Patent Application
20240301153
The present invention provides compounds, especially polymeric compounds, a process for preparation thereof and for the use of these compounds. Intended use is in field of electrochemistry. Anion-conducting properties of disclosed compounds making this material suitable for preparing anion-conducting membranes.
One important example for an electrochemical process is electrolysis of water to gain molecular hydrogen and molecular oxygen. The electrochemical aggregate used to perform such process is called electrolyzer. Such electrolyzer typically comprise many electrochemical cells. Each electrochemical cell comprises two compartments, each equipped with one gas evolving electrode and a membrane separating both compartments. To enable electrolytic splitting of water, the membrane needs to be conductive for ions (cations or anions), while almost impermeable for hydrogen and oxygen gas. Compounds discussed herein are intended to compose such membranes.
As the membranes of electrolyzers are in contact with water, they need to be stable against extensive swelling or deformation (wrinkling) caused by extensive water uptake within the polymeric structure. Extensive swelling may result in mechanical damage of membrane and lead to increased permeability of gases. For the sake of security, gas permeability needs to be limited. Otherwise, there is risk of oxyhydrogen explosion.
However, measures to increase stability against swelling shall not impair anionic conductivity of the material as this would result in poor process efficiency.
Similar requirements relate to membranes used in electrochemical cells performing other electrochemical processes in aqueous/hydrous environment. Examples are fuel cells, redox flow batteries and cells used for electrodialysis.
A polymeric anion-conducting material suitable for preparing a membrane to be used in electrolyzers is known from WO 2019/076860 A1. This material is characterized by at least one imidazole and/or imidazolium unit.
CN 104829814 A discloses a polymer containing a quaternized piperidine group. This polymer is used for preparing an anion exchange membrane as well.
A preparation method for a tertiary amine type polyarylether sulfone (ketone) polymer resin is known from CN110294845A. This polymer is used for preparing an anion exchange membrane.
Several anion exchange membranes for water electrolysis are commercially available. A market overview has been compiled by Henkensmeier et al.:
An example for a commercially available anion exchange membrane is the product called fumasep® FAA-3-50, produced by FUMATECH BWT GmbH, 74321 Bietigheim-Bissingen, DE. According to Henkensmeier et al., this membrane is based on a polyaromatic polymer with ether bonds in the main chain and quaternary ammonium groups attached to the main chain.
The drawbacks of these known materials are extensive water uptake, extensive swelling, rare and expensive precursors, toxic and highly corrosive solvents, complicated preparation conditions being difficult for production at industrial scale. Therefore, these known materials have expensive preparation costs.
Thus, it is object of present invention to provide an easy-to-prepare material with proper anion-conducting properties and controlled swelling especially in aqueous environments. The precursors needed to synthesize the compound shall be inexpensive and synthesis process shall be suitable for industrial production.
Currently undisclosed international patent application PCT/EP2020/070153 relates to a polymeric anion-conducting membrane made from a compound containing at least one unit of the formula (0)
with X being a structure element comprising a nitrogen atom with a positive charge bonded to C1 and C2 and bonded via two bonds to one or two hydrocarbon radical(s) comprising 1 to 12, preferably 1 to 6, more preferably 1 or 5 carbon atoms and Z being a structure element comprising a carbon atom being bonded to C3 and C4 and at least one aromatic 6-ring directly bonded to one of the oxygen atoms, wherein the aromatic rings might be substituted with one or more halogen and/or one or more C1- to C4-alkyl radicals. This material already fulfills aforesaid requirements.
However, the inventors have surprisingly found that this problem can also be solved by the compounds according to the present invention as described hereinafter and in the claims as well.
The present invention therefore provides compounds as defined in the claims and described hereinafter.
