Fluorinated polyaromatic compounds of linear, branched or cross-linked structure for anion exchange membranes and ionomers

Abstract

The description relates to fluorinated polyaromatic polymer comprising at least one fluorinated unit of formula I FU # imgabs 0 # and at least one cationic unit of formula B or C CU # imgabs 1 #

Description

Technical Field

[0001] The present invention relates to fluorinated polyaromatic polymers for anion exchange membranes and ionomers. Background Art

[0002] Anion exchange membranes (AEMs) and ionomers are key materials in many applications, such as anion exchange membrane fuel cells (AEMFCs), anion exchange membrane water electrolyzers (AEMWEs), carbon dioxide electrolyzers, acid / alkali recovery, etc. However, there are still great challenges in developing anion exchange membranes and ionomers with desirable basicity, oxidative stability, mechanical properties, and dimensional stability.

[0003] Yan et al. in 2017 (WO 2017 / 172824 A1) 1 and Bae et al. in 2015 (US11,236,196B2) 2 claimed polyaromatic polymers containing trifluoromethyl ketone for anion exchange membranes and ionomers. However, the fluorine content in the claimed polymers is less than 5%, resulting in limited improvement in hydrophobicity.

[0004] Wu et al. in 2022 3 and Chen et al. in 2019 4 reported branched polyaromatic compounds and crosslinked polyaromatic compounds for anion exchange membranes, respectively. However, the reported polyaromatic polymers do not contain fluorinated elements and thus exhibit low hydrophobicity.

[0005] Based on the above prior art, the object of the present invention is to provide a method and means for preparing fluorinated polyaromatic compounds with linear, branched, or crosslinked structures for anion exchange membranes and ionomers to improve their hydrophobicity and thus mechanical properties. This object is achieved by the subject matter of the independent claims of this specification, and further preferred embodiments are described in the dependent claims, examples, drawings, and the general description of this specification. Summary of the Invention

[0006] A first aspect of the present invention relates to a fluorinated polyaromatic polymer, comprising:

[0007] · at least one fluorinated unit FU of formula I

[0008]

[0009] wherein

[0010] X is C or N,

[0011] Y is C,

[0012] R 1 、R 2 、R5 and R 6 are independently selected from

[0013] -–(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0014] -

[0015] -H,

[0016] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0017] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0018] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0019] where R 1 , R 2 , R 5 and R 6 are at least one of

[0020] -–(CH 2 ) p –(CF 2 ) q –CF 3 or

[0021] -

[0022] R a 3 , R b 4 and R d 7 are independently selected from

[0023] –C 1 ~C 10 Alkyl, wherein –C 1 ~C 10 the alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0024] –C 2 ~C 10 Alkenyl, wherein –C 2 ~C 10 the alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0025] –C 2 ~C 10 Alkynyl, wherein –C 2 ~C 10 the alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0026] a and b are independently 0, 1, 2 or 3, especially 0 or 1, more especially 0,

[0027] d is 0, 1, 2, 3 or 4, especially 0 or 1, more especially 0,

[0028] n is 0 or 1,

[0029] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0030] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0031] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9,

[0032] and

[0033] · at least one cationic unit CU of formula B or formula C

[0034]

[0035] wherein

[0036] R 8 is partially or fully fluorinated –C 1 ~C 6 alkyl, especially –CF 3 ,

[0037] R 9 is selected from

[0038] –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl may be substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0039] –C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl may be substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0040] –C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl may be substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0041] –(CH 2 ) s –N(R 12 ) 2 ,

[0042] –(CH 2 ) s –NHR 12 ,

[0043] –(CH 2 ) s –N + (R 12 ) 3 ,

[0044] where R 12 is independently selected from

[0045] –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl may be substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0046] –C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl may be substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0047] -–C 2 ~C 10 Alkynyl, wherein –C 2 ~C 10 the alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl, s is between 0 and 20,

[0048] -–Ph–R f 13 ,

[0049] R 10 and R 11 are independently selected from

[0050] -H

[0051] -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 the alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0052] -–C 2 ~C 10 alkenyl, wherein –C 2 ~C 10 the alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0053] -–C 2 ~C 10 alkynyl, wherein –C 2 ~C 10 the alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0054] or R 10 and R 11 are joined together to form a cycloalkyl group comprising 4 to 10 C atoms,

[0055] z is 0 or 1,

[0056] A - is an anion.

[0057] The second aspect of the present invention relates to a method for preparing a fluorinated polyaromatic polymer, said polymer comprising linear units LU, said method comprising reacting at least one fluorinated unit precursor FUP and optionally at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP.

[0058] The third aspect of the present invention relates to a method for preparing a fluorinated polyaromatic polymer, the polymer comprising a branched unit BU, the branched unit BU comprising three or more linear units LU connected by a branched unit reagent BUR, the method comprising reacting at least one fluorinated unit precursor FUP and optionally at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP and a branched unit precursor BUP.

[0059] The fourth aspect of the present invention relates to a method for preparing a fluorinated polyaromatic polymer, the polymer comprising a crosslinked unit CU, the crosslinked unit CU comprising two or more linear units LU connected by one or more crosslinking agents CL, the method comprising:

[0060] · Reacting at least one fluorinated unit precursor FUP and at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP to obtain an intermediate polymer; and

[0061] · Reacting the intermediate polymer with at least one crosslinked unit precursor CLUP.

[0062] Terms and Definitions

[0063] For the purposes of interpreting this specification, the following definitions will apply, and wherever appropriate, terms used in the singular will also include the plural and vice versa. If any of the definitions set forth below conflict with any document cited herein, the definition shall control.

[0064] The terms "comprising", "having", "containing", and "including" and other similar forms and their grammatical equivalents are equivalent in meaning and are open-ended, in that one or more entries following any of these words do not mean an exhaustive list of such one or more entries, or mean being limited to the listed one or more entries. For example, an article "comprising" components A, B, and C may consist of (i.e., contain only) components A, B, and C, or may contain not only components A, B, and C, but also one or more other components. Accordingly, it is intended that the disclosure of "comprising" and its similar forms and their grammatical equivalents encompass embodiments of "consisting essentially of" or "consisting of".

[0065] Where a range of values is provided, it is understood that, unless the context clearly dictates otherwise, any other stated value or intermediate value between the upper and lower limits of that range, to one-tenth of the unit of the lower limit, is included in the present disclosure, subject to any explicit exclusions of the stated range. If the range includes one or two limits, ranges excluding one or both of those included limits are also included in the present disclosure.

[0066] As used herein, the term "about" in reference to a value or parameter includes (and describes) variations that are specific to that value or parameter. For example, a description of "about X" includes a description of "X".

[0067] As used herein, including in the appended claims, the singular forms "a", "or", and "the" include plural referents unless the context clearly dictates otherwise.

[0068] The term "and / or", as used herein, is to be understood as specifically listing each of the two particular features or components and either having or not having the other. For example, the term "and / or" in the phrase "A and / or B" is intended to include "A and B", "A or B", "only A", and "only B". Similarly, the term "and / or" in the phrase "A, B, and / or C" is intended to cover each of the following aspects: "A, B, and C", "A, B, or C", "A or C", "A or B", "B or C", "A and C", "A and B", "B and C", "only A", "only B", and "only C".

[0069] Unless defined otherwise, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art (e.g., in the fields of cell culture, molecular genetics, nucleic acid chemistry, hybridization techniques, and biochemistry, organic synthesis, etc.). Chemical methods employ standard techniques.

[0070] In the context of this specification, the term fluorinated polyaromatic polymer refers to a polymer that includes at least one fluorinated unit FU, at least one cationic unit CU, and optionally at least one bifunctional aromatic moiety BA, wherein the polymer includes a linear unit LU or consists of the same, the linear unit LU including at least one fluorinated unit FU, at least one cationic unit CU, and optionally at least one bifunctional aromatic moiety BA; or the polymer includes a branched unit BU or consists of the same, the branched unit BU including three or more linear units LU connected by at least one branching unit reagent BUR; or the polymer includes a crosslinked unit CLU or consists of the same, the crosslinked unit CLU including two or more linear units LU connected by at least one crosslinker CL, wherein the crosslinker CL connects two bifunctional aromatic moieties BA or two cationic units CU of two linear units LU.

[0071] In the context of this specification, the term fluorinated unit or FU refers to the moiety of formula (I) described below.

[0072] In the context of this specification, the term cationic unit or CU refers to the moiety of formula B or formula C described below. The cationic groups in the polymer allow for the transport of anions between the anode and cathode in an electrochemical device. Non-limiting examples of anions are OH- , CO 3 2- , Br - or Cl - . The cationic unit separates the fluorinated unit from the difunctional aromatic moiety or other fluorinated units.

