Ionic liquid-catalyzed isomerization of tetrahydrotricyclopentadiene using various chloroaluminate complexes

Kim, S.G.,Han, J.,Jeon, J.K.,Yim, J.H. Butterworths [etc.] ; Elsevier Science Ltd 2014 Fuel Vol.137 No.-

Isomerization of tetrahydrotricyclopentadiene (THTCPD) was conducted using three kinds of chloroaluminate ionic liquid (IL) catalysts to compare catalytic behavior of the IL catalysts. The effect of various reaction parameters and types of IL catalysts on the THTCPD isomerization has been explored to optimize the reaction process. The conversion of isomerization of THTCPD using IL catalyst strongly dependent on the molar fraction of AlCl<SUB>3</SUB> regardless of the type of IL catalyst, due to an acidity variation. The characterization of the IL catalysts was also performed by means of FT-IR to elucidate the nature of acidic active species on the THTCPD isomerization. It was found that Lewis acidity can be controlled using different types of cationic species as well as by altering the molar fraction of AlCl<SUB>3</SUB>. Moreover, the conversion of THTCPD isomerization was strongly correlated with the Lewis acidity of IL catalyst as well.

Isomerization of endo- to exo-Dicyclopentadiene by metal-organic frameworks (MOFs), MIL-100 (Fe, Cr) and MIL-101 (Fe, Cr) under solvent-free condition

지다혜,김동우,김현국,조득희 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0

MIL-100 (Fe, Cr) and MIL-101 (Fe, Cr), metal-organic frameworks (MOFs), have been assessed in solvent-free isomerization of dicyclopentadiene (DCPD) from the endo- to exo-form. In the isomerization reaction, the conversion of endo-DCPD and selectivity for the exo-dimer strongly depend on the nature of the active metal center. The MIL-100 (Fe) catalyst possessing more acid sites shows the highest catalytic activity among the MILs and it was readily recoverable and reusable in subsequent reaction cycles for the isomerization. The effects of reaction parameters such as temperature, reaction time, and catalyst loading on the reactivity were also investigated.

Study on the Isomerization of Maleic Acid to Fumaric Acid without Catalyst

Zhuo Gao,Wangmi Chen,Xiaoting Chen,Dali Wang,Shouzhi Yi 대한화학회 2018 Bulletin of the Korean Chemical Society Vol.39 No.8

Fumaric acid is an important food additive and industrial intermediate compound. The traditional methods of producing fumaric acid were catalyzed by maleic acid isomerization. In this study, isomerization of maleic acid in water without catalyst was investigated at elevated temperature, which addressed the problem of sewage discharge. HPLC analysis showed maleic acid converted into fumaric acid and small amount of malic acid simultaneously. The effects of concentration of maleic acid, reaction temperature, reaction time, and stirring on the yield of fumaric acid were investigated. The optimum reaction conditions were also explored. The results showed the isomerization of maleic acid reached equilibrium at about 1?h, stirring did not affect the reaction rate, and conversion due to the monomolecular mechanism. In order to achieve ?zero emission,? the recycle of filter liquor was also studied. The pH of filter liquor changing signifies the lower pH was in favor of the conversion of maleic acid to fumaric acid. The high yield and recyclability suggested that this process had promising application in fumaric acid production.

Effect of Ni in palladium β-zeolite on hydroisomerization of n-decane

Dhanapalan Karthikeyan,Nachiappan Lingappan,Bommasamudram Sivasankar 한국화학공학회 2008 Korean Journal of Chemical Engineering Vol.25 No.5

Bifunctional catalysts containing (0.1-0.5 wt%) Nickel and 0.1 wt% of Pd supported on H-β zeolite were synthesized by incipient wetness impregnation method and characterized by XRD, TEM, XPS, TPD and TPR techniques. The catalytic activity of Ni containing and Ni free Pd/H-β Catalysts was studied, and it was found that Ni up to a threshold value (0.3 wt% on β) produced increased the n-decane conversion and isomerization selectivity. When Ni content exceeds the threshold value, the conversion increases but isomerized products decrease. Moreover, Ni containing Pd/H-β showed increased sustainability and favored the protonated cyclopropane (PCP) intermediate mechanism in n-decane isomerization. The catalyst containing 0.3 wt% Ni 0.1 wt% Pd is adjudged as one performing better than other catalysts studied because of the isomerized mixture from it shows better octane number.

