Journal of Korean Society of Environmental Engineers (대한환경공학회지)

Korean Society of Environmental Engineers (대한환경공학회)
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Investigation on Reaction Products From Oxidative Coupling Reactions of 1-Naphthol By Manganese Oxide

망간산화물에 의한 1-Naphthol의 산화-결합 반응에 따른 반응산물 연구

  • Lim, Dong-Min (Department of Environment Engineering, Seoul National University of Technology) ;
  • Lee, Doo-Hee (Eco-Material Education Center, Department of Environmental Engineering, Seoul National University of Technology) ;
  • Kang, Ki-Hoon (Technology Research Institute, Daelim Industrial Co., Ltd.) ;
  • Shin, Hyun-Snag (Department of Environment Engineering, Seoul National University of Technology)
  • 임동민 (서울산업대학교 환경공학과) ;
  • 이두희 (서울산업대학교 환경공학과 친환경소재제품인력양성센터) ;
  • 강기훈 ((주)대림산업 기술연구소) ;
  • 신현상 (서울산업대학교 환경공학과)
  • Published : 2007.09.30
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Abstract

In this study, abiotic transformation of 1-naphthol(1-NP) via oxidative-coupling reaction and its reaction products were investigated in the presence of Mn oxides. The reaction products were characterized for their relative polarity using solvent extraction experiment and reverse-phase HPLC, and for structure using CCMS and LC/MS, and for absorption characteristics using UV-Vis spectrometry. The reaction products present in aqueous phase were more polar than parent naphthol and comprised of 1,4-naphthoquinon(1,4-NPQ) and oligomers such as dimers and trimers. Hydrophilic component present in water phase after solvent$(CH_2Cl_2)$ extractions was identified as naphthol polymerized products having molecular weight(m/z) ranging from 400 to 2,000, and showed similar UV-Vis. absorption characteristics to that of foil fulvic acid. Transformation of 1,4-NPQ, which is non-reactive to Mn oxide, to the polymerized products via cross-coupling reaction in the presence of 1-NP was also verified. In this experimental conditions(20.5 mg/L, 1-NP, 2.5 g/L $MnO_2$, pH 5), the transformation of 1-NP into the oligomers and polymerized products were about 83% of initial 1-NP concentrations, and more than 30% of the reaction products was estimated to be water insoluble fractions, not extracted by $H_2O$ methanol. Results from this study suggest that Mn oxide-mediated treatment of naphthol contaminated soils can achieve risk reduction through the formation of oligomers md polymer precipitation.

본 연구에서는 망간산화물 존재 하에서의 1-naphthol(1-NP)의 산화-결합반응을 통한 변환반응과 반응산물을 조사하였다. 변환 반응에 의해 생성된 반응산물을 대상으로 한 용매 추출과 HPLC, GC/MS, LC/MS 및 UV-Vis. 흡광특성 분석 등을 통해 반응산물의 분자 구조특성을 규명하였다. 반응 상등액에서 검출된 반응산물은 모두 1-NP에 비하여 높은 극성을 보였다. 주요 반응산물로는 1,4-naphthoquinon(1,4-NPQ)와 dimer, trimer 등의 소 중합체(oligomers)를 포함하며 특히, 용매추출$(CH_2Cl_2)$ 후 수용액에 잔류하는 친수성 형태의 반응산물은 다양한 분자량의(m/z=$400\sim2000$) 중합체로서 토양 휴믹물질(풀빅산)과 유사한 형태의 UV-Vis 흡광특성을 보였다. 또한, 비 반응성 생성물인 1,4-NPQ는 1-NP 존재 하에서 망간산화물에 의한 교차-결합(cross-coupling)을 통해 중합체로 변환될 수 있음을 확인하였다. 본 실험조건(20.5 mg/L, 1-NP, 2.5 g/L $MnO_2$, pH 5)에서 산화-결합 반응에 의한 중합체 형성으로 제거되는 1-NP의 양(mg/L)은 초기농도 대비 약 83%에 해당하며, 이들 중 약 30% 정도는 침전층에서 중류수와 메탄올$(CH_3OH)$에 의해 추출되지 않는 안정화된 형태의 불용성 중합체 생성물로 존재하였다. 이상의 결과는 망간산화물에 의한 산화-결합반응이 naphthol 오염토양의 처리에 있어서 소 중합체와 중합체 침전물로의 변환을 통한 오염 저감 및 제거 효과를 나타냄을 제시한다.

Keywords

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