[0073] In the context of this specification, the term difunctional aromatic moiety or BA refers to a moiety comprising 2 to 5, particularly 2 to 3, cycloaliphatic moieties. Non-limiting examples are biphenyl, terphenyl (particularly p-terphenyl or m-terphenyl), 1,1'-methylenedibenzene, (1-methyl-1-phenylethyl)benzene, 2-phenylethylbenzene, 9,9-dimethylfluorene, and 9,9-dibutylfluorene. At least one, particularly all, of the cycloaliphatic moieties are aromatic.

[0074] In the context of this specification, the term unit, when used in a linear unit, branched unit, or crosslinked unit, refers to a repeating moiety in a polymer. The linear unit, branched unit, or crosslinked unit forms a random polymer. In the case of a linear unit, the polymer consists of m – [BA–CU] n or [FU–CU] moieties, where m and n represent the molar ratio of these moieties. However, the sequence within the linear unit is formed randomly, for example: –FU–CU–FU–CU–BA–CU–BA–CU–FU–CU–BA–CU–BA–CU–BA–CU–.

[0075] In the context of this specification, the term C 1 ~ C 10 alkyl, C 1 ~ C 10 alkenyl, and C 1 ~ C 10 alkynyl refer to saturated straight-chain or branched-chain hydrocarbons or unsaturated straight-chain or branched-chain hydrocarbons having 1 to 10 carbon atoms. Non-limiting examples of C 1 ~ C 10 alkyl include n-hexyl, n-heptyl, n-decyl, 3-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, pent-4-ynyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, n-hexyl, n-heptyl, n-decyl, n-butyl, isobutyl, n-propyl, isopropyl, ethyl, methyl.

[0076] In the context of this specification, the term C 1 ~ C 6 alkyl, C 1 ~ C 6 alkenyl, and C 1 ~ C6 An alkynyl group refers to a saturated straight-chain or branched-chain hydrocarbon or an unsaturated straight-chain or branched-chain hydrocarbon having 1, 2, 3, 4, 5, or 6 carbon atoms. Non-limiting C 1 ~C 6 Examples of alkyl groups include those of the above C 1 ~C 10 In certain embodiments, the C 5 alkyl group is pentyl or cyclopentyl, and the C 6 alkyl group is hexyl or cyclohexyl.

[0077] In the broadest sense, the term substituted alkyl group refers to a group covalently bonded to an alkyl group as defined in the broadest sense above, which is linked to a non-carbon or non-hydrogen atom, particularly an atom selected from N, F, Cl, Br, and I, and which itself may - if applicable - be linked to one or more other atoms in this group, or to a hydrogen atom, or to an unsaturated or saturated hydrocarbon (alkyl or aryl in the broadest sense). In a narrower sense, a substituted alkyl group refers to an alkyl group as defined in the broadest sense above, in which one or more carbon atoms are substituted by a group selected from amino NH 2 , alkylamino NHR, imino NH, alkylimino NR, amino(carbonylalkyl) NHCOR or NRCOR, fluorine F, chlorine Cl, bromine Br, iodine I, where the R substituent used in this paragraph, which is different from the definition of R given in other parts of this specification, is itself an unsubstituted or substituted C 1 to C 6 alkyl group, unless otherwise specified. Detailed embodiments

[0078] A first aspect of the present invention relates to a fluorinated polyaromatic polymer, comprising:

[0079] · At least one fluorinated unit FU of formula (I)

[0080]

[0081] where

[0082] X is C or N,

[0083] Y is C,

[0084] R 1 , R 2 , R 5 and R 6 are independently selected from

[0085] -–(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0086] -

[0087] -H,

[0088] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0089] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 10 ~C 6 alkenyl,

[0090] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 10 ~C 6 alkynyl,

[0091] where R 1 、R 2 、R 5 and R 6 is at least one of

[0092] -–(CH 2 ) p –(CF 2 ) q –CF 3 or

[0093] -

[0094] R a 3 、R b 4 and R d 7 are independently selected from

[0095] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0096] -–C 2 ~C 10 alkenyl, where –C2 ~C 10 The alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0097] -–C 2 ~C 10 alkynyl group, wherein –C 2 ~C 10 alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0098] a and b are independently 0, 1, 2 or 3, especially 0 or 1, more especially 0,

[0099] d is 0, 1, 2, 3 or 4, especially 0 or 1, more especially 0,

[0100] n is 0 or 1,

[0101] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0102] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0103] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9,

[0104] and

[0105] · at least one cationic unit CU of formula B or formula C

[0106]

[0107] wherein

[0108] R 8 is a partially or fully fluorinated –C 1 ~C 6 alkyl group, especially –CF 3 ,

[0109] R 9 is selected from

[0110] -–C 1 ~C 10 alkyl group, wherein –C 1 ~C 10 alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0111] -–C 2 ~C 10Alkenyl, where –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0112] -–C 2 ~C 10 Alkynyl, where –C 2 ~C 10 The alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0113] -–(CH 2 ) s –N(R 12 ) 2 ,

[0114] -–(CH 2 ) s –NHR 12 ,

[0115] -–(CH 2 ) s –N+(R 12 ) 3 ,

[0116] where R 12 is independently selected from

[0117] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 The alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0118] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0119] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 The alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0120] s is between 0 and 20,

[0121] –Ph–R f 13 ,

[0122] R 10 and R 11 are independently selected from

[0123] –H

[0124] –C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0125] –C 2 ~C 10 alkenyl, wherein –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0126] –C 2 ~C 10 alkynyl, wherein –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0127] or R 10 and R 11 are joined together to form a cycloalkyl group comprising 4 to 10 C atoms,

[0128] z is 0 or 1,

[0129] A⁻ is an anion.

[0130] In certain embodiments, the at least one fluorination unit FU is of formula (II),

[0131]

[0132] wherein

[0133] X is C or N,

[0134] Y is C,

[0135] R 1 、R 2 、R 5 and R 6 are independently selected from

[0136] –(CH 2 )p –(CF 2 ) q –CF 3 ,

[0137] -

[0138] -H,

[0139] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0140] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0141] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0142] where R 1 , R 2 , R 5 and R 6 at least one is

[0143] -–(CH 2 ) p –(CF 2 ) q –CF 3 or

[0144] -

[0145] n is 0 or 1,

[0146] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0147] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0148] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9,

[0149] In certain embodiments, R 1 , R 2 , R 5 and R 6 are independently selected from –C 1 ~C 10 alkyl, wherein the –C 1 ~C 10 alkyl is either substituted or unsubstituted.

[0150] In certain embodiments, R 1 , R 2 , R 5 and R 6 are independently selected from –C 1 ~C 6 alkyl, wherein the –C 1 ~C 6 alkyl is either substituted or unsubstituted.

[0151] In certain embodiments, R 1 , R 2 , R 5 and R 6 are independently selected from –C 1 ~C 6 alkyl, wherein the –C 1 ~C 6 alkyl is unsubstituted.

[0152] In certain embodiments, z is 1 .

[0153] In certain embodiments, R 9 is selected from

[0154] -–C 1 ~C 10 alkyl, wherein the –C 1 ~C 10 alkyl is either substituted or unsubstituted, particularly –C 1 ~C 6 alkyl,

[0155] -–C 2 ~C 10 alkenyl, wherein the –C 2 ~C 10 alkenyl is either substituted or unsubstituted, particularly –C 2 ~C 6 alkenyl,

[0156] -–C 2 ~C 10 alkynyl, wherein the –C 2 ~C 10 alkynyl is either substituted or unsubstituted, particularly –C2 ~C 6 alkynyl group.

[0157] In certain embodiments, R 9 is selected from –C 1 ~C 10 alkyl group, wherein the –C 1 ~C 10 alkyl group is substituted or unsubstituted.

[0158] In certain embodiments, R 9 is selected from –C 1 ~C 6 alkyl group, wherein the –C 1 ~C 6 alkyl group is substituted or unsubstituted.

[0159] In certain embodiments, R 9 is selected from –C 1 ~C 6 alkyl group, wherein the –C 1 ~C 6 alkyl group is unsubstituted.

[0160] In certain embodiments, R 9 is selected from –C 1 ~C 3 alkyl group, wherein the –C 1 ~C 3 alkyl group is unsubstituted.

[0161] In certain embodiments, R 10 and R 11 are independently selected from

[0162] -H,

[0163] -–C 1 ~C 10 alkyl group, wherein the –C 1 ~C 10 alkyl group is substituted or unsubstituted, particularly the –C 1 ~C 6 alkyl group.

