Branched aryl ether-free polycyclic aromatic hydrocarbon polymers for anion exchange membranes

Abstract

The present invention relates to a polycyclic aromatic hydrocarbon polymer comprising a polyfunctional aromatic moiety MA, a cationic group CG and a difunctional aromatic moiety BA, wherein one or more CG and one or more BA form a linear unit L, and MA is linked to 3 to 6 linear units L. The definitions of MA, CG and BA are as defined in the specification. Furthermore, the present invention relates to a neutral precursor of the polycyclic aromatic hydrocarbon polymer, and an anion exchange membrane comprising the polycyclic aromatic hydrocarbon polymer according to the present invention.

Description

[Technical field]

[0001] The present invention relates to aryl ether-free branched polycyclic aromatic hydrocarbon polymers and anion exchange membranes made therewith. [Background technology]

[0002] Anion exchange membranes (AEMs) are used to transport OH-, CO 3 2 AEMs are solid polymer electrolytes that allow the transport of anions such as -, Br-, and Cl-. AEMs are important components in fuel cells and water electrolyzers. They also have potential applications in desalination, electrodialysis, batteries, and sensors.

[0003] The main requirements for an anion exchange membrane are sufficient durability, electrical conductivity, mechanical properties as well as low water absorption and swelling.

[0004] Many of the commercially available AEMs are based on polystyrene, which can be destroyed during long-term use in AEM fuel cells and water electrolyzers. Other AEMs based on polysulfone, poly(phenylene oxide), poly(benzimidazolium), poly(arylene ether ketone), and poly(arylene ether sulfone) have also been reported. These polymers contain arylene ether bonds in the backbone and cationic groups such as trimethylammonium, benzyltrimethylammonium, and imidazole groups in the side chains. These polymers have proven unstable for long-term operation because the ether groups can be attacked and destroyed. For example, Zhang et al. (2021) reported that linear ether-type polycyclic aromatic hydrocarbons with branched ionic side chains lost 20% of their original conductivity after immersion in 4 M KOH at 80 °C for 400 h.

[0005] Recently, AEMs based on aryl ether-free polycyclic aromatic hydrocarbons have been prepared. Representative molecular structures include Diel-Alder poly(phenylene), poly(perfluoroalkylphenylene), poly(biphenylalkylene), poly(biphenylene piperidinium), spiroionene, and poly(mesityldimethylbenzimidazolium). These AEMs have excellent thermal and chemical stability. For example, Lee et al. (2015) prepared quaternary ammonium-linked poly(biphenylarylene)s that do not have alkali-labile C-O bonds, and the resulting AEMs showed high hydroxide conductivity up to 120 mS / cm and good alkali stability at 80 °C.

[0006] U.S. Patent Application Serial No. 15 / 527,967 discloses anion exchange membranes made using linear quaternized ammonium hydroxide-polyarylene-containing polymers. A limitation of these membranes is their high water absorption (130 wt % at 30° C.).

[0007] Olsson et al. (2018) reported an AEM of the poly(arylpiperidinium) family that lost 5% ion exchange capacity (IEC) over 15 days at 90° C. in 2 M NaOH. Also, U.S. Patent Application No. 16 / 651,622 and CN 111269401 A disclose anion exchange membranes fabricated by using linear poly(arylpiperidinium) polymers with pendant cationic groups.

[0008] However, these aryl ether-free AEMs have poor water absorption, swelling, and mechanical properties, probably due to their relatively low molecular weight.

[0009] Despite much research into improving anion exchange membranes, no membranes have been reported to date that exhibit high electrical conductivity, good alkaline stability, and high mechanical properties while also exhibiting low water absorption and swelling.

[0010] Based on the above technical solutions, the object of the present invention is to provide means and methods for producing improved anion exchange membranes. This object is achieved by the subject matter of the independent claims of this specification, further advantageous embodiments are described in the dependent claims, examples, figures and the summary of this specification. Summary of the Invention [Means for solving the problem]

[0011] The first aspect of the invention is a cyclic hydrocarbon moiety that contains 2 to 6 cyclic hydrocarbon moieties and is unsubstituted or C 1~20 at least one polyfunctional aromatic moiety MA, optionally substituted with one or more substituents independently selected from -alkyl; a cationic group CG independently selected from the moieties of formula 1 or 4;

[0012] [ka]

[0013] (however, R 1 is a fully or partially fluorinated C 1~6 -alkyl, R 12 and R 13 are each independently H, C 1~12 -Alkyl, phenyl, and C 3~10 -cycloalkyl; or R 12 and R 13 are linked together to form a cycloalkyl containing 4 to 10 C atoms, D is -N + (R 2 ) 3 , -P + (R 2 ) 4 or piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, imidazolidinyl cations, where the piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl or imidazolidinyl cations are unsubstituted or C 1~12-substituted with one or more substituents independently selected from alkyl, phenyl; R 2 are each independently H, C 1~12 - any other R selected from alkyl, phenyl 2 and y is 0 or 1; x is an integer between 0 and 12, z is 0 or 1, particularly 1. Independently selected from moieties containing 2 to 5 cyclic hydrocarbon moieties, unsubstituted or 1~10 -Alkyl, -OC 1~10 -Alkyl, fully or partially fluorinated C 1~10 a difunctional aromatic moiety BA, optionally substituted with one or more substituents independently selected from -alkyl, one or more CG and one or more BA form a linear unit L, MA is a polycyclic aromatic hydrocarbon polymer linked to 3 to 6 linear units L.

[0014] A second aspect of the present invention is Contains 2 to 6 cyclic hydrocarbon moieties, unsubstituted or C 1~20 at least one polyfunctional aromatic moiety MA, optionally substituted with one or more substituents independently selected from -alkyl; a neutral group NG independently selected from the moieties of formula 1' or 4';

[0015] [ka]

[0016] (however, R 1 is a fully or partially fluorinated C 1~6 -alkyl, R 12 , H, C 1~12 -Alkyl, phenyl, C 3~10 -cycloalkyl, D is a leaving group, y is 0 or 1; x is an integer between 0 and 12, z is 0 or 1, particularly 1. Independently selected from moieties containing 2 to 5 cyclic hydrocarbon moieties, unsubstituted or 1~10 -Alkyl, -OC 1~10 -Alkyl, fully or partially fluorinated C 1~10 a difunctional aromatic moiety BA, optionally substituted with one or more substituents independently selected from -alkyl, one or more CG and one or more BA form a linear unit L, MA refers to a precursor that is linked to 3 to 6 linear units L.

[0017] A third aspect of the present invention is Contains 2 to 6 cyclic hydrocarbon moieties, unsubstituted or C 1~20 -Alkyl, especially C 1~6 at least one polyfunctional aromatic moiety MA, optionally substituted with one or more substituents independently selected from -alkyl; a ketone independently selected from the moieties of formula 1k or 4k;

[0018] [ka]

[0019] (however, R 1 is a fully or partially fluorinated C 1~6 -alkyl, D is a leaving group, y is 0 or 1; x is an integer between 0 and 12, z is 0 or 1, particularly 1. Independently selected from moieties containing 2 to 5 cyclic hydrocarbon moieties, unsubstituted or 1~10 -Alkyl, -OC 1~10 -Alkyl, fully or partially fluorinated C 1~10a difunctional aromatic moiety BA, optionally substituted with one or more substituents independently selected from -alkyl, The pH of the reaction mixture is less than 1, with respect to the precursor obtained by reaction of the reaction mixture.

[0020] A fourth aspect of the present invention is A precursor according to the second or third aspect of the present invention; HaroC 1~12 -Alkyl, halophenyl or haloC 3~10 -cycloalkyl, or N(R 2 ) 3 , P(R 2 ) 3 (R 2 is defined as follows: ), or and a reactant selected from piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl or imidazolidinyl.

[0021] A fifth aspect of the present invention relates to an anion exchange membrane comprising a polycyclic aromatic hydrocarbon polymer according to the first or fourth aspect of the present invention and a suitable counter ion.