Inventive compound is characterized by at least one unit of the formula (I)
with X being a structure element comprising at least one nitrogen atom with a positive charge bonded to C1 and C2 and bonded via two bonds to one or two hydrocarbon radical(s) comprising 1 to 12, preferably 1 to 6, more preferably 1 or 5 carbon atoms and Z being a structure element comprising a carbon atom being bonded to C3 and C4 and at least one aromatic 6-ring directly bonded to one of the oxygen atoms, wherein said aromatic 6-ring is substituted in position 3 and 5 with the same or different alkyl group having from 1 to 4 carbon atoms, preferably being a methyl, iso-propyl or tert-butyl group, more preferably being a methyl group.
Thus, inventive compounds differ from compounds according to formula (0) at least by a sulfonic group.
The present invention likewise provides a process for preparing such compounds and for the use thereof as anion-conducting membranes in electrochemical cells.
The polymers according to the invention have the advantage that they can be prepared in a simple manner. Precursors are comparable cheap. Thus, preparation is cost efficient.
The membranes produced therefrom have the advantage that they have very high mechanical stability and low swelling characteristics combined with high dimensional stability. In addition, the membranes exhibit quite high anion conductivities. Therefore, inventive compounds are well suited separation active material of membranes, which are employed in electrochemical cells performing electrochemical processes in aqueous/hydrous environments.
In a preferred embodiment, inventive compound is represented by formula (Ia) or (Ib)
with Y=same or different halogen, preferably Y=F and with M being an integer from 1 to 1000, preferably M being an integer from 5 to 500.
According to a preferred embodiment of present invention, structure element X represents a unit of formula (IIa), (IIb) or (IIc)
with R1, R2 and R3 being the same or different alkyl group having from 1 to 6 carbon atoms and two nitrogen atoms being connected with an aliphatic chain having from 1 to 6 carbon atoms (n=1-6), R1, R2 and R3 each preferably being a methyl group.
Most preferably, structure element X present represents in more than 5%, preferably in more than 50%, and most preferred in more than 90% of its occurrence a unit of formula (IIa), (IIb) or (IIc). The occurrence can be determined for example by classical 1H-NMR performed accordingly to 01/2005:20233 (EUROPEAN PHARMACOPOEIA 5.0. 2.2.33. Nuclear magnetic resonance spectrometry) at room temperature in DMSO-d6 as solvent. The occurrence can be calculated via integration of the area of corresponding signal and comparison of normalized area of corresponding signal (peak) with the number of corresponding protons in a target unit, e.g. a unit of formula (IIa) contains 6 hydrogen atoms and as presented in
According to a further preferred embodiment of the invention, the structure element Z of the compound represents a unit of formula (III)
with R4, R5, R6 and R7 being the same or different alkyl group having from 1 to 4 carbon atoms, R4, R5, R6 and R7 each preferably being a methyl, iso-propyl or tert-butyl group, more preferably being a methyl group.
Six preferred embodiments of inventive compound are represented by at least one of formulas (IVa) to (IVf):
with Ma, Mb and Mc each being an integer of from 1 to 1000, preferably Ma, Mb and Mc each being an integer of from 5 to 500.
Even more preferred compounds are cross-linked ones as represented by at least one of formulas (Va) to (Vd):
with at least two polymer chains being connected with an aliphatic chain having from 1 to 10 carbon atoms (m=1-9), with Ma, Mb and Mc each being an integer from 1 to 1000, preferably with Ma, Mb and Mc each being an integer from 5 to 500, with X and Z each being between 0.01 and 0.5, preferably with X and Z each being between 0.01 and 0.25.
As derivable from the formulae (I), (Ia), (Ib), (IVa) to (IVf) and (Va) to (Vd) and related definitions, all inventive compounds comprising an aromatic 6-ring which is directly bonded to one of the oxygen atoms, which is substituted in position 3 and 5 with the same or different alkyl group having from 1 to 4 carbon atoms.
According a first variant of the invention, said aromatic 6-ring is further substituted with one or more halogen and/or one or more C1- to C4-alkyl radicals.
According to a second, preferred variant of the invention, said aromatic 6-ring is free of any further substitution with one or more halogen and/or one or more C1- to C4-alkyl radicals. Precursor materials for preparing such compounds are cheaper. Thus, preparation and final compound is less cost intensive.