[0164] In certain embodiments, R 10 and R 11 are independently selected from

[0165] -H,

[0166] -–C 1 ~C 6 alkyl group, wherein the –C 1 ~C 6 alkyl group is unsubstituted.

[0167] In certain embodiments, R10 and R 11 are independently selected from

[0168] -H,

[0169] -–C 1 ~C 3 alkyl, wherein –C 1 ~C 3 alkyl is unsubstituted.

[0170] In certain embodiments, R 10 and R 11 are independently selected from –H and –Me.

[0171] In certain embodiments, the fluorinated polyaromatic polymer comprises at least one bifunctional aromatic moiety BA, wherein BA is independently selected from moieties comprising 2 to 5, particularly 2 to 3, cycloaliphatic moieties, wherein BA is unsubstituted or substituted with one or more substituents independently selected from –C 1 ~C 10 alkyl, –C 1 ~C 10 alkenyl or –C 1 ~C 10 alkynyl, wherein said one or more substituents are unsubstituted or further substituted with one or more halogen atoms or one or more quaternary ammonium groups.

[0172] In addition to the fluorinated polyaromatic polymer comprising [FU–CU] or consisting of it, the fluorinated polyaromatic polymer may further comprise a bifunctional aromatic moiety BA.

[0173] In certain embodiments, BA is unsubstituted or substituted with one or more substituents independently selected from –C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is unsubstituted or further substituted with one or more halogen atoms or one or more quaternary ammonium groups.

[0174] In certain embodiments, BA is substituted with one or more –C 1 ~C 6 alkyl, wherein one or more –C 1 ~C 6 alkyl is further substituted with one or more quaternary ammonium groups.

[0175] In certain embodiments, BA is unsubstituted.

[0176] In certain embodiments, the fluorinated polyaromatic polymer is arranged in such a way that FU and BA are separated by CU.

[0177] In some embodiments, the fluorinated polyaromatic polymer according to any one of the preceding claims comprises at least one linear unit LU, said linear unit LU comprising

[0178] · one or more FUs and one or more CUs, and / or

[0179] · one or more FUs, one or more CUs and one or more BAs,

[0180] In particular

[0181] · one or more FUs, one or more CUs and one or more BAs,

[0182] wherein LU is arranged as [FU–CU] x –[BA–CU] y ,

[0183] where the ratio of x to y is from 1:99 to 50:50.

[0184] In some embodiments, the ratio of x to y is from 5:95 to 30:70.

[0185] In some embodiments, the ratio of x to y is from 5:95 to 20:80.

[0186] In some embodiments, three or more linear units LU form at least one branched unit BU, wherein said three or more linear units LU are connected by at least one branching unit reagent BUR, wherein said at least one branching unit reagent BUR is independently selected from moieties comprising 3 to 6 cycloaliphatic moieties.

[0187] In some embodiments, two or more linear units LU form at least one crosslinked unit CU, wherein said two or more linear units LU are crosslinked by at least one crosslinking agent CL, wherein said at least one crosslinking agent CL is independently selected from aliphatic or aromatic quaternary diammonium.

[0188] The crosslinked unit CLU can crosslink two linear units by two cationic units CU or two bifunctional aromatic moieties BA.

[0189] In some embodiments, at least one fluorinated unit FU is independently selected from

[0190]

[0191] wherein

[0192] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0193] B, R 3 and R 4 are independently selected from

[0194] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,[

[0195] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,[

[0196] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,[

[0197] C is independently selected from

[0198] where R d 7 is independently selected from

[0199] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,[

[0200] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,[

[0201] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,[

[0202] d is 0, 1, 2, 3 or 4,

[0203] r is 1, 2, 3, 4, 5 or 6, in particular 1, 2 or 3, more particularly 1 or 2,

[0204] p is independently between 1 and 20, in particular between 1 and 15, more particularly between 1 and 9, and

[0205] q is independently between 0 and 20, in particular between 0 and 15, more particularly between 0 and 9,

[0206] a and b are independently 0, 1, 2 or 3.

[0207] In certain embodiments, at least one fluorination unit FU is independently selected from

[0208]

[0209] wherein

[0210] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0211] B, R 3 and R 4 are independently selected from

[0212] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, in particular –C 1 ~C 6 alkyl,

[0213] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, in particular –C 2 ~C 6 alkenyl,

[0214] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, in particular –C 2 ~C 6 alkynyl,

[0215] C is independently selected from

[0216] wherein R d 7 is independently selected from

[0217] -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0218] -–C 2 ~C 10 alkenyl, wherein –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0219] -–C 2 ~C 10 alkynyl, wherein –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0220] d is 0, 1, 2, 3 or 4,

[0221] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0222] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0223] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9,

[0224] a and b are independently 0, 1, 2 or 3.

[0225] In certain embodiments, at least one fluorination unit FU is independently selected from

[0226]

[0227] wherein

[0228] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0229] B is independently selected from

[0230] –C 1 ~C 10 Alkyl, wherein –C 1 ~C 10 the alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0231] –C 2 ~C 10 Alkenyl, wherein –C 2 ~C 10 the alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0232] –C 2 ~C 10 Alkynyl, wherein –C 2 ~C 10 the alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl, C is independently selected from wherein

[0233] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0234] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0235] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9.

[0236] In certain embodiments, at least one fluorination unit FU is independently selected from

[0237]

[0238] wherein

[0239] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0240] C is independently selected from wherein

[0241] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0242] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0243] q is independently between 0 and 20, particularly between 0 and 15, more particularly between 0 and 9.

[0244] In certain embodiments,

[0245] A is –(CH 2 ) p –(CF 2 ) q –CF 3 , and

[0246] C is where

[0247] r is 1, 2, 3, 4, 5 or 6, particularly 1, 2 or 3, more particularly 1 or 2,

[0248] p is independently between 1 and 20, particularly between 1 and 15, more particularly between 1 and 9, and

[0249] q is independently between 0 and 20, particularly between 0 and 15, more particularly between 0 and 9.

[0250] In certain embodiments, at least one fluorination unit FU is

[0251]

[0252] where

[0253] A is –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0254] p is independently between 1 and 20, particularly between 1 and 15, more particularly between 1 and 9, and

[0255] q is independently between 0 and 20, particularly between 0 and 15, more particularly between 0 and 9.

[0256] In certain embodiments, at least one bifunctional aromatic moiety BA is independently selected from

[0257]

[0258] where

[0259] R 14 、R 15 、R 16 、R 17 and R 18 are independently selected from

[0260] -–C 1 ~C10 Alkyl, wherein –C 1 ~C 10 The alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0261] -–C 2 ~C 10 Alkenyl, wherein –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0262] -–C 2 ~C 10 Alkynyl, wherein –C 2 ~C 10 The alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0263] l and m are independently selected from 0, 1, 2, 3 or 4,

[0264] k is from 0 to 4, especially from 1 to 4, more especially 1 or 2.

[0265] In certain embodiments, at least one bifunctional aromatic moiety BA is independently selected from

[0266]

[0267] wherein

[0268] R 16 、R 17 and R 18 are independently selected from

[0269] -–C 1 ~C 10 Alkyl, wherein –C 1 ~C 10 The alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0270] -–C 2 ~C 10 Alkenyl, wherein –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0271] -–C 2 ~C 10 Alkynyl, wherein –C2 ~C 10 The alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0272] k is from 0 to 4, especially from 1 to 4, more especially 1 or 2.

[0273] In certain embodiments, at least one bifunctional aromatic moiety BA is independently selected from

[0274]

[0275] wherein

[0276] R 17 and R 18 are independently selected from

[0277] -–C 1 ~C 10 alkyl group, wherein –C 1 ~C 10 alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0278] -–C 2 ~C 10 alkenyl group, wherein –C 2 ~C 10 alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0279] -–C 2 ~C 10 alkynyl group, wherein –C 2 ~C 10 alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0280] k is from 0 to 4, especially from 1 to 4, more especially 1 or 2.

[0281] In certain embodiments, R 17 and R 18 are independently selected from –C 1 ~C 10 alkyl group, wherein –C 1 ~C 10 alkyl group is substituted or unsubstituted.

[0282] In certain embodiments, R 17 and R 18 are independently selected from –C 1 ~C6 Alkyl, where –C 1 ~C 6 alkyl is substituted by halogen or quaternary ammonium group.

[0283] In certain embodiments, R 17 and R 18 are identically selected from –C 1 ~C 6 alkyl, where –C 1 ~C 6 alkyl is substituted by halogen or quaternary ammonium group.

[0284] In certain embodiments, R 17 and R 18 are identically selected from –C 1 ~C 6 alkyl, where –C 1 ~C 6 alkyl is substituted by bromine or NMe 3 +OH−.