[0022] [Terms and definitions] For purposes of interpreting this specification, the following definitions shall apply, and where appropriate, terms used in the singular shall also include the plural and vice versa. In the event that a definition set forth below conflicts with any document incorporated herein by reference, the definition set forth shall control.

[0023] As used herein, the terms "comprising," "having," "containing," and "including," and other similar forms and grammatically equivalent terms, are equivalent in meaning and open ended, and one or more items following any of these words do not imply an exhaustive list of such one or more items, nor are they limited to only the listed one or more items. For example, an article "comprising" components A, B, and C can consist of (i.e., contain only) components A, B, and C, or can contain not only components A, B, and C, but also one or more other components. Thus, "comprising" and similar forms thereof, and grammatically equivalent terms are intended and understood to include the disclosure of embodiments of "consisting essentially of" or "consisting of."

[0024] Where a range of values ​​is provided, unless the context clearly dictates otherwise, it is to be understood that the upper and lower limits of the range and each intermediate value between any other value within the range or any other value within the range, to one-tenth of the lower limit, are included in the disclosure, subject to any specifically excluded limit in the range. Where the range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.

[0025] Reference herein to "about" a value or parameter includes (and describes) variations on the value or parameter itself. For example, a statement "about X" also includes a statement about "X."

[0026] As used in this specification, including the appended claims, the singular forms "a," "or," and "said" include plural referents unless the context clearly dictates otherwise.

[0027] The term polycyclic aromatic hydrocarbon polymer in the context of this specification relates to a polymer comprising at least one polyfunctional aromatic moiety MA, a cationic group CG and a difunctional aromatic moiety BA. In polycyclic aromatic hydrocarbon polymers, MA constitutes a branch point, also called "branch point intermediate" or "branch unit" (IUPAC recommendations 1997). The moieties CG and BA form a linear unit L. Usually, CG and BA alternate within the linear unit. The linear unit L may also be called a "linear chain" or a "linear subchain". In one polymer, the length of the linear unit L may vary. At least two linear units L, each bonded to MA, constitute a main chain or backbone (L) with at least one intermediate branch point (MA). A third linear unit L bonded to MA constitutes a branch or side chain. The polyfunctional moiety MA may be trifunctional, tetrafunctional, pentafunctional or hexafunctional, i.e. 3, 4, 5 or 6 linear moieties L may be bonded to one moiety MA. If the polymer comprises one or more moieties MA, a dendritic or hyperbranched structure may be observed. Furthermore, the polycyclic aromatic hydrocarbon polymer comprises a terminal unit E, also called an end group. The terminal unit E constitutes the free end of the main chain or a side chain. For example, one end of the first, second or third linker moiety L mentioned above is bonded to a trifunctional moiety MA and the other end is bonded to a terminal unit E. Alternatively, there may be a crosslink in the polymer. The polycyclic aromatic hydrocarbon polymer may comprise a counterion. In particular, the negative charge of the counterion is balanced by the positive charge of the cationic group CG. The polycyclic aromatic hydrocarbon polymer according to the invention does not comprise an aryl ether, i.e. does not comprise two aryl moieties linked to each other by -O-.

[0028] The term polyfunctional aromatic moiety or MA in the context of this specification relates in particular to a moiety comprising and in particular consisting of 2 to 6, in particular 2 to 4, cyclic hydrocarbon moieties, where MA is unsubstituted or 1~20 -Alkyl, especially C 1~6-alkyl. Non-limiting examples include 1,3,5-triphenylbenzene, naphthalene, biphenylene, 1H-phenalene, anthracene, phenanthrene, 1,6-dihydropyrene, 10b,10c-dihydropyrene, pyrene, and 9,9'-spirobi[fluorene]. At least one, and in particular all, of the cyclic hydrocarbon moieties are aromatic.

[0029] The term cationic group or CG in the context of this specification refers to the moiety of formula 1 or formula 4 below. The cationic group in the polymer allows the transport of anions between the anode and cathode of the electrochemical device. Non-limiting examples of anions include OH - , CO 3 2 -,Br - , or Cl - In the linker unit L, the cationic group may form the terminus that is attached to MA.

[0030] The term bifunctional aromatic moiety or BA in the context of this specification relates to a moiety comprising 2 to 5, especially 2 to 3, cyclic hydrocarbon moieties. Non-limiting examples include biphenyl, terphenyl (especially para- or meta-terphenyl), 1,1'-methylenedibenzene, (1-methyl-1-phenyl-ethyl)benzene, 2-phenylethylbenzene, 9,9-dimethylfluorene and 9,9-dibutylfluorene. At least one, especially all, of the cyclic hydrocarbon moieties are aromatic. [Brief description of the drawings]

[0031] [Figure 1] A portion of a polymer (branched poly(terphenyl-triphenylbenzene-piperidine)) is shown, showing the polyfunctional aromatic moiety MA, the difunctional moiety BA, and the cationic group CG. [Diagram 2]A method for preparing aryl ether-free polycyclic aromatic hydrocarbons with a branched structure is shown. The moiety Ar in the polymer corresponds to the moiety BA, the ketone in the structure corresponds to the neutral group NG, and n indicates that the polymer contains several multifunctional moieties MA. [Diagram 3] A possible difunctional aromatic moiety BA is shown. [Figure 4] Possible polyfunctional aromatic moieties MA are shown. [Diagram 5] Possible ketones are shown. [Figure 6] Possible cationic groups CG are shown, with the wavy lines indicating attachment to adjacent portions of the polymer. [Figure 7] 1 shows the chemical structure of branched poly(terphenyl-triphenylbenzene-piperidine). [Figure 8] 1H spectra of (a) branched poly(terphenyl-triphenylbenzene-piperidine) (protonated with TFA) and (b) branched poly(terphenyl-triphenylbenzene-piperidinium). [Figure 9] The stress-strain curves of PTP and b-PTP-x are shown. [Figure 10] 1 shows the residual OH- conductivity of b-PTP-2.5 after treatment in 1M or 3M KOH at 80° C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] The objective of the present invention is to provide an anion exchange membrane with improved properties. An aryl ether-free polycyclic aromatic hydrocarbon polymer with a branched structure was designed to obtain low water absorption, low swelling, and high mechanical properties while maintaining high electrical conductivity and alkaline stability.

[0033] The first aspect of the present invention is containing, in particular consisting of, 2 to 6, in particular 2 to 4, cyclic hydrocarbon moieties, unsubstituted or 1~20 -Alkyl, especially C 1~6at least one polyfunctional aromatic moiety MA, optionally substituted with one or more substituents independently selected from -alkyl; a cationic group CG independently selected from the moieties of formula 1 or formula 4;

[0034] [ka]

[0035] (however, R 1 is a fully or partially fluorinated C 1~6 -Alkyl, especially fully or partially fluorinated C 1~4 -alkyl, more particularly fully or partially fluorinated -CF 3 and R 12 and R 13 are each independently H, C 1~12 -Alkyl, phenyl, and C 3~10 -Cycloalkyl, especially H, C 1~12 - alkyl, and phenyl; or R 12 and R 13 are linked together to form a cycloalkyl containing 4 to 10 C atoms, D is -N + (R 2 ) 3 , -P + (R 2 ) 4 or piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, imidazolidinyl cations, particularly -N + (R 2 ) 3 , -P + (R 2 ) 4 or imidazolyl, pyrazolyl, imidazolidinyl cations, more particularly -N + (R 2 ) 3 or imidazolyl cations, the pyridyl, pyrrolidinyl, imidazolyl, pyrazolyl or imidazolyl cations being unsubstituted or C 1~12- optionally substituted with one or more substituents independently selected from alkyl, phenyl; R 2 are each independently H, C 1~12 -Alkyl, phenyl, especially H, C 1~6 - any other R selected from alkyl, phenyl 2 and y is 0 or 1; x is 0 to 12, particularly 0 to 8, more particularly 6 to 8; z is 0 or 1, particularly 1. Independently selected from moieties containing 2 to 5, particularly 2 to 3, cyclic hydrocarbon moieties, unsubstituted or 1~10 -Alkyl, -OC 1~10 -Alkyl, fully or partially fluorinated C 1~10 a difunctional aromatic moiety BA, optionally substituted with one or more substituents independently selected from -alkyl, one or more CG and one or more BA form a linear unit L, MA relates to a polycyclic aromatic hydrocarbon polymer, linked to 3 to 6, particularly 3 to 4, more particularly 3, linear units L.

