LONG-TERM ANION-CONDUCTING COMPOUND, ITS PREPARATION AND ITS USE IN ELECTROCHEMISTRY

Abstract

The present invention provides compounds, especially polymeric compounds, a process for preparation thereof and for the use of these compounds. Intended use is in the field of electro-chemistry. Anion-conducting properties of disclosed compounds making this material suitable for the preparation of anion-conducting membranes. The object of the present invention is therefore to provide material having an ionic conductivity that is stable over long period of time. This object is solved by compounds containing at least one unit of the formula (I) wherein X being a ketone or sulfone group, wherein Z being a structure element comprising at least one tertiary carbon atom and at least one aromatic 6-ring directly bonded to one of the oxygen atoms, and wherein Y being a structure element comprising at least one nitrogen atom with a positive charge and Y being bonded to said tertiary carbon atom of Z.

##STR00001##

Claims

1. Compound containing at least one unit of the formula (I) ##STR00021## wherein X being a ketone or sulfone group, wherein Z being a structure element comprising at least one tertiary carbon atom and at least one aromatic 6-ring directly bonded to one of the oxygen atoms, and wherein Y being a structure element comprising at least one nitrogen atom with a positive charge and Y being bonded to said tertiary carbon atom of Z.

2. Compound according to claim 1, characterized in that the compound is represented by formula (Ia) or (Ib) ##STR00022## wherein V represents same or different halogen, preferably V being Fluor and with M being an integer from 1 to 1000, preferably M being an integer from 5 to 500.

3. Compound according to claim 1, characterized in that the structure element Y represents a unit of formula (IIa), (IIb) or (IIc) ##STR00023## with n representing number of carbon atoms in the aliphatic chain and n being from 0 to 9, preferably from 0 to 5; R.sub.1, R.sub.2 and R.sub.3 being the same or different alkyl group having from 1 to 9 carbon atoms, preferably R.sub.1, R.sub.2 and R.sub.3 each being a methyl group.

4. Compound according to claim 3, characterized in that the structure element Y present in the compound represents in more than 5% of its occurrence a unit of formula (IIa), (IIb) or (IIc).

5. Compound according to claim 1, characterized in that the structure element Z represents a unit of formula (III) ##STR00024## with R.sub.4, R.sub.5, R.sub.6 and R.sub.7 being the same or different alkyl group having from 1 to 4 carbon atoms, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 each preferably being a methyl, iso-propyl or tert-butyl group, more preferably R.sub.4, R.sub.5, R.sub.6 and R.sub.7 each being a methyl group.

6. Compound according to claim 1, characterized in that the compound is selected from the group consisting of the compounds of formulas (IVa) to (IVf): ##STR00025## ##STR00026## with n representing number of carbon atoms in the aliphatic chain and n being from 0 to 9, preferably from 0 to 5 and with M.sub.a, M.sub.b and M.sub.c each being an integer of from 1 to 1000, preferably M.sub.a, M.sub.b, and M.sub.c each being an integer of from 5 to 500.

7. Compound according to claim 1, wherein said aromatic 6-ring directly bonded to one of the oxygen atoms is further substituted with one or more halogen and/or one or more C.sub.1- to C.sub.4-alkyl radicals.

8. Compound according to claim 1, wherein said aromatic 6-ring directly bonded to one of the oxygen atoms is free of any further substitution with one or more halogen and/or one or more C.sub.1- to C.sub.4-alkyl radicals.

9. Process for preparing a product compound, comprising the following steps: a) providing a first educt, wherein said first educt comprises at least one compound selected from the group consisting of the compounds of formulas (VIa) or (VIb), where each V independently represents the same or a different halogen, ##STR00027## b) providing a second educt, wherein said second educt comprises at least one compound selected from the group consisting of the compounds of formulas (VIIa), (VIIb), (VIIc) or (VIId) ##STR00028## c) Reacting said first educt with said second educt; d) Obtaining a product compound containing at least one unit of the formula (I) ##STR00029## wherein X being a ketone or sulfone group, wherein Z being a structure element comprising at least one tertiary carbon atom and at least one aromatic 6-ring directly bonded to one of the oxygen atoms, and wherein Y being a structure element comprising at least one nitrogen atom with a positive charge and Y being bonded to said tertiary carbon atom of Z.

10. Process according to claim 9, characterized in that an alkylating reagent, preferably a methylating reagent, is used in at least one of its steps.

11. Process according to claim 9, wherein the aromatic 6-ring of the product compound that is directly bonded to one of the oxygen atoms is further substituted with one or more halogen and/or one or more C.sub.1- to C.sub.4-alkyl radicals, and wherein at least one compound of formula (VIa) or (VIb) or (VIIa) or (VIIb) or (VIIc) or (VIId) is provided as first educt or second educt respectively.

