WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 201 a 9/,h05kh0a9t

11— 75k

CARBAZOLIUM SALT AND USE THEREOF IN ANION EXCHANGE

MEMBRANES

CROSS REFERENCE TO RELATED APPLICATIONS

[001] This application claims the benefit of priority from U.S. Provisional Patent

Application No. 62/724,710, filed on August 30, 2018, entitled“USE OF CARBAZOLIUM

SALTS IN ANION-EXCHANGE MEMBRANES”, the contents of which are incorporated

by reference herein in their entirety.

FIELD OF THE INVENTION

[002] The invention relates inter alia to compositions comprising quaternary aryl

ammonium salts, articles comprising the same and methods for preparation thereof.

BACKGROUND

[003] Anion-exchange membranes with long lifetimes are key parts in electrochemical

devices, such as alkaline fuel cells, alkaline water electrolyzers, alkaline redox-flow

batteries, metal-air batteries, among others. Several materials have been previously

developed, and yet, few membranes show long-term performance upon activation of the

device.

[004] Anion-exchange membranes possess cationic groups either as pendent sidechains

or as part of the main chain. Independently of their positioning, these organic cations are

prone to nucleophilic and/or base attack by hydroxide ions, which neutralize the cations and

extinguish their anion-exchange and anion conducting capacity. Given that typical

degradation mechanisms are SN2 type or E2 type, the use of tetraaryl ammonium salts can

inhibit these pathways, leading to more kinetically stable cations which may decompose via

alternative mechanisms such as SNAr and benzyne.

[005] Known synthetic routes to tetraaryl ammonium salts are tedious, requiring

numerous synthetic steps, thus being inefficient and expensive. Therefore, there is a need WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

for optimization of the known synthetic procedures, allowing an efficient synthesis of

tetraaryl ammonium salts and numerous conjugates comprising the same.

[006] The foregoing examples of the related art and limitations related therewith are

intended to be illustrative and not exclusive. Other limitations of the related art will become

apparent to those of skill in the art upon a reading of the specification and a study of the

figures.

SUMMARY

[007] The following embodiments and aspects thereof are described and illustrated in

conjunction with systems, tools and methods which are meant to be exemplary and

illustrative, not limiting in scope.

[008] In one aspect of the invention, there is a composition comprising a tetraaryl

ammonium salt represented by Formula I:

wherein:

each X independently comprises an aryl ring;

each B represents independently a bond, or is absent;

and A- is a counter anion, and if at least one B is a bond then at least one X is selected

from the group consisting of: a substituted aryl ring, a heteroaryl ring, a substituted

heteroaryl ring or any combination thereof.

[009] In one embodiment, the tetraaryl ammonium salt is represented by Formula II: WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 a ha

11—2019/,h05k09t75k wherein Rl, R2, R3, R4 and R5 are each independently selected from the group

consisting of: hydrogen, an alkyl group, an alkoxy group, a halo group, a perfluoroalkyl

group, a perfluoroalkoxy group, a heteroalkyl group, an aryl group, a hydroxy group, an

amino group, an aminoalkyl group, a guanidine group, a thioalkoxy group, a mercapto

group, a cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo group,

a sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a thioalkyl

group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a sulfone

group or any combination thereof; and A- is a counter anion.

[0010] In one embodiment, the tetraaryl ammonium salt is represented by Formula III:

[0011] wherein each R represents a substituent independently selected from the group

consisting of: a halo group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy

group, a heteroalkyl group, an aryl group, a hydroxy group, a mercapto group, an amino

group, an aminoalkyl group, a guanidine group, a thioalkoxy group, a cyano group, a

haloalkyl group, an arylalkyl group, a nitro group, an azo group, a sulfonate group, a sulfinyl

group, a vinyl group, an allyl group, an alkyne, a thioalkyl group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a sulfone group or is absent, and A- is a counter anion; and wherein said tetraaryl ammonium comprises at least one substituent.

[0012] In one embodiment, the tetraaryl ammonium salt is represented by Formula IV:

[0013] wherein each R represents a substituent independently selected from the group consisting of: a halo group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a heteroalkyl group, an aryl group, a hydroxy group, a mercapto group, an amino group, an aminoalkyl group, a guanidine group, a thioalkoxy group, a cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo group, a sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a thioalkyl group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a sulfone group or any combination thereof, and A- is a counter anion; and wherein said tetraaryl ammonium comprises at least one substituent.

[0014] In another aspect of the invention, there is a composition comprising a tetraaryl ammonium salt covalently bound to a polymer.

[0015] In one embodiment, the tetraaryl ammonium salt is represented by Formula I:

WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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wherein:

each X independently comprises an aryl ring;

each B represents independently a bond, or is absent;

and A is a counter anion.

[0016] In one embodiment, the tetraaryl ammonium salt is covalently bound to a polymer

backbone, to a polymer sidechain, or both.

[0017] In one embodiment, the polymer comprises any one of: polycarbonate, polyurea,

polyurethane, vinyl polymers, polyalkyl, polybutadiene, polyamide, PEG, polypropylene

glycol, poly(tetrahydrofuran), polyacrylonitrile (PAN), poly isobutene, polyisoprene,

polychloroprene, polystyrene (PS), polystyrene-coisoprene, poly(vinyl chloride) (PVC),

polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinyl cyclohexane,

poly(vinyl acetate) (PVA), methylated cellulose, polyvinylidene difluoride (PVDF),

polyphenylene oxide (PPE), polysulfone or any combination thereof.

[0018] In one embodiment, a molar ratio of the polymer to the tetraaryl ammonium salt

within said composition is in a range from 1:0.1 to 1:5.

[0019] In one embodiment, the composition substantially maintains its chemical identity

at a pH ranging from 1 to 14.

[0020] In another aspect of the invention there is a method for synthesizing the tetraaryl

ammonium salt of the invention, comprising the steps of:

a. providing a biaryl compound comprising (i) a diazonium salt; (ii) a triaryl amine,

wherein said (i) and (ii) are in a position suitable for intramolecular cyclization;

b. performing an intramolecular cyclization under suitable conditions,

thereby obtaining the tetraaryl ammonium salt.

[0021] In one embodiment, the method further comprises the steps of:

a. providing a diaminobiaryl compound;

b. arylating at least one amino group of the diaminobiaryl compound to obtain a triaryl

amine; WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 h

11—201 a 9/,05kh0a9t75k

c. diazotizing a free amino group by reacting the triaryl amine with a diazotation

compound, to obtain a diazonium salt, thereby obtaining the biaryl compound

comprising the diazonium salt and the triaryl amine.

[0022] In one embodiment, the position suitable for intramolecular cyclization is a 2,2’

position.

[0023] In one embodiment, arylating comprises reacting the diaminobiaryl compound

with an aryl comprising a leaving group, optionally in the presence of a metal-based catalyst.

[0024] In one embodiment, the leaving group comprises any one of: a halo group, a nitro

group, an azo group, a quaternary amino group.

[0025] In one embodiment, the metal-based catalyst is a Cu(I) based catalyst, further

comprising a bidentate ligand.

[0026] In one embodiment, a molar ratio of the diaminobiaryl compound to the metal- based catalyst is at least 1:0.01.

[0027] In one embodiment, a molar ratio of the diaminobiaryl compound to the aryl

comprising the leaving group is at least 1: 1.

[0028] In one embodiment, the diazotation compound comprises a source of nitroso

compound (Nº0+).

[0029] In one embodiment, the suitable conditions comprise a temperature in a range

selected from 20 to l00°C.

[0030] In one embodiment, the suitable conditions further comprise adding a base.

[0031] In one embodiment, providing further comprises mixing the diaminobiaryl

compound or the biaryl compound with a solvent, thereby forming a solution.

[0032] In one embodiment, the diaminobiaryl compound is at a molar concentration

ranging from 0.01 to 3 mol/L within the solution.

[0033] In another aspect of the invention, there is an article comprising the composition

of the invention. _{n , n /ncnnTC}

ru i / IL201 9/050975

[0034] In one embodiment, the article is for use as an anion exchange membrane, an anion

exchange ionomer, and an anion conducting polymer.

[0035] In one embodiment, the article is in a form of an alkaline fuel cell, an alkaline water

electrolyzer, an alkaline redox-flow battery, a metal-air battery, or a capacitor.

[0036] In addition to the exemplary aspects and embodiments described above, further

aspects and embodiments will become apparent by reference to the figures and by study of

the following detailed description.

BRIEF DESCRIPTION OF THE FIGURES

[0037] Exemplary embodiments are illustrated in referenced figures. Dimensions of

components and features shown in the figures are generally chosen for convenience and

clarity of presentation and are not necessarily shown to scale. The figures are listed below.

[0038] Fig. 1A is a graph showing a decomposition of different carbazoliums using 0.5

mol/L hydroxide in dry DMSO-d6. Hydration level of hydroxide is 4 water

molecules/hydroxide, test carried out at room temperature.