[0036] Under standard ambient temperature and pressure conditions, the polycyclic aromatic hydrocarbon polymer is a solid, particularly in the form of a powder. The polymer powder can be used to manufacture anion exchange membranes. After dissolving in a suitable solvent (e.g., dimethyl sulfoxide), the polycyclic aromatic hydrocarbon polymer can be cast onto a glass plate. The AEM can be peeled off from the glass plate in contact with water and used in electrochemical devices.

[0037] The AEMs made from the polycyclic aromatic hydrocarbon polymers described herein are characterized by low water absorption and low swelling. In particular, the aromatic moieties of MA and BA are advantageous for reducing water absorption and further reducing swelling.

[0038] Additionally, AEMs made with the polycyclic aromatic hydrocarbon polymers described herein exhibit good mechanical properties, particularly the branched structure and high molecular weight, which favor high strength and toughness of the polymer.

[0039] The cationic groups in the polymer allow for the transport of anions between the anode and cathode of an electrochemical device. Non-limiting examples of anions include OH - , CO 3 2 -,Br - , or Cl - Examples include:

[0040] The polycyclic aromatic hydrocarbon polymer is a branched polymer. It comprises at least one polyfunctional aromatic moiety MA, a cationic group CG and a difunctional aromatic moiety BA, CG and BA forming a linear unit L. The polyfunctional moiety MA constitutes the branching point of the polymer. The branched structure consists of the moieties MA, CG and BA. The polycyclic aromatic hydrocarbon polymer may be short-chain branched, long-chain branched or hyperbranched, in particular long-chain branched.

[0041] Long chain branching, in particular, can increase the strength, toughness, and glass transition temperature (Tg) of a polymer by increasing the number of entanglements per chain. AEMs made with such polymers exhibit high electrical conductivity, low water absorption and dimensional swelling, ease of castability, and good mechanical properties.

[0042] The polycyclic aromatic hydrocarbon polymers are in particular aryl ether free, ie no aromatic moieties are linked via -O-.

[0043] In some embodiments, the polycyclic aromatic hydrocarbon polymer does not include an aryl ether.

[0044] In some embodiments, the cyclic hydrocarbon moieties of MA and BA are not linked through -O-.

[0045] The linear units L and the polyfunctional moieties MA form the main chain and side chains in the polymer structure. Usually, there are several moieties MA in a polymer. Depending on the number of possible binding sites of MA (trifunctional, tetrafunctional, pentafunctional or hexafunctional), 3, 4, 5 or 6 linear moieties L can be bound to one MA moiety. To form a polymer, both ends of the linear units L can be linked to the corresponding MA moieties, or one end of the linear unit can be bound to the MA moiety and the other end can be left free. The free end of such a polymer chain comprises the terminal unit E. Based on the polymerization mechanism, it is expected that the chain will end with the linear unit L. Thus, the majority of the terminal units E are bound to L. However, to a lesser extent, it also occurs that the chain ends with the polyfunctional moiety MA. In the latter case, the terminal unit E may be bound to a free binding site of MA. The chemical structure of the terminal unit E depends on the quenching conditions applied during the preparation of the polycyclic aromatic hydrocarbon polymer. The polymerization reaction is quenched by adding a solvent to the reaction mixture. Suitable solvents are known to those skilled in the art. For example, water or methanol can be used in the quenching step. If water is used, the moiety E will be -OH. If methanol is used, the moiety E will be -OCH 3 It is.

[0046] In some embodiments, the terminal unit E is -OH, -OC 1~4 -alkyl, phenyl-OH, and phenyl-OC 1~4 -alkyl.

[0047] In some embodiments, the terminal unit E is -OH, -OCH 3 , -OCH 2 CH 3 ,

[0048] [ka]

[0049] is selected from.

[0050] The moieties BA and CG are arranged alternately within the linear unit L. Specifically, the moieties BA and CG are arranged such that the linear unit starts and ends with the moiety CG, i.e. the bond between the linear unit L and the multifunctional moiety MA or the bond between the linear unit L and the terminal unit E is formed by CG.

[0051] In some embodiments, BA and CG alternate within the linear L unit.

[0052] In some embodiments, the linear unit L is n difunctional aromatic moieties BA and n+1 cationic groups CG, or containing n difunctional aromatic moieties BA and n cationic groups CG, n is an integer between 1 and 300, particularly between 50 and 200.

[0053] In some embodiments, the linear unit L comprises n difunctional aromatic moieties BA and n+1 cationic groups CG, where n is an integer between 1 and 300, particularly between 50 and 200.

[0054] Between the two moieties MA, the linear unit L should have a cationic group on both ends.

[0055] In some embodiments, when L is linked to two multifunctional units MA, L comprises n difunctional aromatic moieties BA and n+1 cationic groups CG.

[0056] In some embodiments, MA is linked to 3-6, particularly 3-4, and more particularly 3, linear units L, respectively, and MA and L are linked such that MA is attached to the cationic group CG.

[0057] In some embodiments, the linear unit L is attached to two different multifunctional units MA, or the linear unit L is attached to one multifunctional unit MA and one terminal unit E.

[0058] In some embodiments, the terminal unit E is linked to CG.

[0059] The polycyclic aromatic hydrocarbon polymer may include a counterion. The negative charge of the counterion is balanced by the positive charge of the cationic group CG. The polymer may be used to fabricate an AEM for an electrochemical device. The cationic group in the polymer allows the transport of anions between the anode and cathode of the electrochemical device. In some embodiments, the polycyclic aromatic hydrocarbon polymer comprises one or more counterions.

[0060] In some embodiments, the polycyclic aromatic hydrocarbon polymer is - , Cl - , Br - , I - , CO 3 2 -, HCO 3 -, TFA - (CF 3 CO 2 -), B.F. 4 - , P.F. 6 - , TFSA - (CF 3 SO 3 -),

[0061] In some embodiments, the polycyclic aromatic hydrocarbon polymer is - , CO 3 2 -,Br - Or Cl - The compound includes one or more counter ions selected from:

[0062] In some embodiments, the polycyclic aromatic hydrocarbon polymer is - and Cl - The compound includes one or more counter ions selected from:

[0063] In some embodiments, the cyclic hydrocarbon portion of the moiety MA may be a single bond, a shared bond of one or more covalent bonds (fused rings), a shared bond of a single atom (spirocycles), and / or an alkyl, particularly C1~6 -alkyl, more particularly C 1~2 -alkyl.

[0064] In some embodiments, the cyclic hydrocarbon moieties of the moiety MA are linked to each other by a single bond, by sharing one or more covalent bonds (fused rings), and / or by sharing a single atom (spirocycles).

[0065] In some embodiments, the multifunctional moieties MA are independently selected from 1,3,5-triphenylbenzene, naphthalene, biphenylene, 1H-phenalene, anthracene, phenanthrene, 1,6-dihydropyrene, 10b,10c-dihydropyrene, pyrene, and 9,9'-spirobi[fluorene].

[0066] The polymer may contain only one type of MA, for example only 1,3,5-triphenylbenzene, or a mixture of different types of MA, for example 1,3,5-triphenylbenzene and naphthalene, specifically, only one type of MA is present in the polymer.

[0067] In some embodiments, the multifunctional moiety MA is independently selected from the following:

[0068] [ka]

[0069] (however, (L) or (L m ) represents a bond connecting to the linear unit L, Each m is independently selected from 0, 1 and 2, and the sum of all m's is 3, 4, 5 or 6, particularly 3 or 4, more particularly 3.

[0070] In some embodiments, the multifunctional moiety MA is independently selected from the following:

[0071] [ka]

[0072] The structure shown above shows the preferred positions for the active CH of the benzene ring to react with the ketone to form a bond between the MA and CG precursors. Depending on CH activity and steric hindrance, not all of the positions shown on the MA moiety may bond to the CG moiety, only some may bond. For example, in the case of 1,6-dihydropyrene, six bond positions are shown. This does not necessarily mean that each 1,6-dihydropyrene in the polymer is a hexafunctional branch point. 1,6-dihydropyrene may be present in the polymer, for example, in the form of a trifunctional moiety.