12. Process according to claim 9, wherein the aromatic 6-ring of the product compound is directly bonded to one of the oxygen atoms is free of any further substitution with one or more halogen and/or one or more C.sub.1- to C.sub.4-alkyl radicals, and wherein at least one compound of formula (VIa) or (VIb) or (VIIa) or (VIIb) or (VIIc) or (VIId) is provided as first educt or second educt respectively.

13. An anion-conducting membrane comprising the compound of claim 1.

14. An electrochemical cell comprising the anion-conducting membrane of claim 13.

15. An electrolyzer comprising the electrochemical cell of claim 14.

16. (canceled)

17. (canceled)

Description

[0059] Further details of present invention are derivable from the examples and accompanying figures. The latter show:

[0060] FIG. 1: .sup.1H-NMR spectrum of monomer (VIIa)

[0061] FIG. 2: .sup.1H-NMR spectrum of quaternized piperidine containing polymer from Example 3

[0062] FIG. 3: .sup.1H-NMR spectrum of quaternized piperidine containing polymer from Example 6

[0063] FIG. 4: .sup.1H-NMR spectrum of monomer (VIIb)

[0064] FIG. 5: .sup.1H-NMR spectrum of quaternized piperidine containing polymer from Example 10

[0065] FIG. 6: .sup.1H-NMR spectrum of quaternized piperidine containing polymer from Example 13

[0066] FIG. 7: .sup.1H-NMR spectrum of monomer (VIIc)

[0067] FIG. 8: .sup.1H-NMR spectrum of spiro containing polymer from Example 16

[0068] FIG. 9: .sup.1H-NMR spectrum of monomer (VIId)

[0069] FIG. 10: .sup.1H-NMR spectrum of quaternized piperidine containing polymer from Example 20

[0070] FIG. 11: .sup.1H-NMR spectrum of quaternized piperidine containing polymer from Example 23

EXAMPLES

Example 1: Synthesis of Piperidine Containing Monomer (VIIa)

[0071] Synthesis of piperidine containing monomer (VIIa) was performed in two steps accordingly to reaction scheme 1 (step 1) and reaction scheme 2 (step 2).

##STR00012##

##STR00013##

[0072] A mixture of 227.2 g (662.778 mmol) of Methoxymethyl-triphenyl-phosphine chloride in 1.3 L of dry THF was placed in 6 L three-neck round-bottom flask equipped with thermometer, dropping funnel, mechanical stirrer, ice bath, N.sub.2 atmosphere and cooled down to 0? C. A solution of 99.16 g (883.704 mmol) of potassium tert-butoxide in 900 mL of dry Tetrahydrofuran (THF) was added dropwise and reaction mixture was stirred at room temperature for 30 minutes. After 30 minutes, the reaction mixture was cooled down to 0? C. and a solution of 50 g (441.852 mmol) of 1-Methylpiperydin-4-one in 900 mL of dry THF was added dropwise to the reaction mixture. The mixture was stirred at room temperature overnight. The reaction mixture was divided in two batches (batch 1 and batch 2). Batch 1 was poured onto 1 L of ice water and extracted with 5?200 ml of Dichloromethane (DCM). Combined organic layer was washed with brine, dried over MgSO.sub.4 and solvent was removed under vacuum to give 45.25 g of crude material. Column chromatography with silica as stationary phase and DCM/Methanol (+1% NH.sub.3) as mobile phase were used for purification to give 24.89 g of Intermediate 1 (yield 55%).

[0073] In a three-necked-flask (500 mL) equipped with thermometer, dropping funnel, mechanical stirrer and N.sub.2 atmosphere 16 g. (0.113 mol) of Intermediate 1 were placed. A solution of 37.4 g (0.306 mol) of 2,6-Dimethylphenol in 170 mL acetonitrile was added dropwise at 10? C. Additionally, 26 mL (0.34 mol) of trifluoroacetic acid (TFA) were added dropwise, followed by dropwise addition of 12 mL (0.136 mol) of trifluoromethanesulfonic acid. The resulting solution was stirred at room temperature overnight. The reaction mixture was evaporated under vacuum. The crude residue was treated with diethyl ether (Et.sub.2O, 300 mL) and stirred overnight at room temperature. The solid was filtered, washed with Et.sub.2O (100 mL) and dried under high vacuum at 45? C. Obtained TFA-salt of product was converted to free base by dissolution of it in 90 mL of acetonitrile, followed by addition 6 mL of water and basification with 10% aq. ammonia to pH?8. As result white precipitate was formed. The precipitate was collected by filtration, washed with 10 mL of water and dried under vacuum. Obtained white solid was dissolved in 1 L methanol, concentrated under vacuum until the solution becomes cloudy and stored at room temperature. Crystallized solid was filtered of by vacuum filtration and dried under vacuum. Normal phases column chromatography was used for purification to give 24.97 g (yield 62%) of piperidine containing monomer (VIIa). Chemical structure of monomer (VIIa) was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 1 trideuterio(trideuteriomethylsulfonyl)methane (DMSO-d6) was used as solvent.