[0285] In certain embodiments, at least one bifunctional aromatic moiety BA is independently selected from

[0286]

[0287] where

[0288] k is from 0 to 4, particularly from 1 to 4, more particularly 1 or 2.

[0289] In certain embodiments, k is 2.

[0290] In certain embodiments, at least one branched unit BU is independently selected from

[0291]

[0292] In certain embodiments, at least one crosslinking unit CLU is independently selected from

[0293]

[0294] where

[0295] Z 1 is R 19 R 20 or NR 21 R 22 ,

[0296] Z 2 is R 19 R 20 or N + R 21 R 22 R23 ,

[0297] R 19 and R 20 are independently selected from

[0298] - a halogen group,

[0299] - –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0300] - –C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0301] - –C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0302] R 21 、R 22 and R 23 are independently selected from

[0303] - H,

[0304] - –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0305] - –C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0306] - –C 2 ~C 10 alkynyl, where –C 2 ~C 10The alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0307] t ranges from 0 to 20, especially from 0 to 12, more especially from 0 to 6.

[0308] In certain embodiments, R 19 and R 20 are independently selected from a halogen group or –C 1 ~C 10 alkyl group, wherein the –C 1 ~C 10 alkyl group is substituted or unsubstituted.

[0309] In certain embodiments, R 19 and R 20 are independently selected from a halogen group or –C 1 ~C 6 alkyl group, wherein the –C 1 ~C 6 alkyl group is substituted or unsubstituted.

[0310] In certain embodiments, R 21 , R 22 and R 23 are independently selected from H or –C 1 ~C 10 alkyl group, wherein the –C 1 ~C 10 alkyl group is substituted or unsubstituted.

[0311] In certain embodiments, R 21 , R 22 and R 23 are independently selected from H or –C 1 ~C 6 alkyl group, wherein the –C 1 ~C 6 alkyl group is substituted or unsubstituted.

[0312] In certain embodiments, the fluorine content of the fluorinated polyaromatic polymer is 2.5% to 80%.

[0313] In certain embodiments, the fluorine content of the fluorinated polyaromatic polymer is 5% to 60%.

[0314] A fluorine content higher than 5% increases the hydrophobicity of the polymer, thereby improving mechanical properties such as increasing basic and oxidative stability, as well as tensile strength and swelling strength.

[0315] In certain embodiments, the fluorine content of the fluorinated polyaromatic polymer is 5% to 30%.

[0316] In certain embodiments, the alkali stability of the fluorinated polyaromatic polymer in 3 M KOH at 80 °C exceeds 2000 hours.

[0317] In certain embodiments, the fluorinated polyaromatic polymer in 3% H 2 O 2 The oxidative stability in the Fenton's solution exceeds 1000 hours.

[0318] In certain embodiments, the tensile strength of the fluorinated polyaromatic polymer is greater than 80 MPa.

[0319] In certain embodiments, the swelling strength of the fluorinated polyaromatic polymer is less than 30%.

[0320] In certain embodiments, the swelling strength of the fluorinated polyaromatic polymer is less than 15%.

[0321] A second aspect of the present invention relates to a method for preparing a fluorinated polyaromatic polymer, the polymer comprising a linear unit LU, the method comprising reacting at least one fluorinated unit precursor FUP and optionally at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP.

[0322] In certain embodiments, the fluorinated polyaromatic polymer comprises one or more linear units, the linear unit comprising at least one fluorinated unit FU, at least one cationic unit CU and optionally at least one bifunctional aromatic moiety BA, and the method for preparing the fluorinated polyaromatic polymer comprises the following steps: reacting at least one fluorinated unit precursor FUP, at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP to form a piperidine-functionalized and / or halogen-functionalized intermediate fluorinated polyaromatic polymer; polymerization reaction; forming a polymer film; and forming an anion exchange membrane.

[0323] A third aspect of the present invention relates to a method for preparing a fluorinated polyaromatic polymer, the polymer comprising a branched unit BU, the branched unit BU comprising three or more linear units LU connected by a branched unit reagent BUR, the method comprising reacting at least one fluorinated unit precursor FUP and optionally at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP and a branched unit precursor BUP.

[0324] In some embodiments, the fluorinated polyaromatic polymer comprises a branched unit BU, the branched unit BU comprises three or more linear units LU connected by a branched unit reagent BUR, and the method for preparing the fluorinated polyaromatic polymer comprises the following steps: reacting at least one fluorinated unit precursor FUP and at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP and at least one branched unit precursor BUP to form a piperidine-functionalized intermediate fluorinated polyaromatic polymer and / or a halogen-functionalized intermediate fluorinated polyaromatic polymer; alkylating the piperidine-functionalized intermediate fluorinated polyaromatic polymer and / or aminating the halogen-functionalized intermediate fluorinated polyaromatic polymer; polymerization reaction; forming a polymer film; and forming an anion exchange membrane.

[0325] A fourth aspect of the present invention relates to a method for preparing a fluorinated polyaromatic polymer, the polymer comprising a crosslinked unit CU, the crosslinked unit CU comprising two or more linear units LU connected by one or more crosslinking agents CL, the method comprising:

[0326] · Reacting at least one fluorinated unit precursor FUP and at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP to obtain an intermediate polymer; and

[0327] · Reacting the intermediate polymer with at least one crosslinked unit precursor CLUP.

[0328] In some embodiments, the fluorinated polyaromatic polymer comprises a crosslinked unit CLU, and the method for preparing the fluorinated polyaromatic polymer further comprises the following steps: forming a polymer solution; forming a polymer film; and forming an anion exchange membrane.

[0329] In some embodiments, the fluorinated unit precursor FUP is selected from

[0330]

[0331] wherein

[0332] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0333] B, R 3 , R 4 , R 27 and R 28 are independently selected from

[0334] -–C 1 ~C 10 alkyl, wherein –C1 ~C 10 The alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0335] -–C 2 ~C 10 alkenyl group, where –C 2 ~C 10 the alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0336] -–C 2 ~C 10 alkynyl group, where –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0337] C is independently selected from

[0338] where R d 7 is independently selected from

[0339] -–C 1 ~C 10 alkyl group, where –C 1 ~C 10 the alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0340] -–C 2 ~C 10 alkenyl group, where –C 2 ~C 10 the alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0341] -–C 2 ~C 10 alkynyl group, where –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0342] d is 0, 1, 2, 3 or 4,

[0343] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0344] p is independently between 1 and 20, particularly between 1 and 15, more particularly between 1 and 9, and

[0345] q is independently between 0 and 20, particularly between 0 and 15, more particularly between 0 and 9,

[0346] a and b are independently 0, 1, 2 or 3.

[0347] In certain embodiments, the fluorination unit precursor FUP is selected from

[0348]

[0349] where

[0350] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0351] B, R 3 , R 4 , R 27 and R 28 are independently selected from

[0352] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, particularly –C 1 ~C 6 alkyl,

[0353] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, particularly –C 2 ~C 6 alkenyl,

[0354] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, particularly –C 2 ~C 6 alkynyl,

[0355] C is independently selected from

[0356] where R d 7 is independently selected from

[0357] -–C1 ~C 10 alkyl group, where –C 1 ~C 10 the alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0358] -–C 2 ~C 10 alkenyl group, where –C 2 ~C 10 the alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0359] -–C 2 ~C 10 alkynyl group, where –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0360] d is 0, 1, 2, 3 or 4,

[0361] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0362] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0363] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9,

[0364] a and b are independently 0, 1, 2 or 3.

[0365] In certain embodiments, the fluorination unit precursor FUP is independently selected from

[0366]

[0367] wherein

[0368] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0369] B, R 27 and R 28 are independently selected from

[0370] -–C 1 ~C 10 alkyl group, where –C1 ~C 10 The alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0371] -–C 2 ~C 10 alkenyl group, where –C 2 ~C 10 the alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0372] -–C 2 ~C 10 alkynyl group, where –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group, C is independently selected from wherein

[0373] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0374] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9,

[0375] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2.

[0376] In certain embodiments, the fluorination unit precursor FUP is independently selected from

[0377]

[0378] wherein

[0379] A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 ,

[0380] R 27 and R 28 are independently selected from

[0381] -–C 1 ~C 10 alkyl group, where –C 1 ~C 10 the alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0382] -–C2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0383] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl, C is independently selected from where

[0384] r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2,

[0385] p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and

[0386] q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9.

[0387] In certain embodiments, R 27 and R 28 are selected from –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted. In certain embodiments, R 27 and R 28 are selected from –C 1 ~C 6 alkyl, where –C 1 ~C 6 alkyl is substituted or unsubstituted.