[0073] In some embodiments, the cyclic hydrocarbon portion of the moiety BA is a single bond, C 1~6 -alkyl, linked to each other by the covalent linkage of a single atom (spiro rings) and / or by the covalent linkage of one or more covalent bonds (fused rings). In some embodiments, the cyclic hydrocarbon portion of the moiety BA may be a single bond, an alkyl, particularly C 1~6 -alkyl, more particularly C 1~2 -alkyl, and / or are linked to each other by one or more covalent bonds (fused rings).

[0074] In some embodiments, the cyclic hydrocarbon portion of the moiety BA may be a single bond, an alkyl, particularly C 1~6 -alkyl, more particularly C 1~2 -alkyl or are linked to each other by one or more covalent bonds (fused rings).

[0075] In some embodiments, the cyclic hydrocarbon moiety of the BA is are in particular directly linked to each other by a single bond or a fused ring, or C 1~6 -alkyl; or are directly bonded to each other and further 1~6 - linked by alkyl.

[0076] In some embodiments, each difunctional aromatic moiety BA is independently selected from a moiety of formula 2 or 3.

[0077] [ka]

[0078] (however, R 3 , R 4 , R 5 and R 6 are each independently H, F, or C 1~6 -Alkyl, partially or fully fluorinated C 1~6 -alkyl, R 7 and R 8 are each independently H, F, or C 1~6 -Alkyl, partially or fully fluorinated C 1~6 -alkyl, s and t are each independently an integer between 0 and 4, in particular between 0 and 2; r is an integer between 0 and 3, particularly between 0 and 2, and more particularly between 0 and 1.

[0079] In some embodiments, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently H and C 1~6 -alkyl.

[0080] The polymer may contain only one type of BA, for example only biphenyl, or a mixture of different types of BA, for example biphenyl and paraterphenyl. Specifically, only one type of BA is present in the polymer.

[0081] In some embodiments, each difunctional aromatic moiety BA is independently selected from a moiety of formula 2a, 2b, or 3.

[0082] [ka]

[0083] (however, Equation 3, R 3 , R 4 , R 5 , R 6 The moieties s, r and t are as defined above.

[0084] In some embodiments, each difunctional aromatic moiety BA is independently selected from the following:

[0085] [ka]

[0086] In some embodiments, the cationic group CG is selected from the moieties of formulae 1a, 1b, 1c, 1d, and 4, particularly formulae 1a, 1c, and 4.

[0087] [ka]

[0088] (however, R 1 is a fully or partially fluorinated C 1~6 -Alkyl, especially fully fluorinated C 1~6 -alkyl, more particularly fully fluorinated C 1~3 -Alkyl, more particularly -CF 3 and R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are each independently H, C 1~6 -alkyl, phenyl; R 12 and R 13 are each independently H, C 1~6 -Alkyl, phenyl, C 3~10 -cycloalkyl; or R 12 and R 13 are linked together to form a cycloalkyl containing 4 to 10 C atoms, R 17 and R 18 is independently 1~6 -Alkyl, especially C 1~3 -alkyl, p and q are integers between 0 and 3, in particular 0; R 19 and R 20 are independently H and C 1~6 -Alkyl, especially H and C 1~3 -alkyl, x is an integer between 0 and 12, particularly between 0 and 8, and more particularly between 6 and 8.

[0089] In some embodiments, R 12 and R 13 are each independently H, C 1~6 - alkyl, phenyl, or R 12 and R 13 are linked together to form a cycloalkyl containing 4 to 10 C atoms.

[0090] In some embodiments, R 12 and R 13 are each independently H, C 1~6 -Alkyl, especially H and C 1~3 -alkyl, more particularly CH 3 is selected from.

[0091] In some embodiments, R 12 and R 13 are each independently 1~6 -Alkyl, especially C 1~3 -alkyl, more particularly CH 3 is selected from.

[0092] In some embodiments, the cationic group CG is represented by formula 4 defined above, specifically:

[0093] [ka]

[0094] has.

[0095] A second aspect of the present invention is containing, in particular consisting of, 2 to 6, more in particular 2 to 4, cyclic hydrocarbon groups, unsubstituted or 1~20 -Alkyl, especially C 1~6 at least one polyfunctional aromatic moiety MA, optionally substituted with one or more substituents independently selected from -alkyl; a neutral group NG independently selected from the moieties of formula 1' or 4';

[0096] [ka]

[0097] (however, R 1 is a fully or partially fluorinated C 1~6 -Alkyl, especially fully or partially fluorinated C 1~4 -alkyl, more particularly -CF 3 and R 12 , H, C 1~12 -Alkyl, phenyl, C 3~10 -cycloalkyl, D is a leaving group, in particular a leaving group selected from -I, -Br, -Cl and -OH; y is 0 or 1; x is an integer between 0 and 12, in particular between 0 and 8, more in particular between 6 and 8; z is 0 or 1, particularly 1.

[0098] Independently selected from moieties containing 2 to 5, particularly 2 to 3, cyclic hydrocarbon moieties, unsubstituted or 1~10 -Alkyl, -OC 1~10 -Alkyl, fully or partially fluorinated C 1~10a difunctional aromatic moiety BA, optionally substituted with one or more substituents independently selected from -alkyl, one or more CG and one or more BA form a linear unit L, MA relates to a precursor which is linked to 3 to 6, particularly 3 to 4, more particularly 3, linear units L.

[0099] The polymer according to the first aspect of the invention is synthesised by using a polyfunctional aromatic moiety MA, a difunctional aromatic moiety BA and a neutral group NG. After formation of the polymer precursor, the neutral group is converted to a cationic group CG.

[0100] The general structure of the precursor is essentially the same as that of the polymer according to the first aspect of the invention. The only difference is that the cationic group CG is replaced by a neutral group NG. This means that the moieties BA and NG alternate within the linear units and MA is a branch point linking at least three linear units.

[0101] In some embodiments, the precursor is containing, in particular consisting of, 2 to 6, in particular 2 to 4, cyclic hydrocarbon groups, unsubstituted or 1~20 -Alkyl, especially C 1~6 at least one polyfunctional aromatic moiety MA, optionally substituted with one or more substituents independently selected from -alkyl; a neutral group NG independently selected from the moieties of formula 1' or 4';

[0102] [ka]

[0103] (however, R 1 is a fully or partially fluorinated C 1~6 -Alkyl, especially fully or partially fluorinated C 1~4 -alkyl, more particularly -CF 3 and R 12 , H, C1~12 -Alkyl, phenyl, C 3~10 -cycloalkyl, D is a leaving group, in particular a leaving group selected from -I, -Br, -Cl and -OH; y is 0 or 1; x is an integer between 0 and 12, in particular between 0 and 8, more in particular between 6 and 8; z is 0 or 1, particularly 1. directly bonded to each other, or C 1~6 - linked by alkyl, or are directly bonded to each other and further 1~6 and a difunctional aromatic moiety BA independently selected from moieties containing 2 to 5, in particular 2 to 3, cyclic hydrocarbon moieties linked by -alkyl, BA is unsubstituted or C 1~10 -Alkyl, -OC 1~10 -Alkyl, fully or partially fluorinated C 1~10 -alkyl; The terminal unit E is independently -OH, -OC 1~4 -alkyl, phenyl-OH, and phenyl-OC 1~4 -Alkyl, especially

[0104] [ka]

[0105] is selected from (however, CG and BA form a linear unit L, which is n difunctional aromatic moieties BA and n+1 cationic groups CG, or containing n difunctional aromatic moieties BA and n cationic groups CG, CG and BA occur alternately in the linear unit L and n is an integer between 1 and 100, in particular between 10 and 50, MA is linked to 3 to 6, particularly 3 to 4, more particularly 3, linear units L, respectively, MA and L being linked such that MA is bonded to a cationic group CG; A linear unit L is bonded to two multifunctional units MA or to one multifunctional unit MA and one terminal unit E.