Example 2: Synthesis of Piperidine Containing Polymer

[0074] Synthesis was performed in a 500 mL three-necked flask with oil bath, mechanical stirrer, a packed column with distillation head cooler with adjustable return ratio and condensate removal. At the beginning of synthesis 10.61 g (0.03 mol) of piperidine containing monomer (VIIa) from Example 1, 6.55 g (0.03 mol) of 4,4-Difluorobenzophenon (VIa), 165 mL of N,N-Dimethylacetamide and 9.12 g (0.066 mol) of finely ground K.sub.2CO.sub.3 were mixed under nitrogen atmosphere over one hour at room temperature. Afterwards the temperature of the reaction mixture was increased to 120? C. and generated water was removed using the column over 4 hours. After four hours additional 10 mL of N,N-Dimethylacetamide were added to the reaction mixture and temperature of the reaction mixture was increased to 165? C. After 20 hours the heating of the oil bath was turned off, the viscous reaction product was cooled down and poured into cold water. The precipitated product was washed with hot water three times and was dried under vacuum at 40? C. over 48 hours. The yield was 14.64 g (91.8%).

Example 3: Quaternization of Piperidine Containing Polymer from Example 2

[0075] 10 g of the polymer from Example 2 were dissolved in 40 mL of N,N-Dimethylacetamide under stirring at 60? C. for one hour. After cooling of the polymer solution down to 30? C. dropwise 2.5 mL of iodomethane were added to the polymer solution and polymer solution was stirred for 24 hours at 30? C. leading to quaternization of the polymer. Chemical structure of quaternized piperidine containing polymer from Example 3 was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 2. DMSO-d6 was used as solvent.

Example 4: Membrane Casting of Piperidine Containing Polymer from Example 3

[0076] The solution of the quaternized polymer from Example 3 was directly used for preparation of the membrane. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 ?m Polytetrafluoroethylene (PTFE) filter on a glass plate preheated to 40? C. For the coating of the glass plate, an applicator with doctor blade was automatically pulled over the glass plate at a speed of 5 mm/s. The applied wet layer was pre-dried for 24 hours under N.sub.2 atmosphere at room temperature and then finally dried for 6 hours at 60? C. under vacuum.

Example 5: Synthesis of Piperidine Containing Polymer

[0077] Synthesis was performed in a 500 mL three-necked flask with oil bath, mechanical stirrer, a packed column with distillation head cooler with adjustable return ratio and condensate removal. At the beginning of synthesis 10.61 g (0.03 mol) of piperidine containing monomer (VIIa) from Example 1, 7.63 g (0.03 mol) of 4,4-Difluordiphenylsulfon (VIb), 165 mL of N,N-Dimethylacetamide and 9.12 g (0.066 mol) of finely ground K.sub.2CO.sub.3 were mixed under nitrogen atmosphere over one hour at room temperature. Afterwards the temperature of the reaction mixture was increased to 120? C. and generated water was removed using the column over 4 hours. After four hours additional 10 mL of N,N-Dimethylacetamide were added to the reaction mixture and temperature of the reaction mixture was increased to 165? C. After 20 hours the heating of the oil bath was turned off, the viscous reaction product was cooled down and poured into cold water. The precipitated product was washed with hot water three times and was dried under vacuum at 40? C. over 48 hours. The yield was 15.21 g (89.3%).

Example 6: Quaternization of Piperidine Containing Polymer from Example 5

[0078] 10 g of the polymer from Example 5 were dissolved in 40 mL of N,N-Dimethylacetamide under stirring at 60? C. for one hour. After cooling of the polymer solution down to 30? C. dropwise 2.5 mL of iodomethane were added to the polymer solution and polymer solution was stirred for 24 hours at 30? C. leading to quaternization of the polymer. Chemical structure of quaternized piperidine containing polymer from Example 6 was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 3. DMSO-d6 was used as solvent.

Example 7: Membrane Casting of Piperidine Containing Polymer from Example 6

[0079] The solution of the quaternized polymer from Example 3 was directly used for preparation of the membrane. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 ?m PTFE filter on a glass plate preheated to 40? C. For the coating of the glass plate, an applicator with doctor blade was automatically pulled over the glass plate at a speed of 5 mm/s. The applied wet layer was pre-dried for 24 hours under N.sub.2 atmosphere at room temperature and then finally dried for 6 hours at 60? C. under vacuum.

Example 8: Synthesis of Piperidine Containing Monomer (VIIb)

[0080] Synthesis of piperidine containing monomer (VIIb) was performed in three steps accordingly to reaction scheme 3 (step 1), reaction scheme 4 (step 2) and reaction scheme 5 (step 3).

