceramic composite layer is intended to block dendrite growth and prevent electronic short circuits. Although ceramic-coated separators have been successfully used in Li-ion batteries to improve mechanical properties, their use in lithium metal batteries is limited due to parasitic reactions at the anode caused by the binder material that supports the ceramic coating.

[0006] WO 2018 / 106957 (Sepion Technologies, Inc et al.) describes the use of porous polymers (10-40% porosity, 0.5-2.0 nm pore size) as templates that deliver solution-processed solid precursors and halide-containing salts as conformal coatings between the lithium metal surface and the separator surface to increase the wettability of the separator and increase the lithium ion concentration and mobility at the separator-anode interface. The document also describes an electrochemical cell comprising a separator comprising multiple layers: a first polymer layer comprising a planar substance and a linker. The separator may also comprise a porous support made of PP or PE, which is laminated to the first polymer layer. The separator may also comprise a second membrane layer laminated to the porous support, the second layer comprising a ceramic material.

[0007] The use of intrinsically microporous polymers (PIMs) as selective battery membranes has been explored. PIMs consist of fused rings that provide rigidity and torsion sites, which may be provided by spirocyclic centers, curved or bridged ring portions, or similar structural components that act as barriers to prevent conformational relaxation of the polymer chains. PIMs have been described and studied since 2006 because they can create 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 is formed as a direct result of the shape and rigidity of the component macromolecules. Notably, an article by Li et al. (Nano Lett. 2015, 15, 5724-5729) describes PIMs as membrane platforms for achieving high flux, ion-selective transport in non-aqueous electrolytes.

[0008] Due to the high reactivity of lithium metal, a solid electrolyte interface (SEI) forms 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 inherent consumption of part of the lithium inventory during the in situ SEI formation process reduces the Coulombic efficiency of the electrochemical cell. On the other hand, an optimal SEI can limit the further decomposition of electrolyte components and improve the lithium ion transport at the electrode-separator interface, thereby improving the cycle performance and service life of the battery.

[0009] Artificial SEI layers have been explored to limit the lithium inventory and electrolyte component depletion process located on the surface of the anode material. One of the methods is based on the use of a PIM layer coated on a porous support. It is worth noting that WO 2020 / 037246A1 (Regents of the University of California) describes a microporous ladder polymer according to the formula -[A-AB-B]-, which contains an amine-functionalized monomer segment, an amidoxime-functionalized monomer segment or a combination thereof, and such microporous polymers are used for diaphragms, which may include one or more supporting materials, such as glass fiber. Microporous polymer films on porous supports are described in the embodiments, such as polyolefin battery separators (such as Celgard). The article by Chengyin Fu et al. (Nature Materials, April 2020) describes a lithium electrode laminated with a polyolefin separator coated with TBAF@PIM-1, i.e., a separator coated with a microporous polymer body (such as PIM-1) in combination with tetrabutylammonium fluoride (TBAF), using a separator (Celgard 2325). The coated separator is then assembled into a Li-Li or Li-NMC-622 cell along with a carbonate electrolyte containing an ionizable lithium salt (e.g., LiPF6). The composite is claimed to act as a dendrite-suppressing solid ion conductor (SIC) in lithium metal batteries. Summary of the Invention

[0010] In one embodiment, the present invention provides a polymer of Formula I:

[0011]

[0012] or a salt thereof, wherein:

[0013] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0014] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl;

[0015] Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is independently N, O, or S;

[0016] 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution;

[0017] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0018] 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2;

[0019] R 2a and R2b are each independently hydrogen or C 1-6 alkyl;

[0020] R 3 For hydrogen, C 1-6 Alkyl or -CN;

[0021] X is -N= or -C(R 4 )=;

[0022] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0023] The subscript n is an integer from 10 to 1000,

[0024] When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and

[0025] When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1a and R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

[0026] In another embodiment, the present invention provides a compound of formula II:

[0027]

[0028] in:

[0029] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0030] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C2-6 Alkynyl or C 5-8 cycloalkenyl;

[0031] Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is independently N, O, or S;

[0032] 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution;

[0033] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0034] 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2;

[0035] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl,

[0036] When R2a and R 2b are each hydrogen, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and

[0037] When R 2a and R 2b are each hydrogen, and R 1a and R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

[0038] In another embodiment, the present invention provides a method for preparing a polymer of formula I

[0039]

[0040] or a salt thereof, comprising:

[0041] a) forming a reaction mixture comprising a compound of formula II:

[0042]

[0043] A non-nucleophilic base, a solvent, and a compound of formula III:

[0044]

[0045] wherein the molar ratio of the compound of formula II to the compound of formula III is less than 1.1 under conditions suitable for forming the compound of formula I,

[0046] in:

[0047] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0048] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl;

[0049] Or, R 1a1and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is independently N, O, or S;

[0050] 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution;

[0051] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0052] 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2;

[0053] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl;

[0054] R 3 For hydrogen, C 1-6 Alkyl or -CN;

[0055] X is -N= or -C(R4 )=;

[0056] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0057] n is an integer from 10 to 1000.

[0058] 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

[0059] I. Definition

[0060] Abbreviations used herein have their conventional meanings in the fields of chemistry and biology.

[0061] When substituents are designated by their conventional chemical formula, written left to right, they also encompass chemically equivalent substituents that would result from writing the structure right to left, for example, -CH2O- is equivalent to -OCH2-.

[0062] "Alkyl" refers to a group having the indicated number of carbon atoms (i.e., C 1-6 represents a straight or branched chain saturated aliphatic group of 1 to 6 carbons. Alkyl groups may include any number of carbons, such as C 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 . C 1-6 Alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, and the like.

[0063] "Alkenyl" refers to a group having at least 2 carbon atoms and at least one double bond and having the indicated number of carbon atoms (i.e., C 2-6 Alkenyl groups may include any number of carbons, such as C2, C 2-3 、C 2-4 、C 2-5 、C2-6 、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 4-5 , C5, C 5-6 The C6 alkenyl group may have any suitable number of double bonds, including but not limited to 1, 2, 3, 4, 5 or more. 2-4 Examples of alkenyl groups include, but are not limited to, vinyl (ethenyl), propenyl, isopropenyl, 1-butenyl, 2-butenyl, isobutenyl, or butadienyl.

[0064] "Alkynyl" refers to a group having at least 2 carbon atoms and at least one triple bond and having the indicated number of carbon atoms (i.e., C 2-6 Alkynyl groups may include any number of carbon atoms, such as 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 and C6. C 2-4 Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, 1-butynyl, 2-butynyl, isobutynyl, sec-butynyl, or butadiynyl.

[0065] "Hydroxyalkyl" or "alkoxy" refers to an alkyl group as defined above in which at least one of the hydrogen atoms is replaced by a hydroxy group. Similar to alkyl groups, hydroxyalkyl groups or alkoxy groups may have any suitable number of carbon atoms, for example, C 1-6 . Exemplary C 1-4 Hydroxyalkyl groups include, but are not limited to, hydroxymethyl, hydroxyethyl (wherein the hydroxyl group is at the 1 or 2 position), hydroxypropyl (wherein the hydroxyl group is at the 1, 2, or 3 position), hydroxybutyl (wherein the hydroxyl group is at the 1, 2, 3, or 4 position), 1,2-dihydroxyethyl, and the like.

[0066] "Alkyl-alkoxy" or "alkoxyalkyl" refers to a group having an alkyl component and an alkoxy component, wherein the alkyl component links the alkoxy component to the point of attachment. The alkyl component is as defined above, but the alkyl component is at least a divalent alkylene group to link to the alkoxy component and the point of attachment. The alkyl component can include any number of carbon atoms, for example, 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 In some cases, the alkyl component may be absent. The alkoxy component is as defined above. Examples of alkyl-alkoxy groups include, but are not limited to, 2-ethoxyethyl and methoxymethyl.

[0067] "Halogen" refers to fluorine, chlorine, bromine and iodine.

[0068] "Haloalkyl" refers to an alkyl group as defined above in which some or all of the hydrogen atoms are replaced by halogen atoms. Similar to alkyl, haloalkyl groups may have any suitable number of carbon atoms, for example, C 1-6 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 hydrogens are replaced by fluorine. For example, perfluoromethyl refers to 1,1,1-trifluoromethyl.

[0069] "Haloalkoxy" refers to an alkoxy group in which some or all of the hydrogen atoms are replaced by halogen atoms. Similar to alkyl, haloalkoxy can have any suitable number of carbon atoms, for example, C 1-6 Alkoxy groups may be substituted with 1, 2, 3 or more halogens. When all hydrogens are replaced with halogens (e.g., fluorine), the compound is fully substituted, e.g., perfluorinated. Haloalkoxy groups include, but are not limited to, trifluoromethoxy, 2,2,2-trifluoroethoxy, perfluoroethoxy, and the like.

[0070] "Cycloalkyl" refers to a saturated or partially unsaturated monocyclic, fused bicyclic or bridged polycyclic ring assembly containing 3 to 12 ring atoms or the number of atoms specified. Cycloalkyl can include any number of carbon atoms, such as C 3-6 、C 4-6 、C 5-6 、C 3-8 、C 4-8 、C5-8 、C 6-8 、C 3-9 、C 3-10 、C 3-11 and C 3-12 . Saturated monocyclic cycloalkyl rings include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Saturated bicyclic and polycyclic cycloalkyl rings include, for example, norbornane, [2.2.2]bicyclooctane, decahydronaphthalene, and adamantane. Cycloalkyl groups may also be partially unsaturated, having one or more double or triple bonds in 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 group is a saturated monocyclic C 3-8 When cycloalkyl is a saturated monocyclic C 3-6 In the case of cycloalkyl, exemplary groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The cycloalkyl group may be substituted or unsubstituted.

[0071] "Cycloalkenyl" refers to a partially unsaturated monocyclic, fused bicyclic, or bridged polycyclic ring assembly containing 5 to 12 ring atoms or the number of atoms specified. Cycloalkenyl groups may include any number of carbon atoms, such as C 5-6 、C 5-8 or C 6-8 Cycloalkenyl rings having one or more double or triple bonds in the ring include, but are not limited to, 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.