[0388] In certain embodiments, R 27 and R 28 are selected from –C 1 ~C 6 alkyl, where –C 1 ~C 6 alkyl is unsubstituted.

[0389] In certain embodiments,

[0390] A is –(CH 2 ) p –(CF 2 ) q –CF 3 , and

[0391] C is wherein

[0392] r is 1, 2, 3, 4, 5 or 6, particularly 1, 2 or 3, more particularly 1 or 2,

[0393] p is independently between 1 and 20, particularly between 1 and 15, more particularly between 1 and 9, and

[0394] q is independently between 0 and 20, particularly between 0 and 15, more particularly between 0 and 9.

[0395] In certain embodiments, the fluorination unit precursor FUP is selected from

[0396]

[0397] wherein

[0398] A is –(CH 2 ) p –(CF 2 ) q –CF 3 , and

[0399] R 27 and R 28 are –C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is unsubstituted.

[0400] In certain embodiments, the cationic unit precursor CUP is selected from

[0401]

[0402] wherein

[0403] R 29 、R 30 、R 31 、R 32 、R 33 、R 34 and R 35 are independently selected from

[0404] -H

[0405] -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, particularly –C 1 ~C 6 alkyl,

[0406] -–C2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0407] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0408] h is 0, 1, 2, 3, 4 or 5,

[0409] u is 0, 1, 2 or 3,

[0410] A− is an anion.

[0411] In certain embodiments, the cationic unit precursor CUP is selected from

[0412]

[0413] where

[0414] R 29 、R 33 and R 34 are independently selected from

[0415] -H,

[0416] -–C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0417] -–C 2 ~C 10 alkenyl, where –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0418] -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0419] A - is an anion.

[0420] In certain embodiments, R 29 , R 33 and R 34 are independently selected from

[0421] -H,

[0422] -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted.

[0423] In certain embodiments, R 29 , R 33 and R 34 are independently selected from

[0424] -H,

[0425] -–C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is substituted or unsubstituted.

[0426] In certain embodiments, the bifunctional aromatic moiety precursor BAP is selected from

[0427]

[0428] wherein

[0429] R 14 , R 15 , R 16 , R 17 , R 18 , R 36 , R 37 , R 38 , R 39 , R 40 and R 41 are independently selected from

[0430] -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, particularly –C 1 ~C 6 alkyl,

[0431] -–C 2 ~C 10 alkenyl, wherein –C 2 ~C10 The alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0432] -–C 2 ~C 10 alkynyl group, where –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group, l and m are 0, 1, 2, 3 or 4,

[0433] k is from 0 to 4, especially from 1 to 4, more especially 1 or 2.

[0434] In certain embodiments, the bifunctional aromatic moiety precursor BAP is selected from

[0435]

[0436] wherein

[0437] R 16 、R 17 、R 18 、R 36 、R 37 、R 38 、R 39 、R 40 and R 41 are independently selected from

[0438] -–C 1 ~C 10 alkyl group, where –C 1 ~C 10 the alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0439] -–C 2 ~C 10 alkenyl group, where –C 2 ~C 10 the alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0440] -–C 2 ~C 10 alkynyl group, where –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0441] k is from 0 to 4, particularly from 1 to 4, more particularly 1 or 2.

[0442] In certain embodiments, the bifunctional aromatic moiety precursor BAP is selected from

[0443]

[0444] wherein:

[0445] R 17 、R 18 、R 36 、R 37 、R 40 and R 41 are independently selected from

[0446] -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, particularly –C 1 ~C 6 alkyl,

[0447] -–C 2 ~C 10 alkenyl, wherein –C 2 ~C 10 alkenyl is substituted or unsubstituted, particularly –C 2 ~C 6 alkenyl,

[0448] -–C 2 ~C 10 alkynyl, wherein –C 2 ~C 10 alkynyl is substituted or unsubstituted, particularly –C 2 ~C 6 alkynyl,

[0449] k is from 0 to 4, particularly from 1 to 4, more particularly 1 or 2.

[0450] In certain embodiments, R 17 、R 18 、R 36 、R 37 、R 40 and R 41 are independently selected from –C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted.

[0451] In certain embodiments, R 17 and R 18 are independently selected from –C1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is substituted by a halogen or a quaternary ammonium group.

[0452] In certain embodiments, R 17 and R 18 are identically selected from –C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is substituted by a halogen or a quaternary ammonium group.

[0453] In certain embodiments, R 36 、R 37 、R 40 and R 41 are independently selected from –C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is unsubstituted.

[0454] In certain embodiments, the bifunctional aromatic moiety precursor BAP is selected from

[0455]

[0456] wherein

[0457] R 36 and R 37 are independently selected from –C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is unsubstituted,

[0458] k is from 0 to 4, particularly from 1 to 4, more particularly 1 or 2.

[0459] In certain embodiments, k is 2.

[0460] In certain embodiments, the crosslinking agent CL is selected from

[0461]

[0462] wherein

[0463] R 56 、R 57 、R 58 and R 59 are independently selected from

[0464] - halogen groups,

[0465] - –C 1 ~C10 An alkyl group, wherein –C 1 ~C 10 The alkyl group is substituted or unsubstituted, especially –C 1 ~C 6 alkyl group,

[0466] -–C 2 ~C 10 An alkenyl group, wherein –C 2 ~C 10 The alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl group,

[0467] -–C 2 ~C 10 An alkynyl group, wherein –C 2 ~C 10 The alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group,

[0468] v is independently between 0 and 20.

[0469] In certain embodiments, R 56 、R 57 、R 58 and R 59 are independently selected from halogen groups and –C 1 ~C 10 alkyl group, wherein –C 1 ~C 10 The alkyl group is substituted or unsubstituted.

[0470] In certain embodiments, R 56 、R 57 、R 58 and R 59 are independently selected from halogen groups and –C 1 ~C 6 alkyl group, wherein –C 1 ~C 6 The alkyl group is substituted or unsubstituted.

[0471] In certain embodiments, R 56 、R 57 、R 58 and R 59 are independently selected from halogen groups and –C 1 ~C 6 alkyl group, wherein –C 1 ~C 6 The alkyl group is unsubstituted.

[0472] In certain embodiments, the crosslinking agent CL is selected from

[0473]

[0474] Wherein

[0475] R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 60 are independently selected from

[0476] -H,

[0477] -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl,

[0478] -–C 2 ~C 10 alkenyl, wherein –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl,

[0479] -–C 2 ~C 10 alkynyl, wherein –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl,

[0480] t is independently between 0 and 20.

[0481] In certain embodiments, R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 60 are independently selected from H and –C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted.

[0482] In certain embodiments, R 19, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 60 are independently selected from H and –C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is either substituted or unsubstituted.

[0483] In certain embodiments, R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 60 are independently selected from H and –C 1 ~C 6 alkyl, wherein –C 1 ~C 6 alkyl is unsubstituted.

[0484] The present invention is further illustrated by the following examples and drawings, from which more embodiments and advantages can be elucidated. These examples are intended to illustrate the content of the present invention without limiting its scope. Description of the Drawings

[0485] Figure 1 : Showing the alkali stability test of PF10TP80 AEM in 3M KOH solution at 80 °C; the bottom graph represents the initial sample; the unit of the x-axis is ppm.

[0486] Figure 2 : Showing the oxidation stability test of PF10TP80 AEM in 3% H 2 O 2 solution at 25 °C; the bottom graph represents the initial sample; the unit of the x-axis is ppm.

[0487] Figure 3 : Showing the mechanical properties of PF10TP95 AEM; the y-axis represents the tensile strength (Mpa), and the x-axis represents the elongation at break (%).

[0488] Figure 4 : Showing the OH-conductivity of PF10TP95 AEM; the y-axis represents the conductivity (mS / cm), and the x-axis represents the temperature (°C).

[0489] Figure 5: Shows the expansion ratio of PF10TP95 AEM; the y-axis represents the expansion rate (%), and the x-axis represents the temperature (°C).

[0490] Figure 6 : Shows the water absorption of PF10TP95 AEM; the y-axis represents the water absorption rate (%), and the x-axis represents the temperature (°C).

[0491] Figure 7 : Shows the structure of Nafion 117.

[0492] Figure 8 : Shows the structure of PAP-TP-X (X = 75 - 100).

[0493] Figure 9 : Shows the structure of the prepared AEM examples listed in Table 1.