[0106] In some embodiments, the neutral group NG is independently selected from the moieties of formula 1'', 1'''', or 4''.

[0107] [ka]

[0108] (however, R 1 is a fully or partially fluorinated C 1~6 -Alkyl, especially fully or partially fluorinated C 1~4 -alkyl, more particularly -CF 3 and R 12 , H, C 1~6 -Alkyl, phenyl, C 3~10 -Cycloalkyl, especially C 1~4 -alkyl, x is an integer between 0 and 12, particularly between 0 and 8, and more particularly between 6 and 8.

[0109] In some embodiments, R 12 , H, C 1~4 -Alkyl, especially -CH 3 It is.

[0110] In some embodiments, R 12 is H.

[0111] The precursor containing the neutral group according to formula 4′ is R 12 and R 13 are linked together to form a cycloalkyl containing 4 to 10 C atoms. To achieve such a ring, the neutral group R according to formula 4' is12 must be H. Depending on the pH, the neutral group may be protonated. Reaction with an alkyl dibromide results in ring formation (see Scheme 1).

[0112] [ka]

[0113] Scheme 1: 4-Piperidone is converted to a ketone to give a neutral group, which is then reacted with an alkyl dibromide to form a cationic group containing an additional 6-membered ring (upper pathway) or 5-membered ring (lower pathway). (See also J. Mater. Chem. A, 2018, 6, 16537.)

[0114] In particular, with regard to the definitions of MA and BA, as well as the branch points and the configuration of the polymer chain, reference is made to the examples of the first aspect of the present invention.

[0115] A third aspect of the present invention is containing, in particular consisting of, 2 to 6, more in particular 2 to 4, cyclic hydrocarbon moieties, unsubstituted or 1~20 -Alkyl, especially C 1~6 at least one polyfunctional aromatic moiety MA, optionally substituted with one or more substituents independently selected from -alkyl; a ketone independently selected from the moieties of formula 1k or 4k;

[0116] [ka]

[0117] (however, R 1 is a fully or partially fluorinated C 1~6 -Alkyl, especially fully or partially fluorinated C 1~4 -alkyl, more particularly -CF 3 and D is a leaving group, in particular a leaving group selected from -I, -Br, -Cl and -OH; y is 0 or 1; x is an integer between 0 and 12, in particular between 0 and 8, more in particular between 6 and 8; z is 0 or 1, particularly 1. Independently selected from moieties containing 2 to 5, particularly 2 to 3, cyclic hydrocarbon moieties, unsubstituted or 1~10 -Alkyl, -OC 1~10 -Alkyl, fully or partially fluorinated C 1~10 a difunctional aromatic moiety BA, optionally substituted with one or more substituents independently selected from -alkyl, The pH of the reaction mixture is less than 1, with respect to the precursor obtained by reaction of the reaction mixture.

[0118] The polymerization reaction is catalyzed by a strong acid, so the reaction is carried out under acidic conditions, particularly at pH<1. During the polymerization, the cyclic moiety of BA or MA, particularly the active CH moiety of the benzene ring, reacts with the ketone moiety of the ketone according to formula 1k or 4k. The precursor is then purified. After the polymerization and purification process, a neutral precursor is obtained.

[0119] The specific formulas of MA and BA shown in the first aspect of the invention show a bond to an adjacent moiety. In the first aspect of the invention, MA and BA are referred to as monomers in the polymer. In relation to the third aspect, the moieties MA and BA are used as educts and the bond shows a bond to an H atom rather than a bond to an adjacent moiety. During the polymerization reaction, the bond between the two adjacent moieties is formed at this position.

[0120] For example, the moiety BA of formula 3 according to the first aspect of the invention is bonded to two adjacent moieties, such as two cationic groups CG. In the context of the third aspect, it is bonded to two H atoms. Similar considerations apply to other formulae relating to BA and MA.

[0121] [ka]

[0122] The polymerization reaction can be quenched by adding a solvent to the reaction mixture or by pouring the reaction mixture into a solvent. Suitable solvents are known to those skilled in the art. For example, water or methanol can be used in the quenching step.

[0123] In some embodiments, the reaction according to the third aspect of the invention is followed by a quenching step.

[0124] In some embodiments, an alcohol, particularly methanol, or water is used in the quenching step.

[0125] In some embodiments, the reaction according to the third aspect of the invention is followed by a purification step.

[0126] In some embodiments, an alkaline solution, particularly KOH, more particularly 1M KOH, or water is used in the purification step.

[0127] In some embodiments, water is used in the purification step.

[0128] In some embodiments, an alkaline solution is used in the purification step, particularly KOH, more particularly 1M KOH.

[0129] In some embodiments, the purification step is carried out repeatedly.

[0130] In some embodiments, a purification step is performed after the quenching step.

[0131] The branching degree of the precursor / polycyclic aromatic hydrocarbon polymer is adjusted by selecting the appropriate molar ratio between BA, ketone, and MA.

[0132] In some embodiments, the ratio of the sum of the molar amounts of BA and MA to the molar amount of ketone is between 0.8 and 1.2, in particular 1:1, and / or the ratio of the molar amount of BA to the molar amount of ketone is between 50:100 and 100:100, in particular between 95:100 and 99.5:100, and / or The ratio of the molar amount of MA to the sum of the molar amounts of ketone and BA is between 0.1:100 and 50:100, in particular between 0.5:100 and 5:100, more in particular 1:100.

[0133] In some embodiments, the ratio of the sum of the molar amounts of BA and MA to the sum of the molar amount of ketone is between 0.8 and 1.2.

[0134] In some embodiments, the ratio of the sum of the molar amounts of BA and MA to the sum of the molar amount of ketone is about 1:1.

[0135] In some embodiments, the ratio of the sum of the molar amounts of BA and MA to the sum of the molar amount of ketone is 1:1.

[0136] In some embodiments, the ratio of the molar amount of BA to the molar amount of ketone is between 50:100 and 100:100, particularly between 95:100 and 99.5:100.

[0137] In some embodiments, the ratio of the molar amount of BA to the molar amount of ketone is between 95:100 and 99:100.

[0138] In some embodiments, the ratio of the molar amount of MA to the sum of the molar amounts of ketone and BA is between 0.1:100 and 50:100, particularly between 0.5:100 and 5:100, and more particularly 1:100.

[0139] The polymerization reaction is carried out in a suitable solvent, which will be known to those skilled in the art.

[0140] In some examples, the reaction is carried out in a suitable solvent.

[0141] In some embodiments, the reaction is carried out in dichloromethane, ethylene dichloride or benzene, particularly dichloromethane.

[0142] MA, BA and the ketone are first dissolved in the above solvent, and then the reaction is initiated by lowering the pH to pH<1.

[0143] In some embodiments, MA, BA and the ketone are provided in a suitable solvent, particularly dichloromethane, ethylene dichloride or benzene, more particularly dichloromethane.

[0144] In some embodiments, the pH is adjusted to <1 using TFA and / or TFSA.

[0145] The amount of TFA or TFSA required will vary depending on the temperature and reaction time. The pH is adjusted by standard methods known to those skilled in the art. For example, the pH can be measured and TFA or TFSA can be added until the desired pH is reached.

[0146] In particular with regard to the definitions of MA and BA, as well as the branching points and the configuration of the polymer chain, reference is made to the examples of the first and second aspects of the invention. As mentioned above, the bonds of MA or BA which in the context of the first aspect of the invention indicate a bond to an adjacent moiety (MA and BA being part of a polymer) in the context of the third aspect of the invention indicate a bond to an H atom (MA and BA being educts to form said polymer).

[0147] A fourth aspect of the present invention is A precursor according to the second or third aspect of the present invention; HaroC 1~12 -Alkyl, halophenyl or haloC 3~10 -cycloalkyl, or N(R 2 ) 3 , P(R 2 ) 3 (R 2 has the same meaning as above.) or and a reactant selected from piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl or imidazolidinyl.

