• 한국응용과학기술학회지
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• 제28권1호
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• pp.22-28
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• 2011

Esterification reaction between succinic acid[SA] and 1,4-butanediol [BD] was kinetically investigated in the presence of organometallic catalysts (ESCAT-100Ag18, MBTO) at $150{\sim}180^{\circ}C$. The reaction followed from the measurement of the quantity of water which was distilled from the reaction vessel. The esterification reaction was carried out under the first order kinetics with respect to the concentration of reactants and catalyst, respectively. The overall reaction order was 2nd. From the examination of relationship between apparent reaction rate constants and reciprocal absolute temperature, the activation energy has been calculated as 146.70 kJ/mol(ESCAT-100Ag18) and 87.57 kJ/mol(MBTO), respectively.

• 통합자연과학논문집
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• 제1권3호
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• pp.189-191
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• 2008

Alkylation, carbonylation and cyclization reaction using transition metal(or inner-) complexes as reducing agents or catalysts were investigated.

• 한국표면공학회지
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• 제33권4호
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• pp.261-265
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• 2000

Geometrically and chemically well defined Pt/alumina model catalysts have been prepared. To this end, we fabricated electrochemically alumina supports in which pores of constant size, length and shape were regularly distributed over a wide area of the surface. Platinum particles were dispersed on the pore surfaces via organometallic chemical vapor deposition technique using (trimethyl) methylcyclopentadienylplatinum (IV) as a precursor. The chemical composition of the alumina plane surfaces was examined by Auger electron spectroscopy and the adsorption characteristics of the platinum particles were studied by thermal desorption spectroscopy. A variety of industrial catalytic problems are now open for further investigation utilizing the Pt/alumina model catalysts.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.556-556
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• 2012

Transition metal-based organometallic complexes have shown great talents as a catalyst in various reactions. Designing organic molecules and coordinating them to such active centers have been a promising route to control the catalytic natures. Metallocene, which has transition metal atoms sandwiched by aromatic rings, is one of the representative systems for organometallic catalysts. Group 4-based metallocene catalysts have been most commonly used for the production of polyolefins, which have great world-wide markets in the real life. Graphenes and carbon nanotubes (CNTs) were composed of extended $sp^2$ carbon networks, showing high electron mobility as well as have extremely large steric bulkiness relative to metal centers. We were inspired by these characteristics of such carbon-based nano-materials and assumed that they could intimately interact with active centers of metallocene catalysts. We examined this hypothesis and, recently, reported that CNTs dramatically changed catalytic natures of group 4-based catalysts when they formed hybrid systems with such catalysts. In conclusion, we produced hybrid materials composed of group-4 based metallocenes, $Cp_2ZrCl_2$ and $Cp_2TiCl_2$, and carbon-based nano-materials such as RGO and MWCNT. Such hybrids were generated via simple adsorption between Cp rings of metallocenes and graphitic surfaces of graphene/CNT. The hybrids showed interesting catalytic behaviors for ethylene polymerizations. Resulting PEs had significantly increased Mw relative to those produced from free metallocene-based catalytic systems, which are not adsorbed on carbon-based nano-materials. UHMWPEs with extremely high Mw were obtained at low Tp.

• 폴리머
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• 제29권4호
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• pp.321-330
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• 2005

1990년대에 우리나라의 폴리올레핀 산업이 급속히 성장하였으며, 이러한 석유화학 분야의 상업성은 올레핀 중합 촉매의 발전과 무관하지 않았다. 이러한 중합촉매의 연구개발에 대한 개괄적인 현황을 파악할 수 있도록, 현재 공업적으로 사용되고 있는 담지형 Ziegler-Natta촉매와 최근에 특수 grade의 폴리올레핀 제조에 도입되고 있는 메탈로센 촉매의 발전에 수반된 여러 관점의 연구 결과를 정리하였다. 또한 이들 새로운 중합촉매의 이용으로 고분자 신소재가 개발되었고, 촉매의 담지화 과정에서 얻은 연구결과가 고분자 나노복합체의 in-situ 제조에 응용될 수 있음을 보여 주었다.

• Bulletin of the Korean Chemical Society
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• 제18권1호
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• pp.66-70
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• 1997

The polymerization of 4, 4-bis(acetoxymethyl)-1, 6-heptadiyne (BAH) was carried out by MoCl5 and WCl6 with various organometallic cocatalysts. MoCl5-based catalysts were more effective than WCl6-based ones for the cyclopolymerization of BAH. Poly(BAH) was characterized to have polymer backbone with conjugated double bond and cyclic structure by IR, UV-visible, and 1H-and 13C NMR spectroscopies. The polymer was stable up to 310 ℃ and 5 % weight loss show up at 350 ℃. The resulting dark violet polymer exhibited good solubility in common organic solvents and could be cast on a glass plate to give film with good mechanical properties. It was found that oxygen permeability (PO2) and permselectivity (PO2/PN2) of the resulting polymer were 15.2 barrer and 2.84, respectively.