[0039] Fig. 1B is a graph showing a decomposition of N,N-(4-hydroxyphenyl)- carbazolium bromide and benzyltrimethylammonium chloride using 0.5 mol/F hydroxide in

dry DMSO-d6. Hydration level of hydroxide is less than 0.2 water molecules/hydroxide, at

room temperature.

[0040] Fig. 2 shows a synthetic route for the preparation of N,N-ditolyl carbazolium

hexafluorophosphate.

[0041] Fig. 3 shows a synthetic route for the preparation of N,N-(4-hydroxyphenyl)- carbazolium bromide.

[0042] Fig. 4 shows a synthetic route for the preparation of 9,9-spiro bis-carbazolium

hexafluorophosphate.

[0043] Fig. 5 shows a synthetic route for the preparation of polystyrene polymer

comprising carbazolium groups as sidechains by direct grafting. _{n , n /ncnnTC}

ru i / IL201 9/050975

[0044] Fig. 6 shows a synthetic route for preparation of polystyrene polymer comprising

carbazolium groups as sidechains by copolymerization.

[0045] Fig. 7 shows a synthetic route for the preparation of poly(m-terphenylene) polymer

comprising carbazolium groups as sidechains.

[0046] Fig. 7 shows a synthetic route for the preparation of poly(m-terphenylene) polymer

comprising carbazolium groups as sidechains.

[0047] Fig. 8 shows a synthetic route for the preparation of polyethylene copolymer

comprising carbazolium groups as sidechains.

[0048] Fig. 9 shows a synthetic route for the preparation of methacrylate -based copolymer

comprising carbazolium groups as sidechains.

DETAILED DESCRIPTION

[0049] The present invention, in one aspect thereof, is directed to a composition

comprising a substituted tetraaryl ammonium salt. In some embodiments, the present

invention is directed to a composition comprising a tetraaryl ammonium salt covalently

bound to a polymer. In another aspect, the present invention is directed to a method of

synthesizing a tetraaryl ammonium salt, wherein the tetraaryl ammonium salt is optionally

bound to a polymer.

[0050] The present invention is based in part on a surprising finding, that N,N-(4- hydroxyphenyl)-carbazolium salt exhibited a superior chemical stability under alkaline

conditions, as compared to another tetraaryl ammonium salts and to ammonium salts

comprising aliphatic substituents.

Tetraaryl Ammonium salts

[0051] In one aspect of the invention, there is a composition comprising a tetraaryl

ammonium salt being represented by Formula 1 : WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

wherein:

each X independently comprises an aryl ring;

each B represents independently a bond, or is absent;

and A - is a counter anion, and if at least one B is a bond then at least one X is selected

from the group consisting of: a substituted aryl ring, a heteroaryl ring, a substituted

heteroaryl ring or any combination thereof.

[0052] In some embodiments, a substituted aryl ring comprises one or more substituents

selected from the group consisting of: a hydroxy group, an alkoxy group, an amino group,

an aminoalkyl group, a guanidine group, a thioalkoxy group, a mercapto group, a cyano

group, a haloalkyl group, an arylalkyl group, a nitro group, an azo group, a heteroalkyl, a

sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a thioalkyl group,

an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a sulfone group or

any combination thereof.

[0053] In some embodiments, the one or more substituents are selected from the group

consisting of: a hydroxy group, an alkoxy group, an amino group, an aminoalkyl group, a

mercapto group, a cyano group, an azo group, a vinyl group, an allyl group, an alkyne, a

thioalkyl group, an alkylhydroxy group, and a carboxylic acid derivative, or any combination

thereof.

[0054] In some embodiments, the one or more substituents are selected from the group

consisting of: a hydroxy group, an alkoxy group, an amino group, an aminoalkyl group, a

mercapto group, an azo group, a vinyl group, an allyl group, an alkyne, a thioalkyl group,

and an alkylhydroxy group or any combination thereof. _{n , n /ncnnTC}

ru i / IL201 9/050975

[0055] In some embodiments, the one or more substituents are selected from the group

consisting of: a hydroxy group, an alkoxy group, an amino group, an aminoalkyl group, and

an alkylhydroxy group or any combination thereof.

[0056] Non-limiting examples of counter anions include but are not limited to: chloride,

bromide, fluoride, hydroxide, acetate, and hexafluorophosphate (PF ₆ ) or a combination

thereof.

[0057] In some embodiments, the substituted aryl ring comprises an aromatic ring. In

some embodiments, the substituted aryl ring comprises one or more aromatic rings. In some

embodiments, the substituted aryl ring comprises one or more bicyclic aromatic rings.

[0058] In some embodiments, the tetraaryl ammonium salt comprises a quaternary amine

covalently bound to one or more bicyclic aromatic rings. In some embodiments, the tetraaryl

ammonium salt comprises a quaternary amine covalently bound to two or more bicyclic

aromatic rings.

[0059] Non-limiting examples of bicyclic aromatic rings include but are not limited to: a

fused aromatic ring, bridged aromatic ring, and a spirocyclic aromatic ring or a combination

thereof.

[0060] In some embodiments, the tetraaryl ammonium salt comprises a quaternary amine

covalently bound to one or more biaryl compound. In some embodiments, the tetraaryl

ammonium salt comprises a quaternary amine covalently bound to two or more biaryl

compounds.

[0061] Non-limiting examples of biaryl compounds include but are not limited to:

biphenyl, binaphtyl, bipyridine, terphenyl, terpyridine and a combination or a derivative

thereof.

[0062] In some embodiments, the tetraaryl ammonium salt is represented by Formula 2: WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

wherein Ri, R ₂ , R3, R4 and R ₅ are each independently selected from the group consisting

of: hydrogen, an alkyl group, an alkoxy group, a halo group, a perfluoroalkyl group, a

perfluoroalkoxy group, a heteroalkyl group, an aryl group, a hydroxy group, an amino

group, an aminoalkyl group, a guanidine group, a thioalkoxy group, a mercapto group, a

cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo group, a

sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a thioalkyl

group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a sulfone

group or any combination thereof; and A is a counter anion.

[0063] In some embodiments, Ri, R ₂ , R3, R4 and R ₅ are each independently selected from

the group consisting of: hydrogen, an alkyl group, a hydroxy group, a halo group, an alkoxy

group, an amino group, an aminoalkyl group, a guanidine group, a thioalkoxy group, a

mercapto group, a cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo

group, a sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a

thioalkyl group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a

sulfone group or any combination thereof.

[0064] In some embodiments, Ri, R ₂ , R3, R4 and R ₅ are each independently selected from

the group consisting of: hydrogen, an alkyl group, a hydroxy group, a halo group, an alkoxy

group, an amino group, an aminoalkyl group, a mercapto group, an azo group, a vinyl group,

an allyl group, an alkyne, a thioalkyl group, and an alkylhydroxy group or any combination

thereof.

[0065] In some embodiments, Ri, R ₂ , R3, R4 and R ₅ are each independently selected from

the group consisting of: hydrogen, an alkyl group, a hydroxy group, an alkoxy group, an

amino group, an aminoalkyl group, a halo group, and an alkylhydroxy group or any combination thereof.

[0066] In some embodiments, the tetraaryl ammonium salt is represented by Formula 3:

wherein Ro- ₅ represents 0 to 5 substituents, wherein at least one substituent is independently selected from the group consisting of: a halo group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a heteroalkyl group, an aryl group, a hydroxy group, a mercapto group, an amino group, an aminoalkyl group, a guanidine group, a thioalkoxy group, a cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo group, a sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a thioalkyl group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a sulfone group or any combination thereof, and A is a counter anion; and wherein the tetraaryl ammonium comprises at least one substituent.

[0067] In some embodiments, at least one substituent is independently selected from the group consisting of: a halo group, a hydroxy group, an alkoxy group, an amino group, an aminoalkyl group, a guanidine group, a thioalkoxy group, a mercapto group, a cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo group, a sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a thioalkyl group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a sulfone group or any combination thereof.

[0068] In some embodiments, at least one substituent is independently selected from the group consisting of: hydrogen, a hydroxy group, an alkoxy group, an amino group, an WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 a

11—2019/,h05kh0a9t75k

aminoalkyl group, a mercapto group, an azo group, a vinyl group, an allyl group, an alkyne,

a thioalkyl group, and an alkylhydroxy group or any combination thereof.

[0069] In some embodiments, at least one substituent is independently selected from the

group consisting of: hydrogen, a hydroxy group, a halo group, an alkoxy group, an amino

group, an aminoalkyl group, and an alkylhydroxy group or any combination thereof.

[0070] In some embodiments, at least one substituent is independently selected from the

group consisting of: hydrogen, a hydroxy group, and an alkoxy group or any combination

thereof.

[0071] In some embodiments, the tetraaryl ammonium salt is represented by any of

Formulae 3a-3c:

Formula 3a

Formula 3c

[0072] In some embodiments, the tetraaryl ammonium salt is represented by Formula 4:

wherein R0-5 and A are as described hereinabove.