Yet another object of the present invention is to provide a process for preparing inventive compounds.
This object is solved by a process that comprises a step in which a compound of the formula (VI), where Y is same or different halogen, preferred F,
is reacted with one or both compounds selected from formulas (VIIa) or/and (VIIb)
wherein the aromatic rings might further be substituted with one or more halogen and/or one or more C1- to C4-alkyl radicals. In case compound (VIIa) is used, an additional step (quaternization of nitrogen atom) is required and can be easily performed using an alkylating reagent.
Such process is quite simple to conduct and yields desired compounds.
Preferably, this reaction step is carried out at a temperature of from 100° C. to 300° C., more preferably at a reaction temperature of from 125° C. to 175° C. Most preferably the reaction step is carried out at a temperature where the reaction mixture is boiling, preferably while stirring. The reaction step is most preferably carried out under an inert gas atmosphere, preferably a nitrogen atmosphere. At the top of the reaction vessel, any water formed is preferably removed.
The reaction step is preferably carried out in the presence of a base like KOH, NaOH, K2CO3 or Na2CO3. Preferred base is K2CO3
The reaction step is carried out in the presence of an organic solvent. Preferred solvents are selected from the list consisting of N-Methyl-2-pyrrolidone (NMP), Dimethyl sulfoxide (DMSO), N,N-Dimethylformamide (DMF) and N,N-Dimethylacetamide (DMAC). Preferably N,N-Dimethylacetamide is used as a solvent.
Preferably the process according to the invention comprises a step where an alkylating reagent, preferably a methylating reagent, is used. The preferred methylating agent used is iodomethane.
According to a preferred inventive preparation method, the aromatic rings in the compounds of formula (VI), (VIIa) and (VIIb) are free of any further substitution with one or more halogen or one or more C1- to C4-alkyl radicals.
The compounds of the present invention might be used for different purposes. Preferably the compounds of the present invention are polymers and are used as anion-conducting membranes or for the production of anion-conducting membranes. Such use is a further object of present invention.
Within such membranes inventive compounds serve as separation active material due to their excellent anion-conducting properties, while being very gas tight. Beside inventive compounds, mentioned membranes may comprise further materials, for instance porous support, e.g. a fabric or non-woven material.
Thanks to designed properties of the component disclosed herein, an anion-conducting membrane comprising such material may be employed in an electrochemical cell. Thus, another embodiment of the invention is an electrochemical cell having an anion-conducting membrane, wherein said anion-conducting membrane comprises inventive compound.
The excellent water stability of present compounds makes this material suitable for employment in electrolyzers or a fuel cells or redox flow batteries. Thus, each a preferred embodiment of inventive electrochemical cell is an electrolyzer, a fuel cell or a redox flow battery.
Performing an electrochemical process by means of an inventive electrochemical cell is another embodiment of the invention.
Preferably, said electrochemical process is an electrolysis or an electrodialysis or an electrochemical process taking place during operation of a fuel cell or an electrochemical process taking place during operation of a redox flow battery.
Further details of present invention are derivable from the examples and accompanying figures. The latter show:
One 500 ml three-necked flask with internal thermometer, heating with magnetic stirrer and reflux cooler was fed with 150 g of acetic acid, 17 g (0.15 mol) of N-Methylpiperidone, 49 g (0.40 mol) of 2,6-Dimethylphenol and 30 g of concentrated hydrochloric acid. Subsequently, this solution was heated under stirring to 90° C. Over the reaction time a significant part of the product precipitated. After 40 hours, the reaction mass was cooled to room temperature. The crystallized precipitate was filtered off, washed three times with a small amount of acetic acid and suspended in a mixture of 250 g of water with 400 g of ethanol. Subsequently, the suspension was heated to 80° C. leading to dissolution of suspended solid. By adding ammonia solution 4,4-bis-(4-hydroxy-3,5-dimethyl-phenyl)-1-methyl-piperidine monomer (VIIa) was precipitated. After cooling to room temperature this was filtered off, the filter cake was 3 times washed with water and dried overnight in vacuum at 40° C. Chemical structure of monomer (VIIa) was confirmed by 1H-NMR; 1H-NMR spectrum is given in
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 16.98 g (0.05 mol) of piperidine containing monomer (VIIa) from Example 1, 12.72 g (0.05 mol) of 4,4′-Difluordiphenylsulfon, 180 mL of N,N-Dimethylacetamide and 15.21 g (0.011 mol) of finely ground K2CO3 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 18 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 25.53 g (92.2%).