[0072] "Heterocycle" or "heterocycloalkyl" refers to a saturated or partially unsaturated ring system (heterocycloalkenyl) having 3 to 12 ring members and 1 to 4 heteroatoms of N, O and S. The heteroatoms may also be oxidized, such as, but not limited to, -S(O)- and -S(O)2-. Heterocycloalkyl may include 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 members. Any suitable number of heteroatoms may be included in the heterocycloalkyl, 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 can 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), thiol (tetrahydrothiopyran), oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiolane, morpholine, thiomorpholine, dioxane or dithiane. Heterocycloalkyl can also be fused to aromatic or non-aromatic ring systems to form members including but not limited to dihydroindole. Heterocycloalkyl can be unsubstituted or substituted. For example, heterocycloalkyl can be C 1-6 substituted with alkyl or oxo (=O).

[0073] "Heterocycloalkenyl" refers to a partially unsaturated ring system having 3 to 12 ring members and 1 to 4 heteroatoms of 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-. The heterocycloalkenyl group may include any number of ring atoms, such as 5 to 8 or 6 to 8. Any suitable number of heteroatoms may be included in the 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. The heterocycloalkenyl group may include groups such as 2,5-dihydro-1H-pyrrole, 1,2,3,6-tetrahydropyridine, 2,3,4,7-tetrahydro-1H-aza 2,7-Dihydro-1H-azepine A heterocycloalkenyl group can be unsubstituted or substituted.

[0074] "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. Heteroatoms can also be oxidized, such as, but not limited to, N-oxides, -S(O)-, and -S(O)2-. Nitrogen atoms can also be quaternized. Heteroaryl groups can include 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 members. Any suitable number of heteroatoms can be included in a heteroaryl group, 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 members and 1 to 4 heteroatoms, 5 to 8 ring members and 1 to 4 heteroatoms, or 5 to 8 ring members and 1 to 3 heteroatoms, or 5 to 6 ring members and 1 to 4 heteroatoms, or 5 to 6 ring members 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 can also be fused to aromatic ring systems (e.g., benzene rings) to form members including, but not limited to, benzopyrroles (e.g., indole and isoindole), benzopyridines (e.g., quinoline and isoquinoline), benzopyrazines (quinoxalines), benzopyrimidines (quinazolines), benzopyridazines (e.g., phthalazine and cinnoline), benzothiophenes, and benzofurans. Other heteroaryl groups include heteroaryl rings connected by bonds, such as bipyridine.

[0075] The heteroaryl group can be attached at 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, 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-quinazoline, cinnoline includes 3- and 4-cinnoline, benzothiophene includes 2- and 3-benzothiophene, and benzofuran includes 2- and 3-benzofuran.

[0076] Some heteroaryl groups include heteroaryl groups having 5 to 10 ring members and 1 to 3 ring atoms (including 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 heteroaryl groups having 5 to 8 ring members 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 with 9 to 12 ring members 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 with 5 to 6 ring members and 1 to 2 ring atoms (including N, O, or S), such as pyrrole, pyridine, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole.

[0077] Some heteroaryl groups include 5 to 10 ring members and include 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 include 5 to 10 ring members and include only oxygen heteroatoms, such as furan and benzofuran. Some other heteroaryl groups include 5 to 10 ring members and include only sulfur heteroatoms, such as thiophene and benzothiophene. Still other heteroaryl groups include 5 to 10 ring members 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.

[0078] "Salt" refers to an acid or base salt of a compound used in the methods of the present invention. Salts of the basic compounds of the present invention are salts formed with acids such as mineral acids, organic carboxylic acids, and organic sulfonic acids. Examples of salts include, but are not limited to, halogen salts such as fluoride, chloride, bromide, and iodide salts; oxyanion salts such as chlorate, bromate, iodate, carbonate, nitrate, sulfate, or phosphate; carboxylate salts such as fumarate or acetate; and sulfonate salts such as triflate.

[0079] Also included are base addition salts such as sodium, potassium, calcium, ammonium, organic amino or magnesium salts or similar salts, provided that the acidic group constitutes part of the structure. Illustrative examples of salts are salts with mineral acids (hydrochloric acid, hydrobromic acid, phosphoric acid, etc.), organic acids (acetic acid, propionic acid, glutamic acid, citric acid, etc.), quaternary ammonium (methyl iodide, ethyl iodide, etc.).

[0080] "Sulfonate" refers to a salt containing -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 can contain any compound attached via a single bond to -S(O)3 - chemical groups.

[0081] "Forming a reaction mixture" refers to the process of contacting at least two different substances so that they mix together and are able to react. However, it should be understood that the resulting reaction product can be produced directly from the reaction between the added reagents or from one or more intermediates that can be produced in the reaction mixture from the added reagents.

[0082] "Non-nucleophilic base" refers to a base that is a moderate to strong base but is also a poor nucleophile. Representative non-nucleophilic bases include bases such as 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.

[0083] "Solvent" refers to a substance, such as a liquid, that can dissolve a solute. Solvents can be polar or non-polar, 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 protons that can be removed, such as hydroxyl or carboxyl groups. Aprotic solvents lack such groups. Representative polar protic solvents include alcohols (methanol, ethanol, propanol, isopropanol, etc.), acids (formic acid, acetic acid, etc.) and water. Representative polar aprotic solvents include dichloromethane, chloroform, tetrahydrofuran, ether, acetone, ethyl acetate, dimethylformamide, dimethylacetamide, acetonitrile and dimethyl sulfoxide. Representative non-polar solvents include alkanes (pentane, hexane, etc.), benzene, toluene and 1,4-dioxane. Other solvents can also be used in the present invention.

[0084] An "electrode" is a conductive material in an electrical circuit that is in contact with the non-metallic parts of the circuit, such as the electrolyte. An electrode can be a positive electrode, or cathode, where reduction occurs. An electrode can be a negative electrode, or anode, where oxidation occurs.

[0085] "Anode" refers to the negative electrode as described above.

[0086] "Cathode" refers to the positive electrode as described above.

[0087] "Electrolyte" refers to the solution in an electrochemical cell that contains ions (eg, metal ions and protons, as well as anions) that provides for ionic communication between the positive and negative electrodes.

[0088] "Electrolyte solvents" are molecules that solvate ions in a liquid electrolyte, such as small organic carbonates or ethers, allowing the ions to diffuse through the electrolyte. Electrolyte solvents can also be ionic liquids or gases at standard temperature and pressure.

[0089] "Separator" refers to an electrically insulating film between the positive electrode and the negative electrode that prevents electrical shorting (i.e., provides electronic isolation). The separator also allows ions to move between the positive electrode and the anode electrode. The separator can comprise any suitable electrically insulating polymeric or inorganic material. The separator can comprise multiple layers, including one or more film layers and a porous support material for the film layers.

[0090] "First polymer layer" refers to a layer of a separator that is permeable to the first electrolyte but substantially impermeable to the liquid electrolyte. The membrane layer can be made of any suitable material that provides 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 permeates the membrane layer, or less than 1%, less than 0.1%, less than 0.01%, or less than 0.001% of the liquid electrolyte permeates the membrane layer.

[0091] "Oxide" refers to a chemical compound having oxygen, such as a metal oxide or a molecular oxide.

[0092] "Pore size" or "pore diameter" refers to the average diameter of the interstices not occupied by pore-forming materials. This may include, but is not limited to, the spaces remaining between polymer chains due to inefficient packing, the spaces remaining between organic linkers and metal ions in metal-organic frameworks, the interlayer and intracavity spaces of stacked two-dimensional materials, and the spaces left in amorphous or semi-crystalline carbon due to unevenly distributed covalent bonding. Pore size may also change upon wetting with the electrolyte, or it may remain constant.

[0093] "Surface area" refers to the surface area of ​​a porous material as measured by various methods (eg, nitrogen adsorption BET).

[0094] "Microporous polymer" refers to an amorphous glassy polymer having interconnected pores having an average diameter of less than 10 nm, or less than 5, 4, 3, 2, or less than 1 nm.

[0095] "Microporosity" refers to a layer of membrane comprising pores with a size less than or equal to 2 nm.

[0096] "Intrinsic microporosity" means that the polymer provides a continuous network of interconnected intermolecular voids (preferably less than or equal to 4 nm in size) that form as a direct result of the shape and rigidity of at least a portion of the polymer's constituent monomers. As will be understood by those skilled in the art, intrinsic microporosity arises from the structure of the monomers used to form the polymer and, as the name implies, is an inherent property of polymers formed from such monomers.

[0097] It will be understood that the network polymers disclosed herein have specific properties (i.e., inherent microporosity). Disclosed herein are certain structural requirements in the monomers used to obtain the polymers that perform the disclosed functions, and it will be understood that there are multiple structures that can perform the same function associated with the disclosed monomer structures, and that these structures will generally achieve the same results.

[0098] "Molecular weight" refers to the molecular weight of a polymer as determined by size exclusion chromatography (SEC), laser light scattering, MALDI-TOF or other methods. Molecular weight can be measured by weight average molecular weight or number average molecular weight. "Number average molecular weight" (M N ) refers to the mole fraction of molecules in a polymer sample, that is, 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, emphasizing the weight of a single molecule, so M W Greater than M N . M W / M N The ratio of , the polydispersity index, indicates the distribution of molecular weight in the polymer.

[0099] "Metal" refers to a metallic element in the periodic table, which can be neutral or negatively or positively charged due to having more or fewer electrons in the valence shell than 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 exhibit a variety of different oxidation states, all of which can be used in the present invention. In some cases, the most stable oxidation state is formed, but other oxidation states can also be used in the present invention.

[0100] "Porous support" refers to any suitable material that can support the membrane layer of the present invention and is permeable to electrolyte.

[0101] "Laminated" refers to the deposition of one layer on another, such as a microporous polymer layer or a first polymer layer on a porous support.

