멤브레인 (Membrane Journal)

  • 제24권1호
  • /
  • Pages.1-9
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  • 2014
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  • 1226-0088(pISSN)
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  • 2288-7253(eISSN)
한국막학회 (The Membrane Society of Korea)
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DOI QR코드

DOI QR Code

지환족 다이안하이드라이드를 이용한 용해성 폴리이미드 공중합체 합성 및 메탄/이산화탄소 분리특성

Synthesis of Soluble Copolyimides Using an Alicyclic Dianhydride and Their $CO_2/CH_4$ Separation Properties

  • 박채영 (한국화학연구원 환경자원공정연구센터 자원분리회수연구그룹) ;
  • 이용택 (충남대학교 바이오응용화학과) ;
  • 김정훈 (한국화학연구원 환경자원공정연구센터 자원분리회수연구그룹)
  • Park, Chae Young (Resources Separation and Recovery Research Group, Division of Green Chemistry and Process, Korea Research Institute of Chemical Technology) ;
  • Lee, Yongtaek (Department of Bio-Applied Chemistry, Chungnam National University) ;
  • Kim, Jeong Hoon (Resources Separation and Recovery Research Group, Division of Green Chemistry and Process, Korea Research Institute of Chemical Technology)
  • 투고 : 2013.10.04
  • 심사 : 2013.10.10
  • 발행 : 2014.02.28
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초록

지환족 다이안하이드라이드인 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA)와 4,4'-diaminodiphenyl ether (ODA)에서 합성된 폴리이미드는 유기용매에 잘 용해되는 폴리이미드로 알려져 있다. 이러한 DOCDA-ODA 폴리이미드의 기체 투과특성을 평가하고 투과선택도를 개선시키기 위해서 DOCDA-ODA 반응물에 세 가지 dianhydride 단량체((4,4'-(hexafluoroisoproplidene)diphthalic anhydride (6FDA), 4,4'-biphthalic anhydride (BPDA), 3,3', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA))를 각각 20 mol% 첨가하여 순수중합체 및 공중합체를 합성하였다. 폴리이미드 합성이 성공적으로 이루어졌음을 FT-IR을 통해 확인하였고, 그들의 열적특성은 DSC를 통해 알아보았다. 제조된 폴리이미드들의 $CO_2/CH_4$에 대한 기체투과도와 선택도는 time-lag법을 이용하여 측정하였다. 그 결과 순수고분자인 DOCDA-ODA의 경우 $CO_2$ 투과도는 1.71 barrer, $CO_2/CH_4$ 선택도는 74.35의 우수한 투과특성을 보였다. 세 가지 공중합체의 경우 DOCDA-ODA에 비해 $CO_2$ 투과도는 높게 나타난 반면에 $CO_2/CH_4$ 선택도는 감소하였다. 특히, 6FDA를 첨가한 경우 $CO_2/CH_4$ 선택도는 DOCDA-ODA보다 다소 낮은 결과를 나타내었지만 $CO_2$ 투과도가 크게 증가하였음을 확인할 수 있었다.

In this study, four soluble homo- and co-polyimides using 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA) and 4,4'-diaminodiphenyl ether (ODA) monomers were synthesized to develop the gas separation membrane with good $CO_2/CH_4$ separation properties. To prepare the copolyimides, 20 mol% of three dianhydrides - (4,4'-(hexafluoroisoproplidene)diphthalic anhydride (6FDA), 4,4'-biphthalic anhydride (BPDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) - were added in DOCDA-ODA monomer mixture, respectively. All the synthesized homo- and co-polyimides were characterized by FT-IR. Their thermal properties were analyzed with differential scanning calorimeter (DSC). Dense membranes were prepared from these copolyimides to check their gas permeation properties for $CO_2$ and $CH_4$ gases using a time-lag method. The permeation testing results are as follows; DOCDA/ODA homopolymer showed 1.71 barrer of $CO_2$ permeability and 74.35 of $CO_2/CH_4$ selectivity. The three polyimide copolymers (DOCDA/6FDA-ODA, DOCDA/BPDA-ODA, DOCDA/BTDA-ODA) showed lower $CO_2/CH_4$ selectivities and higher $CO_2$ permeabilities than the homopolymer (DOCDA-ODA). DOCDA/6FDA-ODA showed twice times higher $CO_2$ permeabilities without severe $CO_2/CH_4$ selectivity loss than the DOCDA-ODA.

키워드

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