Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Mesoporous Silica-Carbon Composite Membranes for Simultaneous Hydrolysis and Separation of Chiral Epoxide

카본/메조세공 실리카 복합 막을 응용한 키랄 에폭사이드의 가수분해반응과 동시 분리

  • Choi, Seong Dae (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Jeon, Sang Kwon (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Park, Geun Woo (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Yang, Jin Young (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Kim, Geon-Joong (Department of Chemical Engineering, College of Engineering, Inha University)
  • Received : 2014.07.09
  • Accepted : 2014.08.28
  • Published : 2014.10.10
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Abstract

The carbon/porous silica composite membrane was fabricated in a simple manner, which could be successfully for the simultaneous separation and production of chiral epoxides and 1,2-diols, based on their differences in hydrophilic/hydrophobic natures. The chiral Co(III)-$BF_3$ salen catalyst adopted in the membrane reactor system has given the very high enantioselectivity and recyclability in hydrolysis of terminal epoxides such as ECH, 1,2-EB, and SO. The optically pure epoxide and the chiral catalyst were collected in the organic phase after hydrolysis reaction. The hydrophilic water-soluble 1,2-diol product hydrolyzed by chiral salen diffused into the aqueous phase through the SBA-16 or NaY/SBA-16 silica composite layer during the reaction. The water acted simultaneously as a reactant and a solvent in the membrane system. One optical isomer was obtained with high purity and yield, and furthermore the catalysts could be recycled without observable loss in their activity in the continuous flow-type membrane reactor.

탄소와 다공성 실리카로 구성된 복합막을 용이한 방법으로 제작하고 이들 막을 활용하여, 키랄 에폭사이드와 키랄디올 화합물의 친수성/소수성 특성차이를 기초로 한 동시 합성 및 분리과정에 응용하였다. 막반응기에 도입한 키랄 Co(III)-$BF_3$형 살렌촉매는 ECH, 1,2-EB와 SO 등의 에폭사이드 가수분해반응에 대하여 높은 활성을 나타내었고 여러 차례의 재사용이 가능하였다. 광학순도가 높은 키랄 에폭사이드 생성물은 가수분해반응이 진행된 후에 촉매와 함께 유기용액상에서 취득되었다. 물에 용해되는 친수성의 1,2-디올은 키랄 살렌의 촉매작용에 의하여 가수분해됨으로써 생성되는데, 이들은 반응이 진행되는 동안 SBA-16 또는 NaY/SBA-16 실리카층을 통해 물층으로 확산되었다. 물은 막반응계에서 반응물이면서 동시에 용매로서 거동하였다. 연속흐름형의 막반응기를 적용함으로써, 고순도, 고수율의 광학이성체를 생성물로서 얻을 수 있었으며, 촉매는 큰 활성저하를 나타내지 않아 여러 차례 재사용이 가능하였다.

Keywords

References

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