• Elastomers and Composites
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• 제55권3호
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• pp.199-204
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• 2020

Considering the immense applicability of isoprene rubbers, such as natural rubber (NR) and synthetic polyisoprene rubber (IR), attempts are being made to introduce more functionality within the rubber structure, e.g. epoxidation, to widen their technological viability. Epoxidation introduces polar epoxy bonds into the rubber molecular chain, resulting in enhanced intermolecular interactions among the rubber chains, increasing the oil resistance and air impermeability. Although there have been many reports on the epoxidation of NR in its latex form, there has been no such report using its solid form (or gum), which limits the epoxidation in terms of portability. Furthermore, the gum form has longer lifetime, while the latex form has limited lifetime for its efficient use. In this study, the epoxidation of natural rubber and polyisoprene rubber (using meta-chloroperoxybenzoic acid (mCPBA) as the epoxidizing agent) by dissolving their gum in hexane (i.e., the solution method) have been studied and compared. The effects of the amount of mCPBA, reaction time, and reaction temperature were investigated. The present process is easy and facilitates the epoxidation of rubbers in their solid form; therefore, it can be used for industrial upscaling of epoxidized rubber production.

• Bulletin of the Korean Chemical Society
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• 제22권1호
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• pp.93-96
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• 2001

• Applied Biological Chemistry
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• 제9권
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• pp.1-7
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• 1968

뉴우질랜드 시금치(Tetragonia expansa)잎의 절편(切片)을 $2.0{\times}10^{15}$ quanta $cm^{-2}$ $sec.^{-1}$의 일정 레벌의 에너지를 가지는 각파장(各波長)의 광선(光線)을 쪼였을때 일어나는 violaxanthin의 de-epoxidation과 zeaxanthin의 epoxidationq 반응(反應)의 action spectrum을 측정(測定)하였다. De-epoxidation의 action spectrum에서는 480nm와 648nm에 두 개의 주 피이크를 나타내었고 청색광선(靑色光線)은 적색광선(赤色光線)보다 더 유효(有效)하였으며, 700nm 이상의 파장(波長)에서는 효과(?果)가 없었다. 한편 expoxidation의 spectrum은 440과 670nm 근처(近處)에 피이크를 나타내었고 이것 또한 청색광(靑色光)이 적색광(赤色光)보다 유효(有效)하였으나 700nm 이상의 파장(波長)에 있어서 확실(確實)히 효과(?果)를 나타내었다. Epoxidation과 de-epoxidation의 상반(相反)되는 두 반응(反應)의 정(正)의 결과(結果)는 하나의 cycle scheme 즉 산소(酸素)와 광반응생성물(光反應生性物)을 소비(消費)하는 "violaxanthin cycle"로 보아진다. Action spectra가 지시하는바와 같이 청색광(靑色光)이 적색광(赤色光)보다 더 유효(有效)하다는 것은 청색광(靑色光)에 의한 자극(刺戟)으로 진행(進行)되는 $O_2-uptake$로 간주(看做)된다. 두 action spectrum간(間)의 차이점(差異點)들은 다분히 두 개의 광합성기구(光合成機構)가 동시(同時)에 관련(關聯)되고 있다는 것을 시사한다. 그러므로 violaxanthin cycle은 청색광(靑色光)에 위해서 발생(發生)하는 과잉(過剩)한 광합성생성물(光合成生性物)의 소비경로(消費經路)로서, 또는 그들 생성물(生性物)을 어떤 다른 형태(形態)의 에너지로 전환(轉換)하는 역할(役割)을 하는것이라 보아진다.

• Bulletin of the Korean Chemical Society
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• 제22권9호
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• pp.941-942
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• 2001

• Bulletin of the Korean Chemical Society
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• 제20권7호
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• pp.831-834
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• 1999

Binaphthol-derived chiral ketones 1a-c were synthesized and were shown to serve as active catalysts for asymmetric epoxidation of olefins using Oxone, although their enantioselectivities were not high. However, very interestingly, the stereochemical outcome of the resulting epoxides implicates that in the epoxidation using 1a-c, the planar transition state may be more favorable than the spiro transition state.

