A sustainable and efficient process for the preparation of polyethylene–polystyrene interpolymer based anion exchange membranes by in situ chloromethylation for electrodialytic applications

Bhadja, Vaibhavee; Chakraborty, Souradeep; Pal, Sandip; Mondal, Rakhi; Makwana, B. S.; Chatterjee, Uma

doi:10.1039/c7se00048k

Cited by 13 publications

(7 citation statements)

References 37 publications

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“…Therefore, the membrane preparation technique is very crucial for DD application. A good AEM should have proper water uptake (WU), high anion permeability, excellent thermal and chemical stability, a low swelling ratio, and high H + /M n + selectivity. ,, Organic cations tethered to polymers have been used as functional groups in AEMs for DD in acid recovery. , AEMs prepared from polystyrene and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) are popular due to their low cost and easy functionalization. − However, the performance of many AEMs, in terms of the H + dialysis coefficient ( U H + ) and proton to metal ion (H + /M n + ) selectivity, is still not sufficient for the practical application in acid recovery by DD. A high U H + can be achieved with materials having high ionic content or high WU.…”

Section: Introductionmentioning

confidence: 99%

Alkylated Imidazole Moieties in a Cross-Linked Anion Exchange Membrane Facilitate Acid Recovery with High Purity

Mondal

Pal

Chatterjee

2021

ACS Appl. Polym. Mater.

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An anion exchange membrane (AEM) is applied for acid recovery through the diffusion dialysis (DD) process. However, a specially designed AEM is required to achieve a high dialysis coefficient of acid (U H + ) and separation factor (S). The design of our membrane for acid recovery and metal ion separation is based on the optimization of water swelling, structural stabilization (cross-linking), and introduction of cationic moieties where the delocalization of charge in a ring system (imidazole) is possible. Based on the above design, herein, preparation of a cross-linked AEM using a poly(acrylonitrile)-co-poly(vinyl imidazole) copolymer for the separation of metal ions and acid (HCl) is reported. The AEMs have been prepared by quaternization of the copolymer followed by cross-linking. The effect of a quaternizing agent (alkyl chain length) and copolymer composition on the performance of the membranes has been evaluated. The membrane (AEM2-Bu-2) prepared by the quaternization of the copolymer (AN/VIm = 75:25 mol/mol) with 1-bromobutane followed by cross-linking exhibits the highest acid recovery performance with a U H + of 0.047 m/h and S value of 130 during the separation of the 1 M HCl + 0.18 M FeCl 2 mixture. The quaternized imidazole ring provides stabilization of the cationic charge, which enhances the performance of the membrane. This work provides an insight to design a high-performance AEM for acid recovery through the DD process.

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Section: Introductionmentioning

confidence: 99%

Alkylated Imidazole Moieties in a Cross-Linked Anion Exchange Membrane Facilitate Acid Recovery with High Purity

Mondal

Pal

Chatterjee

2021

ACS Appl. Polym. Mater.

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“…Thermal stabilities of the membrane samples were evaluated by thermogravimetric analysis (TGA). 29,30 The detailed characterization procedures are described in the Supporting Information.…”

Section: Characterizationsmentioning

confidence: 99%

“…The phase-separation behavior of the AEMs was investigated by a combination of dye adsorption, glass transition temperature ( T g ) determined by differential scanning calorimetry (DSC), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analyses. Thermal stabilities of the membrane samples were evaluated by thermogravimetric analysis (TGA). , The detailed characterization procedures are described in the Supporting Information.…”

Section: Characterizationsmentioning

confidence: 99%

“…The water uptake (WU) and swelling ratio (SR, %) of the prepared crosslinked AEMs (MQ1, MQ6, MQ10, and MQ18) and uncrosslinked AEMs (Q1 and Q18) in water were determined. Evidence for the crosslinking reaction was obtained by measuring the extractables (%) in DMF under stirring for 2 h at 60 ο C. , Electrochemical characterizations such as the ion-exchange capacity (IEC), fixed charge density ( X m ), and the activation energy ( E a ) of the crosslinked AEMs were determined at room temperature as per the reported procedure . Experimental details are given in the Supporting Information.…”

Section: Characterizationsmentioning

confidence: 99%

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Preparation of a Monovalent-Selective Anion-Exchange Membrane: Effect of Alkyl Chain Length and Crystallinity

Mondal

Sarkar

Patnaik

et al. 2023

ACS Appl. Polym. Mater.