[0102] II. Spirobiindane Polymers

[0103] 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:

[0104]

[0105] or a salt thereof, wherein:

[0106] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0107] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C2-6 Alkynyl or C 5-8 cycloalkenyl;

[0108] Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is independently N, O, or S;

[0109] 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution;

[0110] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0111] 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2;

[0112] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl;

[0113] R3 For hydrogen, C 1-6 Alkyl or -CN;

[0114] X is -N= or -C(R 4 )=;

[0115] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0116] The subscript n is an integer from 10 to 1000,

[0117] When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and

[0118] When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1a and R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

[0119] In some embodiments, the present invention provides a polymer of Formula I:

[0120]

[0121] or a salt thereof, wherein:

[0122] R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0123] 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-C1-6 Alkyl, -C 1-6 Alkyl-(SO3 - )、-O(P=O)(OR 1d )2, a 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S;

[0124] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0125] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl;

[0126] R 3 For hydrogen, C 1-6 Alkyl or -CN;

[0127] X is -N= or -C(R 4 )=;

[0128] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0129] The subscript n is an integer from 10 to 1000,

[0130] When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and

[0131] When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1a and R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

[0132] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1bEach is independently a 5-10 membered heterocycloalkyl group having 2-4 heteroatoms each independently being N or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substituted; and 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S.

[0133] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group is independently substituted by 0, 1, 2 or 3 R 1c group substitution; and each R 1c Independently C 1-6 Alkyl, =O, -S(O)2-C 1-6 alkyl or a 3-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S.

[0134] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each is a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group is surrounded by 0, 1, 2 or 3 R 1c group substitution; and each R 1c Independently C 1-6 Alkyl, =O, -S(O)2-C 1-6 alkyl or a 3-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S.

[0135] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R1b Each is independently a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group is independently replaced by 0, 1, 2 or 3 R 1c group substitution; and each R 1c Independently C 1-3 Alkyl, =O, -S(O)2-C 1-3 alkyl or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S.

[0136] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each is a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group is surrounded by 0, 1, 2 or 3 R 1c group substitution; and each R 1c Independently C 1-3 Alkyl, =O, -S(O)2-C 1-3 alkyl or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S.

[0137] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each is a 5-6 membered heterocycloalkyl group having 2-3 heteroatoms each independently being N or S, wherein the heterocycloalkyl group is surrounded by 0, 1, 2 or 3 R 1c group substitution; and each R 1c Independently C 1-3 Alkyl, =O, -S(O)2-C 1-3 alkyl or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S.

[0138] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b are each independently pyrrolidine, piperidine, diazine, triazine, morpholine or thiomorpholine, each of which is independently replaced by 0, 1, 2 or 3 R 1c group substitution; and each R 1c are independently methyl, =O, -S(O)2-C 1-3 Alkyl, tetrahydropyran, pyrrolidine, piperidine, diazinane, thiolane, thiohexane or morpholine.

[0139] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1bEach is pyrrolidine, piperidine, diazinane, triazinane, morpholine or thiomorpholine, wherein each is independently substituted by 0, 1, 2 or 3 R 1c group substitution; and each R 1c are independently methyl, =O, -S(O)2-C 1-3 Alkyl, tetrahydropyran, pyrrolidine, piperidine, diazinane, thiolane, thiohexane or morpholine.

[0140] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each independently is:

[0141]

[0142] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each independently is:

[0143]

[0144] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each independently is NR 1a1 R 1a2 ; and each R 1a1 and R 1a2 Independently C 1-3 Alkyl, C 2-4 Alkenyl or C 2-4 In some embodiments, the polymer of Formula I or its salt is the following polymer, wherein R 1a and R 1b Each independently is NR 1a1 R 1a2 ; and each R 1a1 and R 1a2 Independently C 1-3 Alkyl or C 2-4 In some embodiments, the polymer of Formula I or its salt is the following polymer, wherein R 1a and R 1b Each independently is NR 1a1 R 1b1 ; and each R 1a1 and R 1a2are independently methyl, ethyl, propyl, isopropyl, vinyl, 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. In some embodiments, the polymer of Formula I or its salt is the following polymer, wherein R 1a and R 1b Each independently is NR 1a1 R 1b1 ; and each R 1a1 and R 1a2 is independently methyl, ethyl, propyl, isopropyl, vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl or isobutenyl.

[0145] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each independently

[0146] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 1a and R 1b Each independently

[0147] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 2a and R 2b Each is hydrogen.

[0148] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 3 For hydrogen, C 1-3 In some embodiments, the polymer of Formula I or its salt is the following polymer, wherein R 3 It is -CN.

[0149] In some embodiments, the polymer of Formula I or its salt is a polymer wherein X is -N=. In some embodiments, the polymer of Formula I or its salt is a polymer wherein X is -C(R 4 ); and R 4 For hydrogen, C 1-6 Alkyl or -CN.

[0150] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein R 4 It is -CN.

[0151] In some embodiments, the polymer of Formula I or its salt is a polymer wherein the salt comprises an anion selected from the group consisting of tetrafluoroborate, bis(oxalato)borate, difluoro(oxalato)borate, trifluorocyanoborate, cyanotri(2,2,2-trifluoroethyl)borate, carbonate, bicarbonate, carboxylate, acetate, trifluoroacetate, dicarboxylate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, thiocyanate, nitrite, nitrosocyanate, thiocyanate, nitrite, nitrosocyanate, thiocyanate, nitroso ... In some embodiments, the polymer of formula I or its salt is a polymer wherein the salt comprises an anion which is a sulfonate. In some embodiments, the polymer of formula I or its salt is a polymer wherein the salt comprises an anion which is a sulfonate. In some embodiments, the polymer of formula I or its salt is a polymer wherein the salt comprises an anion which is a sulfonate.

[0152]

[0153] In some embodiments, the polymer of Formula I or its salt is a polymer wherein the salt comprises a cation which is

[0154]

[0155] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0156] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-10 membered heterocycloalkyl group having 2-4 heteroatoms each independently being N or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0157] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl;

[0158] Each R 1c Independently C 1-6 Alkyl, C 2-6 Alkenyl, C2-6 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S;

[0159] X is -N= or -C(R 4 )=; and

[0160] R 4 For hydrogen, C 1-6 Alkyl or -CN,

[0161] When X is -C(CN)=, then R 1a and R 1b Each is not morpholine.

[0162] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0163] R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 2-4 heteroatoms each independently being N or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0164] 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S;

[0165] X is -N= or -C(R 4 )=; and

[0166] R 4 For hydrogen, C 1-6 Alkyl or -CN.

[0167] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0168] R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0169] 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S; and

[0170] X is -N=.

[0171] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0172] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0173] Each R 1a1 and R1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl;

[0174] 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S;

[0175] X is -C(R 4 )=; and

[0176] R 4 For hydrogen, C 1-6 Alkyl or -CN,

[0177] When X is -C(CN)=, then R 1a and R 1b Each is not morpholine.

[0178] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0179] R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0180] 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)OR1d 、-S(O)2-C 1-6 Alkyl, -C 1-6 Alkyl-(SO3 - )、-O(P=O)(OR 1d )2, a 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S;

[0181] X is -C(R 4 )=; and

[0182] R 4 For hydrogen, C 1-6 Alkyl or -CN.

[0183] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0184] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group is independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0185] Each R 1a1 and R 1a2 Independently C 1-3 Alkyl or C 2-4 alkenyl;

[0186] Each R 1c Independently C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ) or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S;

[0187] R 2a and R 2b Each is hydrogen;

[0188] R 3 is -CN; and

[0189] X is -N= or -C(CN)=,

[0190] When X is -C(CN)=, then R 1a and R 1b Each is not morpholine.

[0191] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0192] R 1a and R 1b Each is independently a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group is independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0193] Each R 1c Independently C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ) or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S;

[0194] R 2a and R 2b Each is hydrogen;

[0195] R 3 is -CN; and

[0196] X is -N= or -C(CN)=,

[0197] When X is -C(CN)=, then R 1a and R 1b Each is not morpholine.

[0198] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0199] R 1a and R 1b Each is independently a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group is independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0200] Each R 1c Independently C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ) or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S;

[0201] R 2a and R 2b Each is hydrogen;

[0202] R 3 is -CN; and

[0203] X is -N=.

[0204] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0205] R 1a and R 1b Each independently

[0206] R 2a and R 2b Each is hydrogen;

[0207] R 3 is -CN; and

[0208] X is -N= or -C(CN)=,

[0209] When X is -C(CN)=, then R 1a and R 1b Each is not morpholine.

[0210] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0211] R 1a and R 1b Each independently

[0212] R 2a and R 2b Each is hydrogen;

[0213] R 3 is -CN; and

[0214] X is -C(CN)=.

[0215] In some embodiments, the polymer of Formula I or a salt thereof is a polymer wherein:

[0216] R 1a and R 1b Each for

[0217] R 2a and R 2b Each is hydrogen;

[0218] R 3 is -CN; and

[0219] X is -N= or -C(CN)=,

[0220] When X is -C(CN)=, then R 1a and R 1b Each is not morpholine.

[0221] In some embodiments, the polymer of Formula I or a salt thereof is the following polymer:

[0222]

[0223]

[0224] In some embodiments, the polymer of Formula I or a salt thereof is the following polymer:

[0225]

[0226]

[0227] In some embodiments, the polymer of Formula I or a salt thereof is the following polymer:

[0228]

[0229]

[0230] The polymers of the present invention can be prepared from a variety of monomers. In some embodiments, the present invention provides a compound of formula II:

[0231]

[0232] in:

[0233] R 1a and R 1b Each independently is NR 1a1 R 1a2 , a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0234] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl;

[0235] Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is independently N, O, or S;

[0236] Each R 1c Independently C 1-6 Alkyl, C 2-6Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C 1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution;

[0237] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0238] 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2;

[0239] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl,

[0240] When R 2a and R 2b are each hydrogen, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and

[0241] When R 2a and R 2b are each hydrogen, and R 1a and R 1b When each is piperazine, R 1cNot -C(O)OR 1d .

