Crystalline elastomeric block copolymer/ionic liquid membranes with enhanced mechanical strength and gas separation properties

Hyo Jun Min; Young Jun Kim; Miso Kang; Chae Hee Seo; Jeong Hoon Kim; Jong Hak Kim

doi:10.1016/j.memsci.2022.120837

Crystalline elastomeric block copolymer/ionic liquid membranes with enhanced mechanical strength and gas separation properties

Hyo Jun Min, Young Jun Kim, Miso Kang, Chae Hee Seo, Jeong Hoon Kim, Jong Hak Kim

Department of Chemical and Biomolecular Engineering

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

Abstract

We report a high-performance, three-dimensional (3D) interconnected crystalline elastomeric membrane with enhanced mechanical strength and CO₂ separation properties. The membranes were prepared using an amphiphilic crystalline block copolymer, poly(ethylene glycol) monomethyl ether-block-poly(acrylonitrile) (mPEG-b-PAN), synthesized via one-pot free-radical polymerization under environmental-friendly, mild conditions (in water at 50 °C). The strong interaction of the mPEG-b-PAN block copolymer with ionic liquid (IL) resulted in a microphase-separated, interconnected elastomeric structure in which the PAN crystallites acted as crosslinking junctions. Exceptionally high IL loadings of up to 300 wt % were efficiently confined in the crystalline network while maintaining outstanding mechanical properties. The mPEG-b-PAN/IL membrane with 250 wt % IL loading achieved the highest separation performance with a CO₂ permeability of 456.4 barrer, CO₂/N₂ selectivity of 61.4, CO₂/CH₄ of 18.1 and CO₂/H₂ of 12.3. The CO₂/N₂ separation performance exceeds the Robeson upper bound (2008) and approached the upper bound (2019). Both the separation properties and mechanical strength of the mPEG-b-PAN/IL elastomeric membranes outperformed those of homopolymer PAN (H-PAN) and other membranes with ILs. Interestingly, the mPEG-b-PAN/IL membranes were effortlessly prepared regardless of the surface properties of the substrate and IL loading, in contrast to H-PAN/IL, indicating that the amphiphilic property of the polymer plays a pivotal role in turning the interface.

Original language	English
Article number	120837
Journal	Journal of Membrane Science
Volume	660
DOIs	https://doi.org/10.1016/j.memsci.2022.120837
Publication status	Published - 2022 Oct 15

Bibliographical note

Funding Information:
This work was supported by the Korea Research Institute of Chemical Technology , and the "New & Renewable Energy Core Technology Program" (Project No. 20213030040170 ) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy and the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (No. 2019M1A2A2065614 , 2021M3H4A1A03049662 ). HJ Min acknowledges support from an NRF grant funded by the Ministry of Education, Republic of Korea ( 2021R1A6A3A13045294 ).

Publisher Copyright:
© 2022 Elsevier B.V.

All Science Journal Classification (ASJC) codes

Biochemistry
Materials Science(all)
Physical and Theoretical Chemistry
Filtration and Separation

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10.1016/j.memsci.2022.120837

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title = "Crystalline elastomeric block copolymer/ionic liquid membranes with enhanced mechanical strength and gas separation properties",

abstract = "We report a high-performance, three-dimensional (3D) interconnected crystalline elastomeric membrane with enhanced mechanical strength and CO2 separation properties. The membranes were prepared using an amphiphilic crystalline block copolymer, poly(ethylene glycol) monomethyl ether-block-poly(acrylonitrile) (mPEG-b-PAN), synthesized via one-pot free-radical polymerization under environmental-friendly, mild conditions (in water at 50 °C). The strong interaction of the mPEG-b-PAN block copolymer with ionic liquid (IL) resulted in a microphase-separated, interconnected elastomeric structure in which the PAN crystallites acted as crosslinking junctions. Exceptionally high IL loadings of up to 300 wt % were efficiently confined in the crystalline network while maintaining outstanding mechanical properties. The mPEG-b-PAN/IL membrane with 250 wt % IL loading achieved the highest separation performance with a CO2 permeability of 456.4 barrer, CO2/N2 selectivity of 61.4, CO2/CH4 of 18.1 and CO2/H2 of 12.3. The CO2/N2 separation performance exceeds the Robeson upper bound (2008) and approached the upper bound (2019). Both the separation properties and mechanical strength of the mPEG-b-PAN/IL elastomeric membranes outperformed those of homopolymer PAN (H-PAN) and other membranes with ILs. Interestingly, the mPEG-b-PAN/IL membranes were effortlessly prepared regardless of the surface properties of the substrate and IL loading, in contrast to H-PAN/IL, indicating that the amphiphilic property of the polymer plays a pivotal role in turning the interface.",

author = "Min, {Hyo Jun} and Kim, {Young Jun} and Miso Kang and Seo, {Chae Hee} and Kim, {Jeong Hoon} and Kim, {Jong Hak}",

note = "Funding Information: This work was supported by the Korea Research Institute of Chemical Technology , and the {"}New & Renewable Energy Core Technology Program{"} (Project No. 20213030040170 ) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy and the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (No. 2019M1A2A2065614 , 2021M3H4A1A03049662 ). HJ Min acknowledges support from an NRF grant funded by the Ministry of Education, Republic of Korea ( 2021R1A6A3A13045294 ). Publisher Copyright: {\textcopyright} 2022 Elsevier B.V.",