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 2.8 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 1H-NMR; 1H-NMR spectrum is given in
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 μm 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 N2 atmosphere at room temperature and then finally dried for 6 hours at 60° C. under vacuum.
In a 2 L three-necked flask with magnetic stirrer, temperature control and condenser 36 g (0.26 mol) of K2CO3 were dissolved in 150 ml of EtOH. Then 57.3 g (0.40 mol) of 1,4-Dioxa-8-azaspiro[4,5] decane were dissolved in 800 ml of EtOH and transferred in three-necked flask. After that temperature was regulated to 35° C. Subsequently, a solution of 92 g (0.40 mol) of 1,5-Dibrompentane in 150 ml of EtOH was added dropwise over 12 hours. After 70 hours reaction products were cooled to room temperature, precipitated KBr was separated by filtration and the solution was concentrated on a rotary evaporator. During concentration process additional amount of KBr crystallizes and was filtered off. The filtrate solidified at temperature below 80° C., was filtered and used without further purification as one of educts for synthesis of spiro containing monomer (VIIb).
In a 500 ml round bottom flask with magnetic stirrer and oil bath 51.5 g (0.177 mol) of the molecule described above and 0.44 mol of 2,6-Dimethylphenol and 20 g (0.21 mol) of methanesulfonic acid, 1 g of water and 0.90 g (0.005 mol) of Sodium 3-mercapto-1-propanesulfonate were stirred for 70 hours at 100° C. The mixture was cooled to room temperature and mixed three times with 200 g of water. After that it was distilled at 1 kPa (10 mbar) pressure to remove volatile substances. Spiro containing monomer (VIIb) partially solidified and was two times recrystallized in 25 vol % mixture of EtOH in water. Finally, it was dried overnight in vacuum at 40° C. Chemical structure of monomer (VIIb) was confirmed by 1H-NMR; 1H-NMR spectrum is given in
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 4.89 g (0.01 mol) of spiro containing monomer (VIIb) from Example 5, 2.54 g (0.01 mol) of 4,4′-Difluordiphenylsulfon, 45 mL of N,N-Dimethylformamide and 3.03 g (0.022 mol) of finely ground K2CO3 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 6.21 g (88.3%). Chemical structure of spiro containing polymer from Example 6 was confirmed by 1H-NMR; 1H-NMR spectrum is given in
5 g of polymer from Example 6 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 μm 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 N2 atmosphere at room temperature and then finally dried for 6 hours at 60° C. under vacuum.
5 g of the polymer from Example 2 were dissolved in 20 mL of N,N-Dimethylacetamide under stirring at 60° C. for one hour and 4.46 g of (2-Bromoethyl)-trimethylammonium bromide were dissolved in 10 mL of N, N-Dimethylacetamide. Solution of (2-Bromoethyl)-trimethylammonium bromide was dropwise added to the polymer solution and polymer solution was stirred for 48 hours at 100° C. leading to quaternization of the polymer. Chemical structure of piperidine containing polymer quaternized with (2-Bromoethyl)-trimethylammonium bromide was confirmed by 1H-NMR; 1H-NMR spectrum is given in
The solution of the quaternized polymer from Example 8 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 μm 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 N2 atmosphere at room temperature and then finally dried for 6 hours at 60° C. under vacuum.