[0148] For use in AEMs, the polymer needs to be ionic to allow for the transport of anions. Therefore, the neutral precursors are amines or CH 3 The ionic polymers are obtained by reacting the neutral precursor polymer with an appropriate reactant such as I. The reaction is very simple as it only requires mixing the neutral precursor polymer with the reactant in an appropriate solvent such as dimethylsulfoxide for 24 hours.

[0149] HaroC 1~12 -Alkyl, halophenyl or haloC 3~10 -cycloalkyls may be used when NG is a moiety of formula 4', using a ketone of formula 4k to prepare a neutral precursor. In that case, a polymer containing a cationic group CG according to formula 4 is obtained. As mentioned above, alkyls containing two halogens, especially bromine, are used to obtain cationic groups, and R 12 and R 13 are linked to form a cycloalkyl (see Scheme 1).

[0150] N(R 2 ) 3 Or P(R 2 ) 3 can be used when NG is a moiety of formula 1′, i.e. when a neutral precursor was prepared using a ketone of formula 1k, in which case a polymer containing a cationic group CG according to formula 1, in particular according to formula 1a or 1c, is obtained.

[0151] Piperidyl, pyrrolidinyl, imidazolyl, pyrazolyl or imidazolidinyl may be used when NG is a moiety of formula 1', i.e. when a neutral precursor is prepared using a ketone of formula 1k, in which case a polymer containing a cationic group CG according to formula 1, in particular according to formula 1b or 1d, is obtained.

[0152] For neutral groups or ketones, the reactants are used in excess to obtain high yields of the cationic polycyclic aromatic hydrocarbon polymer.

[0153] In some embodiments, the ratio of the molar amount of reactant to the molar amount of neutral group NG or the molar amount of ketone is from 1:1 to 3:1, particularly from 1.5:1 to 3:1, more particularly 3:1.

[0154] To further increase the yield, a base may be added to the reaction mixture, with either the neutral group or the ketone being used in excess to further increase the yield of the cationic polycyclic aromatic hydrocarbon polymer.

[0155] In some embodiments, KOH, K 2 CO 3 , Na 2 CO 3 , NaHCO 3 , K.H.C.O. 3 , CaCO 3 and CaHCO 3 An alkali selected from is added to the reaction mixture.

[0156] In some embodiments, the ratio of the molar amount of alkali to the molar amount of neutral group or ketone is from 1.5:1 to 3:1, more specifically 2:1.

[0157] The above reaction is carried out in a suitable solvent.

[0158] In some embodiments, the precursors and reactants according to the second or third aspect of the invention are dissolved in dimethylsulfoxide, DMSO, DMF, NMP, THF, toluene, ethyl acetate, acetone.

[0159] In particular with regard to the definitions of MA and BA, as well as the branch points and configuration of the polymer chain, reference is made to the examples of the first, second and third aspects of the present invention.

[0160] A fifth aspect of the present invention relates to an anion exchange membrane comprising a polycyclic aromatic hydrocarbon polymer according to the first or fourth aspect of the present invention and a suitable counterion.

[0161] The anion exchange membranes according to the invention are ether-free and therefore highly durable. The branched structure also results in low water absorption and swelling, and improved mechanical properties. The aryl ether-free polycyclic aromatic hydrocarbons according to the invention are characterized by a branched structure in which pendant quaternary ammonium or piperidinium cations are linked to a polyaryl backbone that does not contain aryl ether moieties. Anion exchange membranes made with these polymers exhibit high hydroxide conductivity, low water absorption and dimensional swelling, good mechanical properties, and excellent membrane casting properties.

[0162] In particular, long chain branching can increase the strength, toughness, and glass transition temperature (Tg) of the polymer due to an increased number of entanglements per chain. AEMs made with such polymers exhibit high electrical conductivity, low water absorption and dimensional expansion, ease of castability, and good mechanical properties. In particular, the AEMs according to the present invention have a tensile strength of at least 10 MPa and an elongation at break of at least 5%.

[0163] The cationic groups in the polymer allow for the transport of anions between the anode and cathode of an electrochemical device. Non-limiting examples of anions include OH - , CO 3 2 -,Br - , or Cl - Examples include:

[0164] In some embodiments, the counterion is OH - , Cl - , Br - , I - , CO 3 2 -, HCO 3 - , T.F.A. - (CF 3 CO 2 - ), TFSA-(CF 3 SO 3 - ), B.F. 4 - , P.F. 6 -, and more particularly OH - and Cl - is selected from.

[0165] In some embodiments, the anion exchange membrane is obtained using the polycyclic aromatic hydrocarbon polymer of the first or fourth aspect of the present invention.

[0166] In some embodiments, the anion exchange membrane is characterized by a water absorption of ≦100%, particularly ≦96%, at 40° C., and / or a water absorption of ≦300%, particularly ≦110%, at 80° C., where the water absorption is determined by the OH - is converted to the dry mass of the anion exchange membrane with the counter ion.

[0167] In some embodiments, the anion exchange membrane is characterized by a water absorption of 1% to 100%, particularly 65% ​​to 96%, at 40° C., and / or a water absorption of 5% to 300%, particularly 75% to 110%, at 80° C., where the water absorption is determined by the OH - is converted to the dry mass of the anion exchange membrane with the counter ion. In some embodiments, the anion exchange membrane is characterized by a swelling ratio of ≦50%, particularly ≦35%, at 40° C. and / or a swelling ratio of ≦200%, particularly ≦35%, at 80° C., where the swelling ratio is determined by the addition of OH - is converted to the dry mass of the anion exchange membrane with the counter ion.

[0168] In some embodiments, the anion exchange membrane is characterized by a swelling ratio of 1% to 50%, particularly 20% to 35%, at 40° C., and / or a swelling ratio of 1% to 200%, particularly 25% to 35%, at 40° C., where the swelling ratio is determined by the addition of OH - is converted to the dry mass of the anion exchange membrane with the counter ion.

[0169] In some embodiments, the anion exchange membrane is characterized by an ion exchange capacity between 1.5 mmol / g and 4 mmol / g, in particular between 2.75 mmol / g and 2.9 mmol / g.

[0170] In some embodiments, the anion exchange membrane has an OH concentration between 50 mS / cm and 120 mS / cm, particularly between 81 and 90 mS / cm at 40° C.- Conductivity and / or OH between 80mS / cm and 250mS / cm, especially between 135mS / cm and 150mS / cm at 80°C - Characterized by electrical conductivity.

[0171] In some embodiments, the polycyclic aromatic hydrocarbon polymer according to the first or fourth aspect of the present invention, the precursor according to the second or third aspect of the present invention, or the anion exchange membrane according to the fifth aspect of the present invention does not comprise an aryl ether. In particular, reference is made to the first, second, third and fourth embodiment examples of the present invention with regard to the definitions of MA and BA, as well as the branch points and the configuration of the polymer chain.

[0172] The invention is further illustrated by the following examples and figures from which further embodiments and advantages can be derived, these examples being intended to illustrate the invention without limiting its scope.

[0173] [Example] Example 1: Preparation of polymer and membrane A series of aryl ether-free polycyclic aromatic hydrocarbons with branched structures (see examples shown in Figure 1) were prepared. The polycyclic aromatic hydrocarbons contain a polyfunctional aromatic moiety MA, a bifunctional aromatic moiety BA, and a cationic group CG. The branching degree is between 3 and 20.

[0174] The preparation of aryl ether-free polycyclic aromatic hydrocarbons with branched structures is shown in Figure 2. Difunctional aromatic hydrocarbons, polyfunctional aromatic hydrocarbons, and ketones were dissolved in dichloromethane. Trifluoromethanesulfonic acid (TFSA) was added to form the ether-free polycyclic aromatic hydrocarbon precursor. The polycyclic aromatic hydrocarbon precursor and trialkylamine (NR 3 ) or haloalkanes to give branched polycyclic aromatic hydrocarbons bearing cationic groups.

[0175] In FIG. 2, the difunctional aromatic compound is selected from FIG.

[0176] In FIG. 2, the polyfunctional aromatic compound is selected from FIG.