[0242] In some embodiments, the present invention provides compounds of Formula II:

[0243]

[0244] in:

[0245] R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0246] 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S;

[0247] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0248] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl,

[0249] When R 2a and R 2b are each hydrogen, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and

[0250] When R 2a and R 2b are each hydrogen, and R 1aand R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

[0251] R of Formula II 1a 、R 1b 、R 1c 、R 1d 、R 2a and R 2b Each embodiment of may be defined as described above for the polymer of formula I.

[0252] In some embodiments, the compound of Formula II is:

[0253]

[0254] In some embodiments, the compound of Formula II is:

[0255]

[0256] III. Preparation of Spirobiindane Polymers

[0257] 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:

[0258]

[0259] or a salt thereof, comprising:

[0260] a) forming a reaction mixture comprising a compound of formula II:

[0261]

[0262] A non-nucleophilic base, a solvent, and a compound of formula III:

[0263]

[0264] wherein the molar ratio of the compound of formula II to the compound of formula III is less than 1.1 under conditions suitable for forming the compound of formula I,

[0265] in:

[0266] R 1a and R 1b Each independently is NR 1a1 R 1a2, a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0267] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl;

[0268] Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is independently N, O, or S;

[0269] 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution;

[0270] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0271] Each R 1e Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Hydroxyalkyl, C1-6 Alkoxy, C 2-6 Alkoxyalkyl, halogen, C 1-6 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2;

[0272] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl;

[0273] R 3 For hydrogen, C 1-6 Alkyl or -CN;

[0274] X is -N= or -C(R 4 )=;

[0275] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0276] n is an integer from 10 to 1000.

[0277] In some embodiments, the present invention provides a method for preparing a polymer of formula I:

[0278]

[0279] or a salt thereof, comprising:

[0280] a) forming a reaction mixture comprising a compound of formula II:

[0281]

[0282] A non-nucleophilic base, a solvent, and a compound of formula III:

[0283]

[0284] wherein the molar ratio of the compound of formula II to the compound of formula III is less than 1.0 under conditions suitable for forming the compound of formula I,

[0285] in:

[0286] R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution;

[0287] Each R1c 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S;

[0288] R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl;

[0289] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl;

[0290] R 3 For hydrogen, C 1-6 Alkyl or -CN;

[0291] X is -N= or -C(R 4 )=;

[0292] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0293] n is an integer from 10 to 1000.

[0294] The process of the present invention can prepare the polymers of Formula I described herein.

[0295] The non-nucleophilic base can be any suitable non-nucleophilic base. In some embodiments, the method for preparing a polymer of Formula I or a salt thereof is a method wherein the non-nucleophilic base is an inorganic base. In some embodiments, the method for preparing a polymer of Formula I or a salt thereof is a method wherein the non-nucleophilic base is sodium carbonate, potassium carbonate, rubidium carbonate, or cesium carbonate.

[0296] The non-nucleophilic base can 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.

[0297] The reaction mixture may comprise 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 preparing 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 preparing 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 preparing a polymer of Formula I or a salt thereof is a method in which the solvent is ethyl acetate, acetonitrile, dimethylformamide, dimethylacetamide, or dimethyl sulfoxide.

[0298] 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 molar ratios 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.

[0299] The molar ratio of the compound of formula II to the compound of formula III can 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 can be less than 1.0, or 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 can 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 preparing 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 preparing 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 of preparing the polymer of Formula I or a salt thereof is a method wherein the molar ratio of the compound of Formula II to the compound of Formula III is from 0.98 to 0.99.

[0300] The molar ratio of the compound of formula II to the compound of formula III can 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 can be greater than 1.0, or 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 can 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 preparing 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 preparing 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 of preparing the polymer of Formula I or a salt thereof is a method wherein the molar ratio of the compound of Formula II to the compound of Formula III is from 1.01 to 1.02.

[0301] In some embodiments, the present invention provides a method for preparing a polymer of Formula I or a salt thereof, comprising:

[0302] a) forming a reaction mixture comprising a compound of formula II:

[0303]

[0304] A non-nucleophilic base, a solvent, and a compound of formula III:

[0305]

[0306] wherein the molar ratio of the compound of formula II to the compound of formula III is 1.0 to 1.1 under conditions suitable for forming the compound of formula I,

[0307] in:

[0308] R 1a and R 1b Each independently is NR 1a1 R 1a2 ;

[0309] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl or C 5-8 cycloalkenyl;

[0310] R 2a and R 2bare each independently hydrogen or C 1-6 alkyl;

[0311] R 3 For hydrogen, C 1-6 Alkyl or -CN;

[0312] X is -C(R 4 )=;

[0313] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0314] n is an integer from 10 to 1000.

[0315] In some embodiments, the present invention provides a method for preparing a polymer of Formula I or a salt thereof, wherein:

[0316] R 1a and R 1b Each independently is NR 1a1 R 1a2 ;

[0317] Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl or C 5-8 cycloalkenyl;

[0318] R 2a and R 2b are each independently hydrogen or C 1-6 alkyl;

[0319] R 3 For hydrogen, C 1-6 Alkyl or -CN;

[0320] X is -C(R 4 )=;

[0321] R 4 For hydrogen, C 1-6 Alkyl or -CN; and

[0322] n is an integer from 10 to 1000.

[0323] In some embodiments, the method of preparing a polymer of Formula I or a salt thereof is a method wherein the compound of Formula II is:

[0324]

[0325] Additional embodiments of Formula II that can be used in the methods of preparing polymers of Formula I are described herein.

[0326] In some embodiments, the method of preparing a polymer of Formula I or a salt thereof is a method wherein the compound of Formula III is:

[0327]

[0328] In some embodiments, the method of preparing a polymer of Formula I or a salt thereof is a method wherein the compound of Formula III is:

[0329]

[0330] In some embodiments, the method of preparing a polymer of Formula I or a salt thereof is a method wherein the compound of Formula III is:

[0331]

[0332] In some embodiments, the method for preparing a polymer of Formula I or a salt thereof is a method comprising the following

[0333] a) forming a reaction mixture comprising a compound of formula II:

[0334]

[0335] Potassium carbonate, dimethylformamide and a compound of formula III having the structure:

[0336]

[0337] 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 compound of formula I,

[0338] in:

[0339] R 1a and R 1b Each is independently a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, or a 5-6 membered heteroaryl group having 1-3 heteroatoms each independently being N, O or S;

[0340] Each R 1c Independently C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ), -SO2-C 1-3 Alkyl or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S;

[0341] R 2a and R 2b Each is hydrogen;

[0342] R 3 is -CN;

[0343] X is -N= or -C(R 4 )=;

[0344] R 4 is -CN; and

[0345] The subscript n is an integer from 10 to 1000.

[0346] In some embodiments, the method for preparing a polymer of Formula I or a salt thereof is a method comprising the following

[0347] a) forming a reaction mixture comprising a compound of formula II:

[0348]

[0349] Potassium carbonate, dimethylformamide and a compound of formula III having the structure:

[0350]

[0351] 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 compound of formula I,

[0352] in:

[0353] R 1a and R 1b Each independently is NR 1a1 R 1a2 ;

[0354] Each R 1a1 and R 1a2 Independently C 1-3 Alkyl or C 2-4 alkenyl;

[0355] R 2a and R 2b Each is hydrogen;

[0356] R 3 is -CN;

[0357] X is -C(CN)=; and

[0358] The subscript n is an integer from 10 to 1000.

[0359] In some embodiments, the method of preparing a polymer of Formula I or a salt thereof is the following method, wherein:

[0360] R 1a and R 1b Each independently is NR1a1 R 1a2 ;

[0361] Each R 1a1 and R 1a2 Independently C 1-3 Alkyl or C 2-4 alkenyl;

[0362] R 2a and R 2b Each is hydrogen;

[0363] R 3 is -CN;

[0364] X is -C(CN)=; and

[0365] The subscript n is an integer from 10 to 1000.

[0366] Each step of the preparation method of the present invention can be carried out for any suitable reaction time. For example, the reaction time can be several minutes, several hours, or several days. In some embodiments, the reaction time can be several hours, for example, at least eight hours. In some embodiments, the reaction time can be several hours, for example, at least overnight. In some embodiments, the reaction time can be several days. In some embodiments, the reaction time can be at least two hours. In some embodiments, the reaction time can be at least eight hours. In some embodiments, the reaction time can be at least several days. In some embodiments, the reaction time can be about two 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 can 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 about more than 1 week.

[0367] Each step of the preparation method of the present invention can be carried out at any suitable reaction temperature. Representative temperatures include, but are not limited to, below room temperature, at room temperature, or above room temperature. Other temperatures that can be used in the method 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 can be at a temperature of about room temperature, or at a temperature of about 15°C, or at about 20°C, or at about 25°C, or at about 30°C, or at about 35°C, or at about 40°C, or at about 45°C, or at about 50°C, or at about 55°C, or at about 60°C, or at about 65°C.

[0368] IV. Electrochemical Cells

[0369] 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.

[0370] The separator may comprise only the polymer of the present invention or a combination of the polymer of the present invention and other components. In some embodiments, the present invention provides a coated separator comprising:

[0371] a porous support having a first surface and an opposing second surface; and

[0372] a microporous polymer layer comprising a first polymer having intrinsic microporosity (PIM),

[0373] The microporous polymer layer is coated on the first surface of the porous support.

[0374] In some embodiments, the coated membrane further comprises 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 multilayer coated membrane comprising:

[0375] a porous support having a first surface and an opposing second surface;

[0376] a first polymer layer; and

[0377] a microporous polymer layer comprising a first polymer having intrinsic microporosity (PIM),

[0378] The first polymer layer is coated on the first surface of the porous support, and the microporous polymer layer is coated on the first polymer layer.

[0379] porous support

[0380] In some embodiments, the pore size of the porous support is between about 0.01 microns and 5 microns, or more specifically between about 0.02 microns and 0.5 microns. The porosity of the porous support may be between about 20% and 85%, or more specifically, between about 30% and 60%. A person with ordinary skill in the art will understand that the pore size may be affected by the composition of the electrolyte provided in the pores of the diaphragm. For example, some components of the diaphragm (e.g., the porous support or the first polymer layer) may swell when in contact with some electrolyte materials, resulting in a change in pore size. Unless specifically stated, pore size and other similar parameters refer to the components of the diaphragm before contact with the electrolyte.