5 g of the polymer from Example 2 were dissolved in 20 mL of N,N-Dimethylacetamide under stirring at 60° C. for one hour and 0.25 mL of iodomethane were dissolved in 5 mL of N,N-Dimethylacetamide. After cooling of the polymer solution down to 30° C. solution of iodomethane was dropwise added to the polymer solution and polymer solution was stirred for 24 hours at 30° C. leading to partial quaternization of the polymer.
0.15 g of 1,6-Diiodohexane were dissolved in 5 mL of N,N-Dimethylacetamide and dropwise added to the polymer solution from Example 10. The polymer solution was steered for additional 10 minutes at 30° C. and directly used for casting of the membrane. The required amount of polymer solution was taken up with a syringe and applied directly through a 1 μm 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 covered with metal cover to slow down the evaporation of the solvent and coated glass plate was heated in the oven for 48 hours at 80° C. Finally, the membrane was dried for 6 hours at 60° C. under vacuum without metal cover. Obtained membrane was insoluble in DMSO-d6.
The membranes prepared in Examples 4, 7, 9 and 11 respectively were ion-exchanged: Samples of the membranes were placed in fresh portions of 1 M KOH solution 3 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 3 times for 1 hour each at 60° C. Subsequently, the membrane samples were stored in a fresh portion of the deionized water overnight at 60° C. and finally rinsed with deionized water at room temperature. Commercially available anion exchange membrane FAA-3-50 was ion exchanged in the same way.
The ionic conductivity (IC) of ion-exchanged membrane samples from Example 12 were 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 2 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 (Rmembrane) was carried out by fitting acquired EIS spectrum using a widely used R (RC) Randles equivalent circuit.
The ionic conductivity (o) of the membrane sample is given by Equation (1):
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 3 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. The results of the measurements are given in Table 1.
Ion-exchanged membrane samples from Example 12 (3 samples per each membrane tested) were used for measurement of water uptake (WU). All samples were dried for 24 hours in a vacuum oven at 40° C. and 2.5 kPa (25 mbar), then cooled in a desiccator to room temperature and weighted. For the measurement of the water uptake, membrane samples were stored for 24 hours in deionized water at 25° C. Subsequently, the weight of each sample was determined again. For this purpose, adhering water was removed from the membrane with the aid of a filter paper. Each measurement was repeated 3 times and a mean±standard deviation was calculated.
The water uptake (WU) results from Equation (2):
with mwet the mass of the sample after swelling and mdry the mass of the sample after drying. Commercially available anion exchange membrane FAA-3-50 was tested in the same way. The results of the measurements are given in Table 1.
Ion-exchanged membrane samples from Example 12 (3 samples per each membrane tested) were used for the measurement of dimensional stability (DS). All samples were dried for 24 hours in a vacuum oven at 40° C. and 2.5 kPa (25 mbar), then cooled in a desiccator to room temperature. Such parameters as the sample length, the sample width and the sample thickness were determined. To determine the swelling behavior, membrane samples were stored for 24 hours in deionized water at 25° C. Subsequently, the sample length, the sample width and the sample thickness were determined again. For this purpose, adhering water was removed from the membrane with the aid of a filter paper. Each measurement was repeated 3 times and a mean±standard deviation was calculated.
The swelling behavior in length (referred as DSl), width (referred as DSw) and thickness (referred as DSt) was calculated by Equation (3):
with xwet the length, width or thickness of the sample after swelling and xdry the dry length, dry width or dry thickness of the sample. DS value is calculated as (DSl+DSw+DS1)/3. Commercially available anion exchange membrane FAA-3-50 was tested in the same way. The results of the measurements are given in Table 1.
FAA-3-50 is a commercially available anion exchange membrane from FUMATECH BWT GmbH, 74321 Bietigheim-Bissingen, DE.
It can be seen from Table 1, that the membranes according to the invention show up to two times higher ionic conductivity combined with at least three times better dimensional stability and up to two times lower water uptake compared to commercially available anion-conducting membrane FAA-3-50.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21152487.1 | Jan 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/050298 | 1/10/2022 | WO |