##STR00014##

##STR00015##

##STR00016##

[0081] Aqueous solution of 6 N HCl was added to Batch 2 from Example 1 to pH=1. Reaction mixture was stirred with 1.5 L of Et.sub.2O for 30 minutes. Then organic phase was separated, and aqueous phase was extracted again with 1 L of Et.sub.2O. Obtained aqueous phase was basified with 3 N NaOH to pH ?10 and extracted with DCM (3?1 L). Organic phase was separated and concentrated to dryness to give 45.5 g of crude product (Intermediate 2).

[0082] In a four-necked-flask (6 L) equipped with thermometer, dropping funnel, mechanical stirrer, ice bath and N.sub.2 atmosphere 259.84 g (0.758 mol) of Methoxymethyl-triphenyl-phosphine chloride was suspended in 1.55 L of dry THF and cooled down to 0? C. To this suspension, a solution of 127.58 g (1.137 mol) of Potassium tert-butoxide in 1 L of THF was added dropwise. The resulting solution was stirred at room temperature for 1 hour. The reaction mixture was cooled down to 0? C. and a solution of 45.5 g of crude product (Intermediate 2) in 780 mL of THF was added to the reaction mixture. The resulting reaction mixture was stirred at room temperature overnight. The reaction mixture was poured into 3 L of ice-cold water, extracted with 3?3 L of DCM until the wp showed no more product, combined organic phase was washed with brine, dried over MgSO.sub.4 and concentrated under vacuum. Column chromatography with silica as stationary phase and DCM/Methanol (+1% NH.sub.3) as mobile phase were used for purification to give 52.89 g of Intermediate 3.

[0083] In a three-necked-flask (500 mL) equipped with thermometer, dropping funnel, mechanical stirrer, ice bath and N.sub.2 atmosphere 47.5 g (0.306 mol) of Intermediate 3 were placed. A solution of 101 g (0.827 mol) of 2,6-Dimethylphenol in 230 mL acetonitrile was added dropwise at 10? C. Additionally, 70 mL (0.919 mol) of TFA were added dropwise, followed by dropwise addition of 32 mL (0.367 mol) of trifluoromethanesulfonic acid and the resulting solution was stirred at room temperature overnight. Reaction mixture was concentrated to dryness in vacuum and obtained crude was stirred with 1 L of Et.sub.2O. The Et.sub.2O filtrate was decanted and again 1 L of Et.sub.2O was added. The sticky solid was filtered, washed with Et.sub.2O (500 mL) and dried under vacuum. A brown solid was stirred in 300 mL ethyl acetate for 30 minutes, the off-white solid was filtered, washed with ethyl acetate (100 mL) and dried under high vacuum to give an off-white solid. Obtained TFA-salt of product was converted to free base by suspension it in 100 mL of water and neutralization of it with 200 mL of 25% NH.sub.3 leading to precipitation of piperidine containing monomer (VIIb) as a white solid. Obtained product was dried under vacuum overnight and 20.67 g of product were purified by normal phase column chromatography to give 12.13 g (yield 59%) of piperidine containing monomer (VIIb). Chemical structure of monomer (VIIb) was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 4. DMSO-d6 was used as solvent.

Example 9: Synthesis of Piperidine Containing Polymer

[0084] Synthesis was performed in a 500 mL three-necked flask with oil bath, mechanical stirrer, a packed column with distillation head cooler with adjustable return ratio and condensate removal. At the beginning of synthesis 11.03 g (0.03 mol) of piperidine containing monomer (VIIb) from Example 8, 6.55 g (0.03 mol) of 4,4-Difluorobenzophenon (VIa), 165 mL of N,N-Dimethylacetamide and 9.12 g (0.066 mol) of finely ground K.sub.2CO.sub.3 were mixed under nitrogen atmosphere over one hour at room temperature. Afterwards the temperature of the reaction mixture was increased to 120? C. and generated water was removed using the column over 4 hours. After four hours additional 10 mL of N,N-Dimethylacetamide were added to the reaction mixture and temperature of the reaction mixture was increased to 165? C. After 20 hours the heating of the oil bath was turned off, the viscous reaction product was cooled down and poured into cold water. The precipitated product was washed with hot water three times and was dried under vacuum at 40? C. over 48 hours. The yield was 15.14 g (92.4%).

Example 10: Quaternization of Piperidine Containing Polymer from Example 9

[0085] 10 g of the polymer from Example 9 were dissolved in 40 mL of N,N-Dimethylacetamide under stirring at 60? C. for one hour. After cooling of the polymer solution down to 30? C. dropwise 2.5 mL of iodomethane were added to the polymer solution and polymer solution was stirred for 24 hours at 30? C. leading to quaternization of the polymer. Chemical structure of quaternized piperidine containing polymer from Example 10 was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 5. DMSO-d6 was used as solvent.