• 대한화학회지
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• 제31권1호
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• pp.79-83
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• 1987

Triphenylmetal(IVA) methoxide 또는 triphenylmetal(IVA) methoxide와 phenylisocyanate를 1 : 500mole비로 혼합하여 여러온도에서 반응시켰다. Methyltrimethylsilyl ether, methyltriphenylsilyl ether 및 triphenyltin methoxide는 100$^{\circ}C$에서도 phenylisocyanate의 cyclid dimer(N,N'-diphenyluretidine-2,4-dione)를 생성하였으나, 다른 화합물들은 주로 cyclic trimer(phenylisocyanate)만을 생성하였다. 또한 200$^{\circ}C$이상에서는 모든 화합물들이 상당량의 diphenylcarbodiimide를 생성하였다. 이와 같은 반응결과로부터 phenylisocyanate의 cyclic polymerization의 mechanism과 (p-d)$\pi$ overlap에 대한 금속의 치환기 효과를 고찰하였다.

• 폴리머
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• 제36권1호
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• pp.53-58
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• 2012

본 연구에서는 Al 계 화합물 혼합촉매 시스템의 L-lactide 벌크중합을 통해 단일 Al계 화합물과 혼합된 Al계 화합물의 중합 특성의 차이를 확인하였다. Al 화합물 촉매를 조성비를 변화시킨 혼합촉매를 사용하여 벌크중합한 polylactic acid (PLA)는 FTIR, DSC, GPC 등으로 분석하였다. 선정된 Al계 화합물로는 aluminum isopropoxide($Al(O-i-Pr)_3$), trimethylaluminum(TMA), trioctylaluminum(TOA), triisobutylaluminum(TIBA)이었으며 TIBA를 기준 촉매로 선정하여 나머지 세 Al화합물을 각각 혼합하여 사용하였다. $Al(O-i-Pr)_3$와 TIBA를 혼합한 촉매의 경우 혼합촉매 내 $Al(O-i-Pr)_3$의 양이 증가함에 따라 전환율도 증가하였고 생성된 PLA의 분자량은 13000까지 증가하였으며 분자량분포도도 약간의 증가를 보였다. 분자량 분포곡선은 혼합촉매 시스템의 경우 고분자량 부분에서 약간의 tail 또는 shoulder 형태가 형성되었다. TOA와 TIBA를 혼합한 촉매를 이용하여 L-lactide를 벌크중합한 결과 전환율은 혼합촉매 내 TOA의 양이 증가함에 따라 낮아졌다. TOA와 TIBA를 혼합한 촉매를 이용하여 벌크중합한 PLA의 분자량은 혼합촉매 내 TOA 조성이 60 mol%까지 분자량이 14000 g/mol까지 증가하다가 감소하였다. 이러한 Al계 혼합촉매 시스템을 통해 PLA의 고분자량 tail이나 shoulder을 생성할 수 있었으며 이를 통해 PLA의 기계적 물성을 향상시킬 수 있는 역할을 기대할 수 있다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.198-198
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• 2011

Organocatalysis is a relatively new and popular area within the field of chiral molecule synthesis. It is one of the main branches of enantioselective synthesis with enzymatic and organometallic catalysis. In recent years, immense high quality studies on catalysis by chiral secondary amines were reported. These progresses instantly led to different organocatalytic activation concepts, so thousands of researchers from academia and the chemical industry are currently involved in this field and new ideas, new approaches, and creative thinking have been rapidly emerged. Organocatalysts, some of which are natural products, appear to solve the problems of metal catalysts. Compared to metal-based catalysis, they have many advantages including savings in cost, time, and energy, easier experimental procedure, and reduction of chemical waste. These benefits originate from the following factors. First, organocatalysts are generally stable in oxygen and water in the atmosphere, there is no need for special equipments or experimental techniques to operate under anhydrous or anaerobic conditions. Second, organic reagents are naturally available from biological materials as single enantiomers that they are easy and cheap to prepare which makes them suitable for small-scale to industrial-scale reactions. Third, in terms of safety related catalysis, small organic molecules are non-toxic and environmentally friendly. Therefore, the purpose of this research is to develop novel synthetic methods and design for various organocatalyst. Furthermore, it is expected that these organocatalysts can be applied to a variety of asymmetric reactions and study the transition state of these reactions using a metal sulface. Here, we report the synthesis of unprecedented organocatalysts, proline and pyrrolidine derivatives with quaternary carbon center.

• Elastomers and Composites
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• 제48권1호
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• pp.61-66
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• 2013

일반식을 $[N(CH_3)(CH_2)_2(Bm-R)_2]CrCl_3$ [여기에서 Bm = benzimidazolyl, R = H (3a); -Me(3b); -Bn(3c)]으로 나타낼 수 있는 일련의 세 다리 dibenzimidazolyl 리간드를 갖는 크롬(III) 착물을 합성, 메틸알루미녹산으로 활성화시켜 이를 부타디엔의 입체규칙성 중합을 통해 trans-1,4-polybutadiene을 제조하였다. 크롬 착물의 부타디엔 중합 활성은 리간드의 구조에 따라 달라졌으며, 활성은 3a > 3c > 3b 순으로 낮아졌다. 모든 착물을 이용하여 제조된 폴리부타디엔의 미세구조를 조사한 결과 거의 완벽한 trans-1,4 구조를 보였으며, 분자량도 비교적 높게 나타났다.