[0494] Example

[0495] General Preparation Procedure

[0496] Step 1: Form a piperidine-functionalized and / or halogen-functionalized intermediate fluorinated polyaromatic polymer

[0497] [FU–CU] x Preparation of Fluorinated Poly-Aromatic Polymer with

[0498] Dissolve 1 equivalent of FU and 1 equivalent of CU in dichloromethane and stir at 0 °C. Add trifluoroacetic acid (1.5 equivalents) and trifluoromethanesulfonic acid (10 equivalents). When the solution becomes viscous, slowly pour the resulting gel into excess water to form fibers. Wash the fibers once with 1M KOH solution and three times with water. After vacuum drying overnight at 120 °C, a piperidine-functionalized and / or halogen-functionalized intermediate polymer is obtained.

[0499] [FU–CU] x –[BA–CU] y Preparation of Fluorinated Poly-Aromatic Polymer with

[0500] Dissolve 0.1 to 0.2 equivalents of FU, 0.8 to 0.9 equivalents of BA, and 1 to 1.1 equivalents of CU in dichloromethane and stir at 0 °C. Add trifluoroacetic acid (1.5 equivalents) and trifluoromethanesulfonic acid (10 equivalents). When the solution becomes viscous, slowly pour the resulting gel into excess water to form fibers. Wash the fibers once with 1M KOH solution and three times with water. After vacuum drying overnight at 120 °C, a piperidine-functionalized and / or halogen-functionalized intermediate polymer is obtained.

[0501] Step 2: Form a polymer membrane

[0502] Suspend the piperidine-functionalized and / or halogen-functionalized intermediate polymer in dimethyl sulfoxide. Add CH 3 I (3 equivalents for Cu) and K 2 CO 3 (2 equivalents for Cu). Stir the solution in the dark at room temperature for 1 day. The resulting viscous solution is precipitated with ethyl acetate, washed twice with water, and dried under vacuum at 80 °C until completely dry to obtain the piperidine -functionalized and / or halogen-functionalized polymer.

[0503] Step 3: Form an anion exchange membrane (AEM)

[0504] Dissolve the piperidine -functionalized and / or halogen-functionalized polymer in dimethyl sulfoxide, filter it through a 0.45-μm PTFE membrane, and coat it on a glass plate. The anion exchange membrane (iodide form) is contacted with deionized water and then peeled off from the glass plate. Ion exchange is carried out in a 1 M salt solution at 80 °C to obtain the anion exchange membrane in halide form. Ion exchange is carried out in a 1 M KOH solution at 80 °C to obtain the anion exchange membrane in hydroxide form.

[0505] Example 1: Preparation of PF10TP80 anion exchange membrane

[0506]

[0507] Step 1: Dissolve p-terphenyl (0.8 equivalent), 9,9-bis(3,3,4,4,4-pentafluorobutyl)-9H-fluorene (0.2 equivalent), and 1-methyl-4-piperidone (1.1 equivalents) in dichloromethane. Stir the solution at 0 °C. Add trifluoroacetic acid (1.5 equivalents) and trifluoromethanesulfonic acid (10 equivalents). When the solution becomes viscous, slowly pour the resulting dark blue gel into excess water to form white fibers. Wash the fibers once with 1 M KOH solution and three times with water. After drying under vacuum at 120 °C overnight, obtain the piperidine-functionalized intermediate polymer (yield 92%).

[0508] Step 2: Suspend the piperidine-functionalized intermediate polymer in dimethyl sulfoxide. Add CH 3 I (3 equivalents for the piperidone group) and K 2 CO 3 (2 equivalents for the piperidone group). Stir the solution in the dark at room temperature for 1 day. The resulting viscous solution is precipitated with ethyl acetate, washed twice with water, and dried under vacuum at 80 °C until completely dry. The yield of the piperidine -functionalized polymer is approximately 100%.

[0509] Step 3: The piperidine The functionalized polymer was dissolved in dimethyl sulfoxide, filtered through a 0.45-μm PTFE membrane, and coated on a glass plate. The anion exchange membrane (in iodide form) was contacted with deionized water and then peeled off from the glass plate. Ion exchange was carried out in a 1 M salt solution at 80 °C to obtain the anion exchange membrane in halide form. Ion exchange was carried out in a 1 M KOH solution at 80 °C to obtain the anion exchange membrane in hydroxide form. The anion exchange membrane is designated as PF10TP80, where 10 represents the number of fluorine atoms in the monomer and 80 represents the proportion of terphenyl monomers.

[0510] Characterization: The PF10TP80 anion exchange membrane has excellent alkaline stability (>2000 h in 3 M KOH at 80 °C, Figure 1 ), and exhibits excellent oxidative stability (>1000 h in Fenton's solution (3 wt% H 2 O 2 and 4 ppm Fe 2+ ), Figure 2 ). The PF10TP80 anion exchange membrane has excellent mechanical properties (tensile strength >80 MPa and elongation at break >35%), OH− conductivity (>150 mS / cm at 80 °C), and dimensional stability (swelling rate <15% and water uptake <90%).

[0511] Example 2: Preparation of PF26TP85 anion exchange membrane

[0512]

[0513] Step 1: p-Terphenyl (0.85 equiv), 9,9-bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-9H-fluorene (0.15 equiv), and 1-methyl-4-piperidone (1.1 equiv) were dissolved in dichloromethane. The solution was stirred at 0 °C. Trifluoroacetic acid (1.5 equiv) and trifluoromethanesulfonic acid (10 equiv) were added. When the solution became viscous, the resulting dark blue gel was slowly poured into excess water to form white fibers. The fibers were further washed once with 1 M KOH solution and three times with water. After drying under vacuum at 120 °C overnight, the piperidine-functionalized intermediate polymer was obtained (yield 91%).

[0514] Step 2: The piperidine-functionalized intermediate polymer was suspended in dimethyl sulfoxide. CH 3 I (3 equiv for the piperidone group) and K 2 CO 3 (2 equiv for the piperidone group) were added. The solution was stirred in the dark at room temperature for 1 day. The resulting viscous solution was precipitated with ethyl acetate, washed twice with water, and dried under vacuum at 80 °C until completely dry. Piperidine The yield of the functionalized polymer is approximately 100%.

[0515] Step 3: Piperidine The functionalized polymer is dissolved in dimethyl sulfoxide, filtered through a 0.45 μm PTFE membrane and coated on a glass plate. The anion exchange membrane (iodide form) is contacted with deionized water and peeled off from the glass plate. Ion exchange is carried out in a 1 M salt solution at 80 °C to obtain an anion exchange membrane in halide form. Ion exchange is carried out in a 1 M KOH solution at 80 °C to obtain an anion exchange membrane in hydroxide form. The anion exchange membrane is designated as PF26TP85, where 26 represents the number of fluorine atoms in the monomer and 85 represents the proportion of terphenyl monomers.

[0516] Example 3: Preparation of PF42TP85 anion exchange membrane

[0517]

[0518] Step 1: p-Terphenyl (0.85 equivalents), 9,9-bis(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyl)-9H-fluorene (0.15 equivalents) and 1-methyl-4-piperidone (1.1 equivalents) are dissolved in dichloromethane. The solution is stirred at 0 °C. Trifluoroacetic acid (1.5 equivalents) and trifluoromethanesulfonic acid (10 equivalents) are added. When the solution becomes viscous, the resulting dark blue gel is slowly poured into excess water to form white fibers. The fibers are further washed once with 1 M KOH solution and three times with water. After vacuum drying overnight at 120 °C, a piperidine-functionalized intermediate polymer (yield 91%) is obtained.

[0519] Step 2: The piperidine-functionalized intermediate polymer is suspended in dimethyl sulfoxide. CH 3 I (3 equivalents for the piperidone group) and K 2 CO 3 (2 equivalents for the piperidone group) are added. The solution is stirred for 1 day in the dark at room temperature. The resulting viscous solution is precipitated with ethyl acetate, washed twice with water, and vacuum dried at 80 °C until completely dry. Piperidine The yield of the functionalized polymer is approximately 100%.

[0520] Step 3: Piperidine The functionalized polymer was dissolved in dimethyl sulfoxide, filtered through a 0.45-μm PTFE membrane, and coated on a glass plate. The anion exchange membrane (in iodide form) was contacted with deionized water and peeled off from the glass plate. Ion exchange was carried out in a 1M salt solution at 80 °C to obtain the anion exchange membrane in halide form. Ion exchange was carried out in a 1M KOH solution at 80 °C to obtain the anion exchange membrane in hydroxide form. The anion exchange membrane is called PF42TP85, where 42 represents the number of fluorine atoms in the monomer and 85 represents the proportion of terphenyl monomers.