Polymer - Tetraaryl Ammonium salt conjugates

[0073] In another aspect of the invention, there is a composition comprising a tetraaryl ammonium salt covalently bound to a polymer.

[0074] In some embodiments, the tetraaryl ammonium salt covalently bound to a polymer is represented by Formula 5:

WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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wherein each Xi independently comprises an alkyl, a substituted alkyl, an aryl ring, a

substituted aryl ring, a heteroaryl ring, a substituted heteroaryl ring or any combination

thereof; and wherein B and A are as described hereinabove.

[0075] In some embodiments, the tetraaryl ammonium salt covalently bound to a polymer

is represented by any one of Formulae 6-8:

Formula 6

WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 h

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[0076] In some embodiments, the tetraaryl ammonium salt covalently bound to a polymer

is represented by Formula 2.

[0077] In some embodiments, each R’i-5 represents 1 to 5 substituents independently

selected from the group consisting of: hydrogen, a halo group, an alkoxy group, a

perfluoroalkyl group, a perfluoroalkoxy group, a heteroalkyl group, an aryl group, a hydroxy

group, a mercapto group, an amino group, an aminoalkyl group, a guanidine group, a

thioalkoxy group, a cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo

group, a sulfonate group, a sulfinyl group, a vinyl group, an allyl group, an alkyne, a

thioalkyl group, an alkylhydroxy group, a keto group, a carboxylic acid derivative, and a

sulfone group or any combination thereof; and A is a counter anion.

[0078] In some embodiments, each R’i-5 represents 1 to 5 substituents independently

selected from the group consisting of: hydrogen, a halo group, an alkoxy group, a

perfluoroalkyl group, a perfluoroalkoxy group, a heteroalkyl group, an aryl group, a hydroxy

group, a mercapto group, an amino group, an aminoalkyl group, a guanidine group, a

thioalkoxy group, a cyano group, a haloalkyl group, an arylalkyl group, a nitro group, an azo

group, a vinyl group, an allyl group, an alkyne, a thioalkyl group, an alkylhydroxy group, or

any combination thereof.

[0079] In some embodiments, each R’i-5 represents 1 to 5 substituents independently

selected from the group consisting of: hydrogen, a halo group, an alkoxy group, a

perfluoroalkyl group, a perfluoroalkoxy group, a heteroalkyl group, an aryl group, a hydroxy

group, an amino group, an aminoalkyl group, a mercapto group, a vinyl group, an allyl group,

an alkyne, a thioalkyl group, an alkylhydroxy group, or any combination thereof

[0080] In some embodiments, each R’i-5 represents 1 to 5 substituents independently

selected from the group consisting of: hydrogen, a halo group, an alkoxy group, a hydroxy

group, a mercapto group, an amino group, an aminoalkyl group, a vinyl group, an allyl group,

an alkyne, a thioalkyl group, and an alkylhydroxy group, or any combination thereof.

[0081] In some embodiments, each R’i-5 represents 1 to 5 substituents independently

selected from the group consisting of: hydrogen, an alkoxy group, a hydroxy group, a an

amino group, a vinyl group, an allyl group, an alkyne, and an alkylhydroxy group, or any

combination thereof. _{n , n /ncnnTC}

ru i / IL201 9/050975

[0082] In some embodiments, each R” independently comprises an alkyl, a substituted

alkyl, or any combination thereof.

[0083] In some embodiments, the composition comprises the tetraaryl ammonium salt

covalently bound to a sidechain and/or to a backbone of a polymer. In some embodiments,

the tetraaryl ammonium salt covalently bound to a sidechain and/or to a backbone of a

polymer via a substituent (e.g. R’i- ₅ ).

[0084] In some embodiments, the tetraaryl ammonium salt is covalently bound to a

sidechain of a polymer, thereby forming a direct adduct. In some embodiments, the tetraaryl

ammonium salt is grafted to a sidechain of a polymer. In some embodiments, the tetraaryl

ammonium salt is covalently bound to a sidechain of a polymer via a linker, thereby forming

a linker based conjugate. In some embodiments, the tetraaryl ammonium salt is bound to a

sidechain of a polymer by a click reaction. In some embodiments, a plurality of polymeric

chains are crosslinked by a linker comprising the tetraaryl ammonium salt.

[0085] In some embodiments, any of a direct adduct and a linker based conjugate

independently comprise a covalent bond, selected from the group consisting of: -0-,

S-, -P(Ri”)-, -N(Ri”)-, a disulfide bond, a phosphodiester, a phosphonate, a sulphonyl, a

sulfonate, and a carboxyl acid derivate or any combination thereof.

[0086] In some embodiments, any of a direct adduct and a linker based conjugate

independently comprise an oxime, a tetrazole, a Diels Alder adduct, a hetero Diels Alder

adduct, an aromatic substitution reaction product, a nucleophilic substitution reaction

product, a maleimide, a Huisgen-cycloaddition product, or a Michael reaction product.

[0087] In some embodiments, the polymer is a homopolymer comprising the tetraaryl

ammonium salt covalently bound to a sidechain thereof. In some embodiments, the polymer

is a copolymer. In some embodiments, the polymer is a block copolymer. In some

embodiments, the polymer is a graft copolymer. In some embodiments, the polymer is a

random copolymer. In some embodiments, the polymer is a block copolymer. In some

embodiments, the polymer is an alternating copolymer. In some embodiments, the polymer

is a branched polymer.

[0088] Non-limiting examples of polymers include but are not limited to: polycarbonate, polyurea, polyurethane, vinyl polymers, polyalkyl, polybutadiene, polyamide, PEG, polypropylene glycol, poly(tetrahydrofuran), polyacrylonitrile (PAN), polyisobutene, polyisoprene, polychloroprene, polystyrene (PS), polystyrene-coisoprene, poly(vinyl chloride) (PVC), polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinyl cyclohexane, poly(vinyl acetate) (PVA), methylated cellulose, polyvinylidene difluoride (PVDF), polyphenylene oxide (PPE), polysulfone or any combination thereof.

[0089] In some embodiments, the polymer is compatible with an electronic device such as an alkaline fuel cell, an alkaline battery or any other electrochemical device as described hereinbelow. In some embodiments, the polymer is stable under oxidizing and/or alkaline conditions.

[0090] In some embodiments, the polymer is a hydrophobic polymer.

[0091] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently bound to a sidechain of a polymer is represented by any of Formulae 9-11 :

Formula 9

WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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Formula 10

wherein:

M represents a repeating unit of a polymer, wherein the polymer is as described

hereinabove;

H represents a heteroatom selected from the group consisting of: oxygen, nitrogen,

sulfur, phosphorus;

1 represents an integer, ranging from 0 to 20;

m represents an integer, ranging from 0 to 100,000; WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

n represents an integer, ranging from 1 to 100,000;

and Xi, B and A are as described hereinabove.

[0092] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently

bound to a sidechain of a polymer is represented by any of Formulae 12-14:

Formula 12

WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

Formula 14

wherein M, Xi, B and A are as described hereinabove.

[0093] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently

bound to a sidechain of a polymer is represented by Formula 15:

wherein R’i-5, M, Xi, B and A are as described hereinabove. _{n , n /ncnnTC}

ru i / IL201 9/050975

[0094] In some embodiments, M is polystyrene or is absent. In some embodiments, R’i- ₅

is a hydroxy group or is absent.

[0095] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently

bound to a sidechain of a polymer is represented by Formula l5a:

[0096] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently

bound to a sidechain of a polymer is represented by Formula 16:

wherein R’1-5, M, Xi, B and A are as described hereinabove.

[0097] In some embodiments, M is polyethylene or is absent. In some embodiments, R’ i-5 is a hydroxy group or is absent.

[0098] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently bound to a sidechain of a polymer is represented by Formula 16a:

[0099] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently bound to a sidechain of a polymer is represented by Formula 17:

WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 at

11—201 a 9/,h05kh0975k wherein R’i- ₅ , M, Xi, B and A are as described hereinabove.

[00100] In some embodiments, M is absent. In some embodiments, R’ i- ₅ is a hydroxy group

or is absent.

[00101] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently

bound to a sidechain of a polymer is represented by Formula l7a:

[00102] In some embodiments, the direct adduct of the tetraaryl ammonium salt covalently bound to a sidechain of a polymer is represented by Formula l7b:

[00103] In some embodiments, a molar ratio of the polymer to the tetraaryl ammonium salt within the composition is in a range from 1:0.1 to 1:5, from 1 :0.1 to 1:0.2, from 1 :0.2 to 1:0.3, from 1 :0.3 to 1:0.4, from 1:0.4 to 1:0.6, from 1:0.6 to 1:0.8, from 1 :0.8 to 1: 1, from 1: 1 to 1 : 1.5, from 1: 1.5 to 1 :2, from 1 :2 to 1:3, from 1:3 to 1 :4, from 1 :4 to 1:5, including any range or value therebetween.