[0381] The larger pore size allows the use of a porous support that is much thicker than the first polymer layer without significantly compromising the overall permeability of the membrane to the first substance. In some embodiments, the porous support has a thickness between about 5 microns and 500 microns, or in specific embodiments, between about 5 microns and 50 microns, or more specifically, between about 10 microns and 30 microns. In the same or other embodiments, the porous support may be about 1 to 50 times thicker than the first polymer layer, or more specifically, about 5 to 25 times thicker.

[0382] Some examples of suitable materials for the porous support include, but are not limited to, fluoropolymer fibers of poly(ethylene-co-tetrafluoroethylene) (PETFE) and poly(ethylene chloride-co-trifluoroethylene) (e.g., fabrics woven from these, either by themselves 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, polyacrylic acid, polyacetal, polycarbonate, polyester, polyetherimide, polyimide, polyketone, polyphenylene oxide, polyphenylene sulfide, polymethylpentene, polysulfone, non-woven glass, glass fiber materials, ceramics, metal oxides, composites of organic and inorganic substances, and polypropylene membranes. The porous support may also be provided with an additional coating of a second suitable material, including, but not limited to, PTFV, PVDF, and PETFE. These examples of porous supports may or may not be commercially available under the CELGARD name from Celanese Plastic Company, Inc. of Charlotte, North Carolina, USA, and Asahi Kasei Chemical Industry Co. of Tokyo, Japan, Tonen Corporation of Tokyo, Japan, Ube Industries of Tokyo, Japan, Nitto Denko KK of Osaka, Japan, Nippon Kodoshi Corporation of Kochi, Japan, Entek of Lebanon, Oregon, USA, SK Innovation of Jongno, South Korea, Sumitomo Corporation of Tokyo, Japan, Toray Industries of Tokyo, Japan, Dupont USA of Wilmington, Delaware, USA, W-Scope of Japan, and Parker Hannifin Filtration Group of Carson, California, USA.

[0383] In some embodiments, the coated membrane is a membrane wherein the porous support comprises polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), cellulose, ceramic, or a combination thereof. In some embodiments, the coated membrane is a membrane wherein the porous support comprises polyethylene.

[0384] The porous support may have a thickness between about 3 and 200 microns, or between about 5 and 100 microns, or between about 10 and 50 microns, or between about 9 and 25 microns, or between about 10 and 20 microns, or more specifically between about 15 and 30 microns. The porous support may have a thickness of about 5 microns, or about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 microns.

[0385] First polymer layer

[0386] The selective blocking properties of the one or more polymer layers used in the separator come from the composition or specific pore structure of these layers. For the purposes of this disclosure, the term "blocking" means screening, selecting or excluding. In some embodiments, the pore structure of the polymer layer is manifested as an interconnected network of pores having small pore size, narrow pore size distribution, high surface area and high porosity, as further described below. In some embodiments, the pore structure of the polymer layer is manifested as an array of channels having small pore size, narrow pore size distribution, high surface area and high porosity, as further described below. In addition to these blocking properties, the first polymer layer also has a variety of other properties that make it suitable for electrochemical cell applications, such as chemical and electrochemical stability, wettability, thickness, thermal stability, etc.

[0387] The blocking mechanism is based on chemical repulsion (non-wetting) or size exclusion effects occurring at the nanometer to sub-nanometer scale, where tortuous ion permeation pathways are established in the polymer layer. For example, the polymer layer may allow lithium ions (or other similar substances described below) to pass through while blocking larger electrolyte solvents, etc. The membrane can be formed from a ladder-shaped polymer having an angular helical center and no rotatable bonds in the polymer backbone or bonds in the backbone having restricted bond rotation. These properties provide inefficient solid-state packing with a porosity between about 10% and 40% of the bulk powder, or more specifically, between about 20% and 30%. The pores can then be filled with an inorganic component, leaving a non-porous or partially porous polymer layer.

[0388] The first polymer layer can comprise any suitable polymer. In some embodiments, the multilayer coated separator is one in which the first polymer layer is substantially insoluble in a carbonate electrolyte. Representative carbonate electrolytes are described herein. For example, the first polymer layer can be more than 50% insoluble in a carbonate electrolyte, or more than 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or more than 99% insoluble in a carbonate electrolyte.

[0389] The first polymer layer can include one or more different polymer layers. For example, the first polymer layer can include a first polymer layer, a second polymer layer or more polymer layers. In some embodiments, the multilayer coated membrane is a membrane in which the first polymer layer includes polyacrylonitrile, poly(acrylonitrile-methyl acrylate), poly(acrylonitrile-to-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-vinyl pyridine), poly(acrylonitrile-vinyl chloride), poly(acrylonitrile-vinyl acetate), poly(vinylidene fluoride-to-hexafluoropropylene) (PVDF-HFP), a second polymer having inherent microporosity different from the first polymer having inherent microporosity, or a combination thereof. In some embodiments, the multilayer coated membrane is a membrane wherein the first polymer layer comprises poly(acrylonitrile-co-methyl acrylate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), a second polymer having inherent microporosity that is different from the first polymer having inherent microporosity, or a combination thereof.

[0390] PIM polymer layer

[0391] Polymers with inherent microporosity that can be used in the electrochemical devices of the present invention include those described in U.S. Patent Nos. 10,710,065 and 11,394,082, U.S. Publication Nos. 2021 / 0309802 and 2019 / 0326578, each of which is incorporated herein by reference in its entirety.

[0392] To achieve the extremely high ion transport required for fast charging and high-power applications, high free volume and microporosity are sought after. Polymers that exhibit these properties are so-called high-free-volume polymers. These highly permeable polymers have been primarily applied in gas separations. Examples include certain substituted polyacetylenes (e.g., PTMSP), some perfluorinated polymers (e.g., Teflon AF), certain poly(norbornene), polymers with inherent microporosity, and some polyimides. Their microporosity has been confirmed 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 distorted shape. These rigid polymer macromolecules cannot pack properly in the solid state, resulting in a high free volume. The free volume distribution consists of unconnected elements and continuous microvoids, as in glassy polymers. In Teflon perfluorinated polymers, the high free volume is due to the high rotation barrier between adjacent dioxolanes, combined with weak interchain interactions, which are well known for fluoropolymers. This results in a low packing density and, therefore, high permeability. In the case of polynorbornene and PTMSP, the presence of bulky trimethylsilyl groups on the ring greatly limits the polymer's freedom to undergo conformational changes. In polymers with intrinsic microporosity (PIMs), molecular linkers containing torsion points are held in a non-coplanar orientation by rigid molecules, which prevents the resulting polymer from packing tightly and ensures high microporosity. The PIM concept has been reported for polyamides [PM Budd and NB McKewon, "Highly permeable polymers for gas separation membranes," Polymer Chemistry, 1, 63-68, 2010].

[0393] There are two different types of PIMs, i) non-network (linear) polymers, which may be soluble in organic solvents, and ii) network polymers, which are generally insoluble, depending on the choice of monomers. PIMs have an internal molecular free volume (IMFV), which is a measure of concavity and is defined by Swager as the volume difference of a concave unit cell compared to a non-concave shape [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 intrinsic microporosity in linear PIMs is claimed to originate from the impenetrable concavities imparted by their twisted structure, in network PIMs, microporosity is also claimed to originate from the concavities associated with the macrocycles. In non-network PIMs, rotation about single bonds must be avoided, whereas branching and crosslinking in network PIMs are believed to prevent structural rearrangements that could lead to loss of microporosity (McKeown, 2010), allowing single bonds to exist without loss of microporosity. In general, network PIMs have been observed to have greater microporosity than non-network PIMs due to macrocyclization [NB McKewon, PM Budd, "Explotation of Intrinsic Microporosity in Polymer-Based Materials," Macromolecules, 43, 5163-5176, 2010]. However, because network PIMs in the prior art are insoluble, they can only be incorporated into membranes by mixing them with microporous soluble materials (including soluble PIMs or other soluble polymers) as fillers. In non-network PIMs, there is a strict requirement that the polymer backbone be free of single bonds to prevent rotational freedom and thus provide intrinsic microporosity. A highly rigid and torsionally oriented molecular structure is required to provide irregular macromolecular shapes that cannot be efficiently packed in space. Molecules with irregular shapes are those that cause packing problems due to their concave surfaces. However, in order to have microporosity in non-network PIMs, concave molecules are not sufficient because the voids must be sufficiently interconnected for transport with minimal energy (i.e., intrinsic microporosity) [Macromolecules, 43, 5163-5176, 2010]. Non-network PIMs may be soluble and therefore suitable for casting membranes by phase inversion or for coating supported membranes to prepare 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].

[0394] U.S. Patent No. 7,690,514 B2 describes materials with inherent microporosity comprising organic macromolecules composed of first, generally planar species connected by linkers having torsion points, such that two adjacent first, planar species connected by the linker maintain a non-coplanar orientation. Preferred torsion points are spirocyclic groups, bridged ring moieties, and sterically crowded bonds around which rotation is restricted. These non-network PIMs are potentially soluble in common organic solvents, allowing them to be cast into films or coated onto other support membranes to produce thin film composites.

[0395] PIM-1 (soluble PIM) membranes exhibit gas permeabilities second only to very high free volume polymers such as Teflon AF2400 and PTMSP, showing selectivities above the upper limits for gas pairs such as CO2 / CH4 and O2 / N2 proposed by Robeson in 1991. Studies have shown that permeability can be enhanced by methanol treatment, which helps to flush out residual casting solvent and allow 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].

[0396] Ghanem et al. prepared several polyimides with properties similar to those of microporous polymers (PIMs), and membrane gas permeation experiments showed that these PIM-polyimides are the most permeable of all polyimides and have selectivities close to the upper limit for several important gas pairs [BG Ghanem, NB McKeown, PM Budd, NM Al-Harbi, DFritsch, K Heinrich, L Starannikova, A Tokarev and Y Yampolskii, "Synthesis, characterization, and gas permeation properties of a novel group of polymers with intrinsic micro porosity: PIM-polyimides", Macromolecules, 42, 7781-7888, 2009].