[0521] Example 4: Preparation of PF10FA90 anion exchange membrane

[0522]

[0523] Step 1: 9,9-Bis(6-bromohexyl)-9H-fluorene (0.9 equivalent), 9,9-bis(3,3,4,4,4-pentafluorobutyl)-9H-fluorene (0.1 equivalent), and 1,1,1-trifluoropropan-2-one (1.1 equivalents) were dissolved in dichloromethane. The solution was stirred at 0 °C. Trifluoroacetic acid (1.5 equivalents) and trifluoromethanesulfonic acid (10 equivalents) were added. After the solution became viscous, the resulting dark blue gel was slowly poured into excess water to form white fibers. The fibers were further washed once with 1M KOH solution and three times with water. After vacuum drying overnight at 120 °C, the bromine-functionalized intermediate polymer was obtained (yield 93%).

[0524] Step 2: The bromine-functionalized intermediate polymer was dissolved in tetrahydrofuran, filtered through a 0.45-μm PTFE membrane, and coated on a glass plate. The membrane was contacted with deionized water to peel it off from the glass plate.

[0525] Step 3: The membrane was soaked in an excess of 45% trimethylamine solution for 2 days in the dark at room temperature. The resulting anion exchange membrane was in bromide form. Ion exchange was carried out in a 1M salt solution at 80 °C to obtain the anion exchange membrane in halide form. Ion exchange was carried out in a 1M KOH solution at 80 °C to obtain the anion exchange membrane in hydroxide form. The anion exchange membrane is called PF10FA90, where 10 represents the number of fluorine atoms in the monomer and 90 represents the proportion of 9,9-bis(6-bromohexyl)-9H-fluorene monomers.

[0526] Example 5: Preparation of PF26BP90 anion exchange membrane

[0527]

[0528] Step 1: Dissolve terphenyl (0.9 eq), 9,9-bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-9H-fluorene (0.1 eq), and 1-methyl-4-piperidone (1.1 eq) in dichloromethane. Stir the solution at 0 °C. Add trifluoroacetic acid (1.5 eq) and trifluoromethanesulfonic acid (10 eq). When the solution becomes viscous, slowly pour the resulting dark blue gel into excess water to form white fibers. Wash the fibers once with 1 M KOH solution and three times with water. After vacuum drying overnight at 120 °C, a piperidine-functionalized intermediate polymer is obtained (yield 91%).

[0529] Step 2: Suspend the piperidine-functionalized intermediate polymer in dimethyl sulfoxide. Add CH 3 I (3 eq for the piperidone group) and K 2 CO 3 (2 eq for the piperidone group). Stir the solution in the dark at room temperature for 1 day. Precipitate the resulting viscous solution with ethyl acetate, wash it twice with water, and vacuum dry it at 80 °C until completely dry. The yield of the piperidine -functionalized polymer is approximately 100%.

[0530] Step 3: Dissolve the piperidine -functionalized polymer in dimethyl sulfoxide, filter it through a 0.45 μm PTFE membrane, and coat it on a glass plate. The anion exchange membrane (iodide form) is contacted with deionized water and peeled off from the glass plate. Perform ion exchange in a 1 M salt solution at 80 °C to obtain an anion exchange membrane in halide form. Perform ion exchange in a 1 M KOH solution at 80 °C to obtain an anion exchange membrane in hydroxide form. The anion exchange membrane is designated as PF26BP90, where 26 represents the number of fluorine atoms in the monomer and 90 represents the proportion of terphenyl monomers.

[0531] Example 6: Preparation of PF6TP90 anion exchange membrane

[0532]

[0533] Step 1: Dissolve p-terphenyl (0.9 eq), 9,9-bis(4-(trifluoromethyl)benzyl)-9H-fluorene, and 1-methyl-4-piperidone (1.1 eq) in dichloromethane. Stir the solution at 0 °C. Add trifluoroacetic acid (1.5 eq) and trifluoromethanesulfonic acid (10 eq). When the solution becomes viscous, slowly pour the resulting dark blue gel into excess water to form white fibers. Wash the fibers once with 1 M KOH solution and three times with water. After vacuum drying overnight at 120 °C, a piperidine-functionalized intermediate polymer is obtained (yield 91%).

[0534] Step 2: Suspend the piperidine-functionalized intermediate polymer in dimethyl sulfoxide. Add CH 3 I (3 equivalents for the piperidone group) and K 2 CO 3 (2 equivalents for the piperidone group). Stir the solution in the dark at room temperature for 1 day. The resulting viscous solution is precipitated with ethyl acetate, washed twice with water, and dried under vacuum at 80 °C until completely dry. The yield of the piperidine -functionalized polymer is approximately 100%.

[0535] Step 3: Dissolve the piperidine -functionalized polymer in dimethyl sulfoxide, filter it through a 0.45 μm PTFE membrane, and coat it on a glass plate. The anion exchange membrane (in iodide form) is contacted with deionized water and peeled off from the glass plate. Ion exchange is carried out in a 1 M salt solution at 80 °C to obtain an anion exchange membrane in halide form. Ion exchange is carried out in a 1 M KOH solution at 80 °C to obtain an anion exchange membrane in hydroxide form. The anion exchange membrane is designated as PF6TP90, where 6 represents the number of fluorine atoms in the monomer and 90 represents the proportion of the terphenyl monomer.

[0536] Fluorine Content and Ion Exchange Capacity of Different Fluorinated Polyaromatic Polymers

[0537] Membrane Ion Exchange Capacity (mmol / g) Percentage of Fluorine Content Nafion 117 0.97 67.6％ <![CDATA[PAP-TP-X (X = 75 - 100) 1 > 2.37 2.4％ PF10TP80 2.48 9.4％ PF10TP85 2.56 7.3％ PF10TP90 2.63 5％ PF10TP95 2.71 2.6％ PF26TP85 2.22 16.4％ PF26TP90 2.38 11.8％ PF26TP95 2.57 6.4％ PF42TP85 1.96 23.4％ PF42TP90 2.17 17.4％ PF42TP95 2.45 9.8％ PF26BP90 2.84 14％

[0538] Table 1: Ion exchange capacity and fluorine content of the prior art anion exchange membrane PAP-TP-X and the fluorinated polyaromatic polymer reported herein

[0539] Nafion 117 is a proton exchange membrane known to have a high fluorine content, indicating that a high fluorine content contributes to the excellent performance of the proton exchange membrane.

[0540] The prior art fluorinated anion exchange membrane PAP-TP-X has a relatively low fluorine content of 2.4%, but as a hydroxide exchange membrane, it exhibits a good ion exchange capacity (2.37 mmol / g).

[0541] Compared with PAP-TP-X, the fluorine content of the fluorinated anion exchange membrane of the present invention can be significantly increased to more than 5% and can be as high as 23%, while its ion exchange capacity remains at a high level (1.96 mmol / g) or can even be increased to 2.84 mmol / g (Table 1).

[0542] Measurement of Alkaline Stability and Oxidation Stability

[0543] The alkali stability of the model FPAP membrane was tested by soaking it in 3 M KOH solution at 80 °C for more than 2000 hours. The oxidative stability of the model FPAP membrane was tested by soaking it in Fenton's reagent (3 wt% H 2 O 2 and 4 ppm Fe 2+ ) at room temperature. After a certain treatment time, the samples were taken out, rinsed with degassed deionized water, and ion-exchanged to I - form by 1 M NaI. The structural changes of the membrane were monitored by 1H NMR spectra.

[0544] Measurement of Mechanical Properties

[0545] The mechanical properties of PAP and FPAP-x anion exchange membranes were measured by a universal testing machine (UTM; model: AGS-500NJ, Shimadzu, Tokyo, Japan) at a strain rate of 1 mm·min -1 under ambient conditions.

[0546] Measurement of Conductivity

[0547] The ionic conductivity of PAP and FPAP-x anion exchange membranes in the OH - form was tested by an Autolab PGSTAT302N equipped with a Scribner 740MTS. The samples were cut into a size of 10 mm × 30 mm and subjected to alternating current (AC) impedance testing using platinum electrodes in a four-electrode cell, with a frequency range from 1 Hz to 0.1 MHz. The assembly and measurement processes were carried out under N 2 atmosphere to avoid CO 2 pollution. The impedance measurements were carried out at different temperatures and 100% relative humidity.

[0548] Measurement of Water Absorption and Swelling Ratio

[0549] The water uptake (WU) and swelling ratio (SR) of PAP and FPAP-x anion exchange membranes can be calculated by the following formula:

[0550]

[0551] where W 干 and L 干 are the mass and length of the sample after drying in a vacuum oven at 80 °C, respectively, and W 湿 and L 湿 are the mass and length of the sample after soaking in degassed deionized water for 12 hours under N 2 .

[0552] Cited prior art documents:

[0553] 1. Yan, Y., Hu, K., Wang, J., et al., Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers; Patent Application WO 2017 / 172824 A1.

[0554] 2. Bae, C., Lee W., Polymers and methods for their manufacture; US Patent US11236196 B2.