Tetraaryl ammonium based monomers and copolymers comprising thereof

[00104] In another aspect of the invention, there is a composition comprising the tetraaryl ammonium salt covalently bound to a backbone of a polymer. In some embodiments, the tetraaryl ammonium salt covalently bound to a backbone and to a side chain of a polymer. In some embodiments, the backbone of a polymer is a copolymer selected from the group consisting of: a random copolymer, a block copolymer, and an alternating copolymer.

[00105] In some embodiments, the backbone of a copolymer comprises a first monomer copolymerized with a second monomer. In some embodiments, the first monomer is a tetraaryl ammonium salt based monomer. In some embodiments, the backbone of a copolymer comprises a tetraaryl ammonium salt based monomer copolymerized with a second monomer. In some embodiments, a tetraaryl ammonium salt based monomer is as described hereinbelow.

[00106] Non-limiting examples of a second monomer include but are not limited to: a diisocyanate, a diisothiocyanate, a vinyl based monomer (e.g. metacrylate, acrylate, styrene, divinyl benzene), a lactone (e.g. caprolactone), a bifunctional monomer (e.g. di-acyhalide, dicarboxylate), a dialkoxysilane or any combination thereof. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

[00107] In some embodiments, the second monomer is a diisocyanate. In some

embodiments, the second monomer is a hexamethylenediisocyanate.

[00108] In some embodiments, a tetraaryl ammonium based monomer is represented by

any of Formulae 18, 19, 3a and 3c:

Formula 18

WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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Formula 3a

[00109] In some embodiments, the copolymer comprises monomers of diisocyante

copolymerized with tetraaryl ammonium based monomers.

[00110] In some embodiments, the copolymer is represented by Formula 20:

wherein H is oxygen or NH and n is from 1 to 100,000. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 h

11—201 a 9/,05kh0a9t75k

[00111] In some embodiments, the copolymer is represented by Formula 20a:

[00112] In some embodiments, the copolymer further comprises a third monomer

copolymerized with the tetraaryl ammonium based monomer and the second monomer. In

some embodiments, the copolymer further comprises an additional polymeric block, wherein

the additional polymeric block is a polymerization product of a plurality of the third

monomer. In some embodiments, the additional polymeric block comprises a polymer as

described hereinabove.

[00113] In some embodiments, a molar ratio of the second monomer to the tetraaryl

ammonium based monomer within the copolymer is in a range from 1 :0.1 to 1:5, from 1:0.1

to 1:0.2, from 1:0.2 to 1 :0.3, from 1 :0.3 to 1:0.4, from 1 :0.4 to 1:0.6, from 1 :0.6 to 1:0.8,

from 1:0.8 to 1: 1, from 1: 1 to 1: 1.5, from 1: 1.5 to 1:2, from 1:2 to 1:3, from 1:3 to 1:4, from

1:4 to 1 :5, including any range or value therebetween.

[00114] In some embodiments, one or more compositions disclosed herein are stable under

oxidizing and/or alkaline conditions.

[00115] As used hereinthroughout, the term "stable", or any grammatical derivative

thereof, may refer to chemical stability. "Chemical stability" means that an acceptable

percentage of degradation of the composition disclosed hereinthroughout produced by

chemical pathways such as oxidation or alkaline degradation is formed. In particular, the

composition is considered chemically stable if no more than about 10% degradation

products are formed after e.g., 2 days of incubation at alkaline and/or oxidizing conditions.

[00116] In some embodiments, the composition is chemically stable under alkaline

conditions. In some embodiments, the tetraaryl ammonium salt is stable under alkaline WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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conditions. In some embodiments, the composition comprising the tetraaryl ammonium salt

covalently bound to a sidechain of a polymer is chemically stable under alkaline conditions.

In some embodiments, the copolymer is chemically stable under alkaline conditions. In some

embodiments, the copolymer comprising the polymerization product of tetraaryl ammonium

based monomers and optionally a plurality of second monomers is chemically stable under

alkaline conditions.

[00117] In some embodiments, alkaline conditions comprise a pH value above 7. In some

embodiments, alkaline conditions comprise a pH value ranging from 7 to 14, from 7 to 10,

from 10 to 12, from 12 to 14.

[00118] In some embodiments, alkaline conditions correspond to an aqueous solution. In

some embodiments, alkaline conditions correspond to an organic solution. In some

embodiments, alkaline conditions correspond to a 0.5M hydroxide solution in a dry organic

solvent (e.g. dimethylsulfoxide).

[00119] The chemical stability of exemplary tetraaryl ammonium salts is represented by

Figures 1A-B.

Method

[00120] In another aspect of the invention, there is a method for synthesizing a tetraaryl

ammonium salt, comprising the steps of:

a) providing a biaryl compound comprising (i) a diazonium salt; (ii) a triaryl amine,

wherein said (i) and (ii) are in a position suitable for intramolecular cyclization;

b) performing an intramolecular cyclization under suitable conditions,

thereby obtaining the tetraaryl ammonium salt.

[00121] In some embodiments, the method further comprises the steps of:

a) providing a diaminobiaryl compound;

b) arylating at least one amino group of the diaminobiaryl compound to obtain a triaryl

amine;

c) diazotizing a free amino group by reacting the triaryl amine with a diazotation

compound, to obtain a diazonium salt, thereby obtaining the biaryl compound

comprising the diazonium salt and the triaryl amine. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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[00122] In some embodiments, the biaryl compound is any compound comprising a

plurality of aryl rings bound head to tail. In some embodiments, the biaryl compound

comprises a first aryl and a second aryl bound head to tail, such as biphenyl. In some

embodiments, the biaryl compound comprises a triaryl amine bound to a first aryl and a

diazonium salt bound to a second aryl.

[00123] In some embodiments, the biaryl compound comprises a fused ring system (e.g.

phenanthrene) substituted by a triaryl amine and diazonium salt, wherein the triaryl amine

and diazonium salt are positioned so as to enable an intramolecular cyclization.

[00124] In some embodiments, the biaryl compound comprises a triaryl amine and a

diazonium salt at positions suitable for intramolecular cyclization. In some embodiments,

the biaryl compound further comprises one or more substituents. In some embodiments, a

triaryl amine and a diazonium salt are positioned so as to enable an intramolecular reaction.

In some embodiments, a triaryl amine and a diazonium salt are positioned at a distance of at

least 3 carbon-carbon bonds. In some embodiments, a triaryl amine and a diazonium salt are

optionally in the same plane. In some embodiments, a triaryl amine and a diazonium salt are

in the close proximity so as to enable a bonding interaction. In some embodiments, a triaryl

amine and a diazonium salt are in the close proximity so as to enable a reaction. In some

embodiments, a triaryl amine and a diazonium salt are positioned so as to enable a

nucleophilic attack of the triaryl amine on the diazonium salt. In some embodiments, the

position suitable for intramolecular cyclization is a 2,2’ position.

[00125] In some embodiments, the biaryl compound is represented by Formula 21:

[00126] In some embodiments, the method comprises the step of providing a diaminobiaryl

compound. In some embodiments, the diaminobiaryl compound is optionally mixed with an

organic solvent, thereby resulting in a solution. In some embodiments, a molar concentration

of the diaminoaryl compound within the solution is ranging from 0.01 to 3 mol/L, from 0.01

to 0.1 mol/L, from 0.1 to 0.5 mol/L, from 0.5 to 1 mol/L, from 1 to 1.5 mol/L, from 1.5 to 2 mol/L, from 2 to 2.5 mol/L, from 2.5 to 3 mol/L, including any range therebetween.

[00127] In some embodiments, an organic solvent is aprotic solvent. In some embodiments, an organic solvent is anhydrous solvent, with a weight per weight water content of less than

1%.

[00128] Non-limiting examples of appropriate solvents for the arylation step include but are not limited to: a halogenated hydrocarbon, acetonitrile, n-butyronitrile, iso-butyronitrile, a hydrocarbon (e.g. hexane, pentane, cyclohexane) or any combination thereof.

[00129] In some embodiments, the diaminobiaryl is a diaminobiphenyl compound represented by Formula 22:

[00130] In some embodiments, the diaminobiaryl compound is optionally substituted.

[00131] In some embodiments, the diaminobiaryl compound is synthesized from a corresponding dinitro compound by hydrogenation. In some embodiments, the diaminoaryl compound is synthesized from a corresponding dinitro compound, in the presence of a catalyst (e.g. by Zn[0]) under acidic conditions.

[00132] In some embodiments, the dinitro compound is represented by Formula 23:

[00133] In some embodiments, at least one amino group of the diaminoaryl compound is optionally protected by a labile protecting group. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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[00134] In some embodiments, the method comprises the step of arylating at least one

amino group of the diaminobiaryl compound (also referred to as a“arylation step”) to obtain

a triaryl amine.

[00135] In some embodiments, arylating comprises reacting the diaminobiaryl compound

with an aryl comprising a leaving group, optionally in the presence of a metal-based catalyst.

In some embodiments, the aryl comprising a leaving group is a fused ring based compound.

In some embodiments, the aryl comprising a leaving group is a biaryl based compound.