[0177] In FIG. 2, the ketone compound is selected from FIG. 5, where n is 1 to 20 and R is H or alkyl. After reaction with an amine or haloalkane, the cationic group (CG) of the aryl ether-free polycyclic aromatic hydrocarbon will be one of the groups listed in Figure 6, where n is 1-20 and R1, R2, R3, R4, and R5 are alkyl.

[0178] An example of an aryl ether-free polycyclic aromatic hydrocarbon having a branched structure is shown in FIG.

[0179] [Polymer production] p-Terphenyl (1 equivalent), 1,3,5-triphenylbenzene, and 1-methyl-4-piperidone (1 equivalent) were dissolved in dichloromethane. Different equivalents of 1,3,5-triphenylbenzene were used as follows: the polymer obtained using 0.01 equivalent of 1,3,5-triphenylbenzene is designated as b-PTP-1; the polymer obtained using 0.025 equivalent of 1,3,5-triphenylbenzene is designated as b-PTP-2.5; the polymer obtained using 0.05 equivalent of 1,3,5-triphenylbenzene is designated as b-PTP-5. PTP refers to linear polymers without 1,3,5-triphenylbenzene.

[0180] The solution was stirred at 0°C. Trifluoroacetic acid (1.5 equiv.) and trifluoromethanesulfonic acid (10 equiv.) were added. After 6 h, the solution became viscous and was stirred for another hour. The resulting deep blue gel was slowly poured into excess water to form white fibers. The fibers were further washed three times with 1 M KOH solution and water. After drying overnight at 120°C under vacuum, branched poly(terphenyl-triphenylbenzene-piperidine) (92% yield) was obtained. Figure 8(a) shows the structure of branched poly(terphenyl-triphenylbenzenepiperidine) (protonated by TFA). 1The H spectrum is shown. Branched poly(terphenyl-triphenylbenzene-piperidine) was suspended in dimethyl sulfoxide. 3 I (3 equivalents per piperidone group) and K 2 CO 3 (2 equivalents relative to the piperidone group) was added. The solution was stirred at room temperature in the dark for 1 day. The resulting viscous solution was precipitated from dichloromethane, washed twice with water, and dried completely under vacuum at 80 °C. The yield of branched poly(terphenyl-triphenylbenzene-piperidinium) was about 100%. Figure 8(b) shows the structure of branched poly(terphenyl-triphenylbenzene-piperidinium). 1 H spectrum is shown.

[0181] [Membrane production] The polymer was dissolved in dimethylsulfoxide, filtered through a 0.45 μm PTFE filter, and cast onto a glass plate. AEM (iodide form) was peeled off from the glass plate in contact with deionized water. Ion-exchanged in 1M KCl solution at 80° C. gave AEM in chloride ion form. Ion-exchanged in 1M KOH solution at 80° C. gave AEM in hydroxide form. AEM is designated b-PTP-x, where x is the percentage of triphenylbenzene to p-terphenyl.

[0182] Figure 9 shows the stress-strain curves of PTP and b-PTP-x at ambient conditions. In comparison, PTP is an AEM with a linear structure and has a stress of 48 MPa and a breaking strain of 17% at 50% RH and room temperature. b-PTP-2.5 has a branched structure and has a stress of 58 MPa and a breaking strain of 14%. Table 1 shows the ion exchange capacity (IEC), water absorption rate, swelling rate, and OH of PTP and b-PTP-x. - b-PTP-2.5 has a high OH group compared to other reported aromatic AEMs (e.g., quaternized poly(phenylene oxide), poly(arylene ether ketone), and poly(arylene ether sulfone)). -The electrical conductivity of the material increases with temperature because ions move faster and the diffusion rate increases with increasing temperature. b-PTP-2.5 has the same IEC and OH groups as PTP. - It has electrical conductivity but lower water absorption and swelling rates. These advantages can be beneficial for constructing membrane electrode assemblies (MEAs) in AEM fuel cells / water electrolyzers.

[0183] [Table 1]

[0184] FIG. 10 shows the residual OH of b-PTP-2.5 after treatment in 1M or 3M KOH at 80° C. - Conductivity is shown in Figure 1. b-PTP-2.5 showed little loss of conductivity over 1500 hours at 80°C in 1M KOH, demonstrating the excellent ex-situ durability of our AEM. A 20% decrease in conductivity was observed over 1500 hours in 3M KOH.

[0185] [Example 2: Comparison with known polymers] The polymers according to the invention are characterized by high molecular weight as measured by intrinsic viscosity. A comparison with known polymers is shown in Table 2. The polymers according to the invention have higher intrinsic viscosity than other polymers, indicating higher molecular weight. Improved mechanical properties are associated with higher molecular weight.

[0186] [Table 2]

[0187] b-PTP-2.5: branched poly(terphenylpiperidinium), where X is the molar ratio (percent) of 1,3,5-triphenylbenzene to total aryl monomers.

[0188] [References] Chen N, Wang H H, Kim S P, et al. Poly (fluorenyl aryl piperidinium) membranes and ionomers for anion exchange membrane fuel cells[J]. Nature communications, 2021, 12(1): 1-12. Chen N, Hu C, Wang H H, et al. Poly (Alkyl-Terphenyl Piperidinium) Ionomers and Membranes with an Outstanding Alkaline‐Membrane Fuel‐Cell Performance of 2.58 W cm- 2[J]. Angewandte Chemie, 2021, 133(14): 7789-7797. IUPAC recommendations 1997. “Source-based nomenclature for non-linear macromolecules and macromolecular assemblies”. Pure & Appl. Chem. Vol. 69, No. 12, pp. 2511-2521, 1997 Lee, W. H.; Kim, Y. S.; Bae, C., Robust hydroxide ion conducting poly (biphenyl alkylene)s for alkaline fuel cell membranes. ACS Macro Letters 2015, 4 (8), 814-818. Lee W H, Mohanty A D, Bae C. Fluorene-based hydroxide ion conducting polymers for chemically stable anion exchange membrane fuel cells[J]. ACS Macro Letters, 2015, 4(4): 453-457. Olsson, J. S.; Pham, T. H.; Jannasch, P., Poly (arylene piperidinium) hydroxide ion exchange membranes: synthesis, alkaline stability, and conductivity. Advanced Functional Materials 2018, 28 (2), 1702758. Thanh Huong Pham, Joel S. Olsson and Patric Jannasch. Poly(arylene alkylene)s with pendant N-spirocyclic quaternary ammonium cations for anion exchange membranes. J. Mater. Chem. A, 2018, 6, 16537 Wang J, Zhao Y, Setzler B P, et al. Poly (aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells[J]. Nature Energy, 2019, 4(5): 392-398. Zhang F, Li T, Chen W, et al. Highly stable electron-withdrawing C=O link-free backbone with branched cationic side chain as anion exchange membrane[J]. Journal of Membrane Science, 2021, 624: 119052.

Claims

1. Contains 2 to 6 cyclic hydrocarbon moieties, unsubstituted or C １～２０ at least one polyfunctional aromatic moiety MA optionally substituted with one or more substituents independently selected from -alkyl; a cationic group CG independently selected from the moieties of formula 1 or 4; 【Chemical 1】 (however, R １ is a fully or partially fluorinated C １～６ - alkyl, R １２ and R １３ are each independently H, C １～１２ - alkyl, phenyl, and C ３～１０ -cycloalkyl, or R １２ and R １３ are linked together to form a cycloalkyl containing 4 to 10 C atoms, D is -N ＋ (R ２ ) ３ , -P ＋ (R ２ ) ４ or piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, imidazolidinyl cations, wherein the piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl or imidazolidinyl cations are unsubstituted or C １～１２ -substituted with one or more substituents independently selected from alkyl, phenyl; R ２ are each independently H, C １～１２ any other R selected from alkyl, phenyl ２ and y is 0 or 1; x is an integer between 0 and 12; z is 0 or 1. independently selected from moieties containing 2 to 5 cyclic hydrocarbon moieties, unsubstituted or C １～１０ -alkyl, -O-C １～１０ -Alkyl, fully or partially fluorinated C １～１０ a difunctional aromatic moiety BA optionally substituted with one or more substituents independently selected from -alkyl, one or more CGs and one or more BAs form a linear unit L; MA is a polycyclic aromatic hydrocarbon polymer linked to 3 to 6 linear units L.