Catalytic performance of MIL-100 (Fe, Cr) and MIL-101 (Fe, Cr) in the isomerization of endo- to exo-dicyclopentadiene

Kim, D.W.,Kim, H.G.,Cho, D.H. Elsevier 2016 CATALYSIS COMMUNICATIONS - Vol.73 No.-

MIL-100 (Fe, Cr) and MIL-101 (Fe, Cr), metal-organic frameworks (MOFs), have been assessed in solvent-free isomerization of dicyclopentadiene (DCPD) from the endo- to exo-form. In the isomerization reaction, the conversion of endo-DCPD and selectivity for the exo-dimer strongly depend on the nature of the active metal center. The MIL-100 (Fe) catalyst possessing more acid sites shows the highest catalytic activity among the MILs and it was readily recoverable and reusable in subsequent reaction cycles for the isomerization. The effects of reaction parameters such as temperature, reaction time, and catalyst loading on the reactivity were also investigated.

Influence of preparation method on the catalytic performances of Re2O7/SiO2-Al2O3 catalysts in the metathesis of ethylene and 2-pentene

Weena Phongsawat,Joongjai Panpranot,Benjamas Netiworaruksa,Kongkiat Suriye,Piyasan Praserthdam 한국공업화학회 2014 Journal of Industrial and Engineering Chemistry Vol.20 No.1

The metathesis of ethylene and 2-pentene for propylene production was investigated over Re2O7/SiO2-Al2O3 catalysts. The SiO2-Al2O3 (50 wt% Al2O3) were obtained by co-precipitation, physical mixing, andsol–gel coating. The presence of isolated layers/grains g-Al2O3 either in bulk (physical mixing) or on thesurface (sol–gel coating) resulted in isomerization-free metathesis. On the contrary, the Re2O7 catalystssupported on co-precipitated SiO2-Al2O3 or the direct synthesis showed both metathesis and doublebondshift isomerization activities and as a consequence, higher propylene yield was obtained via thesecondary metathesis reaction. The catalytic properties were also correlated with the Al-atomrearrangements and the acidic characters/strengths.

N-2-(2-부텐일)에테인아마이드와 N-2-(2-부텐일)에테인나이트릴리움 이온의 가수분해와 이성질화

홍석 ( Seok Hong ) 경남대학교 기초과학연구소 2010 기초과학지 Vol.27 No.-

N-2-(2-부텐일)에테인아마이드 (1)의 구조 변화에 따른 에너지 값 비교와 N-2-(2-부텐일)에테인나이트릴리움 이온으로부터 가수분해 되어 목표 생성물이 얻어지는 과정과 이성질화와 더불어 궁극적으로 아세트산, 부탄온 및 암모늄 이온으로 분해되는 구조들과 에너지 변화를 다루었으며, 1의 시스 아마이드가 트랜스 아마이드보다 수소 이동의 에너지 값이 낮았고, NH의 수소가 탄소-탄소 이중결합의 탄소로 이동하는 에너지 값도 높지 않았다. The energy values for the structures of N-2-(2-butenyl)ethanamide(1) have been compared with them each other on the stepwise procedure. Starting from N-2-(2-butenyl)ethanenitrilium, the target product (1) was constructed, and eventually the products like acetic acid, butanone and ammonium ion would been obtained. All structures on this progress were energetically treated with its hydrolysis and isomerization. The interchanging energy values of cis-type amide for the hydrogen migration between NH and CO were lower than trans-type, whereas for the migration of hydrogen of NH to the carbon atom of carbon-carbon double bond were not high.