Example 11: Membrane Casting of Piperidine Containing Polymer from Example 10

[0086] The solution of the quaternized polymer from Example 3 was directly used for preparation of the membrane. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 ?m PTFE filter on a glass plate preheated to 40? C. For the coating of the glass plate, an applicator with doctor blade was automatically pulled over the glass plate at a speed of 5 mm/s. The applied wet layer was pre-dried for 24 hours under N.sub.2 atmosphere at room temperature and then finally dried for 6 hours at 60? C. under vacuum.

Example 12: Synthesis of Piperidine Containing Polymer

[0087] Synthesis was performed in a 500 mL three-necked flask with oil bath, mechanical stirrer, a packed column with distillation head cooler with adjustable return ratio and condensate removal. At the beginning of synthesis 11.03 g (0.03 mol) of piperidine containing monomer (VIIb) from Example 8, 7.63 g (0.03 mol) of 4,4-Difluordiphenylsulfon (VIb), 165 mL of N,N-Dimethylacetamide and 9.12 g (0.066 mol) of finely ground K.sub.2CO.sub.3 were mixed under nitrogen atmosphere over one hour at room temperature. Afterwards the temperature of the reaction mixture was increased to 120? C. and generated water was removed using the column over 4 hours. After four hours additional 10 mL of N,N-Dimethylacetamide were added to the reaction mixture and temperature of the reaction mixture was increased to 165? C. After 20 hours the heating of the oil bath was turned off, the viscous reaction product was cooled down and poured into cold water. The precipitated product was washed with hot water three times and was dried under vacuum at 40? C. over 48 hours. The yield was 15.39 g (88.1%).

Example 13: Quaternization of Piperidine Containing Polymer from Example 12

[0088] 10 g of the polymer from Example 12 were dissolved in 40 mL of N,N-Dimethylacetamide under stirring at 60? C. for one hour. After cooling of the polymer solution down to 30? C. dropwise 2.5 mL of iodomethane were added to the polymer solution and polymer solution was stirred for 24 hours at 30? C. leading to quaternization of the polymer. Chemical structure of quaternized piperidine containing polymer from Example 10 was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 6. DMSO-d6 was used as solvent.

Example 14: Membrane Casting of Piperidine Containing Polymer from Example 13

[0089] The solution of the quaternized polymer from Example 13 was directly used for preparation of the membrane. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 ?m PTFE filter on a glass plate preheated to 40? C. For the coating of the glass plate, an applicator with doctor blade was automatically pulled over the glass plate at a speed of 5 mm/s. The applied wet layer was pre-dried for 24 hours under N.sub.2 atmosphere at room temperature and then finally dried for 6 hours at 60? C. under vacuum.

Example 15: Synthesis of Spiro Containing Monomer (VIIc)

[0090] Synthesis of spiro containing monomer (VIIc) was performed in four steps accordingly to reaction scheme 6 (step 1), reaction scheme 7 (step 2), reaction scheme 8 (step 3) and reaction scheme 9 (step 4). Intermediate 4 was synthesized following exact same steps like by synthesis of monomer (VIIb) but starting with 1-Benzylpiperidin-4-one instead of 1-Methylpiperydin-4-one.

##STR00017##

##STR00018##

##STR00019##

##STR00020##

[0091] In a three-necked round-bottom flask (1000 mL) equipped with thermometer, dropping funnel, mechanical stirrer, ice bath and N.sub.2 atmosphere 20 g (45.1 mmol) of Intermediate 4 was dissolved in 451 mL of DCM and 18.4 g (270.5 mmol) of Imidazole was added. The mixture was carefully evacuated & refilled with N.sub.2 (three times). Reaction mixture was cooled with ice bath and 16.31 g (108.2 mmol) of tert-Butyldimethylchlorosilane (TBDMSCI) in 20 mL of DCM added to the reaction mixture dropwise. After addition, cooling was removed, and reaction mixture was stirred at room temperature overnight leading to formation of white precipitate. The reaction mixture was quenched with 200 mL of saturated NH.sub.4Cl solution and 200 mL of water were added following by extraction with 600 mL of DCM. The water phase was washed with 300 mL of DCM and the combined organic layers were washed two times with 400 mL of water and with 400 mL of brine, dried over MgSO.sub.4, filtered and the solvent was removed under reduced pressure. Crude product was purified by normal phase column chromatography to give 24.92 g (65% yield) of Intermediate 5.

[0092] In a three-necked round-bottom flask (1000 mL) equipped with mechanical stirrer, N.sub.2 atmosphere and H.sub.2 atmosphere 24.7 g (36.7 mmol) of Intermediate 5 was dissolved in 150 mL DCM/Methanol (3/1) under N.sub.2. To that mixture 4.45 g Pd/C (10%, 50% wet) was added and the atmosphere was changed to H.sub.2 (three times). The reaction mixture was stirred under H.sub.2 atmosphere overnight at room temperature.

