Disulfonated poly(arylene ether sulfone) random copolymer blends tuned for rapid water permeation via cation complexation with poly(ethylene glycol) oligomers

Chang Hyun Lee; Desmond Vanhouten; Ozma Lane; James E. McGrath; Jianbo Hou; Louis A. Madsen; Justin Spano; Sungsool Wi; Joseph Cook; Wei Xie; Hee Jeung Oh; Geoffrey M. Geise; Benny D. Freeman

doi:10.1021/cm1032173

Disulfonated poly(arylene ether sulfone) random copolymer blends tuned for rapid water permeation via cation complexation with poly(ethylene glycol) oligomers

Chang Hyun Lee, Desmond Vanhouten, Ozma Lane, James E. McGrath, Jianbo Hou, Louis A. Madsen, Justin Spano, Sungsool Wi, Joseph Cook, Wei Xie, Hee Jeung Oh, Geoffrey M. Geise, Benny D. Freeman

Research output: Contribution to journal › Article › peer-review

39 Scopus citations

Abstract

Here we present fundamental studies of a new blending strategy for enhancing water permeability in ionomeric reverse osmosis membrane materials. A random disulfonated poly(arylene ether sulfone) copolymer containing 20 mol percent hydrophilic units (BPS-20) in the potassium salt (-SO₃K) form was blended with hydroxyl-terminated poly(ethylene glycol) oligomers (PEG, M_n= 600-2?000) to increase the water permeability of BPS-20. Blending PEG with the copolymer resulted in pseudoimmobilization of the BPS-20 polymer chains because PEG complexes with cations in the sulfonated polymer matrix. Strong ion-dipole interactions between the potassium ions of the BPS-20 sulfonate groups (-SO₃K) and the PEG oxyethylene (-CH ₂CH₂O-) groups were observed via NMR spectroscopy. These interactions are similar to those reported between crown ethers and free alkali metal systems. The PEG oligomers were compatible with the copolymer at 30 °C in an aqueous environment. Transparent and ductile BPS-20-PEG blend films exhibited a Fox-Flory-like glass transition temperature depression as the PEG volume fraction increased. This depression depended on both PEG chain length and concentration. Both ion-dipole interactions and high coordination of -CH ₂CH₂O- with -SO₃K yielded a defined and interconnected hydrophilic channel structure. The water permeability and free volume of BPS-20-PEG blend films containing 5 or 10 wt % PEG increased relative to BPS-20. The blend films, however, exhibited reduced sodium chloride (NaCl) rejection compared to BPS-20. Addition of PEG did not significantly alter the materials dry- and hydrated-state mechanical properties. Unlike commercial state-of-the-art polyamide RO membranes, the blend materials do not degrade when exposed to aqueous chlorine (hypochlorite) at pH 4. This comprehensive suite of measurements provides understanding of the molecular and morphological features needed for rational design of next-generation, chlorine-tolerant water purification materials.

Original language	English (US)
Pages (from-to)	1039-1049
Number of pages	11
Journal	Chemistry of Materials
Volume	23
Issue number	4
DOIs	https://doi.org/10.1021/cm1032173
State	Published - Feb 22 2011

All Science Journal Classification (ASJC) codes

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/cm1032173

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Lee, C. H., Vanhouten, D., Lane, O., McGrath, J. E., Hou, J., Madsen, L. A., Spano, J., Wi, S., Cook, J., Xie, W., Oh, H. J., Geise, G. M., & Freeman, B. D. (2011). Disulfonated poly(arylene ether sulfone) random copolymer blends tuned for rapid water permeation via cation complexation with poly(ethylene glycol) oligomers. Chemistry of Materials, 23(4), 1039-1049. https://doi.org/10.1021/cm1032173

@article{3c04267e024045118eff3ef68d338edc,

title = "Disulfonated poly(arylene ether sulfone) random copolymer blends tuned for rapid water permeation via cation complexation with poly(ethylene glycol) oligomers",

abstract = "Here we present fundamental studies of a new blending strategy for enhancing water permeability in ionomeric reverse osmosis membrane materials. A random disulfonated poly(arylene ether sulfone) copolymer containing 20 mol percent hydrophilic units (BPS-20) in the potassium salt (-SO3K) form was blended with hydroxyl-terminated poly(ethylene glycol) oligomers (PEG, Mn= 600-2?000) to increase the water permeability of BPS-20. Blending PEG with the copolymer resulted in pseudoimmobilization of the BPS-20 polymer chains because PEG complexes with cations in the sulfonated polymer matrix. Strong ion-dipole interactions between the potassium ions of the BPS-20 sulfonate groups (-SO3K) and the PEG oxyethylene (-CH 2CH2O-) groups were observed via NMR spectroscopy. These interactions are similar to those reported between crown ethers and free alkali metal systems. The PEG oligomers were compatible with the copolymer at 30 °C in an aqueous environment. Transparent and ductile BPS-20-PEG blend films exhibited a Fox-Flory-like glass transition temperature depression as the PEG volume fraction increased. This depression depended on both PEG chain length and concentration. Both ion-dipole interactions and high coordination of -CH 2CH2O- with -SO3K yielded a defined and interconnected hydrophilic channel structure. The water permeability and free volume of BPS-20-PEG blend films containing 5 or 10 wt % PEG increased relative to BPS-20. The blend films, however, exhibited reduced sodium chloride (NaCl) rejection compared to BPS-20. Addition of PEG did not significantly alter the materials dry- and hydrated-state mechanical properties. Unlike commercial state-of-the-art polyamide RO membranes, the blend materials do not degrade when exposed to aqueous chlorine (hypochlorite) at pH 4. This comprehensive suite of measurements provides understanding of the molecular and morphological features needed for rational design of next-generation, chlorine-tolerant water purification materials.",