[00136] In some embodiments, the leaving group comprises any one of: a halo group, a

nitro group, an azo group, a quaternary amino group. In some embodiments, the aryl

comprising a leaving group is a haloaryl.

[00137] In some embodiments, the haloaryl is iodoaryl (e.g. iodobenzene). In some

embodiments, the metal-based catalyst is a Cu(I) based catalyst, further comprising a

bidentate ligand.

[00138] In some embodiments, Cu(I) based catalyst further comprises a bidentate ligand.

In some embodiments, the ligand is sufficient to complex a Cu(I) atom. In some

embodiments, the bidentate ligand is 1,10 phenantroline or a derivative thereof.

[00139] In some embodiments, reacting comprises mixing the diaminobiaryl comprising a

leaving group compound with a haloaryl, in the presence of a Cu(I) based catalyst, thereby

obtaining a reaction mixture. In some embodiments, reacting comprises mixing the solution

of the diaminobiaryl comprising a leaving group compound with a haloaryl, in the presence

of a Cu(I) based catalyst. In some embodiments, reacting further comprises adding a base

(e.g. an alkoxylate salt, such as MeO , tBuO ) to the solution of the diaminobiaryl comprising

a leaving group compound prior to adding a haloaryl.

[00140] In some embodiments, reacting comprises heating the reaction mixture to a

temperature ranging from 30 to 200°C, from 30 to 50°C, from 50 to 70°C, from 70 to 90°C,

from 90 to l00°C, from 100 to H0°C, from 110 to l20°C, from 120 to l30°C, from 130 to

l40°C, from 140 to l50°C, from 150 to l70°C, from 170 to 200°C, including any range

therebetween.

[00141] In some embodiments, reacting comprises incubating the reaction mixture for a time period ranging from 0.1 to 24h, from 0.5 to lh, from 1 to l.5h, from 1.5 to 2h, from 2 to 2.5h, from 2.5 to 3h, from 3 to 3.5h, from 3.5 to 4h, from 4 to 5h, from 5 to 6h, from 6 to 7h, from 7 to lOh, from 10 to 24h, including any range therebetween.

[00142] In some embodiments, the arylation step results in a formation of a diaryl amine, a triaryl amine or both. In some embodiments, the arylation step results in a selective substitution of only one amino group of the diaminobiaryl comprising a leaving group compound. In some embodiments, a compound(s) formed by the arylation step is represented by Formula 24:

[00143] In some embodiments, a molar ratio of Cu(I) atom to the bidentate ligand within the Cu(I) based catalyst is at least 1:0.8, at least 1 : 1, at least 1 : 1.5, including any value therebetween.

[00144] In some embodiments, a molar ratio of the diaminobiaryl comprising a leaving group compound to the Cu(I) based catalyst is at least 1:0.01, at least 1 :0.03, at least 1:0.05, at least 1:0.07, at least 1:0.1, at least 1:0.15, at least 1:0.2, at least 1 :0.3, at least 1:0.5, including any value therebetween.

[00145] In some embodiments, a molar ratio of the diaminobiaryl comprising a leaving group compound to a haloaryl is at least 1: 1, at least 1: 1.2, at least 1: 1.5, at least 1 : 1.7, at least 1: 1.9, at least 1:2, at least 1:2.1, at least 1 :2.2, at least 1 :2.3, at least 1:2.4, at least 1:2.5, at least 1:2.6, at least 1 :2.7, at least 1:3, at least 1:4, including any value therebetween.

[00146] In some embodiments, the arylation step results in a product mixture comprising di-, and tri-substituted amines. In some embodiments, the arylation step further comprises a purification step, so as to separate the product mixture. In some embodiments, the product mixture comprising di-, and tri-substituted amines is used for the subsequent synthetic step without a purification. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 01 a 9/,h05kh0a

11—2 97t5k

[00147] In some embodiments, the method comprises the step of diazotizing a free amino

group (also referred to as a“diazotation step”) by reacting the triaryl amine or the product

mixture comprising the triaryl amine with a diazotation compound, to obtain a diazonium

salt. In some embodiments, the triaryl amine is represented by Formula 24. In some

embodiments, a free amino group corresponds to an unreacted amino group.

[00148] In some embodiments, a diazotation compound comprises a source of nitroso

compound (Nº0 ⁺ ). In some embodiments, a diazotation compound comprises a nitrite salt,

nitrous acid or both. In some embodiments, the diazotation step comprises a nitrite salt (e.g.

NaNCF) and an acid (e.g. HC1, acetic acid).

[00149] In some embodiments, the diazotation step is selective to the unreacted amino

group. In some embodiments, the diazotation step further comprising mixing the triaryl

amine or the product mixture comprising the same with an aqueous solvent prior to addition

of the diazotation compound. In some embodiments, the diazotation step comprises cooling

a reaction mixture to a temperature below 25 °C. In some embodiments, the diazotation step

is performed at a temperature ranging from -10 to l0°C.

[00150] In some embodiments, a diazonium salt is represented by Formula 21.

[00151] In some embodiments, the method comprises a step of intramolecular cyclization

(also referred to as a“cyclization step”) of the diazonium salt under appropriate conditions,

thereby obtaining the tetraaryl ammonium salt. In some embodiments, the

[00152] In some embodiments, the appropriate conditions comprise a temperature ranging

from 20 to l00°C, from 20 to 30°C, from 30 to 35°C, from 35 to 40°C, from 40 to 45°C,

from 45 to 50°C, from 50 to 55°C, from 55 to 60°C, from 60 to 70°C, from 70 to 80°C, from

80 to l00°C, including any range therebetween.

[00153] In some embodiments, the cyclization step comprises adding a base prior to heating

the reaction mixture as described herein above. In some embodiments, the base is an

inorganic base. In some embodiments, the base is a weak inorganic base.

[00154] In some embodiments, the base is selected from the group consisting of: urea, an

acetate salt, a carbonate salt, ammonia, and basic alumina or any combination thereof. In

some embodiments, the base is urea. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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[00155] In some embodiments, the method further comprises a purification step to obtain a

substantially pure tetraaryl ammonium salt.

[00156] Exemplary methods for synthesizing tetraaryl ammonium salts are described in

greater detail in the Examples section and illustrated by Figures 2-4.

[00157] In another aspect of the invention, there is a method for synthesizing a polymer

bound to the tetraaryl ammonium salt. In some embodiments, a polymer is a copolymer

comprising the tetraaryl ammonium salt bound to a side chain of the polymer, to a backbone

of the polymer, or both.

[00158] In some embodiments, the method for synthesizing a polymer comprising the

tetraaryl ammonium salt bound to a backbone of the polymer comprises:

a. providing a tetraaryl ammonium based monomer and optionally a second monomer;

b. mixing the tetraaryl ammonium based monomer and optionally the second monomer

with a catalytic amount of a catalyst, thereby obtaining a reaction mixture;

c. incubating the reaction mixture under appropriate conditions, thereby forming a

polymeric backbone comprising the tetraaryl ammonium salt.

[00159] In some embodiments, the tetraaryl ammonium based monomer and the second

monomer are as described hereinabove. In some embodiments, providing further comprises

mixing the tetraaryl ammonium based monomer and optionally the second monomer with

an organic solvent, thereby forming a solution of monomers.

[00160] In some embodiments, a catalyst is a tin(II)-based catalyst. In some embodiments,

a catalyst is dibutyltin dilaurate.

[00161] In some embodiments, appropriate conditions comprise providing the reaction

mixture to a temperature ranging from 30 to 200°C, from 30 to 50°C, from 50 to 70°C, from

70 to 90°C, from 90 to l00°C, from 100 to H0°C, from 110 to l20°C, from 120 to l30°C,

from 130 to l40°C, from 140 to l50°C, from 150 to l70°C, from 170 to 200°C, including

any range therebetween. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

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[00162] In some embodiments, appropriate conditions comprise reaction time ranging from

1 to 50h, from 1 to 5h, from 5 to lOh, from 10 to l5h, from 15 to 20h, from 20 to 25h, from

25 to 30h, from 30 to 40h, from 40 to 50h, including any range therebetween.

[00163] In some embodiments, the copolymer comprising the tetraaryl ammonium salt

bound to a backbone is represented by Formula 20a.

[00164] In some embodiments, the method for synthesizing a polymer comprising the

tetraaryl ammonium salt bound to a sidechain of the polymer comprises:

a. providing a polymer comprising a reactive group bound to a sidechain of the polymer;

b. reacting the polymer with the tetraaryl ammonium salt;

wherein the reactive group has a reactivity to the tetraaryl ammonium salt.

[00165] In some embodiments, the method further comprises adding a base prior to reacting

the polymer with the tetraaryl ammonium salt.

[00166] In some embodiments, the tetraaryl ammonium salt comprises a substituent having

a reactivity to the sidechain of the polymer. In some embodiments, the tetraaryl ammonium

salt comprises a substituent having a reactivity to the reactive group bound to the sidechain

of the polymer.

