Hexanoic acid - crown ether system을 이용한 europium과 yttrium의 용매추출효과의 향상

심대선,한혜림,김세미,김정훈,김영운,정노희,강호철 한국유화학회 2015 한국응용과학기술학회지 Vol.32 No.1

용매추출법에서 희토류 금속을 효과적으로 분리하기 위해 추출제만 사용하는 것이 아니라 crown ether와 같은 첨가제를 이용하는 연구를 하였다. Host-guest 화합물인 macrocyclic ligand는 금 속과 착화물을 형성하는데, 이 때 crown ether의 cavity 크기와 비슷한 크기의 금속 이온들과 안정한 착 화물을 형성한다. 이전 연구에서 europium과 yttrium을 분리하기 위해 여러 사슬 길이의 지방산 추출제 를 이용한 추출실험을 행하였었다. 이를 토대로 분리효율이 좋지 않았던 hexanoic acid에 크기가 다른 crown ether (18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether)를 첨가하여 분리효과가 증가 하는 것을 연구하였다. hexanoic acid의 농도별로 분리효율을 본 후 가장 분리 효율이 좋은 농도에서 crown ether를 종류와 농도를 다르게 하여 첨가하였다. 그 결과 0.05 M hexanoic acid에서 분리능이 1.72으로 가장 높게 나타났고, crown ether를 첨가하였을 시 분리능이 0.002 M 15-crown-5 ether에서 가장 높게 나왔으며 기존의 분리능보다 2배 이상 더 높았다. 또한 crown ether를 첨가하였을 때 두 금 속이 MLR3·3RH의 형태로 추출되는 것도 확인 할 수 있었다. The synergistic solvent extraction of rare earth elements such as europium and yttrium has been investigated by the extractant with crown ether as an additive. Macrocyclic ligand as host-guest compounds form more stable complexes with metal ions which have the similar size of the cavity of crown ether. In our previous study[14] founded that the extraction used fatty acid of the various alkyl chain length. Based on the results of the previous experiment, the synergistic separation effect of two metals investigated that the hexanoic acid had was the worst extraction effect which added a crown ether such as 18-crown-6 ether, 15-crown-5 ether, and 12-crown-4 ether. In this study, the concentrations of hexanoic acid have showed the separation effect, and then the concentrations and kind of crown ether are performed for synergistic extraction at the hexanoic acid concentration of the highest separation effect. As a results, the separation rate is the highest value of 1.72 at 0.05 M hexanoic acid, and 0.002 M 15-crown-5 ether is the best value in other concentrations and kind of crown ether, it is about twice of using only hexanoic acid. Moreover, the extraction species of two metals has been founded MLR3·3RH form when added the crown ether.

Hexanoic acid - crown ether system을 이용한 europium과 yttrium의 용매추출효과의 향상

심대선(Dea-Seon Sim),한혜림(Hye-Rim Han),김세미(Se-Mi Kim),김정훈(Jeong-Hoon Kim),김영운(Young-Wun Kim),정노희(Noh-Hee Jeong),강호철(Ho-Cheol Kang) 한국유화학회 2015 한국응용과학기술학회지 Vol.32 No.1

용매추출법에서 희토류 금속을 효과적으로 분리하기 위해 추출제만 사용하는 것이 아니라 crown ether와 같은 첨가제를 이용하는 연구를 하였다. Host-guest 화합물인 macrocyclic ligand는 금속과 착화물을 형성하는데, 이 때 crown ether의 cavity 크기와 비슷한 크기의 금속 이온들과 안정한 착화물을 형성한다. 이전 연구에서 europium과 yttrium을 분리하기 위해 여러 사슬 길이의 지방산 추출제를 이용한 추출실험을 행하였었다. 이를 토대로 분리효율이 좋지 않았던 hexanoic acid에 크기가 다른 crown ether (18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether)를 첨가하여 분리효과가 증가하는 것을 연구하였다. hexanoic acid의 농도별로 분리효율을 본 후 가장 분리 효율이 좋은 농도에서 crown ether를 종류와 농도를 다르게 하여 첨가하였다. 그 결과 0.05 M hexanoic acid에서 분리능이1.72으로 가장 높게 나타났고, crown ether를 첨가하였을 시 분리능이 0.002 M 15-crown-5 ether에서가장 높게 나왔으며 기존의 분리능보다 2배 이상 더 높았다. 또한 crown ether를 첨가하였을 때 두 금속이 MLR3·3RH의 형태로 추출되는 것도 확인 할 수 있었다. The synergistic solvent extraction of rare earth elements such as europium and yttrium has been investigated by the extractant with crown ether as an additive. Macrocyclic ligand as host-guest compounds form more stable complexes with metal ions which have the similar size of the cavity of crown ether. In our previous study[14] founded that the extraction used fatty acid of the various alkyl chain length. Based on the results of the previous experiment, the synergistic separation effect of two metals investigated that the hexanoic acid had was the worst extraction effect which added a crown ether such as 18-crown-6 ether, 15-crown-5 ether, and 12-crown-4 ether. In this study, the concentrations of hexanoic acid have showed the separation effect, and then the concentrations and kind of crown ether are performed for synergistic extraction at the hexanoic acid concentration of the highest separation effect. As a results, the separation rate is the highest value of 1.72 at 0.05 M hexanoic acid, and 0.002M 15-crown-5 ether is the best value in other concentrations and kind of crown ether, it is about twice of using only hexanoic acid. Moreover, the extraction species of two metals has been founded MLR3·3RH form when added the crown ether.