2. 2. The polycyclic aromatic hydrocarbon polymer according to claim 1, wherein the cyclic hydrocarbon moieties of BA and MA are not linked by —O—.

3. The cyclic hydrocarbon moieties of BA and MA are single bond, one or more covalent bonds (fused rings), Covalent bonding of a single atom (spirocycle), and / or Alkyl The polycyclic aromatic hydrocarbon polymer of claim 2, wherein the polycyclic aromatic hydrocarbon polymer is linked by

4. 2. The polycyclic aromatic hydrocarbon polymer according to claim 1, wherein BA and CG alternate within the linear unit L.

5. 2. The polycyclic aromatic hydrocarbon polymer of claim 1, wherein the polyfunctional aromatic moieties MA are independently selected from 1,3,5-triphenylbenzene, naphthalene, biphenylene, 1H-phenalene, anthracene, phenanthrene, 1,6-dihydropyrene, 10b,10c-dihydropyrene, pyrene, and 9,9'-spirobi[fluorene].

6. 2. The polycyclic aromatic hydrocarbon polymer of claim 1, wherein the polyfunctional aromatic moieties MA are independently selected from the following: 【Chemistry 2】 (however, (L) or (Lm) represents a bond to the linear unit L; Each m is independently selected from 0, 1, and 2, and the sum of all m's is 3, 4, 5, or 6.

7. 2. The polycyclic aromatic hydrocarbon polymer of claim 1, wherein the polyfunctional aromatic moieties MA are independently selected from the following: 【Chemistry 3】

8. Each difunctional aromatic moiety BA is independently selected from a moiety of formula 2 or 3: 【Chemistry 4】 (however, R ３ , R ４ , R ５ , and R ６ are each independently H, F, or C １～６ -Alkyl, partially or fully fluorinated C １～６ - alkyl, R ７ and R ８ are each independently H, F, or C １～６ -Alkyl, partially or fully fluorinated C １～６ - alkyl, s and t are each independently selected from integers between 0 and 4; r is an integer between 0 and 3. The polycyclic aromatic hydrocarbon polymer according to claim 1 .

9. The difunctional aromatic moieties BA are each independently selected from moieties of formula 2a, 2b, or 3: 【Chemistry 5】 (however, R 3 , R 4 , R 5 and R 6 are each independently selected from H, F, C 1-6 -alkyl, partially or fully fluorinated C 1-6 -alkyl; R 7 and R 8 are each independently selected from H, F, C 1-6 -alkyl, partially or fully fluorinated C 1-6 -alkyl; s and t are each independently selected from integers between 0 and 4; r is an integer between 0 and 3. The polycyclic aromatic hydrocarbon polymer according to claim 1 .

10. 2. The polycyclic aromatic hydrocarbon polymer of claim 1, wherein each difunctional aromatic moiety BA is independently selected from the following: 【Chemistry 6】

11. 2. The polycyclic aromatic hydrocarbon polymer of claim 1, wherein the cationic group CG is selected from the moieties of formula 1a, 1b, 1c, 1d, or 4: 【Chemistry 7】 (however, R １ is a fully or partially fluorinated C １～６ - alkyl, R ９ , R １０ , R １１ , R １４ , R １５ , and R １６ are each independently H, C １～６ - selected from alkyl, phenyl, R １２ and R １３ are each independently H, C １～６ - alkyl, phenyl, C ３～１０ -cycloalkyl, or R １２ and R １３ are linked together to form a cycloalkyl containing 4 to 10 C atoms, R １７ and R １８ are independently １～６ - alkyl, p and q are integers between 0 and 3; R １９ and R ２０ are independently H and C １～６ - alkyl, x is an integer between 0 and 12; z is 0 or 1.

12. R １ is CF ３ 2. The polycyclic aromatic hydrocarbon polymer according to claim 1, wherein

13. Contains 2 to 6 cyclic hydrocarbon moieties, unsubstituted or C １～２０ at least one polyfunctional aromatic moiety MA optionally substituted with one or more substituents independently selected from -alkyl; a neutral group NG independently selected from the moieties of formula 1' or 4'; 【Chemistry 8】 (however, R １ is a fully or partially fluorinated C １～６ - alkyl, R １２ is H, C １～１２ - alkyl, phenyl, C ３～１０ -cycloalkyl, D is a leaving group, y is 0 or 1; x is an integer between 0 and 12; z is 0 or 1. independently selected from moieties containing 2 to 5 cyclic hydrocarbon moieties, unsubstituted or C １～１０ -alkyl, -O-C １～１０ -Alkyl, fully or partially fluorinated C １～１０ a difunctional aromatic moiety BA optionally substituted with one or more substituents independently selected from -alkyl, one or more NG and one or more BA form a linear unit L, MA is a precursor linked to 3-6 linear units L.

14. The precursor of claim 13, wherein R 1 is CF 3 .

15. 14. The precursor of claim 13, wherein the neutral groups NG are independently selected from the moieties of formula 1'', 1''', or 4''. 【Chemistry 9】 (however, R １ is a fully or partially fluorinated C １～６ - alkyl, R １２ is H, C １～６ - alkyl, phenyl, C ３～１０ -cycloalkyl, x is an integer between 0 and 12.

16. A precursor obtained by reaction of the reaction mixture, Contains 2 to 6 cyclic hydrocarbon moieties, MA is unsubstituted or C １～２０ at least one polyfunctional aromatic moiety MA optionally substituted with one or more substituents independently selected from -alkyl; a ketone independently selected from the moieties of formula 1k or 4k; 【Chemistry 10】 (however, R １ is a fully or partially fluorinated C １～６ - alkyl, D is a leaving group, R １２ is H, C １～１２ - alkyl, phenyl, C ３～１０ -cycloalkyl, y is 0 or 1; x is an integer between 0 and 12; z is 0 or 1. independently selected from moieties containing 2 to 5 cyclic hydrocarbon moieties, unsubstituted or C １～１０ -alkyl, -O-C １～１０ -Alkyl, fully or partially fluorinated C １～１０ a difunctional aromatic moiety BA optionally substituted with one or more substituents independently selected from -alkyl, The pH of the reaction mixture is less than 1.

17. the ratio of the sum of the molar amounts of BA and MA to the molar amount of ketone is between 0.8 and 1.2; and / or the ratio of the molar amount of BA to the molar amount of ketone is between 50:100 and 100:100; and / or 17. The precursor according to claim 16, wherein the ratio of the molar amount of MA to the sum of the molar amounts of the ketone and BA is between 0.1:100 and 50:

100.

18. A polycyclic aromatic hydrocarbon polymer obtained by reacting a reaction mixture, A precursor according to claim 13; Haro C １～１２ - alkyl, halophenyl or haloC ３～１０ -cycloalkyl, or N (R ２ ) ３ , P(R ２ ) ３ (R ２ is the same as above.) or and a reactant selected from piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, or imidazolidinyl.

19. 19. The polycyclic aromatic hydrocarbon polymer according to claim 18, wherein the ratio of the molar amount of the reactant to the molar amount of the neutral group NG or the molar amount of the ketone is 1:1 to 3:

1.

20. 20. An anion exchange membrane comprising the polycyclic aromatic hydrocarbon polymer according to any one of claims 1 to 12 or 18 to 19 and a suitable counterion.

21. OH － , Cl － ,Br － , I － , CO ３ ２ -, HCO ３ － , T.F.A. － (CF ３ CO ２ － ), TFSA － (CF ３ SO ３ － ), B.F. ４ － , P.F. ６ 20. The polycyclic aromatic hydrocarbon polymer according to any one of claims 1 to 12 or 18 to 19, which comprises one or more counter ions selected from:

22. The anion exchange membrane described in claim 20, wherein the counter ion is selected from OH -, Cl -, Br -, I -, CO 3 2-, HCO 3 -, TFA - (CF 3 CO 2 -), TFSA - (CF 3 SO 3 -), BF 4 -, and PF 6 -.

Images