[00167] In some embodiments, the tetraaryl ammonium salt comprises a nucleophilic

substituent having a reactivity to an electrophilic reactive group bound to the sidechain of

the polymer, as represented by Formulae 3a and 3c.

[00168] In some embodiments, the method for synthesizing a polymer comprising the

tetraaryl ammonium salt bound to a sidechain of the polymer comprises:

a. providing a monomer comprising the tetraaryl ammonium salt;

b. providing a catalyst;

c. reacting the monomer under appropriate conditions, thereby forming the polymer

comprising the tetraaryl ammonium salt bound to a sidechain thereof.

[00169] In some embodiments, a catalyst is a radical initiator. In some embodiments, a

catalyst is a UV-light. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 t

11—201 a 9/,h05kh0a975k

[00170] In some embodiments, providing a monomer further comprises mixing the

monomer with a solvent.

[00171] In some embodiments, appropriate conditions are as described hereinabove.

[00172] In some embodiments, a polymer comprising the tetraaryl ammonium salt bound

to a sidechain is represented by Formulae 9-l7a.

[00173] Exemplary methods for synthesizing a polymer comprising the tetraaryl

ammonium salt bound to a sidechain are described in greater detail in the Examples section

and illustrated by Figures 5-9.

[00174] It will be apparent to those skilled in the art that the exact reaction conditions (such

as reaction temperature, concentration, reagents ratios, mixing speed, and solvents) may

vary, depending inter alia on the exact structure of reactants, a solvent, a desired yield, and

on a setup of the manufacturing process.

Articles

[00175] In another aspect of the invention, there is an article comprising the composition

of the invention.

[00176] In some embodiments, an article is for use as: an anion exchange membrane, and

an anion conducting polymer.

[00177] In some embodiments, the article is characterized by a stability under alkaline

conditions, as described herein above.

[00178] In some embodiments, the article being in form of an anion exchange membrane

(AEM) is manufactured by a method comprising a mold casting, spin casting, and

electrospinning. Exemplary method for manufacturing of an anion exchange membrane is

described in greater detail in the Examples section. In some embodiments, the polymer of

the invention may be blended or mixed with another polymer to form a composite

membrane. Any suitable mixing or blending process may be used, and such methods are

known in the art. Examples of materials that may be desirable to blend with the polymer

according to exemplary embodiments of the invention include cation exchange

poly electrolytes, Teflon AF, silicone, inorganic particles such as T1O2, AIO2 and sol-gel

materials. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 h

11—201 a 9/,05kh0a9t75k

[00179] In some embodiments, the membrane is formed by reinforcing a fabric with the

polymer of the invention. A liquid mixture of the reactants can be applied to the fabric by

casting the liquid monomer mixture onto the fabric or by soaking the fabric in the liquid

mixture using individual pieces of fabric, multiple pieces of fabric arranged in stacks or with

fabric from a roll in a continuous process. When heat is applied, the reaction between the

reactants and polymerization will occur to form a crosslinked anion exchange membrane

supported by a fabric.

[00180] In some embodiments, the anion exchange membrane as laminated or attached to

at least one other anion exchange polyelectrolyte, another polymer or another type of

material to form a composite membrane. This lamination may benefit the resulting properties

(e.g., conductivity) of the membrane or may be provided for dimensional stability and/or

handling efficiency. The substrate for lamination and the lamination method may, for

example, be a porous substrate such as a non-woven fabric of e.g. polyethylene,

polypropylene or polytetrafluoroethylene, or a microporous membrane obtainable by a

stretch expansion method. The lamination method may be a method wherein a preliminarily

prepared anion exchange membrane and a porous substrate are bonded by a so-called wet

lamination method using a solution of a precursor of the anion exchanger as an adhesive.

[00181] The polymer of the invention can also be polymerized into a solid mass, processed

and pulverized into small particles. The small particles can then be blended in an extruder

and heated with a melted plastic, such as polyethylene or polypropylene. The plastic and ion

exchange mixture can then be extruded into thin sheets of AEMs.

[00182] The AEMs formed from the polymer of the invention may be any suitable

thickness. However, in some embodiments, the thickness of the AEM may be in a range of

about 10 pm to about 1000 pm, and in some embodiments, in a range of about 20 pm to

about 200 pm.

[00183] The AEMs may have any suitable ion exchange capacity. In some embodiments,

the ion exchange capacity is in a range of about 0.1 to about 10 meq/g to about 10 meq/g,

and in some embodiments, in a range of about 1 meq/g to about 5 meq/g. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

[00184] The AEMs may have any suitable conductivity. In some embodiments, the

conductivity is in a range of about l0 ^_4 to about 1 S/cm, and in some embodiments, the

conductivity is in a range of about 10 ^-3 to about 0.3 S/cm.

[00185] AEMs are known and are used in various separation and purification applications,

for example in electrodialysis, salt-splitting and metathesis. For example, anion exchange

membranes described herein may be used in a method for concentrating an electrolyte by

electrodialysis, wherein a cation exchange membrane or a hydrogen ion selective permeation

membrane, and an anion exchange membrane, are alternately disposed between a cathode

and an anode, and a voltage is applied while supplying an electrolyte solution. AEMs may

also be used for water purification, as battery electrolytes and for use in carbon dioxide

removal and absorption.

Alkaline Fuel Cells

[00186] The AEMs formed from the polymer described herein may be used in any suitable

fuel cell, including alkaline fuel cells. A solid alkaline fuel cell according to the present

invention typically includes two electrodes and an AEM defined above. In some

embodiments, the electrodes for alkaline fuel cells are manufactured by a method of wet

fabrication followed by sintering or by a method of dry fabrication through rolling and

pressing components into the electrode structure. The electrode generally consists of a

hydrophilic catalyzed layer on top of a porous conductive diffusion layer (homogeneous

distribution of the fuel and oxidant, respectively), which is in turn bonded to a current

collector that is usually metallic. In some embodiments, the electrode structure is built up

from several layers obtainable by, e.g., sequential deposition of catalyst and catalyst

electrolyte mixtures.

[00187] In the some alkaline fuel cells, air or oxygen may be used as the oxidizer and an

alcohol, such as methanol, ethanol, or isopropanol, or an organic compound, such as

dimethyl ether, may be used as the fuel in the form of a solution containing a water

component. A water component contained in those fuels may be transported to the oxidizer

in the heating/humidifying part to humidify the oxidizer. The structure, components and

methods of forming and using fuel cells are known in the art as described in Unlit, M.; Zhou,

J.; Kohl, P. A. Hybrid Polymer Electrolyte Fuel cells: Alkaline Electrodes with Proton WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 a

11—2019/,h05kh0a9t75k

Conducting Membrane. Angewandte Chemie 2010, 49, pp 1321-1323; Zhou, J; Unlu, M.;

Anestis-Richard, I.; Kohl, P. A. Crosslinked, epoxy -based anion conductive membranes for

alkaline membrane fuel cells. Journal of Membrane Science 2010, 350, pp 286-292; Unlu,

M.; Zhou, J.; Kohl, P. A. Hybrid Anion and Proton Exchange Membrane Fuel Cells. Journal

of Physical Chemistry 2009 , 113, pp 11416-11423.

[00188] Further, the article of the present invention may be formed not only into a common

flat shape but also into a bag, hollow fiber, hollow tube shape, or any other suitable shape.

In some embodiments, the article has a shape of a film, a membrane, a tissue, a mesh, and a

powder or any combination thereof.

[00189] In some embodiments, the article is in the form of alkaline fuel cell, alkaline water

electrolyzer, alkaline redox-flow battery, metal-air battery, and a capacitor or any

combination thereof.

General

[00190] As used herein the term“about” refers to [Symbol] 10 %.

[00191] The terms "comprises", "comprising", "includes", "including",“having” and their

conjugates mean "including but not limited to". The term“consisting of’ means“including

and limited to”. The term "consisting essentially of' means that the composition, method or

structure may include additional ingredients, steps and/or parts, but only if the additional

ingredients, steps and/or parts do not materially alter the basic and novel characteristics of

the claimed composition, method or structure.

[00192] The word“exemplary” is used herein to mean“serving as an example, instance or

illustration”. Any embodiment described as“exemplary” is not necessarily to be construed

as preferred or advantageous over other embodiments and/or to exclude the incorporation of

features from other embodiments.

[00193] The word“optionally” is used herein to mean“is provided in some embodiments

and not provided in other embodiments”. Any particular embodiment of the invention may

include a plurality of“optional” features unless such features conflict. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 201 a 9/,h05kh0a9t

11— 75k

[00194] As used herein, the singular form "a", "an" and "the" include plural references

unless the context clearly dictates otherwise. For example, the term "a compound" or "at

least one compound" may include a plurality of compounds, including mixtures thereof.