매우 높은 분자량을 갖는 Nylon 4 및 Nylon 4/6 공중합체의 합성 및 그 특성 분석

김남철(Nam Cheol Kim),김지흥(Ji Heung Kim),남성우(Sung Woo Nam),전붕수(Boong Soo Jeon),유영태(Young Tai Yoo),김영준(Young Jun Kim) 한국고분자학회 2013 폴리머 Vol.37 No.2

Potassium tert-butoxide(t-BuOK)와 CO2 및 혹은 benzoyl chloride(BzC)를 각각 nylon 4 및 nylon 4/6 공중합체의 중합 개시제 시스템으로, 18-crown-6 ether(crown ether) 또는 tetramethyl ammonium chloride(TMAC)를 촉매로 사용하여 2-pyrrolidone(C4) 및 ε-caprolactam(C6)의 음이온 개환반응을 통하여 분자량이 매우 높은 polypyrrolidone(이하 nylon 4) 및 nylon 4 공중합체를 합성하였다. 개시제 시스템, crown ether 또는 TMAC가 중합반응에 미치는 영향을 분자량 및 수율 면에서 평가하였다. Crown ether나 TMAC를 사용하면 중합수율이 향상되었고 nylon 4의 경우 고유점도가 6.35 dL/g인 중합체를 합성할 수 있었다. 이 때 TMAC보다는 crown ether가 중합체의 분자량 상승에 더 효과적임을 확인할 수 있었다. 또한 제조된 중합체에 대해 TGA 및 DSC 열분석을 실시하였으며 분자량이 nylon 4 또는 nylon 4 공중합체의 열적 특성에 큰 영향을 미치지 않음을 확인하였다. Potassium tert-butoxide (t-BuOK) with CO2 or benzoyl chloride (BzC) as a polymerization initiator system was used with crown ether or TMAC as catalyst to synthesize very high molecular weight nylon 4 homo- and copolymers by anionic ring opening polymerization. Effect of different amounts of catalyst, crown ether and TMAC on the polymerization was studied in terms of intrinsic viscosity, yield and thermal properties. By adding crown ether or TMAC, polymers with very higher intrinsic viscosity values were obtained in a high yield. It was possible to synthesize nylon 4 homopolymer with such a high intrinsic viscosity value of 6.36 dL/g. Crown ether was found to be more efficient in terms of intrinsic viscosity and polymer yields than TMAC. Thermal analysis confirmed that molecular weight effect on the thermal properties of both nylon 4 and nylon 4 copolymer was marginal.

이온성 크라운에테르 포스포닉산에 의한 알칼리 금속 양이온과 알칼리 토금속 양이온의 용매추출

정영진 ( Yeong Jin Chung ) 한국유화학회 2005 한국응용과학기술학회지 Vol.22 No.1

N/A A comparison of alkali metal cation and alkaline earth cation solvent extraction was made for three additional monoionizable crown ethers and one diionizable crown ether. sym-(n-Octyldibenzo)-16-crown-5-oxyacetic acid 1 exhibited high efficiency and selecvity in solvent extraction of alkali metal cations with respect to that observed with alkaline earth cations. Sizes of Na^+ and Ca^(2+) appropriately match with the cavity size of monoethyl sym-bis[4(5)-tert-butylbenzol-16-crown-5-oxymethylphosphonic acid 3. As the result, Na^+ and Ca^(2+) are the best extracted. sym-(n-Octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid 4 was found to be somewhat selective for Na^+ over Li^+ and other alkaline earth metal cations. In the complexation of alklaine earth cations by crown ether diphosphonic acid 4, Ca^(2+) and Sr^(2+) are the appropriate sizes, but lager Ba^(2+) may be due to favorable formation of a sandwich type complex between the crown ether cavity and the dianion of the deprotonated crown ether phoaphonic acid moiety.

Analysis of 89Sr, 90Sr in Soil Sample Using Crown Ether/Chloroform Solvent Extraction Method

Lee,Chang-Woo,Kim,Sang-Bog,Choi,Kun-Sik,Kim,Sam-Rang,Choi,Yong-Ho,Park,Hyo-Guk,Lee,Myong-Ho,Hong,Kwang-Hee 대한방사선 방어학회 1996 방사선방어학회지 Vol.21 No.1

