Membrane Journal (멤브레인)

The Membrane Society of Korea (한국막학회)
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Proton Conducting Composite Membranes Consisting of PVC-g-PSSA Graft Copolymer and Heteropolyacid

PVC-g-PSSA가지형 공중합체와 헤테로폴리산을 이용한 수소이온 전도성 복합 전해질막

  • Kim, Jong-Hak (Department of Chemical and Biomolecular Engineering, Yonsei University) ;
  • Koh, Jong-Kwan (Department of Chemical and Biomolecular Engineering, Yonsei University) ;
  • Choi, Jin-Kyu (Department of Chemical and Biomolecular Engineering, Yonsei University) ;
  • Yeon, Seung-Hyeon (Department of Chemical and Biomolecular Engineering, Yonsei University) ;
  • Ahn, Ik-Sung (Department of Chemical and Biomolecular Engineering, Yonsei University) ;
  • Park, Jin-Won (Department of Chemical and Biomolecular Engineering, Yonsei University)
  • 김종학 (연세대학교 화공생명공학과) ;
  • 고종관 (연세대학교 화공생명공학과) ;
  • 최진규 (연세대학교 화공생명공학과) ;
  • 연승현 (연세대학교 화공생명공학과) ;
  • 안익성 (연세대학교 화공생명공학과) ;
  • 박진원 (연세대학교 화공생명공학과)
  • Published : 2009.06.30
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Abstract

A series of organic-inorganic composite membranes from poly(vinyl chloride) (PVC) graft copolymer electrolyte and heteropolyacid (HPA) were prepared for proton conducting membranes. First, poly(vinyl chloride)-g-poly(styrene sulfonic acid) (PVC-g-PSSA) was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. HPA nanoparticles were then incorporated into the PVC-g-PSSA graft copolymer though the hydrogen bonding interactions, as confirmed by FT-IR spectroscopy. The proton conductivity of the composite membranes increased from 0.049 to 0.068 S/cm at room temperature with HPA contents up to 0.3 weight traction of HPA, presumably due to both the intrinsic conductivity of HPA particles and the enhanced acidity of the sulfonic acid of the graft copolymer. The water uptake decreased from 130 to 84% with the increase of HPA contents up to 0.45 of HPA weight traction, resulting from the decrease in number of water absorption sites due to hydrogen bonding interaction between the HPA particles and the polymer matrix. Thermal gravimetric analysis (TGA) demonstrated the enhancement of thermal stabilities of the composite membranes with increasing concentration of HPA.

본 연구에서는 poly(vinyl chloride) (PVC)가지형 공중합체 전해질과 헤테로폴리산(HPA)을 이용하여 유무기 합성 전해질막을 제조하였다. poly(vinyl chloride)-g-poly(styrene sulfonic acid) (PVC-g-PSSA)는 PVC의 이차 염소의 직접적인 개시를 이용한 atom transfer radical polymerization (ATRP)로 합성하였다. 이때, HPA 나노입자는 수소 결합을 통해 PVC-g-PSSA 가지형 공중합체와 결합하는 것을 FT-IR spectroscopy를 통하여 확인하였다. 전해질막의 수소이온 전도도는 HPA의 질량 분율이 0.3이 될 때까지 상온에서 0.049에서 0.068 S/cm로 증가하였다. 이것은 HPA 나노입자 고유의 전도도와 가지형 공중합체가 가지고 있는 술폰산의 강화된 산도 때문이라고 추정된다. 합습률은 HPA의 질량 분율이 0.45까지 증가할수록 130에서 84%로 감소하였다. 이것은 HPA나노입자와 고분자 메트릭스 사이의 수소 결합의 상호작용 때문에 물을 흡수하는 site의 수가 감소한 결과라고 볼 수 있다. 열중량 분석결과 HPA의 농도가 증가할수록 전해질막의 열적 안정성이 강화된다는 것을 알 수 있었다.

Keywords

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