ANION EXCHANGE MEMBRANES AND POLYMERS FOR USE IN SAME
Embodiments of the invention relate generally to anion exchange membranes and, more particularly, to anion exchange membranes comprising a styrene block copolymer and methods for their manufacture. In one embodiment, the invention provides a polymer according to formula IV, wherein x and y are mol %, QA is or each of R1 and R2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain.
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This application is a continuation of U.S. patent application Ser. No. 16/696,186, filed Nov. 26, 2019, which is a continuation of U.S. patent application Ser. No. 16/351,989, filed Mar. 13, 2019, which is a continuation of U.S. patent application Ser. No. 15/326,538, filed Jan. 16, 2017, which is a national stage filing of International Patent Application No. PCT/US2015/041487, filed Jul. 22, 2015, which claims the benefit of U.S. Provisional Patent Application No. 62/027,497, filed Jul. 22, 2014, which are hereby incorporated herein as though set forth in their entireties.
STATEMENT REGARDING FEDERALLY-SPONSORED RESEARCH OR DEVELOPMENTThis invention was made with government support under grant number DMR1261331 awarded by the National Science Foundation. The government has certain rights in the invention.
BACKGROUNDAlkaline exchange membranes or anion exchange membranes (AEMs) allow for the transportation of anions (e.g., OH−, Cl−, Br−) from the cathode to the anode in an electrochemical reaction. AEMs are a critical component of AEM fuel cells, where hydrogen and oxygen are used to generate electricity, with water as a byproduct. AEMs are also used in water electrolysis, where water is split into hydrogen and oxygen using electricity. In both AEM fuel cells and water electrolysis, hydroxide ions (OH−) are transported through the AEM, along with water molecules. AEMs may also be used, for example, in batteries, sensors, and as actuators.
Known AEMs are generally unsuitable for use in AEM fuel cells or water electrolysis. Many commercially-available AEMs are based on polystyrene, which is generally considered a poor choice for AEM fuel cells or water electrolysis. Other AEM materials contain an arylene ether linkage (—O—) in the mid-chain and a benzyltrimethyl ammonium group in the side-chain. This combination, however, has been found to be chemically unstable and to degrade easily under highly alkaline conditions.
BRIEF DESCRIPTION OF THE INVENTIONIn one embodiment, the invention provides a polymer according to formula IX
wherein x and y are mol % and n is 1-10.
In another embodiment, the invention provides a polymer according to formula XII
wherein x and y are mol % and n is 1-10.
In still another embodiment, the invention provides a polymer according to formula IV
wherein x and y are mol % and n is 1-10, QA is
each of R1 and R2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain.
In yet another embodiment, the invention provides an anion exchange membrane comprising at least one polymer selected from a group consisting of:
a polymer of formula IV
wherein x and y are mol % and n is 1-10, QA is
each of R1 and R2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain;
a polymer of compound IX
wherein x and y are mol and n is 1-10; and
a polymer of compound XII
wherein x and y are mol % and n is 1-10.
These and other features of this invention will be more readily understood from the following detailed description of the various aspects of the invention taken in conjunction with the accompanying drawings that depict various embodiments of the invention, in which:
It is noted that the drawings of the invention are not to scale. The drawings are intended to depict only typical aspects of the invention, and therefore should not be considered as limiting the scope of the invention.
DETAILED DESCRIPTION OF THE INVENTIONEmbodiments of the invention include a new class of quaternized ammonium hydroxide-containing polymers prepared from a styrene-butadiene block copolymer (SEBS). This new class of polymers may be used in alkaline exchange membranes (AEMs), lack an arylene ether linkage in the polymer main-chain, and can prepared with any of a number of quaternized ammonium groups in the polymer side-chains.
A palladium-catalyzed Suzuki coupling reaction is then carried out with an aryl bromide-containing amine to yield compound III. Various amine groups may be substituted for the boronic ester group in compound II, depending on the aryl bromide-containing amine employed. For example, the R group of the aryl bromide-containing amine may be of formula V or formula VI below, wherein each of R.sub.1 and R.sub.2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl (e.g., —(CH2)n—) chain, a cyclic alkyl chain, and an alkylene ether chain (e.g., —(CH2CH2O)n—CH2CH2—).
The resulting polymer is then cast into a film, followed by methylation of the amine groups in the polymer and an ion exchange reaction to form compound IV, a quaternary ammonium-containing styrene block copolymer (SEBS-QA) according to one embodiment of the invention. Applicants have found the SEBS-QAs of the invention to be chemically stable and suitable for use in AEMs, even in highly alkaline environments.
Any of a number of quaternary ammonium groups may be incorporated into the SEBS-QAs of the invention, some of which may be sterically hindered and chemically stable.
Table 1 below shows comparative properties of SEBS-QAs according to embodiments of the invention.
The results in Table 1 show that these SEBS-QAs have high anion conductivity (Cl−, HCO3−, OH−), which allows them to be used in a solid electrolyte membrane (in this case AEM) and as an ionomer in the electrodes in electrochemical devices.
Because SEBS exhibits a nano-scale phase-separated morphology, the SEBS-QAs of the invention will similarly exhibit nano-scale ion-transporting channels, allowing for the highly effective conduction of ions.
According to other embodiments of the invention, SEBS-based anion exchange membranes may be prepared without the use of an expensive transition metal catalyst such as iridium or palladium.