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Crosslinked anion-exchange membranes (AEMs) with reasonable water uptake are used for the separation of monovalent anions from their mixture with bivalent anions by electrodialysis (ED). Herein, we report the preparation of a series of monovalent-selective crosslinked AEMs containing imidazole rings from the polyacrylonitrile-co-poly(vinylimidazole) (PAN-co-PVIm) copolymer (AN/VIm ratio = 75:25 mol/mol), followed by N-alkylation with alkyl halide of different chain lengths (carbon number: 1,6,10,18), followed by reaction with 1,6-diamino hexane. The difference in the obtained permselectivity (P SO4 2– Cl– ) was compared with those of un-crosslinked and commercial Ionsep membranes. The effects of crosslinking, the chain length of the alkyl spacer attached to imidazolium nitrogen of the membrane matrix, and the partial crystallinity occurring due to the arrangement of long alkyl chains on P SO4 2– Cl– were investigated. A representative crosslinked membrane (MQ18) with an octadecyl alkyl chain length (C18) attached to the imidazole moiety exhibited moderate water uptake (22%), high fixed charge density (0.037 meq/cm3), and high P SO4 2– Cl– (6.4) during the separation of a mixture of 0.01 M sodium chloride and 0.01 M sodium sulfate (2000 mg/L) by the ED process. The P SO4 2– Cl– value is further increased from 6.4 to 16.7 by increasing the electrolyte concentration to 0.05 M sodium chloride and 0.05 M sodium sulfate. The rigid imidazolium structure, locally organized higher chain length of the alkylating group, and the crosslinked network structure provide steric hindrance for the passage of more hydrophilic sulfate anions, which facilitates higher selectivity.

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“…Common MCPMs are achieved by modifying the surface or interior of CEMs to allow the preferential passage of monovalent cations by enhancing the Donnan effect or size-sieving effect, thereby achieving the separation of ions of different sizes or valence states . Most CEMs contain sulfonic acid groups as ion exchange groups, which are typically obtained by selecting materials such as polyetheretherketone, polyphenylsulfone, polyvinylidene fluoride, polystyrene, or copolymer-based materials. − …”

Section: Introductionmentioning

confidence: 99%

Cation Exchange Membrane with Internal-Blocking Sites for Mono/Multivalent Ion Separation

Zhao,

Sun,

Zhao

et al. 2024

ACS EST Water

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In this work, monovalent cation perm-selective membranes (MCPMs) with multiple internal-blocking sites were designed to enhance the Donnan effect and size-based exclusion effect. Polypyrrole (PPy), as the internal-blocking sites for ion transport, was introduced within the membrane matrix by in situ polymerization, which was prominent to mono-and multivalent ion separation in electrodialysis (ED). The precise growth of the internal-blocking sites was manipulated via optimization of the polymerization time and polymerization steps. The optimized SPPSU@3PPy membrane exhibits excellent separation performance: the SPPSU@3PPy membrane demonstrates perm-selectivity for Na + /Mg 2+ (PNa Mg = 2.08) and a higher Na + flux (J Na + = 3.29 × 10 −8 mol cm −2 s −1 ). This in situ polymerization method to fabricate internal-blocking sites in a cation exchange membrane is a potential pathway to construct MCPMs.

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A sustainable and efficient process for the preparation of polyethylene–polystyrene interpolymer based anion exchange membranes by in situ chloromethylation for electrodialytic applications

Abstract: The present article describes the preparation of efficient and stable anion exchange membranes (AEMs) from the inter-polymer of polyethylene and polystyrene-co-polydivinylbenzene.

Cited by 13 publications

References 37 publications

Alkylated Imidazole Moieties in a Cross-Linked Anion Exchange Membrane Facilitate Acid Recovery with High Purity

Alkylated Imidazole Moieties in a Cross-Linked Anion Exchange Membrane Facilitate Acid Recovery with High Purity

Preparation of a Monovalent-Selective Anion-Exchange Membrane: Effect of Alkyl Chain Length and Crystallinity

Cation Exchange Membrane with Internal-Blocking Sites for Mono/Multivalent Ion Separation

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