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doi = "10.1016/j.memsci.2022.120837",

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T1 - Crystalline elastomeric block copolymer/ionic liquid membranes with enhanced mechanical strength and gas separation properties

AU - Min, Hyo Jun

AU - Kim, Young Jun

AU - Kang, Miso

AU - Seo, Chae Hee

AU - Kim, Jeong Hoon

AU - Kim, Jong Hak

N1 - Funding Information: This work was supported by the Korea Research Institute of Chemical Technology , and the "New & Renewable Energy Core Technology Program" (Project No. 20213030040170 ) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy and the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (No. 2019M1A2A2065614 , 2021M3H4A1A03049662 ). HJ Min acknowledges support from an NRF grant funded by the Ministry of Education, Republic of Korea ( 2021R1A6A3A13045294 ). Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/10/15

Y1 - 2022/10/15

N2 - We report a high-performance, three-dimensional (3D) interconnected crystalline elastomeric membrane with enhanced mechanical strength and CO2 separation properties. The membranes were prepared using an amphiphilic crystalline block copolymer, poly(ethylene glycol) monomethyl ether-block-poly(acrylonitrile) (mPEG-b-PAN), synthesized via one-pot free-radical polymerization under environmental-friendly, mild conditions (in water at 50 °C). The strong interaction of the mPEG-b-PAN block copolymer with ionic liquid (IL) resulted in a microphase-separated, interconnected elastomeric structure in which the PAN crystallites acted as crosslinking junctions. Exceptionally high IL loadings of up to 300 wt % were efficiently confined in the crystalline network while maintaining outstanding mechanical properties. The mPEG-b-PAN/IL membrane with 250 wt % IL loading achieved the highest separation performance with a CO2 permeability of 456.4 barrer, CO2/N2 selectivity of 61.4, CO2/CH4 of 18.1 and CO2/H2 of 12.3. The CO2/N2 separation performance exceeds the Robeson upper bound (2008) and approached the upper bound (2019). Both the separation properties and mechanical strength of the mPEG-b-PAN/IL elastomeric membranes outperformed those of homopolymer PAN (H-PAN) and other membranes with ILs. Interestingly, the mPEG-b-PAN/IL membranes were effortlessly prepared regardless of the surface properties of the substrate and IL loading, in contrast to H-PAN/IL, indicating that the amphiphilic property of the polymer plays a pivotal role in turning the interface.

AB - We report a high-performance, three-dimensional (3D) interconnected crystalline elastomeric membrane with enhanced mechanical strength and CO2 separation properties. The membranes were prepared using an amphiphilic crystalline block copolymer, poly(ethylene glycol) monomethyl ether-block-poly(acrylonitrile) (mPEG-b-PAN), synthesized via one-pot free-radical polymerization under environmental-friendly, mild conditions (in water at 50 °C). The strong interaction of the mPEG-b-PAN block copolymer with ionic liquid (IL) resulted in a microphase-separated, interconnected elastomeric structure in which the PAN crystallites acted as crosslinking junctions. Exceptionally high IL loadings of up to 300 wt % were efficiently confined in the crystalline network while maintaining outstanding mechanical properties. The mPEG-b-PAN/IL membrane with 250 wt % IL loading achieved the highest separation performance with a CO2 permeability of 456.4 barrer, CO2/N2 selectivity of 61.4, CO2/CH4 of 18.1 and CO2/H2 of 12.3. The CO2/N2 separation performance exceeds the Robeson upper bound (2008) and approached the upper bound (2019). Both the separation properties and mechanical strength of the mPEG-b-PAN/IL elastomeric membranes outperformed those of homopolymer PAN (H-PAN) and other membranes with ILs. Interestingly, the mPEG-b-PAN/IL membranes were effortlessly prepared regardless of the surface properties of the substrate and IL loading, in contrast to H-PAN/IL, indicating that the amphiphilic property of the polymer plays a pivotal role in turning the interface.

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U2 - 10.1016/j.memsci.2022.120837

DO - 10.1016/j.memsci.2022.120837

M3 - Article

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SN - 0376-7388

VL - 660

JO - Journal of Membrane Science

JF - Journal of Membrane Science

M1 - 120837

ER -

Crystalline elastomeric block copolymer/ionic liquid membranes with enhanced mechanical strength and gas separation properties

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

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