[0397] US Patent No. 7,410,525 Bl describes polymer / polymer mixed matrix membranes incorporating soluble inherently microporous polymers as microporous fillers for gas separation applications.

[0398] International Patent Publication No. WO 2005 / 113121 (PCT / GB2005 / 002028) describes forming a thin film composite membrane from PIM by coating a solution of the PIM in an organic solvent onto a support membrane, and then optionally crosslinking the PIM film to enhance its stability in organic solvents.

[0399] To improve the gas transport properties of soluble PIM membranes, U.S. Patent No. 7,758,751 B1 describes high-performance UV-exposed membranes from polymers with intrinsic microporosity (PIMs) and their use in both gas separations and liquid separations involving deep desulfurization of organic solvents such as olefins / paraffins, gasoline and diesel, and ethanol / water separations.

[0400] In some embodiments, the microporous polymer layer comprises a polymer having a chain of repeating units bonded to each other. Each unit may comprise a first substantially planar substance comprising at least one aromatic ring and further comprising a rigid linker having a torsion site, wherein the torsion site is a spirocyclic group, a bridged ring moiety, or a spatially crowded single covalent bond. The rigid linker restricts the rotation of the first planar substance in a non-coplanar orientation. In some embodiments, at least 50% (or 70%, 80%, or even 90%) of the first planar substance in the chain is connected to a maximum of two other planar substances via a rigid linker, and thus does not have a cross-linked covalently bonded three-dimensional structure. Therefore, this polymer may comprise a rigid linker having a torsion site. Because these polymer chains do not stack together due to their rigid torsion structure, the microporous polymer layer has inherent microporosity, and in some cases, inherent nanoporosity. Therefore, this combination of non-stacking and non-crosslinked polymer chains extends in three dimensions. It can also be considered a non-network polymer. Cross-linked polymers are also within the scope of the present invention.

[0401] In some embodiments, the surface area of ​​the PIM polymer layer prior to loading with the inorganic component (as measured by nitrogen adsorption of the dry powder before membrane treatment or related techniques) can be at least 200 m 2 / g or at least 500m 2 / g, for example, at 200m 2 / g and 2200m 2 / g, or more specifically between 600m 2 / g and 900m 2 / g. Representative methods for measuring surface area include nitrogen adsorption BET. Surface area is directly related to porosity, which is critical for efficient transport of supporting electrolyte between electrodes and higher power battery operation. Typical porosity ranges from 20% to 70%, or more specifically 30% to 60%. The surface area of ​​a PIM polymer layer can be 100m 2 / g to 3000m 2 / g, for example 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 is a separator in which the microporous polymer layer has a 100 m 2 / g to 3000m 2 / g of surface area.

[0402] In some embodiments, the diaphragm of coating is following diaphragm, wherein before filling inorganic component, the average pore size of microporous polymer layer is less than 100nm, or is about 0.1nm to about 20nm, or is about 0.1nm to about 10nm, or is about 0.1nm to about 5nm, or is about 0.1nm to about 2nm, or is about 0.1nm to about 1nm. For example, the average pore size of microporous polymer layer can be less than about 10nm, or is less than about 9, 8, 7, 6, 5, 4, 3, 2 or 1nm. For example, the average pore size of microporous polymer layer can be about 10nm, or is about 9, 8, 7, 6, 5, 4, 3, 2 or 1nm. This aperture ensures that some materials (for example, materials with a unit size greater than the pore size) are blocked by microporous polymer layer, while other materials are allowed to pass through (for example, materials with smaller unit sizes). In some embodiments, the diaphragm of coating is a diaphragm in which microporous polymer layer has an average pore size of 0.1nm to 10nm. In some embodiments, the coated separator is one 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 one in which the microporous polymer layer has an average pore size of 0.1 nm to 1 nm.

[0403] In some embodiments, the coated separator is a separator in which the number average molecular weight (M n ) in 1x10 3 and 2000x10 3 kg / mol(kDa), or more specifically between 15x10 3 and 500x10 3 kg / mol(kDa) or between 20x10 3 and 200x10 3 The larger number average molecular weight polymer contributes to the enhanced mechanical properties of the formed film.

[0404] In some embodiments, the coated separator is a separator in which the weight average molecular weight (M w ) in 1x10 3 and 2000x10 3 kg / mol(kDa), or more specifically between 15x10 3 and 500x10 3 kg / mol(kDa) or between 20x10 3 and 200x10 3 The larger number average molecular weight polymer contributes to the enhanced mechanical properties of the formed film.

[0405] The microporous polymer layer can be a membrane cast, sprayed or coated from a solution (eg, on a porous support), a composite of multiple individual membrane layers, a freestanding membrane or a supported membrane (eg, supported by a porous support).

[0406] In some embodiments, the coated separator is a separator wherein the microporous polymer layer has a thickness between about 5 nanometers and 20 micrometers, or between about 100 nanometers and 10 micrometers, or more specifically between about 500 nanometers and 5 micrometers.

[0407] The microporosity of the polymer layer can be seen through its high surface area (about 680-850m 2 The surface area is determined by nitrogen adsorption measurements (BET calculations). The presence of the cyano and methyl groups is optional and may be omitted or substituted with other simple substituents. Each phenyl group may contain one or more substituents. In addition, the nature and arrangement of the substituents on the spirocyclic indane moiety may be selected to provide any desired configuration around the carbon atoms common to the two five-membered rings.

[0408] electrolytes

[0409] The electrochemical cell of the present invention further comprises an electrolyte. The electrolyte may have various components, such as alkyl carbonate, fluorinated carbonate, diisocyanate, lithium salt or a combination thereof.

[0410] 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.

[0411] 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)OCH2CF2CF3, CH3CH2OC(O)OCH2CF2CF3, CH3CH2OC(O)OCH2CF2CHF2, or CH3OC(O)OCH2CF2CF2CF3.

[0412] Representative diisocyanates for the electrolyte include, but are not limited to, toluene-2,4-diisocyanate or toluene-2,6-diisocyanate.

[0413] The lithium salt in the electrolyte composition of the present invention can be any suitable lithium salt. For example, suitable lithium salts include, but are not limited to: lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, 4,5-dicyano-2-trifluoromethylimidazolium lithium, difluoro(oxalate)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or a combination thereof. In some embodiments, the lithium salt can be lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, 4,5-dicyano-2-trifluoromethylimidazolium lithium, difluoro(oxalate)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or a combination thereof.

[0414] 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).

[0415] The first lithium salt can be present in the electrolyte composition in any suitable amount. For example, the first lithium salt can be present in the electrolyte composition in an amount of 0.1 to 20 mol%, 0.1 to 20 mol%, 1 to 20 mol%, 5 to 20 mol%, 5 to 15 mol%, 8 to 12 mol%, or 9 to 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%.

[0416] The electrolyte may comprise one or more lithium salts. For example, the electrolyte may comprise 1, 2, 3, 4, or more different lithium salts as defined above. In some embodiments, the electrolyte comprises a single lithium salt. In some embodiments, the electrolyte comprises two different lithium salts. In some embodiments, the electrolyte comprises three different lithium salts.

[0417] The electrolyte may include a second lithium salt different from the first lithium salt. In some embodiments, the electrolyte includes a second lithium salt different from the first lithium salt.

[0418] In some embodiments, the electrolyte comprises a second lithium solvent, which may be 4,5-dicyano-2-(trifluoromethyl)imidazolium lithium, difluoro(oxalate)borate lithium, bis(trifluoromethanesulfonyl)imide lithium, difluorophosphate lithium, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or a combination thereof. In some embodiments, the electrolyte comprises a second lithium salt, which may be 4,5-dicyano-2-(trifluoromethyl)imidazolium lithium, difluoro(oxalate)borate lithium, or a combination thereof. In some embodiments, the electrolyte comprises a second lithium salt, which may be 4,5-dicyano-2-(trifluoromethyl)imidazolium lithium. In some embodiments, the electrolyte comprises a second lithium salt, which may be difluoro(oxalate)borate lithium. In some embodiments, the electrolyte comprises a second lithium salt, which may be lithium nitrate.

[0419] The second lithium salt can be present in the electrolyte composition in any suitable amount. For example, the second lithium salt can be present in the electrolyte composition in an amount of 0.1 to 10 mol%, 0.1 to 5 mol%, 0.5 to 5 mol%, 0.5 to 4 mol%, 0.5 to 3.5 mol%, 1 to 3 mol%, 1.0 to 2.5 mol%, or 1.5 to 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%.

[0420] In some embodiments, the electrolyte comprises a second lithium salt, which may be present in the electrolyte in an amount of 0.1 to 5 mol%. In some embodiments, the electrolyte comprises a second lithium salt, which may 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, which may be present in the electrolyte in an amount of 1 to 3 mol%. In some embodiments, the electrolyte comprises a second lithium salt, which may be present in the electrolyte in an amount of 1.5 to 2.5 mol%.

[0421] V. Examples

[0422] The molecular weight information of PIM-13 and the novel PIM samples 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 generated from polystyrene standards with molecular weights ranging from 0.266 to 1760 kg / mol (kDa).

[0423] Example 1: Synthesis of PIM-1-Py(a1)

[0424]

[0425] To a 500 mL two-necked round-bottom flask equipped with a vacuum adapter, a septum, and a stir bar, 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (4.83 g, 14.2 mmol, 1 eq) and tetrafluorocyanopyridine (2.50 g, 14.2 mmol, 1 eq) were added. The flask was then purged with argon and subjected to three evacuation and refill cycles. 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 eq) was added, which had been previously dried under vacuum at 150°C and ground with a mortar and pestle. The reaction mixture was stirred at 65° C. for 18 hours, after which it was precipitated in water (500 mL) and then washed with additional water (2×100 mL) and ethanol (2×100 mL). The resulting solid was dried under vacuum and then dissolved in tetrahydrofuran (THF) at 50 mg / mL. This solution was precipitated in 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 bright yellow solid. 1 H-NMR (400MHz, CDCl3, δ): 6.76 (1H, d), 6.39 (1H, D), 2.23 (2H, d), 1.33 (6H, d).