author = "Lee, {Chang Hyun} and Desmond Vanhouten and Ozma Lane and McGrath, {James E.} and Jianbo Hou and Madsen, {Louis A.} and Justin Spano and Sungsool Wi and Joseph Cook and Wei Xie and Oh, {Hee Jeung} and Geise, {Geoffrey M.} and Freeman, {Benny D.}",

year = "2011",

month = feb,

day = "22",

doi = "10.1021/cm1032173",

language = "English (US)",

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Lee, CH, Vanhouten, D, Lane, O, McGrath, JE, Hou, J, Madsen, LA, Spano, J, Wi, S, Cook, J, Xie, W, Oh, HJ, Geise, GM & Freeman, BD 2011, 'Disulfonated poly(arylene ether sulfone) random copolymer blends tuned for rapid water permeation via cation complexation with poly(ethylene glycol) oligomers', Chemistry of Materials, vol. 23, no. 4, pp. 1039-1049. https://doi.org/10.1021/cm1032173

TY - JOUR

T1 - Disulfonated poly(arylene ether sulfone) random copolymer blends tuned for rapid water permeation via cation complexation with poly(ethylene glycol) oligomers

AU - Lee, Chang Hyun

AU - Vanhouten, Desmond

AU - Lane, Ozma

AU - McGrath, James E.

AU - Hou, Jianbo

AU - Madsen, Louis A.

AU - Spano, Justin

AU - Wi, Sungsool

AU - Cook, Joseph

AU - Xie, Wei

AU - Oh, Hee Jeung

AU - Geise, Geoffrey M.

AU - Freeman, Benny D.

PY - 2011/2/22

Y1 - 2011/2/22

N2 - Here we present fundamental studies of a new blending strategy for enhancing water permeability in ionomeric reverse osmosis membrane materials. A random disulfonated poly(arylene ether sulfone) copolymer containing 20 mol percent hydrophilic units (BPS-20) in the potassium salt (-SO3K) form was blended with hydroxyl-terminated poly(ethylene glycol) oligomers (PEG, Mn= 600-2?000) to increase the water permeability of BPS-20. Blending PEG with the copolymer resulted in pseudoimmobilization of the BPS-20 polymer chains because PEG complexes with cations in the sulfonated polymer matrix. Strong ion-dipole interactions between the potassium ions of the BPS-20 sulfonate groups (-SO3K) and the PEG oxyethylene (-CH 2CH2O-) groups were observed via NMR spectroscopy. These interactions are similar to those reported between crown ethers and free alkali metal systems. The PEG oligomers were compatible with the copolymer at 30 °C in an aqueous environment. Transparent and ductile BPS-20-PEG blend films exhibited a Fox-Flory-like glass transition temperature depression as the PEG volume fraction increased. This depression depended on both PEG chain length and concentration. Both ion-dipole interactions and high coordination of -CH 2CH2O- with -SO3K yielded a defined and interconnected hydrophilic channel structure. The water permeability and free volume of BPS-20-PEG blend films containing 5 or 10 wt % PEG increased relative to BPS-20. The blend films, however, exhibited reduced sodium chloride (NaCl) rejection compared to BPS-20. Addition of PEG did not significantly alter the materials dry- and hydrated-state mechanical properties. Unlike commercial state-of-the-art polyamide RO membranes, the blend materials do not degrade when exposed to aqueous chlorine (hypochlorite) at pH 4. This comprehensive suite of measurements provides understanding of the molecular and morphological features needed for rational design of next-generation, chlorine-tolerant water purification materials.

AB - Here we present fundamental studies of a new blending strategy for enhancing water permeability in ionomeric reverse osmosis membrane materials. A random disulfonated poly(arylene ether sulfone) copolymer containing 20 mol percent hydrophilic units (BPS-20) in the potassium salt (-SO3K) form was blended with hydroxyl-terminated poly(ethylene glycol) oligomers (PEG, Mn= 600-2?000) to increase the water permeability of BPS-20. Blending PEG with the copolymer resulted in pseudoimmobilization of the BPS-20 polymer chains because PEG complexes with cations in the sulfonated polymer matrix. Strong ion-dipole interactions between the potassium ions of the BPS-20 sulfonate groups (-SO3K) and the PEG oxyethylene (-CH 2CH2O-) groups were observed via NMR spectroscopy. These interactions are similar to those reported between crown ethers and free alkali metal systems. The PEG oligomers were compatible with the copolymer at 30 °C in an aqueous environment. Transparent and ductile BPS-20-PEG blend films exhibited a Fox-Flory-like glass transition temperature depression as the PEG volume fraction increased. This depression depended on both PEG chain length and concentration. Both ion-dipole interactions and high coordination of -CH 2CH2O- with -SO3K yielded a defined and interconnected hydrophilic channel structure. The water permeability and free volume of BPS-20-PEG blend films containing 5 or 10 wt % PEG increased relative to BPS-20. The blend films, however, exhibited reduced sodium chloride (NaCl) rejection compared to BPS-20. Addition of PEG did not significantly alter the materials dry- and hydrated-state mechanical properties. Unlike commercial state-of-the-art polyamide RO membranes, the blend materials do not degrade when exposed to aqueous chlorine (hypochlorite) at pH 4. This comprehensive suite of measurements provides understanding of the molecular and morphological features needed for rational design of next-generation, chlorine-tolerant water purification materials.

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Disulfonated poly(arylene ether sulfone) random copolymer blends tuned for rapid water permeation via cation complexation with poly(ethylene glycol) oligomers

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