[0093] After 24 hours additional 3 g Pd/C (10%, 50% wet) was added to the reaction mixture and reaction was stirred under H.sub.2 for additional 24 hours at room temperature. Crude product was two times filtered via Celite and washed with DCM (100 mL). Filtrate was evaporated giving 21 g (69% crude yield) of Intermediate 6.

[0094] In a three-necked round-bottom flask (1 L) equipped with thermometer, mechanical stirrer, ice bath and N.sub.2 atmosphere 21 g (36.1 mmol) of Intermediate 6 was suspended in 500 mL acetonitrile and 35.3 g (108.2 mmol) Cs.sub.2CO.sub.3 was added in one portion. The reaction mixture was cooled to 0? C. and 10 g (43.3 mmol) 1,5-dibromopentane was added at once. The reaction mixture was stirred at 0? C. for 2 hours and then stirred at room temperature overnight. After total 24 hours of reaction at room temperature additional 3 g 1,5-dibromopentane and 5 g Cs.sub.2CO.sub.3 was added to the reaction mixture. Additionally, the reaction mixture was evacuated with N.sub.2 (three times) and was stirred at room temperature for additional 6 hours. The reaction mixture was filtered off via paper filter by gravity and reaction mixture was evaporated followed by precipitation in Et.sub.2O, filtering and drying under high vacuum to give 18.17 g (69% yield) of Intermediate 7.

[0095] In a three-necked round-bottom flask (1 L) equipped with thermometer, dropping funnel, mechanical stirrer, ice bath and N.sub.2 atmosphere 186 mL of methanol were placed and 5.7 mL of acetyl bromide was dropwise added at 0? C. To that mixture 17 g (23.25 mmol) of Intermediate 7 in 50 mL of methanol was dropwise added at 0? C. The reaction mixture was stirred at room temperature overnight. After total 24 hours of reaction the reaction mixture was evaporated followed by precipitation in Et.sub.2O, filtering and drying under high vacuum to give 12.35 g of crude product. Purification was performed using reverse phase column chromatography under neutral conditions to give 5.51 g (44% yield) of spiro containing monomer (VIIc). Chemical structure of monomer (VIIc) was confirmed by 1H-NMR; 1H-NMR spectrum is given in FIG. 7. DMSO-d6 was used as solvent.

Example 16: Synthesis of Spiro Containing Polymer

[0096] Synthesis was performed in a 250 mL three-necked flask with oil bath, mechanical stirrer, a packed column with distillation head cooler with adjustable return ratio and condensate removal. At the beginning of synthesis 5.02 g (0.01 mol) of spiro containing monomer (VIIc) from Example 15, 2.18 g (0.01 mol) of 4,4-Difluorobenzophenon (VIa), 70 mL of N,N-Dimethylformamide and 3.04 g (0.022 mol) of finely ground K.sub.2CO.sub.3 were mixed under nitrogen atmosphere over one hour at room temperature. Afterwards the temperature of the reaction mixture was increased to 120? C. and generated water was removed using the column over 4 hours. After four hours additional 5 mL of N,N-Dimethylformamide were added to the reaction mixture and temperature of the reaction mixture was increased to 154? C. After 20 hours the heating of the oil bath was turned off, the viscous reaction product was cooled down and poured into cold water. The precipitated product was washed with hot water three times and was dried under vacuum at 40? C. over 48 hours. The yield was 5.48 g (85.6%). Chemical structure of spiro containing polymer from Example 16 was confirmed by 1H-NMR; 1H-NMR spectrum is given in FIG. 8. DMSO-d6 was used as solvent.

Example 17: Membrane Casting of Spiro Containing Polymer from Example 16

[0097] 5 g of polymer from Example 16 were dissolved in 20 mL of N,N-Dimethylformamide under stirring at 60? C. for one hour. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 ?m PTFE filter on a glass plate preheated to 40? C. For the coating of the glass plate, an applicator with doctor blade was automatically pulled over the glass plate at a speed of 5 mm/s. The applied wet layer was pre-dried for 24 hours under N.sub.2 atmosphere at room temperature and then finally dried for 6 hours at 60? C. under vacuum.

