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The Membrane Society of Korea (한국막학회)
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Gas Transport Properties of Crosslinked Polyimide Membranes Induced by Aliphatic Diamines with Different Chain Length

사슬 길이가 다른 지방족 디아민으로 가교된 폴리이미드 분리막의 기체 투과 특성

  • Lee, Hye Rim (Department of Materials Engineering and Convergence Technology, Engineering Research Institute, Gyeongsang National University) ;
  • Lee, Jung Moo (.Aekyung Petrochemical Co., LTD.) ;
  • Nam, Sang Yong (Department of Materials Engineering and Convergence Technology, Engineering Research Institute, Gyeongsang National University)
  • 이혜림 (경상대학교 나노신소재융합공학과, 공학연구원) ;
  • 이정무 (애경유화 중앙연구소) ;
  • 남상용 (경상대학교 나노신소재융합공학과, 공학연구원)
  • Received : 2013.11.24
  • Accepted : 2013.12.23
  • Published : 2013.12.31
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Abstract

2,3,5,6-Tetramethyl-1,4-phenylenediamine (TMPD) based polyimide (PI) were crosslinked with 1,2-Diaminoethane (DAE) and 1,6-Diaminohexane (DAH) to enhance gas transport properties. Fourier transform infrared (FT-IR) studies show that imide groups were converted into amide groups during crosslinking process. Thermogravimetric analysis (TGA) results indicate that the degradation temperature of crosslinked PI membranes decreased after crosslinking. This is due to degradation of alkyl group in crosslinking agent. The d-space of crosslinked PI membranes decreased with increasing crosslinking time. The ideal permeability for $CH_4$, $N_2$, $O_2$, and $CO_2$ decreased after crosslinking and the ideal permeability of crosslinked PI membranes induced by DAH is larger than that by DAE. In contrast, the permselectivity of $CO_2/CH_4$, $CO_2/N_2$ and $O_2/N_2$ increased during crosslinking. For the gas pair of $CO_2/CH_4$, the maximum increment is about 39.5% after 6 minutes of DAE crosslinking. Also, that of $O_2/N_2$ gas pair is about 20.5% after 6 minutes of DAE crosslinking. According to these result, DAE is more suitable for enhanced permselectivity than DAH. On the contrary, DAE is not useful for $CO_2/N_2$ separation due to reduction in $CO_2/N_2$ permselectivity after 3 minutes DAE crosslinking.

폴리이미드 기체 분리막의 기체 분리 성능을 향상시키기 위해서 2,3,5,6-Tetramethyl-1,4-phenylenediamine(TMPD) 구조를 지닌 폴리이미드를 1,2-Diaminoethane (DAE)과 1,6-Diaminohexane (DAH)으로 가교시켜 분리막을 제조하였다. Fourier transform infrared spectroscopy (FT-IR)를 이용해 가교 후 이미드 고리가 아미드 그룹으로 전환됨을 확인하였다. 폴리이미드의 열분해 온도는 가교 후 감소하였으며, 이는 가교제의 알킬기 분해 때문이다. 가교된 폴리이미드 분리막의 d-spacing은 가교 시간이 증가함에 따라 감소하였다. 가교 후 $CH_4$, $N_2$, $O_2$, $CO_2$ 기체의 투과도는 가교 전 보다 감소하였으며, DAH로 가교된 분리막이 DAE보다 더 높은 투과도를 나타냈다. 투과도와 달리 $CO_2/CH_4$, $CO_2/N_2$, $O_2/N_2$ 기체 선택도 모두 가교 시간이 길어질수록 증가된 결과가 나타났다. $CO_2/CH_4$ 기체의 선택도는 DAE로 6분 가교 시 최대 증가치를 나타냈으며 39.5%까지 증가하였다. $O_2/N_2$ 선택도 또한 DAE로 6분 가교 시 최대 증가치를 가지며 20.5%까지 증가하였다. 이를 통해서 DAE가 DAH보다 선택도 증가에 적합한 가교제임을 예상할 수 있으며 이와 달리 $CO_2/N_2$ 선택도는 DAE로 3분 가교 시 감소해 $CO_2/N_2$ 분리에는 적합하지 않은 결과가 나타났다.

Keywords

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