[0555] 3. Wu, X., Chen, N., Klok, H.K., et al., Angew. Chem. Int. Ed., 2022, 61(7): e202114892.

[0556] 4. Chen, N., Lu, C., Li, Y., et al., J. Membr. Sci., 2019, 588: 117120.

[0557] All scientific publications and patent documents cited in this specification are hereby incorporated by reference into this specification.

Claims

1. A fluorinated polyaromatic polymer comprising · at least one fluorinated unit FU of formula I wherein X is C or N, Y is C, R 1 , R 2 , R 5 and R 6 Independently selected from -–(CH 2 ) p –(CF 2 ) q –CF 3 , - -H， –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl, –C 2 ~C 10 Alkenyl, where –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl, -–C 2 ~C 10 Alkynyl group, where –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group, where R 1 、R 2 、R 5 and R 6 at least one of them is -–(CH 2 ) p –(CF 2 ) q –CF 3 or - R a 3 , R b 4 and R d 7 are independently selected from –C 1 ~C 10 alkyl, where –C 1 ~C 10 the alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl -–C 2 ~C 10 Alkenyl, where –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 Alkenyl, -–C 2 ~C 10 Alkynyl, where –C 2 ~C 10 the alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl, a and b are independently 0, 1, 2 or 3, especially 0 or 1, more especially 0, d is 0, 1, 2, 3 or 4, especially 0 or 1, more especially 0, n is 0 or 1, r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2, p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9, and · at least one cationic unit CU of formula B or formula C wherein R 8 is a partially or fully fluorinated –C 1 ~C 6 alkyl group, especially –CF 3 , R 9 selected from -–C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl, –C 2 ~C 10 Alkenyl, where –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 Alkenyl, -–C 2 ~C 10 alkynyl, where –C 2 ~C 10 alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl, -–(CH 2 ) s –N(R 12 ) 2 , -–(CH 2 ) s –NHR 12 , -–(CH 2 ) s –N + (R 12 ) 3 , wherein R12 is independently selected from –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl, –C 2 ~C 10 an alkenyl group, wherein –C 2 ~C 10 the alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 the alkenyl group –C 2 ~C 10 Alkynyl group, where –C 2 ~C 10 The alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 Alkynyl group s is between 0 and 20, -–Ph–R f 13, R 10 and R 11 are independently selected from -H –C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl -–C 2 ~C 10 Alkenyl, wherein –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl, –C 2 ~C 10 Alkynyl group, where –C 2 ~C 10 The alkynyl group is substituted or unsubstituted, especially –C 10 ~C 6 Alkynyl group, or R 10 and R 11 are linked together to form a cycloalkyl group having 4 to 10 carbon atoms, z is 0 or 1, A - is an anion.

2. The fluorinated polyaromatic polymer according to any one of the preceding claims, comprising at least one bifunctional aromatic moiety BA, where BA is independently selected from moieties comprising 2 to 5, in particular 2 to 3, cycloaliphatic moieties, where BA is unsubstituted or substituted by one or more substituents, said substituents being independently selected from –C 1 ~C 10 alkyl, –C 1 ~C 10 alkenyl or –C 1 ~C 10 alkynyl, where the one or more substituents are unsubstituted or further substituted by one or more halogen atoms or one or more quaternary ammonium groups.

3. The fluorinated polyaromatic polymer according to any one of the preceding claims, comprising at least one linear unit LU, said linear unit LU comprising · one or more FUs and one or more CUs, and / or · one or more FUs, one or more CUs and one or more BAs, especially · one or more FUs, one or more CUs and one or more BAs, where the LU arrangement is [FU–CU] x –[BA–CU] y , where the ratio of x to y is from 1:99 to 50:

50.

4. The fluorinated polyaromatic polymer according to any one of the preceding claims, wherein three or more linear units LU form at least one branched unit BU, wherein said three or more linear units LU are connected by at least one branching unit reagent BUR, wherein said at least one branching unit reagent BUR is independently selected from moieties comprising 3 to 6 cycloaliphatic moieties.

5. The fluorinated polyaromatic polymer according to any one of the preceding claims, wherein two or more linear units LU form at least one crosslinked unit CU, wherein said two or more linear units LU are crosslinked by at least one crosslinking agent CL, wherein said at least one crosslinking agent CL is independently selected from aliphatic or aromatic quaternary diammonium.

6. The fluorinated polyaromatic polymer according to any one of the preceding claims, wherein said at least one fluorinated unit FU is independently selected from wherein A is independently selected from –(CH 2 ) p –(CF 2 ) q –CF 3 , B, R 3 and R 4 are independently selected from –C 1 ~C 10 alkyl, where –C 1 ~C 10 the alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl –C 2 ~C 10 an alkenyl group, wherein –C 2 ~C 10 the alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 the alkenyl group –C 2 ~C 10 Alkynyl group, where –C 2 ~C 10 The alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 Alkynyl group, C is independently selected from wherein R d 7 is independently selected from –C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl –C 2 ~C 10 An alkenyl group, wherein –C 2 ~C 10 The alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 The alkenyl group -–C 2 ~C 10 Alkynyl group, where –C 2 ~C 10 The alkynyl group is substituted or unsubstituted, especially –C 10 ~C 6 Alkynyl group, d is 0, 1, 2, 3 or 4, r is 1, 2, 3, 4, 5 or 6, especially 1, 2 or 3, more especially 1 or 2, p is independently between 1 and 20, especially between 1 and 15, more especially between 1 and 9, and q is independently between 0 and 20, especially between 0 and 15, more especially between 0 and 9, a and b are independently 0, 1, 2 or 3.

7. The fluorinated polyaromatic polymer according to any one of the preceding claims, wherein at least one bifunctional aromatic moiety BA is independently selected from wherein R 14 、R 15 、R 16 、R 17 and R 18 are independently selected from –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl, -–C 2 ~C 10 alkenyl, wherein –C 2 ~C 10 alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl, –C 2 ~C 10 Alkynyl, where –C 2 ~C 10 the alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl, l and m are independently selected from 0, 1, 2, 3 or 4, k is from 0 to 4, especially from 1 to 4, more especially 1 or 2.

8. The fluorinated polyaromatic polymer according to any one of the preceding claims, wherein at least one branched unit BU is independently selected from 9. The fluorinated polyaromatic polymer according to any one of the preceding claims, wherein at least one crosslinked unit CLU is independently selected from wherein Z 1 is R 19 R 20 or NR 21 R 22 , Z 2 is R 19 R 20 or N + R 21 R 22 R 23 , R 19 and R 20 are independently selected from - a halogen group, –C 1 ~C 10 alkyl, where –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl –C 2 ~C 10 An alkenyl group, wherein –C 2 ~C 10 The alkenyl group is substituted or unsubstituted, especially –C 2 ~C 6 The alkenyl group –C 2 ~C 10 alkynyl group, wherein –C 2 ~C 10 the alkynyl group is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl group R 21 , R 22 and R 23 Independently selected from -H， –C 1 ~C 10 alkyl, wherein –C 1 ~C 10 alkyl is substituted or unsubstituted, especially –C 1 ~C 6 alkyl –C 2 ~C 10 Alkenyl, where –C 2 ~C 10 The alkenyl is substituted or unsubstituted, especially –C 2 ~C 6 alkenyl, -–C 2 ~C 10 Alkynyl, where –C 2 ~C 10 the alkynyl is substituted or unsubstituted, especially –C 2 ~C 6 alkynyl, t is between 0 and 20, especially between 0 and 12, more especially between 0 and 6.

10. The fluorinated polyaromatic polymer according to any one of the preceding claims, having a fluorine content of from 2.5% to 80%, in particular from 5% to 60%, more particularly from 5% to 30%.

11. A process for preparing a fluorinated polyaromatic polymer, said polymer comprising linear units LU, said process comprising reacting at least one fluorinated unit precursor FUP and optionally at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP.

12. A process for preparing a fluorinated polyaromatic polymer, said polymer comprising branched units BU, said branched units BU comprising three or more linear units LU linked by a branched unit reagent BUR, said process comprising reacting at least one fluorinated unit precursor FUP and optionally at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP and a branched unit precursor BUP.

13. A process for preparing a fluorinated polyaromatic polymer, said polymer comprising crosslinked units CU, said crosslinked units CU comprising two or more linear units LU linked by one or more crosslinking agents CL, said process comprising: · reacting at least one fluorinated unit precursor FUP and at least one cationic unit precursor CUP and optionally at least one bifunctional aromatic moiety precursor BAP to obtain an intermediate polymer; and · reacting the intermediate polymer with at least one crosslinked unit precursor CLUP.

Images