[0426] Example 2: Preparation of PIM-13(b2) Synthesis of SBI-morpholine (b1):

[0427]

[0428] To a 1-L, two-necked, round-bottom flask equipped with a reflux condenser were added paraformaldehyde (4.41 g, 147 mmol, 2.5 eq), morpholine (12.65 mL, 147 mmol, 2.5 eq), 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'-spirobiindane (20 g, 58.8 mmol, 1 eq) 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 x 50 mL), and dried under vacuum to yield SBI-morpholine (5.22 g, 16.5% yield). 1H-NMR (400 MHz, DMSO-d6, δ): δ 11.01 (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). Synthesis of PIM-13 (b2)

[0429]

[0430] SBI-morpholine (12.50 g, 23.2 mmol, 0.98 equivalent) and tetrafluoroterephthalonitrile (4.74 g, 23.68 mmol, 1 equivalent) were added to a 500 mL double-necked round-bottom flask equipped with a vacuum joint, a septum, and a stirring rod. The flask was then purged with argon, and after three vacuum extractions and refill cycles, dry N,N-dimethylformamide (250 mL) was 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 equivalents) previously 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, after which it was precipitated in water (500 mL) and then washed with additional water (2 x 50 mL) and ethanol (2 x 50 mL). The resulting solid was vacuum dried and then dissolved in THF with 50 mg / mL. The solution was precipitated into ethanol (500 mL), and 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 bright 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).

[0431] Lowering this mole fraction from 1 to 0.98 increases the proportion of high molecular weight segments in the polymer, as evidenced by the increase in Mw and Mz with this change.

[0432] Table 1 Study on the molar fraction of SBI-morpholine (b1)

[0433]

[0434] Table 2 Comparison with existing methods

[0435]

[0436]

[0437] Example 3: Synthesis of PIM-13-Py(b3)

[0438]

[0439] To a dry 250mL two-necked round-bottom flask was added SBI-morpholine (1, 5.81g, 10.79mmol, 1.0 equivalent), tetrafluorocyanopyridine (1.90g, 10.79mmol, 1 equivalent) and anhydrous dimethylformamide (114mL). The reaction mixture was purged with argon for 25 minutes and then heated to 65°C. After reaching 65°C, anhydrous potassium carbonate (6.08g, 44.03mmol, 4.08 equivalents) previously dried under vacuum at 150°C and ground with a mortar and pestle was added. The reaction mixture was then stirred at 65°C under argon for 18 hours, after which it was precipitated in water (500mL) and then washed with additional water (2x 50mL) and ethanol (2x 50mL). The resulting solid was vacuum dried and then dissolved in THF at 50mg / mL. The solution was precipitated into ethanol (500 mL), and the precipitated polymer was isolated by vacuum filtration and dried under vacuum to obtain 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).

[0440] Example 4: Synthesis of PIM-13S (c2)

[0441] Synthesis of SBI-thiomorpholine (c1)

[0442]

[0443] To a 1-L, two-necked, round-bottom flask equipped with a reflux condenser were added paraformaldehyde (4.41 g, 147 mmol, 2.5 eq), thiomorpholine (14.71 mL, 147 mmol, 2.5 eq), 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'-spirobiindane (20 g, 58.8 mmol, 1 eq) 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 x 50 mL), and dried under vacuum to yield SBI-thiomorpholine (5.23 g, 15.6% yield).

[0444] 1H-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).

[0445] Synthesis of PIM-13S(c2)

[0446]

[0447] To a dry 250mL two-necked round-bottom flask was added SBI-thiomorpholine (3, 3.71g, 6.49mmol, 0.99 equivalent), tetrafluoroterephthalonitrile (1.31g, 6.56mmol, 1 equivalent) and anhydrous dimethylformamide (65mL). The reaction mixture was purged with argon for 25 minutes and then heated to 65°C. After reaching 65°C, anhydrous potassium carbonate (3.70g, 26.75mmol, 4.08 equivalents) previously dried under vacuum at 150°C and ground with a mortar and pestle was added. The reaction mixture was then stirred at 65°C under argon for 18 hours, after which it was precipitated in water (500mL) and then washed with additional water (2x 50mL) and ethanol (2x50mL). The resulting solid was vacuum dried, dissolved in THF at 50mg / mL, and precipitated in ethanol (500mL). The precipitated polymer was isolated by vacuum filtration and dried in vacuo to afford 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).

[0448] Table 3 Study on the molar fraction of SBI-thiomorpholine (c1)

[0449]

[0450] Example 5: PIM-13SO 0.5 Synthesis of (c3)

[0451]

[0452] 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 m-chloroperbenzoic acid (77%, 324 mg, 1.45 mmol, 1 equivalent) 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 filtered, washed with water (100 mL) and ethanol (100 mL), and dried under vacuum to afford PIM-13SO. 0.5 , a bright yellow powder. 1 H-NMR (400 MHz, CDCl3, δ): δ 6.85 (2H, m), 2.75 (24H, m, broad peak), 1.41 (6H, s), 1.32 (6H, s).

[0453] Example 6: Synthesis of PIM-13SO1 (c4)

[0454]

[0455] 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 m-chloroperbenzoic acid (77%, 649 mg, 2.89 mmol, 2 equivalents) 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 filtered, washed with water (100 mL) and ethanol (100 mL), and dried under vacuum to afford PIM-13SO. 0.5 , a bright yellow powder. 1 H-NMR (400 MHz, CDCl3, δ): δ 6.85 (2H, m), 2.75 (24H, m, broad peak), 1.41 (6H, s), 1.32 (6H, s).

[0456] Example 7: PIM-13SO 1.5 Synthesis of (c5)

[0457]

[0458] 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 m-chloroperbenzoic acid (77% purity, 973 mg, 4.34 mmol, 3 equivalents) 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 filtered, washed with water (100 mL) and ethanol (100 mL), and dried under vacuum to afford PIM-13SO. 1.5 , a bright yellow powder. 1 H-NMR (400 MHz, CDCl3, δ): δ 6.85 (2H, broad peak), 2.75 (24H, m, broad peak), 1.41 (6H, broad peak), 1.32 (6H, broad peak).

[0459] Example 8: Synthesis of PIM-13S-Py(c6)

[0460]

[0461] To a dry 250mL two-necked round-bottom flask was added SBI-thiomorpholine (3, 6.35g, 11.13mmol, 0.98 equivalent), tetrafluorocyanopyridine (2.00g, 11.36mmol, 1 equivalent) and anhydrous dimethylformamide (120mL). The reaction mixture was purged with argon for 25 minutes and then heated to 65°C. After reaching 65°C, anhydrous potassium carbonate (6.40g, 46.34mmol, 4.08 equivalent) previously dried under vacuum at 150°C and ground with a mortar and pestle was added. The reaction mixture was then stirred at 65°C under argon for 18 hours, after which it was precipitated in water (500mL) and then washed with additional water (2x 50mL) and ethanol (2x50mL). The resulting solid was vacuum dried and then dissolved in THF at 50mg / mL. The solution was precipitated into ethanol (500 mL), and the precipitated polymer was isolated by vacuum filtration and dried under vacuum 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).

[0462] Example 9: Synthesis of PIM-4-morpholinopiperidine (e2) Synthesis of SBI-4-morpholinopiperidine (e1)

[0463]

[0464] The compounds can be prepared by methods known in the art.

[0465] Synthesis of PIM-4-morpholinopiperidine (e2)

[0466]

[0467] The polymer PIM-4-morpholinopiperidine can be prepared by the methods described herein.

[0468] Example 10: Synthesis of PIM-piperazine-MeSO2 (f2)

[0469] Synthesis of SBI-piperazine-MeSO2(f1)

[0470]

[0471] To a 250 L two-necked round-bottom flask equipped with a reflux condenser were added paraformaldehyde (1.10 g, 36.7 mmol, 2.5 eq), piperazine methylsulfate (6.03 g, 36.7 mmol, 2.5 eq), and ethanol (75 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'-spirobiindane (5 g, 14.7 mmol, 1 eq) was added, and the reaction mixture was stirred at reflux under argon for 24 hours, after which a white precipitate was observed. The reaction was then cooled to room temperature, the solvent was removed by rotary evaporation, and the resulting solid was purified by column chromatography on silica gel using a mixture of ethyl acetate and hexane as the mobile phase and dried under vacuum to afford 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).

[0472] Synthesis of PIM-piperazine-MeSO2(f2)

[0473]

[0474] The polymer PIM-piperazine-MeSO2 can be prepared by the methods described herein.

[0475] Example 11: Other polymers

[0476] The following polymers can be prepared using the methods described herein.

[0477]

[0478] Example 12: Synthesis of PIM-diallylamine Synthesis of SBI-diallylamine (g1)

[0479]

[0480] To a two-neck 2L round-bottom flask equipped with a reflux condenser and a septum was added paraformaldehyde (14.7 g, 490 mmol, 2.5 eq), toluene (1000 mL), and diallylamine (47.6 g, 490 mmol, 2.5 eq). The mixture was then heated to reflux under nitrogen until homogeneous (~30 min). 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (66.7 g, 196 mmol, 1 eq) was then added, and the reaction mixture was stirred at reflux for 4 hours. The reaction mixture was then cooled to room temperature, the solvent removed by rotary evaporation, and the resulting solid was recrystallized from isopropanol to afford SBI-diallylamine (59.8 g, 54.6%) as a white crystalline solid. 1H-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).

[0481] Synthesis of PIM-diallylamine (g2)

[0482]

[0483] To a 500 mL round-bottom flask were 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, after which it was 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), then dried under vacuum. The crude solid was then stirred with a 25 mg / mL mixture of 1:1 methyl ethyl ketone / ethanol (vol / vol) for 16 hours and filtered to yield PIM-diallylamine (8.31 g, 81.6%) as a bright yellow solid. 1H-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).