Example 18: Synthesis of Amine Containing Monomer (VIId)

[0098] A solution of 138.05 g (1.13 mol) of 2,6-dimethylphenol in 500 mL of acetic acid was placed in 2 L three-neck round-bottom flask equipped with thermometer, dropping funnel, mechanical stirrer and N.sub.2 atmosphere, 500 mL of conc aq. HCl solution and 74.59 g (0.56 mol) of 2,2-Dimethoxy-N,N-dimethylethanamine were added dropwise. The reaction mixture was stirred at room temperature overnight and additional 250 mL of conc aq. HCl were added after 24 hours of reaction. The reaction mixture was stirred at room temperature overnight. After total 48 hours of reaction it was directly concentrated under vacuum to dryness and was mixed with 1.5 L of water and sonicated for 30 minutes. The solid product was collected by filtration and washed with water, then suspended in 500 mL of acetonitrile and concentrated under vacuum to give 97 g of crude product. Then 40 g of it was purified by reverse phase column chromatography to give 30.8 g of pure product as HCl-salt followed by conversion of it in free amine form by suspension in 700 mL of 25% ammonia solution and stirring at room temperature overnight. Obtained solid was collected by filtration, washed with water and directly freeze dried to give 25.03 g (63% yield) of amine containing monomer (VIId). Chemical structure of monomer (VIId) was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 9. DMSO-d6 was used as solvent.

[0099] Same reaction conditions can be applied for synthesis of similar monomers with different length n of aliphatic chain, e.g. in case 3,3-Dimethoxy-N,N-dimethyl-1-propanamine will be used, than n is equal to 2.

Example 19: Synthesis of Amine Containing Polymer

[0100] Synthesis was performed in a 500 mL three-necked flask with oil bath, mechanical stirrer, a packed column with distillation head cooler with adjustable return ratio and condensate removal. At the beginning of synthesis 9.4 g (0.03 mol) of amine containing monomer (VIId) from Example 18, 6.55 g (0.03 mol) of 4,4-Difluorobenzophenon (VIa), 150 mL of N,N-Dimethylacetamide and 9.12 g (0.066 mol) of finely ground K.sub.2CO.sub.3 were mixed under nitrogen atmosphere over one hour at room temperature. Afterwards the temperature of the reaction mixture was increased to 120? C. and generated water was removed using the column over 4 hours. After four hours additional 10 mL of N,N-Dimethylacetamide were added to the reaction mixture and temperature of the reaction mixture was increased to 165? C. After 20 hours the heating of the oil bath was turned off, the viscous reaction product was cooled down and poured into cold water. The precipitated product was washed with hot water three times and was dried under vacuum at 40? C. over 48 hours. The yield was 13.36 g (90.6%).

Example 20: Quaternization of Amine Containing Polymer from Example 19

[0101] 10 g of the polymer from Example 19 were dissolved in 40 mL of N,N-Dimethylacetamide under stirring at 60? C. for one hour. After cooling of the polymer solution down to 30? C. dropwise 2.5 mL of iodomethane were added to the polymer solution and polymer solution was stirred for 24 hours at 30? C. leading to quaternization of the polymer. Chemical structure of quaternized amine containing polymer from Example 20 was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 10. DMSO-d6 was used as solvent.

Example 21: Membrane Casting of Amine Containing Polymer from Example 20

[0102] The solution of the quaternized polymer from Example 20 was directly used for preparation of the membrane. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 ?m PTFE filter on a glass plate preheated to 40? C. For the coating of the glass plate, an applicator with doctor blade was automatically pulled over the glass plate at a speed of 5 mm/s. The applied wet layer was pre-dried for 24 hours under N.sub.2 atmosphere at room temperature and then finally dried for 6 hours at 60? C. under vacuum.

Example 22: Synthesis of Amine Containing Polymer

[0103] Synthesis was performed in a 500 mL three-necked flask with oil bath, mechanical stirrer, a packed column with distillation head cooler with adjustable return ratio and condensate removal. At the beginning of synthesis 9.4 g (0.03 mol) of amine containing monomer (VIId) from Example 18, 7.63 g (0.03 mol) of 4,4-Difluordiphenylsulfon (VIb), 160 mL of N,N-Dimethylacetamide and 9.12 g (0.066 mol) of finely ground K.sub.2CO.sub.3 were mixed under nitrogen atmosphere over one hour at room temperature. Afterwards the temperature of the reaction mixture was increased to 120? C. and generated water was removed using the column over 4 hours. After four hours additional 10 mL of N,N-Dimethylacetamide were added to the reaction mixture and temperature of the reaction mixture was increased to 165? C. After 20 hours the heating of the oil bath was turned off, the viscous reaction product was cooled down and poured into cold water. The precipitated product was washed with hot water three times and was dried under vacuum at 40? C. over 48 hours. The yield was 13.87 g (87.6%).

Example 23: Quaternization of Amine Containing Polymer from Example 22

[0104] 10 g of the polymer from Example 22 were dissolved in 40 mL of N,N-Dimethylacetamide under stirring at 60? C. for one hour. After cooling of the polymer solution down to 30? C. dropwise 2.5 mL of iodomethane were added to the polymer solution and polymer solution was stirred for 24 hours at 30? C. leading to quaternization of the polymer. Chemical structure of quaternized piperidine containing polymer from Example 6 was confirmed by .sup.1H-NMR; .sup.1H-NMR spectrum is given in FIG. 11. DMSO-d6 was used as solvent.

