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Macromolecular Research

, Volume 14, Issue 2, pp 199–204 | Cite as

FT-raman studies on ionic interactions in π-complexes of poly(hexamethylenevinylene) with silver salts

  • Jong Hak Kim
  • Byoung Ryul Min
  • Jongok Won
  • Yong Soo Kang
Article

Abstract

Remarkably high and stable separation performance for olefin/paraffin mixtures was previously reported by facilitated olefin transport through π-complex membranes consisting of silver ions dissolved in poly(hexamethylenevinylene) (PHMV). In this study, the π-complex formation of AgBF4, AgClO4 and AgCF3SO3 with PHMV and their ionic interactions were investigated. FT-Raman spectroscopy showed that the C=C stretching bands of PHMV shifted to a lower frequency upon incorporation of silver salt, but the degree of peak shift depended on the counteranions of salt due to different complexation strengths. The symmetric stretching modes of anions indicated the presence of only free ions up to [C=C]∶[Ag]=1∶1, demonstrating the unusually high solubility of silver salt in PHMV. Above the solubility limit, the ion pairs and higher-order ionic aggregates started to form. The coordination number of silver ion for C=C of PHMV was in the order AgBF4>AgClO4>AgCF3SO3, but became similar at [C=C]∶[Ag]=1∶1. The different coordination number was interpreted in terms of the different transient crosslinks of silver cations in the complex, which may be related to both the interaction strength of the polymer/silver ion and the bulkiness of the counteranion.

Keywords

π-complex silver ion poly(hexamethylenevinylene) ionic interaction spectroscopy 

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Copyright information

© The Polymer Society of Korea and Springer 2006

Authors and Affiliations

  1. 1.Department of Chemical EngineeringYonsei UniversitySeoulKorea
  2. 2.Department of Applied ChemistrySejong UniversitySeoulKorea
  3. 3.Division of Chemical EngineeringHanyang UniversitySeoulKorea

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