[0484] Example 13: Synthesis of PIM-allylmethylamine Synthesis of SBI-allylmethylamine (h1)

[0485]

[0486] To a two-necked 500 mL round-bottom flask equipped with a reflux condenser and a septum was added 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 to reflux under nitrogen until homogeneous (~30 minutes). 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (10.0 g, 29.4 mmol, 1 equiv) was then added, and the reaction mixture was stirred at reflux for 4 hours. The reaction mixture was then cooled to room temperature, the solvent removed by rotary evaporation, and the resulting solid was recrystallized from isopropanol to afford SBI-allylmethylamine (14.9 g, 46.5%) as a white crystalline solid. 1H-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).

[0487] Synthesis of PIM-allylmethylamine (h2)

[0488]

[0489] To a 20 mL scintillation vial were added 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, 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 hours, 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 as a 25 mg / mL suspension in 1:1 methyl ethyl ketone / ethanol (vol / vol) for 16 hours, filtered, and dried under vacuum to yield PIM-allylmethylamine (784 mg, 85%) as a bright 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).

[0490] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, those skilled in the art will appreciate that certain changes and modifications may be made within the scope of the appended claims. In addition, each reference provided 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 the present application and a reference provided herein, the present application shall prevail.

Claims

1. Polymers of formula I: or a salt thereof, wherein: R 1a and R 1b Each independently is NR 1a1 R 1a2 , 5-10 membered heterocycloalkyl having 1-4 heteroatoms each independently being N, O or S, or 5-10 membered heteroaryl having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl and heteroaryl are each independently replaced by 0, 1, 2 or 3 R 1c group substitution; Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl; Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution; R 1d C 1-6 Alkyl or C 1-6 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 alkyl; R 3 For hydrogen, C 1-6 Alkyl or -CN; X is -N= or -C(R 4 )=; R 4 For hydrogen, C 1-6 Alkyl or -CN; and The subscript n is an integer from 10 to 1000, When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1a and R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

2. The polymer or salt thereof according to claim 1, wherein: R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 5-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl group and the heteroaryl group are each independently replaced by 0, 1, 2 or 3 R 1c group substitution; 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S; R 1d C 1-6 Alkyl or C 1-6 hydroxyalkyl; R 2a and R 2b are each independently hydrogen or C 1-6 alkyl; R 3 For hydrogen, C 1-6 Alkyl or -CN; X is -N= or -C(R 4 )=; R 4 For hydrogen, C 1-6 Alkyl or -CN; and The subscript n is an integer from 10 to 1000, When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and When R 2a and R 2b Each is hydrogen, R 3 is -CN, X is -C(CN)=, and R 1a and R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

3. The polymer or salt thereof according to claim 1, wherein: R 1a and R 1b Each is independently a 5-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group is independently replaced by 0, 1, 2 or 3 R 1c group substitution; and Each R 1c Independently C 1-6 Alkyl, =O, -S(O)2-C 1-6 alkyl or a 3-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S.

4. The polymer or salt thereof according to any one of claims 1 to 3, wherein: R 1a and R 1b Each is independently a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group is independently replaced by 0, 1, 2 or 3 R 1c group substitution; and Each R 1c Independently C 1-3 Alkyl, =O, -S(O)2-C 1-3 alkyl or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S.

5. The polymer or salt thereof according to any one of claims 1 to 4, wherein: R 1a and R 1b are each independently pyrrolidine, piperidine, diazine, triazine, morpholine or thiomorpholine, each of which is independently replaced by 0, 1, 2 or 3 R 1c group substitution; and Each R 1c are independently methyl, =O, -S(O)2-C 1-3 Alkyl, tetrahydropyran, pyrrolidine, piperidine, diazinane, thiolane, thiohexane or morpholine.

6. The polymer or salt thereof according to any one of claims 1 to 5, wherein R 1a and R 1b Each independently is:

7. The polymer or salt thereof according to claim 1, wherein: R 1a and R 1b Each independently is NR 1a1 R 1a2 ;as well as Each R 1a1 and R 1a2 Independently C 1-3 Alkyl or C 2-4 Alkenyl.

8. The polymer or salt thereof according to claim 7, wherein: R 1a and R 1b Each independently is NR 1a1 R 1b1 ;as well as Each R 1a1 and R 1a2 is independently methyl, ethyl, propyl, isopropyl, vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl or isobutenyl.

9. The polymer or salt thereof according to claim 7 or 8, wherein R 1a and R 1b Each independently 10. The polymer or salt thereof according to any one of claims 1 to 9, wherein R 2a and R 2b Each is hydrogen.

11. The polymer or salt thereof according to any one of claims 1 to 10, wherein R 3 For hydrogen, C 1-3 Alkyl or -CN.

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

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

14. The polymer or salt thereof according to any one of claims 1 to 13, wherein: X is -C(R 4 );as well as R 4 For hydrogen, C 1-6 Alkyl or -CN.

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

16. The polymer of any one of claims 1 to 15, wherein the salt comprises an anion selected from the group consisting of tetrafluoroborate, bis(7-oxalato)borate, difluoro(7-oxalato)borate, trifluorocyanoborate, cyanotri(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, tetrafluoro(7-oxalato)phosphate, difluoro(bisoxalato)phosphate, phosphonate, sulfite, hydrogensulfite, sulfate, hydrogensulfate, thiosulfate, sulfonate, trifluoromethanesulfonate, p-toluenesulfonate, halide, hypochlorite, chlorite, chlorate, perchlorate, bromate, iodate, chromate, dichromate or permanganate.

17. The polymer or salt thereof according to any one of claims 1 to 16, wherein: R 1a and R 1b Each independently R 2a and R 2b Each is hydrogen; R 3 is -CN; as well as X is -N= or -C(CN)=, When X is -C(CN)=, then R 1a and R 1b Each is not morpholine.

18. The polymer or salt thereof according to any one of claims 1 to 17, wherein the polymer is:

19. The polymer or salt thereof according to any one of claims 1 to 18, wherein the polymer is:

20. Compounds of formula II: in: R 1a and R 1b Each independently is NR 1a1 R 1a2 , 5-10 membered heterocycloalkyl having 1-4 heteroatoms each independently being N, O or S, or 5-10 membered heteroaryl having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl and heteroaryl are each independently replaced by 0, 1, 2 or 3 R 1c group substitution; Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl; Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution; R 1d C 1-6 Alkyl or C 1-6 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 alkyl, When R 2a and R 2b are each hydrogen, and R 1c If it does not exist, then R 1a and R 1b Not pyrrolidine and morpholine, and When R 2a and R 2b are each hydrogen, and R 1a and R 1b When each is piperazine, R 1c Not -C(O)OR 1d .

21. The compound of claim 20, wherein the compound is:

22. A method for preparing a polymer of formula I or a salt thereof, comprising: a) forming a reaction mixture comprising a compound of formula II: A non-nucleophilic base, a solvent, and a compound of formula III: wherein under conditions suitable for forming the compound of formula I, the molar ratio of the compound of formula II to the compound of formula III is less than 1.1, in: R 1a and R 1b Each independently is NR 1a1 R 1a2 , 5-10 membered heterocycloalkyl having 1-4 heteroatoms each independently being N, O or S, or 5-10 membered heteroaryl having 1-4 heteroatoms each independently being N, O or S, wherein the heterocycloalkyl and heteroaryl are each independently replaced by 0, 1, 2 or 3 R 1c group substitution; Each R 1a1 and R 1a2 Independently C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 5-8 cycloalkenyl; Or, R 1a1 and R 1a2 are combined with the atoms to which they are attached to form a 5- to 8-membered heterocycloalkenyl group having 0 or 1 additional heteroatom which is 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 Halogenated alkyl, 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 3-10 membered heterocycloalkyl group having 1-4 heteroatoms each independently being N, O or S, or a 3-10 membered heteroaryl group having 1-4 heteroatoms each independently being N, O or S, wherein each heterocycloalkyl group and heteroaryl group is independently replaced by 0, 1, 2, 3, 4, 5 or 6 R 1e group substitution; R 1d C 1-6 Alkyl or C 1-6 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 Halogenated alkyl, C 1-6 Haloalkoxy, =CH2, =O, =NH, -CN or -NO2; R 2a and R 2b are each independently hydrogen or C 1-6 alkyl; R 3 For hydrogen, C 1-6 Alkyl or -CN; X is -N= or -C(R 4 )=; R 4 For hydrogen, C 1-6 Alkyl or -CN; and n is an integer from 10 to 1000.

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

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

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

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

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

31. The method of any one of claims 22 to 30, comprising a) forming a reaction mixture comprising a compound of formula II: Potassium carbonate, dimethylformamide and a compound of formula III having the structure: wherein under conditions suitable for forming the compound of formula I, the molar ratio of the compound of formula II to the compound of formula III is from 0.98 to 0.99, in: R 1a and R 1b Each is independently a 5-6 membered heterocycloalkyl group having 1-3 heteroatoms each independently being N, O or S, or a 5-6 membered heteroaryl group having 1-3 heteroatoms each independently being N, O or S; Each R 1c Independently C 1-3 Alkyl, =O, -C 1-3 Alkyl-(SO3 - ), -SO2-C 1-3 Alkyl or a 5-6 membered heterocycloalkyl group having 1-2 heteroatoms each independently being N, O or S; R 2a and R 2b Each is hydrogen; R 3 is -CN; X is -N= or -C(R 4 )=; 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) forming a reaction mixture comprising a compound of formula II: Potassium carbonate, dimethylformamide and a compound of formula III having the structure: wherein under conditions suitable for forming the compound of formula I, the molar ratio of the compound of formula II to the compound of formula III is from 1.01 to 1.03, in: R 1a and R 1b Each independently is NR 1a1 R 1a2 ; Each R 1a1 and R 1a2 Independently C 1-3 Alkyl or C 2-4 alkenyl; R 2a and R 2b Each is 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 membrane comprising a polymer according to any one of claims 1 to 19; and electrolytes.

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