[00195] Throughout this application, various embodiments of this invention may be

presented in a range format. It should be understood that the description in range format is

merely for convenience and brevity and should not be construed as an inflexible limitation

on the scope of the invention. Accordingly, the description of a range should be considered

to have specifically disclosed all the possible subranges as well as individual numerical

values within that range. For example, description of a range such as from 1 to 6 should be

considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1

to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that

range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[00196] Whenever a numerical range is indicated herein, it is meant to include any cited

numeral (fractional or integral) within the indicated range. The phrases“ranging/ranges

between” a first indicate number and a second indicate number and“ranging/ranges from”

a first indicate number“to” a second indicate number are used herein interchangeably and

are meant to include the first and second indicated numbers and all the fractional and integral

numerals there between.

[00197] As used herein the term "method" refers to manners, means, techniques

and procedures for accomplishing a given task including, but not limited to, those manners,

means, techniques and procedures either known to, or readily developed from known

manners, means, techniques and procedures by practitioners of the chemical,

pharmacological, biological, biochemical and medical arts.

[00198] In those instances where a convention analogous to "at least one of A, B, and C,

etc." is used, in general such a construction is intended in the sense one having skill in the

art would understand the convention (e.g., "a system having at least one of A, B, and C"

would include but not be limited to systems that have A alone, B alone, C alone, A and B

together, A and C together, B and C together, and/or A, B, and C together, etc.).

[00199] It will be further understood by those within the art that virtually any disjunctive

word and/or phrase presenting two or more alternative terms, whether in the description, WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

claims, or drawings, should be understood to contemplate the possibilities of including one

of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be

understood to include the possibilities of "A" or "B" or "A and B."

[00200] As used herein, the term "alkyl" describes an aliphatic hydrocarbon including

straight chain and branched chain groups. The alkyl group has 1 to 100 carbon atoms, and

more preferably 1-50 carbon atoms. Whenever a numerical range; e.g.,“1 -100”, is stated

herein, it implies that the group, in this case the alkyl group, may contain 1 carbon atom, 2

carbon atoms, 23 carbon atoms, etc., up to and including 100 carbon atoms. In the context

of the present invention, a "long alkyl" or“high alkyl” is an alkyl having at least 10, or at

least 15 or at least 20 carbon atoms in its main chain (the longest path of continuous

covalently attached atoms), and may include, for example, 10-100, or 15-100 or 20-100 or

21-100, or 21-50 carbon atoms. A“short alkyl” or“low alkyl” has 10 or less main-chain

carbons. The alkyl can be substituted or unsubstituted, as defined herein.

[00201] The term "alkyl", as used herein, also encompasses saturated or

unsaturated hydrocarbon, hence this term further encompasses alkenyl and alkynyl.

[00202] The term "alkenyl" describes an unsaturated alkyl, as defined herein, having at least

two carbon atoms and at least one carbon-carbon double bond. The alkenyl may be

substituted or unsubstituted by one or more substituents, as described hereinabove.

[00203] The term "alkynyl", as defined herein, is an unsaturated alkyl having at least two

carbon atoms and at least one carbon-carbon triple bond. The alkynyl may be substituted or

unsubstituted by one or more substituents, as described hereinabove.

[00204] The term "cycloalkyl" or“cycloalkane” describes an all-carbon monocyclic or

fused ring (i.e., rings that share an adjacent pair of carbon atoms) group where one or more

of the rings does not have a completely conjugated pi-electron system. The cycloalkyl group

may be substituted or unsubstituted, as indicated herein.

[00205] The term "aryl",“aryl ring” or“aromatic” describes an all-carbon monocyclic or

fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups having

a completely conjugated pi-electron system. The aryl ring may have one or more WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 ha

11—201 a 9/,h05k09t75k

heteroatoms within the ring structure. The aryl group may be substituted or unsubstituted, as

indicated herein.

[00206] The term "alkoxy" describes both an -O-alkyl and an -O-cycloalkyl group, as

defined herein.

[00207] The term "aryloxy" describes an -O-aryl, as defined herein.

[00208] Each of the alkyl, cycloalkyl and aryl groups in the general formulas herein may

be substituted by one or more substituents, whereby each substituent group can

independently be, for example, halide, alkyl, alkoxy, cycloalkyl, alkoxy, nitro, amine,

hydroxyl, thiol, thioalkoxy, thiohydroxy, carboxy, amide, aryl and aryloxy, depending on

the substituted group and its position in the molecule. Additional substituents are also

contemplated.

[00209] The term "halide", "halogen" or“halo” describes fluorine, chlorine, bromine or

iodine.

[00210] The term“haloalkyl” describes an alkyl group as defined herein, further substituted

by one or more halide(s).

[00211] The term“hydroxyl” or "hydroxy" describes a -OH group.

[00212] The term "thiohydroxy" or“thiol” describes a -SH group.

[00213] The term "thioalkoxy" describes both an -S-alkyl group, and a -S-cycloalkyl group,

as defined herein.

[00214] The term "thioaryloxy" describes both an -S-aryl and a -S-heteroaryl group, as

defined herein.

[00215] The term“amine” describes a -NR’R’’ group, with R’ and R’’ as described herein.

[00216] The term "heteroalicyclic" or "heterocyclyl" describes a monocyclic or fused ring

group having in the ring(s) one or more atoms such as nitrogen, oxygen and sulfur. The rings

may also have one or more double bonds. However, the rings do not have a completely

conjugated pi-electron system. Representative examples are piperidine, piperazine,

tetrahydrofuran, tetrahydropyrane, morpholino and the like. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 h

11—201 a 9/,05kh0a9t75k

[00217] The term "carboxy" or "carboxylate" describes a -C(=0)-0R' group, where R' is

hydrogen, alkyl, cycloalkyl, alkenyl, aryl, heteroaryl (bonded through a ring carbon)

or heteroalicyclic (bonded through a ring carbon) as defined herein. The term "amide" as

used herein encompasses C-amide and N-amide.

[00218] The term "C-amide" describes a -C(0)NR'R" end group or a -C(0)NR'-linking

group, as these phrases are defined hereinabove, where R' and R" are as defined herein.

[00219] The term "N-amide" describes a -NR"C(0)R' end group or a -NR'C(O)- linking

group, as these phrases are defined hereinabove, where R' and R" are as defined herein.

[00220] The term“carboxylic acid derivative” or“acyl” encompasses carboxy, amide,

carbonyl, anhydride, carbonate ester, and carbamate.

[00221] The term “carbonyl” describes a -C(=0)-R' group, where R' is as defined

hereinabove.

[00222] The above-terms also encompass thio-derivatives thereof (thiocarboxy and

thiocarbonyl).

[00223] The term“thiocarbonyl” describes a -C(=S)-R' group, where R' is as defined

hereinabove.

[00224] A "thiocarboxy" group describes a -C(=S)-OR' group, where R' is as defined

herein.

[00225] A "sulfinyl" group describes an -S(=0)-R' group, where R' is as defined herein.

[00226] A "sulfonyl" or“sulfonate” group describes an -S(=0) ₂ -R' group, where Rx is as

defined herein.

[00227] A "carbamyl" or“carbamate” group describes an -OC(=0)-NR'R" group, where R'

is as defined herein and R" is as defined for R'.

[00228] A "nitro" group refers to a -NO2 group.

[00229] A "cyano" or "nitrile" group refers to a -CºN group.

[00230] As used herein, the term“azide” refers to a -N3 group. _{n , n /ncnnTC}

ru i / IL201 9/050975

[00231 ] The term“sulfonamide” refers to a -S(=0)2-NR'R" group, with R' and R" as defined

herein.

[00232] The term“phosphonyl” or“phosphonate” describes an -0-P(=0)(0R')2 group,

with R' as defined hereinabove.

[00233] The term“phosphinyl” describes a -PR'R" group, with R' and R" as defined

hereinabove.

[00234] The term“alkaryl” or“arylalkyl” describes an alkyl, as defined herein, which

substituted by an aryl, as described herein. An exemplary alkaryl is benzyl.

[00235] The term "heteroaryl" describes a monocyclic or fused ring (i.e., rings which share

an adjacent pair of atoms) group having in the ring(s) one or more atoms, such as, for

example, nitrogen, oxygen and sulfur and, in addition, having a completely conjugated pi- electron system. Examples, without limitation, of heteroaryl groups include pyrrole, furane,

thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine,

quinoline, isoquinoline and purine. The heteroaryl group may be substituted or unsubstituted

by one or more substituents, as described hereinabove. Representative examples

are thiadiazole, pyridine, pyrrole, oxazole, indole, purine and the like.

[00236] As used herein, the terms "halo" and "halide", which are referred to herein

interchangeably, describe an atom of a halogen, that is fluorine, chlorine, bromine or iodine,

also referred to herein as fluoride, chloride, bromide and iodide.

[00237] The term“haloalkyl” describes an alkyl group as defined above, further substituted

by one or more halide(s).

[00238] It is appreciated that certain features of the invention, which are, for clarity,

described in the context of separate embodiments, may also be provided in combination in

a single embodiment. Conversely, various features of the invention, which are, for brevity,

described in the context of a single embodiment, may also be provided separately or in any

suitable subcombination or as suitable in any other described embodiment of the invention.