Example 24: Membrane Casting of Amine Containing Polymer from Example 23

[0105] The solution of the quaternized polymer from Example 23 was directly used for preparation of the membrane. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 ?m PTFE filter on a glass plate preheated to 40? C. For the coating of the glass plate, an applicator with doctor blade was automatically pulled over the glass plate at a speed of 5 mm/s. The applied wet layer was pre-dried for 24 hours under N.sub.2 atmosphere at room temperature and then finally dried for 6 hours at 60? C. under vacuum.

Example 25: Ion Exchange of Membranes in Hydroxide Form

[0106] The membranes prepared in Example 4 of WO 2021/013694 A1 (labeled as Membrane #1), Example 11 of present disclosure (labeled as Membrane #2), Example 17 of present disclosure (labeled as Membrane #3), membrane made of polymer prepared using a tertiary amine bisphenol monomer (MPDDP) described in CN 110294845 A under reaction conditions similar to Example 2 of present disclosure (labeled as Membrane #4) and commercially available anion exchange membrane FAA-3-50 were ion-exchanged using following procedure: six samples of each membrane (40?40 mm) were placed in fresh portions of 1 M KOH solution three times for 1 hour each at 60? C. and subsequently in fresh portion of 1 M KOH solution for 24 hours at 60? C. Afterwards the membrane samples were rinsed off with deionized water and placed in fresh portions of the deionized water three times for 1 hour each at room temperature. Subsequently, the membrane samples were stored in a fresh portion of the deionized water overnight at room temperature.

Example 26: Degradation of Membrane Samples in 2 M KOH at 80? C.

[0107] All samples from Example 25 (six samples of each membrane type per bottle) were placed in 250 mL bottle made of thick PTFE material and equipped with gas tight screw cap, filled with 2 M KOH solution and placed in drying cabinet at 80? C. for 2000 hours. After that samples were rinsed with deionized water and the ionic conductivity of each sample was measured.

Example 27: Measurement of Ionic Conductivity (IC)

[0108] The ionic conductivity (IC) of ion-exchanged membrane samples from Example 25 and Example 26 was measured by means of impedance spectroscopy (EIS) in a conventional 4-electrode arrangement. The membrane sample was mounted in a commercial BT-112 cell (Bekk Tech LLC), so that the two outer Pt wires were placed under the sample and the two midpoint Pt wires above the sample. The BT-112 cell was mounted between two PTFE plates and filled with deionized water. The temperature of the deionized water was controlled by a water bath and deionized water was pumped permanently through the cell. The calculation of the membrane resistance (R.sub.membrane) was carried out by fitting acquired EIS spectrum using a widely used R (RC) Randles equivalent circuit.

[0109] The ionic conductivity (a) of the membrane sample is given by Equation (1):

?=L/(R.sub.membrane*A)(1)

[0110] where L is the distance between Pt wires (5 mm) and A is the area of the membrane sample between the two outer Pt wires. Each measurement was repeated for six samples per each membrane and a mean?standard deviation was calculated. Commercially available anion exchange membrane FAA-3-50 was tested in the same way. Additionally, the IC of native membrane samples (non-degraded samples of as prepared membranes) from Example 25 was measured as reference.

[0111] Table 1 summarizes all measurement results. Normalized initial IC represents the normalized IC of native membrane samples (non-degraded samples of as prepared membranes), while remaining normalized IC represents the IC of degraded over 2000 hours samples.

TABLE-US-00001 TABLE 1 Experimental data obtained according to Examples 25 to 27 with membranes from Example 4 of WO 2021/013694 A1 (labeled as Membrane #1), Example 11 of present disclosure (labeled as Membrane #2), Example 17 of present disclosure (labeled as Membrane #3), membrane made of polymer prepared using a tertiary amine bisphenol monomer (MPDDP) described in CN 110294845 A under reaction conditions similar to Example 2 of present disclosure (labeled as Membrane #4) and commercially available anion exchange membrane FAA-3-50 from FUMATECH BWT GmbH. Normalized Remaining initial IC normalized IC Qualification [%] [%] Membrane 1 prior art 100 88.6 ? 0.1 Membrane 2 invention 100 90.2 ? 0.1 Membrane 3 invention 100 94.5 ? 0.1 Membrane 4 prior art 100 n/a* FAA-3-50 prior art 100 n/a** *Membrane 4 disintegrated into several small pieces after 1000 hours in 2M KOH at 80? C. **FAA-3-50 membrane completely disintegrated after 120 hours in 2M KOH at 80? C.

[0112] It can be seen from Table 1, that the membranes according to present invention show a higher remaining normalized IC value than the prior art membranes. Therefore, inventive compounds will maintain their ionic conductivity for longer period of time.