Unusual Facilitated Olefin Transport through Polymethacrylate/Silver Salt Complexes

Jong Hak Kim, Seung Hwan Joo, Chang Kon Kim, Yong Soo Kang, Jongok Won

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Silver salt complex membranes with glassy poly(methyl methacrylate) (PMMA) unexpectedly showed higher propylene permeance than those with rubbery poly(butyl methacrylate) (PBMA) where as neat PMMA is much less permeable to propylene than that of neat PBMA. Such unusual facilitated olefin transport has been systematically investigated by changing the side chain length of polymethacrylates (PMAs) from methyl, ethyl to butyl. The ab initio calculation showed almost the same electron densities of the carbonyl oxygens in the three PMAs, expecting very similar intensity of the interaction between carbonyl oxygen and silver ion. However, the interaction intensity decreases with the length of the alkyl side chain: PMMA 〉 PEMA 〉 PBMA according to wide angle X-ray scattering and FT-Raman spectroscopy. The difference in the interaction intensity may arise from the difference in the hydrophilicity of the three PMAs, as confirmed by the contact angle of water, which determines the concentrations of the ionic constituents of silver salts: free ion, contact ion pair and higher order ionic aggregate. However, propylene solubilities and facilitated propylene transport vary with the side chain length significantly even at the same concentration of the free ion, the most active olefin carrier, suggesting possible difference in the prohibition of the molecular access of propylene to silver ion by the side chains: the steric hindrance. Therefore, it may be concluded that both the hydrophilicity and the steric hindrance associated with the side chain length in the three PMAs are of pivotal importance in determining facilitated olefin transport through polymer/silver salt complex membranes.

Original languageEnglish
Pages (from-to)375-381
Number of pages7
JournalMacromolecular Research
Volume11
Issue number5
DOIs
Publication statusPublished - 2003 Jan 1

Fingerprint

Alkenes
Silver
Olefins
Propylene
Salts
Ions
Polymethyl Methacrylate
Polymethyl methacrylates
Chain length
Hydrophilicity
Oxygen
Membranes
X ray scattering
Contact angle
Carrier concentration
Raman spectroscopy
Polymers
Solubility
propylene
polymethacrylic acid

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Cite this

Kim, Jong Hak ; Joo, Seung Hwan ; Kim, Chang Kon ; Kang, Yong Soo ; Won, Jongok. / Unusual Facilitated Olefin Transport through Polymethacrylate/Silver Salt Complexes. In: Macromolecular Research. 2003 ; Vol. 11, No. 5. pp. 375-381.
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Unusual Facilitated Olefin Transport through Polymethacrylate/Silver Salt Complexes. / Kim, Jong Hak; Joo, Seung Hwan; Kim, Chang Kon; Kang, Yong Soo; Won, Jongok.

In: Macromolecular Research, Vol. 11, No. 5, 01.01.2003, p. 375-381.

Research output: Contribution to journalArticle

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AB - Silver salt complex membranes with glassy poly(methyl methacrylate) (PMMA) unexpectedly showed higher propylene permeance than those with rubbery poly(butyl methacrylate) (PBMA) where as neat PMMA is much less permeable to propylene than that of neat PBMA. Such unusual facilitated olefin transport has been systematically investigated by changing the side chain length of polymethacrylates (PMAs) from methyl, ethyl to butyl. The ab initio calculation showed almost the same electron densities of the carbonyl oxygens in the three PMAs, expecting very similar intensity of the interaction between carbonyl oxygen and silver ion. However, the interaction intensity decreases with the length of the alkyl side chain: PMMA 〉 PEMA 〉 PBMA according to wide angle X-ray scattering and FT-Raman spectroscopy. The difference in the interaction intensity may arise from the difference in the hydrophilicity of the three PMAs, as confirmed by the contact angle of water, which determines the concentrations of the ionic constituents of silver salts: free ion, contact ion pair and higher order ionic aggregate. However, propylene solubilities and facilitated propylene transport vary with the side chain length significantly even at the same concentration of the free ion, the most active olefin carrier, suggesting possible difference in the prohibition of the molecular access of propylene to silver ion by the side chains: the steric hindrance. Therefore, it may be concluded that both the hydrophilicity and the steric hindrance associated with the side chain length in the three PMAs are of pivotal importance in determining facilitated olefin transport through polymer/silver salt complex membranes.

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