• Bulletin of the Korean Chemical Society
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• 제27권9호
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• pp.1381-1385
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• 2006

Cobalt (cyclam) complex has been successfully immobilized onto SBA-15, and proven to be an active catalyst for the epoxidation of styrene with tert-butyl hydroperoxide as a terminal oxidant. The selectivity for styrene oxide was observed to be up to 66% with 40% styrene conversion after 12h reaction time. The reversible redox cycle between Co(III) and Co(II) couple which was supposed to play key role during the epoxidation reaction was supported by a cyclic voltametry analysis. The textural properties of the catalyst was characterized by XRD, N2 adsorption-desorption, and TEM analysis.

• Fibers and Polymers
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• 제3권3호
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• pp.109-112
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• 2002

Polybutadiene(PB) was epoxidized to various extents with m-chloroperbenzoic acid (MCPBA) in homogeneous solution. The thermal properties of the epoxidized PBs were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). As a result of epoxidation the glass transition temperature (Tg) of PB increased by approximately $0.8^{\circ}$ for each 1 mol% of epoxidation. The thermal decomposition of the epoxidised PBs occurred in two-step process, while that of PB exhibited apparent one-step degradation process.

• Bulletin of the Korean Chemical Society
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• 제26권6호
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• pp.887-891
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• 2005

Novel nickel catalyst deposited on nanoporous carbon was found to be an efficient catalyst for the epoxidation of simple alkenes with $O_2$ and isobutyraldehyde under mild conditions. Alkenes exhibited different reactivities towards Ni-catalyst and epoxidation with stilbene proceeds stereospecifically. This may be rationalized with the mechanism involving coordinated acylperoxy radical intermediate. Nickel contents depend on the preparative methods and the KNI-3 catalyst, which was synthesized by wet impregnation of $Ni(NO_3)_2$ into nanoporous carbon, shows the highest activity. The activity of the catalyst is well correlated with contents of nickel. Recycled catalysts suffer considerable loss of activity due to leaching of catalytic active species, nickel.

• Bulletin of the Korean Chemical Society
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• 제15권12호
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• pp.1112-1118
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• 1994

Epoxidation of olefins has been studied using iodosylbenzene (PhIO) as the terminal oxidant and binuclear and mononuclear complexes of $Mn^{2+}$, $Co^{2+}$, and $Cu^{2+}$ as catalysts. Epoxides were the predominant products with trace amounts of allylic oxidation products, and the metal complexes were found to be effective catalysts in the epoxidation reactions. The reactivity of binuclear copper complexes was greater than that of the mononuclear copper complexes, whereas the binuclear and mononuclear complexes of $Mn^{2+}$ and $Co^{2+}$ showed similar reactivities. The nature of the ligands bound to copper did not influence the reactivity of the binuclear copper complexes so long as copper ions were held in close proximity. A metal-iodosylbenzene complex, such as suggested previously for Lewis acidic metal complex-catalyzed epoxidation by iodosylbenzene, is proposed as the active epoxidizing species. Some mechanistic aspects are discussed as well.

• Bulletin of the Korean Chemical Society
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• 제17권7호
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• pp.625-630
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• 1996

The cobalt-substituted polyoxotungstate [(CoPW11O39)5-] has been used as a catalyst in olefin epoxidation and alkane hydroxylation reactions. The epoxidation of olefins by iodosylbenzene in CH3CN yielded epoxides predominantly with trace amounts of allylic oxidation products. cis-Stilbene was streoselectively oxidized to cis-stilbene oxide with small amounts of trans-stilbene oxide and benzaldehyde formation. The epoxidation of carbamazepine (CBZ) by potassium monopersulfate in aqueous solution gave the corresponding CBZ 10,11-oxide product. Other transition metal-substituted polyoxotungstates (M=Mn2+, Fe2+, Ni2+, and Cu2+) were inactive in the CBZ epoxidation reaction. The cobalt-substituted polyoxotungstate also catalyzed the oxidation of alkanes with m-chloroperbenzoic acid to give the corresponding alcohols and ketones. The presence of CH2Br2 in the hydroxylation of cyclohexane afforded the formation of bromocyclohexane, suggesting the participation of cyclohexyl radical. In the 18O-labeled water experiment, there was no incorporation of 18O into the cyclohexanol product when the hydroxylation of cyclohexane by MCPBA was carried out in the presence of H218O. Some mechanistic aspects are discussed as well.