Synthesis and characterization of sulfonated poly(arylene biphenylsulfone ether) copolymers containing hydroquinone moiety for polymer electrolyte membrane

고분자 전해질 멤브레인용 하이드로퀴논 부분이 포함된 설폰화된 폴리(아릴렌 비페닐설폰 에테르) 공중합체의 합성과 특성평가

  • Yoo, Dong-Jin (Department of Chemistry & Medical Technology, Seonam University)
  • 유동진 (서남대학교 화학과/임상병리학과)
  • Received : 2010.04.19
  • Accepted : 2010.06.11
  • Published : 2010.06.30

Abstract

In present work, sulfonated poly(arylene biphenyklsulfone ether) copolymers containing hydroquinone moiety were successfully synthesized using 4,4'-bis[(4-chlorophenyl)sulfonyl]-1,1'-biphenyl(BCPSBP), hydroquinone sulfonic acid potassium salt(sHQ), 4,4'-sulfonyldiphenol and evaluated their characteristics. Three kinds of polymer electrolyte membranes, PBPSEH-HQ00, PBPSEH-HQ10 and PBPSEH-HQ30 were prepared by using mole fraction of sulfonated hydroquinone(sHQ). The structure of the fabricated polymers was analyzed using NMR, IR and GPC. The Mw(weight-average molecular weights) of the polymers were in the range of 62,000-213,000 g $mol^{-1}$, and the molecular weight distribution (Mw/Mn) varied from 1.66-4.04. The thermal analysis of the copolymers was carried out by TGA and DSC. The temperature of Td5% and Td10% was decreased with the mole fraction of sHQ but Tg was increased with the mole fraction. The water uptake, IEC and ion conductivity were increased with increasing the ionic cluster of the polymers. The proton conductivity equal to 9.4 mS $cm^{-1}$ was measured for the PBPSEH-HQ30 membrane at $90^{\circ}C$ and 100% relative humidity. From the observed results it is clear that the prepared hydrocarbon membrane can be considered as suitable polymer electrolyte membrane for the application of PEMFC.

본 연구에서는 4,4'-bis[(4-chlorophenyl)sulfonyl]-1,1'-biphenyl(BCPSBP), 술폰화된 하이드로퀴논, 4,4'-sulfonyldiphenol를 이용하여 새로운 폴리(아릴렌 비페닐설폰 에테르) 공중합체를 합성하였고 이들의 특성을 평가하였다. 첨가한 술폰화된 하이드로퀴논의 몰분율에 따라 PBPSEH-HQ00, PBPSEH-HQ10, PBPSEH-HQ30의 고분자전해질막을 합성하였다. 제조한 공중합체의 구조분석은 NMR, IR, GPC를 사용하여 실시하였고, GPC에서 평균분자량은 62,000-213,000 g $mol^{-1}$이며, 이때 PDI는 1.66-4.04였다. TGA와 DSC를 통하여 열분석을 실시하였고, 고분자의 이온화정도가 많아짐에 따라 $T_{d5%}$$T_{d10%}$는 낮아 졌으며, $T_g$값은 점점 상승하였다. 함습율과 IEC, 이온전도도는 술폰화된 하이드로퀴논 몰분율이 증가함에 따라 증가하였다. 고분자전해질막에서 중요한 양이온 전도도는 $60^{\circ}C$ 및 100%상대습도에서 약 9.4 mS $cm^{-1}$이었다. 측정된 결과로부터 본 연구에서 제조한 탄화수소계 멤브레인은 연료전지용 고분자전해질막으로 사용될 수 있다.

Keywords

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