2P-209 Synthesis and behavior of azobenzene liquid crystalline polymeric elastomer light driven actuator

최정미,임채진,송슬기,김형준 한국공업화학회 2017 한국공업화학회 연구논문 초록집 Vol.2017 No.1

광 감응성 고분자는 분자의 구조가 특정 파장에 따라 바뀌는 광이성화 특성을 가지고 있으며 이를 통해 재료의 물리적, 화학적 특성이 변화된다. 광발색성 분자인 아조벤젠은 안정한 구조인 isomer가 자외선 350 에서는 불안정한 isomer로 바뀌며 450 파장에서는 다시 isomer로 다시 가역반응을 일으키며 광이성화 현상이 일어난다. 이러한 이성질화 현상을 이용하면 친환경적 정밀제어가 가능하다. 본 연구에서는 액정탄성폴리머의 rigid moiety의 부분을 아조벤젠을 이용해 광반응에 의한 분자의 구조 변형을 일으키고 액정탄성폴리머의 가교결합 부분 acrylate와 diacrylate를 사용해 결합을 형성하였고, 이를 열 개시제를 이용해 액정탄성폴리머(LCE) 필름을 제조하였다. 액정탄성폴리머(LCE)는 근육과 비슷한 성질을 가지고 있어 인공근육의 재료로 주로 쓰이며, 나노/마이크로 밸브와 모터, 정밀기계 등과 같은 액츄에이터 응용분야에 적용될 수 있다.

Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

Hyung Soo Lee*,Gab Yong Lee 대한화학회 2005 Bulletin of the Korean Chemical Society Vol.26 No.3

Transition metal complexes have been utilized in the homogeneous catalysis because of selectivity and catalytic activity under mild conditions.1 The isomerization of olefins catalyzed by transition metal complexes constitutes one of important type of reaction in organometallic chemistry.2 The isomerization of olefins occurs either by a metal hydride addition-elimination or by a -allyl metal hydride inter- mediate.2b HCo(CO)4, [(C2H4)2RhCl]2, Ni[P(OEt)3]4, and PtCl2(PPh3)2-SnCl2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechan- ism,3,4 and Fe3(CO)12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN)2PdCl2 occur via a -allyl metal hydride mech- anism.4,5 The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh3)3 has also been investigated.6 The skeletal isomerization of olefins catalyzed by (R3P)2NiCl2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene.7 Titanium com- plexes serve as an effective catalysts for a variety of reactions such as hydroalumination,8,9 hydroboration,10 and hydrogenation11 of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydro- carbons by using titanium and zirconium compounds.9-12 The reagent system composed of LiAlH4/Cp2TiCl2  2 in the molar ratio promotes the isomerization of 1-octene,8b,d but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp2TiCl2 (Cp=cyclopentadienyl) and LiAlH4.

Tetrahydrotricyclopentadiene(THTCPD) 유도체의 이성화 반응 연구

성민준(Minjun Seong),주형욱(Hyeong Uk Joo),서동욱(Donguk Seo),권태수(Teasoo Kwon),정병훈(Byeonghun Jeong),한정식(Jeongsik Han) 한국추진공학회 2014 한국추진공학회 학술대회논문집 Vol.2014 No.12

본 연구는 고에너지 액체 추진제인 Tetrahydrotricyclopentadiene(THTCPD) 유도체에 대한 이성화 반응 효과를 알아보기 위한 것으로 THTCPD 이성화 반응시간을 인자로 하여 이성화 거동 및 이성화 전환율이 물성 특성(점도, 발열량, 비중 및 어는점)에 미치는 영향을 살펴보았다.. Aluminum Chloride(AlCl₃)를 이성화 촉매로 사용하여 THTCPD의 이성화 반응을 수행한 결과 THTCPD major isomer(endo-exo-endo형)의 이성화 전환율이 증가할수록 다른 이성질체(endo-exo-exo형 및 exo-exo-exo형)로 변화되는 수율이 증가하는 것을 확인하였고, 이성화 전환율이 증가할수록 THTCPD의 점도 특성이 향상되는 것을 확인하였다. The study was to find out the isomerization reaction effect for the high-energy liquid propellant, Tetrahydrotricyclopentadiene(THTCPD) derivative. When the THTCPD isomerization reaction variable is reaction time, isomerization change and isomerization conversion were investigated to confirm that affect the physical properties(specific gravity, heat of combustion, Freezing point and Viscosity) of THTCPD. THTCPD isomerization reaction was investigated over Aluminum Chloride(AlCl₃) catalyst. Isomerization conversion of THTCPD major isomer(endo-exo-endo type) was increased with increase of other isomers(endo-exo-exo type and exo-exo-exo type) yield. Also, the viscosity property(-18 ℃: 179.8 cst, 20 ℃: 25.4 cst, 50 ℃: 8.9 cst) of THTCPD were confirmed to be improved.