The inset within
Referring now to the inset of
The methyl 6-bromohexanoate ester (4.8 g, 23.0 mmol) and anhydrous THF (20 mL) are added to a 100 mL round bottom flask under nitrogen and cooled in an ice bath. A mixture of methyl magnesium bromide [(CH3MgBr, 3 M in ether) 23 mL, 69 mmol] in anhydrous THF (10 mL) is then added to the flask, e.g., by syringe. The ice bath is removed and the reaction mixture stirred at room temperature for 3 hours. The reaction is then slowly quenched with saturated NH.sub.4Cl (10 mL), water (10 mL), and diethyl ether (20 mL). The resulting product is then extracted with diethyl ether (3×15 mL), dried over MgSO4, and concentrated, e.g., using a rotary evaporator. The resulting tertiary alcohol (compound 3) is a colorless liquid (4.28 g, 92% yield). It should be noted that Grignard reagents or alkyllithium compounds other than methyl magnesium bromide can be used for preparation of similar tertiary alcohols.
Preparation of the polymer according to the embodiment in
Anhydrous dichloromethane (5 mL) is added, e.g. by syringe, and the polymer stirred until dissolved. The vial is then cooled in an ice bath and trifluoromethanesulfonic acid (0.55 mL, 6.22 mmol) is added. The reaction is stirred in the ice bath for one hour, after which the reaction is poured into methanol to precipitate the polymer.
The polymer is then filtered, redissolved in chloroform, and precipitated in methanol, yielding the SEBS-alkBr polymer of compound VIII after isolation and vacuum drying at room temperature for 6 hours. In practice, Applicants found 59.3% of the styrene units of compound VIII to be reacted (17.7 mol % alkyl-bromide and 12.2 mol % unfunctionalized styrene units). Molecular weights measured by GPC at 30° C. with THF as the eluent were SEBS-Mn=106,315 g/mol (PDI=1.04) and SEBS-alkBr-Mn=60,228 g/mol (PDI=2.07). Viscosities measured in toluene at 30° C. were SEBS=0.82 dL/g and SEBS-alkBR=0.68 dL/g.
Next, 0.15 g of compound VIII is dissolved in toluene (3 mL), filtered, cast onto a Teflon plate, and dried under a gentle flow of air at 80° C. The thin SEBS-alkBr film (approximately 30-40 m thick) is then removed from the plate by immersion in water and immersed in aqueous trimethylamine (45 wt % in water) and heated to 50° C. for 48 hours. The film is then ion exchanged to hydroxide form by immersion in 1 M NaOH at room temperature for 48 hours, yielding compound IX of
After stirring to dissolve the polymer, the flask is cooled in an ice bath and AlCl.sub.3 powder (0.93 g, 6.96 mmol) is added all at once. The mixture is then stirred in an ice bath for 45 minutes and at room temperature for 12 hours. The reaction mixture is then poured into methanol to precipitate the polymer, which is filtered, redissolved in chloroform, and precipitated in methanol to yield the SEBS-acylBr polymer of compound X. After vacuum drying at room temperature for 6 hours, 0.38 g of the polymer of compound X was obtained, in which 100% of the styrene units were reacted (i.e., the polymer contained 29.9 mol % acyl-bromide).
The ketone of the SEBS-acylBr of compound X may then be reduced to yield the SEBS-alkBr of compound XI. To do so, SEBS-acylBr of compound X (0.38 g, 0.91 mmol ketone) is added to a 100 mL round bottom flask, which is evacuated and purged with nitrogen. Anhydrous dichloromethane (19 mL) is added and the solution stirred until the polymer is dissolved. Triethylsilane (Et3SiH; 0.58 mL, 3.64 mmol) and trifluoroacetic acid (0.56 mL, 7.28 mmol) are added, e.g., by syringe, and the mixture stirred in a 45° C. oil bath. After 14 hours, the reaction is poured into methanol to precipitate the polymer, which is filtered, redissolved in chloroform, and precipitated in methanol to yield the SEBS-alkBr of compound XI. After vacuum drying at room temperature for 6 hours, 0.30 g of the polymer of compound XI was obtained in which 100% of the ketone was reduced.
The SEBS-alkBr of compound XI may then be aminated to yield the SEBS-alkTMA of compound XII. To do so, SEBS-alkBr (compound XI; 0.15 g) is dissolved in toluene (3 mL), filtered, cast onto a Teflon plate, and dried under a gentle flow of air at 80° C. The thin SEBS-alkBr film (approximately 30-40 m thick) is removed from the plate by immersion in water, immersed in aqueous trimethylamine (45 wt % in water) and heated to 50° C. for 48 hours. After 48 hours, the film is rinsed with water and ion exchanged to hydroxide form by immersion in 1 M NaOH at room temperature for 48 hours, yielding the SEBS-alkTMA polymer of compound XII.
Polymers according to embodiments of the invention may be employed in any number of contexts, including, for example, as fuel cell alkaline exchange membranes, fuel cell ionomers, electrolysis alkaline exchange membranes, as actuators, and in any number of battery applications, as will be apparent to one skilled in the art.
One skilled in the art will also recognize, of course, that various changes, additions, or modifications of or to the methods described above may be made without substantively altering the compounds obtained or their characteristics. Such changes, additions, and modifications are therefore intended to be within the scope of the invention.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any related or incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims
1. A polymer according to formula IX
- wherein x and y are mol % and n is 1-10.
2.-12. (canceled)
Type: Application
Filed: Jun 15, 2021
Publication Date: May 12, 2022
Applicant: Rensselaer Polytechnic Institute (Troy, NY)
Inventors: Chulsung Bae (Cohoes, NY), Angela Dee Mohanty (Clifton Park, NY)
Application Number: 17/347,805