Certain features described in the context of various embodiments are not to be considered

essential features of those embodiments, unless the embodiment is inoperative without those

elements. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 t

11—201 a 9/,h05kh0a975k

[00239] Various embodiments and aspects of the present invention as delineated

hereinabove and as claimed in the claims section below find experimental support in the

following examples.

EXAMPLES

EXAMPLE 1

Synthesis of N,N-ditolyl carbazolium hexafluorophosphate

[00240] In an oven dried Schlenk flask (50 mL), 2,2’-biphenyldiamine (1.00 g, 5.42 mmol)

and 4-iodotoluene (2.367 g, 10.84 mmol) were dissolved in xylenes (15 mL) and the flask

deoxygenated using 3 freeze -pump-thaw cycles. The flask was backfilled with argon.

KOtBu (1.33 g, 1 l.92mmol) was then added and the mixture left for 10 min stirring at room

temperature. Then, Cul (0.201 g, 1.084 mmol) and l,lO-phenanthroline (0.195 g, 1.084

mmol) were added and the mixture was stirred for 3.5 h at l25°C. The mixture was allowed

to cool to room temperature and was filtered. The solids were washed with chloroform and

then dissolved in 25% NH4OH (30 mL). The aqueous phase was then extracted with CHCI3 _.

The organic phases were combined, and the solvents evaporated. The concentrated paste was

re-dissolved in CHCI3 and extracted with NH4OH until no blue color was observed. To

separate the unreacted diamine, HC1 was added to the organic phase and extracted. The

organic phase was then washed with saturated NaHCCL, dried over Na ₂ S04, filtered and

evaporated. At this stage, the mixture could be used for the next step without further

purification. Part of the solid (0.3 g, 0.824 mmol) was dissolved in glacial acetic acid (4 mL)

in an Erlenmeyer (25 mL). The solution was cooled to 0°C in an ice bath. The frozen acetic

acid is crushed with a metallic spatula before NaNCT (0.3 g, 4.35 mmol) in water (0.4 mL)

was added, and the slurry mechanically stirred for 20 min. Urea (0.23 g, 3,8 mmol) was

added next, and the mixture stirred for 1 h at 40 °C. The solvents were evaporated, and the

residue dissolved in CHCI3. The non-soluble part was filtered and washed with CHCI3 _. The

filtrate was concentrated in vacuo and separated using extraction with water and ether. Water

and acetic acid were removed in vacuo by freeze-drying. The acetate was converted to the

hexafluorophosphate by addition to a saturated solution of NH4PF6. The salt precipitates and WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 5kh0a9t

11—201 a 9/,h0 75k

the solids are filtered and washed with water and ether. The red brown solids are then dried

under vacuum (220 mg, 54% yield). The reaction scheme is represented by Figure 2.

EXAMPLE 2

Stability test of quaternary ammonium salts and polymers

[00241] Two solutions are prepared in the dry glove box and mixed for each test at t=0: (1)

dry KOH in l8-crown-6 (0.5 mmol, prepared by water titration of potassium) dissolved in

DMSO-d6 (400 pL); and (2) quaternary ammonium salt (0.035 mmol) and mesitylene (1.5

pL, used as internal standard) dissolved in DMSO-d6 (100 pL). For experiments with l>0,

the DMSO-d6 used to dissolve the quaternary ammonium was reduced by the volume of

water needed to achieve the desired l. This water is added to (1) before the addition of the

QA solution (2). As an example, the stability of the above molecules in hydroxide at room

temperature is shown in Figure 1A and Figure 1B.

EXAMPLE 3

Synthesis of N,N-(4-hydroxyphenyl)-carbazolium hexafluorophosphate

[00242] N,N-(4-methoxyphenyl)-carbazolium hexafluorophosphate is prepared by the

same procedure as for Example 1, but using 4-iodoanisole instead of 4-iodotoluene.

[00243] Subsequently, N,N-(4-methoxyphenyl)-carbazolium hexafluorophosphate (525

mg, 1 mmol) is dissolved in dry CH2CI2 in a glove box, and added, slowly, to a BBr ₃ 1.0 M

solution in CH2CI2 (10 mL). The reaction is stirred at room temperature for 3 days. Methanol

is added slowly to neutralize excess BBn, and the whole solution is evaporated. Ethyl acetate

is washed, leaving the solid product clean as a white solid. This is filtered and dried under

vacuum (253 mg, 58% yield). The reaction scheme is represented by Figure 3.

EXAMPLE 4

Synthesis of 9,9-spiro bis-carbazolium hexafluorophosphate

[00244] The compound is prepared using the same procedure as for Example 1, using 2,2’- diiodobiphenyl instead of 4-iodotoluene. WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5

11—201 a 9/,h05kh0a9t75k

EXAMPLE 5

Synthesis of polyurethane containing carbazolium groups in the main chain

[00245] N,N-(4-hydroxyphenyl)-carbazolium bromide (432 mg, 1 mmol) and

hexamethylenediisocyanate (168 mg, 1 mmol) are mixed in THF (5 mL). A drop of dibutyl- tin laurate is added, and the solution is refluxed for 24h. The solvent is evaporated, providing

the desired polyurethane as a rubbery solid.

EXAMPLE 6

Synthesis of polystyrene containing carbazolium groups in the side-chain

[00246] A copolymer of styrene and 4-chloromethyl styrene (1 : 1) is prepared using NMP.

The polymer is than dissolved in a DMSO solution containing excess N,N-(4- hydroxyphenyl)-carbazolium bromide and potassium t-butoxide. The solution is mixed at

90C for 1 day. The polymer is precipitated by pouring the solution into ether. The solid

polymer is washed with water until pure. The reaction scheme is represented by Figure 5.

EXAMPLE 7

Synthesis of polystyrene membrane containing carbazolium groups in the side-chain by co

polymerization

[00247] These membranes can be prepared by two different approaches:

1. Direct casting of the polymer described in Example 6: solvent cast from water, or hot

press above the Tg.

2. Direct polymerization of monomers in mold:

Direct polymerization approach:

[00248] N,N-(4-hydroxyphenyl)-carbazolium bromide (432 mg, 1 mmol) and 4- chloromethylstyrene (100 mg, 0.66 mmol) are mixed with KOH in THF (5 mL). The mixture

is heated to reflux for 3 days. The THF is evaporated and the solid washed dissolved in

methanol and filtered. The filtrate is then evaporated. Styrene (as desired) is added to the

solid, and the mixture is dissolved in small amounts of t-BuOH. The solution is poured into WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 a

11—2019/,h05kh0a9t75k

a mold of the desired membrane shape and cured using a strong UV source until a brittle

solid membrane is obtained. The reaction scheme is represented by Figure 6.

EXAMPLE 8

Synthesis of poly(m-terphenylene) membrane containing carbazolium groups in the

side-chain

[00249] A copolymer of 7-bromo-l,l,l-trifluoroheptan-2-one and m-terphenyl (m-TPN)

obtained commercially is cast into a membrane using dimethyl acetamide as a solvent. The

membrane is added to a DMSO solution containing excess N,N-(4-hydroxyphenyl)- carbazolium bromide and potassium t-butoxide. The solution is mixed at 90C for 2 weeks.

The membrane is than washed continuously with water. The reaction scheme is represented

by Figure 7.

EXAMPLE 9

Synthesis of polyethylene membrane containing carbazolium groups in the side-chain

[00250] A polyethylene membrane functionalized with alkyl bromide groups was obtained

commercially. The membrane is added to a DMSO solution containing excess N,N-(4- hydroxyphenyl)-carbazolium bromide and potassium t-butoxide. The solution is mixed at

90C for 2 weeks. The membrane is than washed continuously with water. The reaction

scheme is represented by Figure 8.

EXAMPLE 10

Synthesis of methacrylic co-polymer based membrane containing carbazolium groups in

the side-chain

[00251] These membranes can be prepared by two different approaches:

1. Direct casting of the polymer described in Example 7 : solvent cast from water, or hot

press above the Tg.

2. Direct polymerization of monomers in mold:

[00252] Direct polymerization of monomers in mold: WO 2020/044348 PCT/IL2019/0 r5u09 i7 /5 a

11—2019/,h05kh0a9t75k

[00253] N,N-(4-hydroxyphenyl)-carbazolium bromide (432 mg, 1 mmol) and 4- chloromethylstyrene (100 mg, 0.66 mmol) are mixed with KOH in THF (5 mL). The mixture

is heated to reflux for 3 days. The THF is evaporated and the solid washed dissolved in

methanol and filtered. The filtrate is then evaporated. 2-hydroxyethylmethacrylate (1

equivalent), benzoyl peroxide (7.5 mg) and N,N-dimethylaniline (5 mΐ) and 2 drops of DMF

are added and the mixture is mixed until all the carbazolium salt dissolved. The solution is

degassed and inserted into a glove box where it is poured into a Teflon mold of the desired

membrane shape. The mold is heated to 50C for 12 hours and then taken out of the mold.

The reaction scheme is represented by Figure 9.