환경시료중 토양에 대한 방사성 스트론튬인 89Sr과 90Sr의 분석을 위해 Ca과 Sr을 분리하기 위한 방법으로 Crown ether를 이용한 추출방법을 사용하여 기존의 발연질산법과 비교하여 보았다. Crown ether를 이용한 추출방법을 기존으 발연질산법과 비교하여 보았을때 높은 Sr수율을 보였을뿐만 아니라 분석에 소요되는 시간과 절차가 훨씬 빠르고 간단했다. Crown ether를 이용한 추출방법으로 완전주변 토양에 대한 방사성 스트론튬의 분석을 수행하였으며, 방사성핵종 분석에 의한 환경감시의 효율적인 수행을 위한 스트론튬의 분석법을 제시하였다. For the determination of radiostrontium, 89Sr and 90Sr in environmental soil sample, a solvent extraction method for the separation of Ca and Sr from matrix using crown ether was investigated. In comparison with the existing frming nitric acid method, the extraction method showed high chemical yeeld of strontium and provided simple and rapid analytical steps. The new analytical method applied to the determination of radiostrontium in some soil sample around a nuclear power station to show that the analytical procedure is readily applicable to the practical radioactivity monitoring.

이온성 크라운에테르 포스포닉산에 의한 알칼리 금속 양이온과 알칼리 토금속 양이온의 용매추출

정연진 한국유화학회 2005 한국응용과학기술학회지 Vol.22 No.1

A comparison of alkali metal cation and alkaline earth cation solvent extraction was made for three additional monoionizable crown ethers and one diionizable crown ether. sym-(n-Octyldibenzo)-16-crown-5-oxyacetic acid _1 exhibited high efficiency and selecvity in solvent extraction of alkali metal cations with respect to that observed with alkaline earth cations. Sizes of Na+ and Ca2+ appropriately match with the cavity size of monoethyl sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid _3. As the result, Na+ and Ca2+ are the best extracted. sym-(n-Octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid _4was found to be somewhat selective for Na+ over Li+ and other alkaline earth metal cations. In the complexation of alklaine earth cations by crown ether diphosphonic acid _4, Ca2+ and Sr2+ are the appropriate sizes, but lager Ba2+ may be due to favorable formation of a sandwich type complex between the crown ether cavity and the dianion of the deprotonated crown ether phoaphonic acid moiety.

포타슘 술포네이트 폴리스타이렌 아이오노머의 기계적인 성질에 미치는 Crown ether의 영향

나연화,조규성,이법원,김준섭,유지강,박기주 조선대학교 생산기술연구소 1999 生産技術硏究 Vol.21 No.1

The effects of crown ether on the dynamic mechanical properties of potassium sulfonated polystyrene ionomer were investigated. As expected, it was found that when crown ether molecules were added to the ionomer, the crown ether molecules interacted with K^(+) cations and weakened the ionic interaction between K^(+)/sulfonate ion pairs of the ionomer significantly. Thus, no multiplets were present, and, in turn, no clustering was found. When the ether was added to interact with 50% of K^(+) cations, weak clustering was observed: the clustering was slightly stronger than that of a 50% neutralized ionomer. From this result, it was speculated that in the 50% neutralized sample H^(+) ⇔ K^(+) cation exchange occurs rapidly between -SO₃H and -S0₃K groups in multiplets. which weakens ionic interactions. In the 50% crown ether-added sample, however, -S0₃- group, instead of -S0₃H, is present, and thus no cation exchange is expected to occur.

Development and Application of Crown Ether-Based HPLC Chiral Stationary Phases

Myung Ho Hyun 대한화학회 2005 Bulletin of the Korean Chemical Society Vol.26 No.8

Crown ether-based HPLC chiral stationary phases (CSPs) have been successfully utilized in the resolution of various racemic compounds containing a primary amino group. Especially, CSPs based on chiral crown ethers incorporating chiral binaphthyl unit or tartaric acid unit and based on phenolic pseudo chiral crown ethers have shown high chiral recognition efficiency. In this account paper, a review on the development of crown ether-based HPLC CSPs, their structural characteristics and applications to the resolution of racemic compounds including chiral drugs containing a primary or secondary amino group with the variation of the type and the content of mobile phase components and with the variation of the column temperature is presented.

Development and Application of Crown Ether-based HPLC Chiral Stationary Phases

Hyun, Myung-Ho Korean Chemical Society 2005 Bulletin of the Korean Chemical Society Vol.26 No.8

Crown ether-based HPLC chiral stationary phases (CSPs) have been successfully utilized in the resolution of various racemic compounds containing a primary amino group. Especially, CSPs based on chiral crown ethers incorporating chiral binaphthyl unit or tartaric acid unit and based on phenolic pseudo chiral crown ethers have shown high chiral recognition efficiency. In this account paper, a review on the development of crown etherbased HPLC CSPs, their structural characteristics and applications to the resolution of racemic compounds including chiral drugs containing a primary or secondary amino group with the variation of the type and the content of mobile phase components and with the variation of the column temperature is presented.

Crown-ether,계면활성제,Crown-ether/계면활성제를 운반체로하는 벌크액막에서의 카드뮴 이온의 추출

강석원(Seok-Won Kang),유동석(Dong-Suk Yoo),조정식(Jung-Shik Cho),이찬기(Chan-Ki Lee),조문환(Moon-Hwan Cho),이광래(Kwang-Rae Lee) 강원대학교 환경연구소 1997 環境硏究 Vol.14 No.-