• 공업화학
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• 제8권2호
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• pp.308-314
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• 1997

폴리우레탄 전선도료 제조시의 TDI와 MDI의 blocking 반응에 미치는 촉매와 blocking reagents(BR)의 영향에 대하여 조사하였다. 1,4-diazabicyclo[2.2.2]octane(DABCO)와 tetramethyl guanidine(TMG)와 같은 촉매들은 NCO의 blocking 반응을 완결시키는데 필요한 것으로 나타났다. TMG는 DABCO에 비해 매우 빠른 반응속도를 보였다. TMG의 농도는 1%까지 반응도에 대하여 정량적으로 비례하였다. DABCO의 경우는 0.25%의 농도에서 가장 높은 반응도를 나타내었다. BR의 입체영향을 알아보기 위해 phenol, p-cresol, m-cresol, o-cresol, 2,4-xylenol과 같은 BR 등을 사용하였다. 예측한대로 입체장애가 적은 BR이 높은 반응도를 보였다. 또한 이 반응 시스템에서는 온도와 BR의 농도가 증가할수록 반응도가 증가하였다.

• 한국세라믹학회지
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• 제40권2호
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• pp.167-171
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• 2003

기계적 방법으로 합성된 CeO$_2$분말을 연마입자로 하여 STI용 CMP 슬러리를 제조하였다. 연마입자는 정전기적 방법과 입체적 방법으로 수계에서 안정화시킬 수 있었으며, 장기 안정성을 위해서는 입체적 방법에 의한 안정화가 유효하였다. 50$0^{\circ}C$와 $700^{\circ}C$에서 합성된 CeO$_2$를 이용하여 CMP 슬러리를 제조하고, SiO$_2$와 Si$_3$N$_4$가 블랭킷 형태로 증착된 웨이퍼를 연마한 결과 연마능률과 선택비는 연마입자의 합성조건과 분산 안정성, 슬러리의 pH 등에 의해 영향을 받았다.

• 분석과학
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• 제5권3호
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• pp.239-247
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• 1992

메틸기가 한 개 또는 두 개 치환된 10가지 메틸아닐리늄 이온과 18-크라운-6와의 착물 형성 및 선택성을 메탄올에서 적하수은 전극에 의해 조사하였다. 메틸아닐리늄 이온과 18-크라운-6와의 착물의 안정도 상수는 메틸기의 위치와 개수에 따른 입체장애 효과에 의해 큰 차이를 나타내었다. 또한 반파전위의 차가 매우 작아 일반적인 방법으로는 분석이 불가능한 메틸아닐리늄 이성질체 혼합물 등에 보조 착화제로 18-크라운-6를 첨가하여 입체장애에 의한 착물반응의 선택성을 이용하여 분석을 시도하였다. 그 결과 18-크라운-6와 두 게스트 이온의 안정도 상수의 차, ${\Delta}log\;K$가 대략 0.7~1.3인 경우 이성분 혼합물의 확인이 정성적으로 가능하였으며, 1.6 이상인 경우에는 정량적인 개별분석도 가능하였다. 이는 18-크라운-6가 아닐리늄의 메틸치환기의 위치에 따라 입체장애의 정도를 선별적으로 인식하여 큰 착물형성 선택성을 나타낸 결과로 각 환원파의 음전위 이동 정도가 크게 달라지기 때문이다.

• 대한화학회지
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• 제7권1호
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• pp.85-90
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• 1963

The Knoevenagel reaction of fluorinated carbonyl compounds, 1,1,1-trifluoro-propanone-2-heptafluoro-butyraldehyde, 1,3-dichloro-1,1,3,3-tetrafluoro-acetone, tetradecafluoro-heptanone-4 and 2,2,2-trifluoro-acetophenone yielded fluorinated ${\beta},{\beta}$-dialkyl-${\beta}$-hydroxy acids. Dehydration of the acids do not give the olefinic acid in the case of the perfluorinated system and gave a lactone. From the consideration of electronic and steric effects a mechanismic path of the reaction via a carbanion intermediate was proposed for the reaction. Preparation of related derivatives are also described.

• Archives of Pharmacal Research
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• 제15권1호
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• pp.5-8
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• 1992

5-Alkyl-3-(1-thioxolanyl-cyclohexenyl)-resorcinol derivatives are readily prepared by boron trifluoride-on-alumina-catalyzed formation of 5-alkylresorcinols with 1-thioxolanyl-2-cyclohexenol; their formation depends on the nature of the alkylgroup. The yield is the highest with 5-(1, 1-dimethylheptyl)-resorcinol. The one with 5-pentylresorcinol is higher than 5-methylresorcinol and resorcinol apparently because of steric effects. The yields of the products increases: 3a (10%), 3b (20%) 3c (48%) and 3d (77%).

• 한국염색가공학회지
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• 제15권5호
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• pp.321-326
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• 2003

In order for disperse dye based ink to be fitted with the critical requirements of ink jet printing, this study was undertaken to investigate the effects of 6 different dispersants on the milling efficiency of insoluble dye particles and dispersion stability of the final ink. It was found that a polystyrene dispersant with high molecular weight exerted relatively better dispersion stability which may be associated with its steric stabilization effect in the ink solution.

• Bulletin of the Korean Chemical Society
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• 제5권6호
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• pp.226-230
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• 1984

LIS's of cis and trans-methyl-2-phenylcyclopropanecarboxylate, cis and trans-t-butyl-2-phenylcyclopropanecarboxylate, cis and trans-N,N-dimethylcyclopropanecarboxamide, trans-2-phenylcyclopropyl methyl ketone and trans-2-phenylcyclopropyl t-butyl ketone have been studied. The LIS's hold the McConnell-Robertson relation and are mainly influenced by the steric effect. LIS's of trans isomers are larger than those of cis isomers. In trans isomers, the LIS's decrease in the following order: methyl ketone > methyl ester > N,N-dimethyl amide > t-butyl ketone${\sim}$t-butyl ester.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3880-3886
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• 2011

The nucleophilic substitution reactions of diisopropyl thiophophinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.80-0.96). The anilinolyses of ten P=S systems in MeCN are reviewed on the basis of DKIEs and selectivity parameters to obtain systematic information on the DKIEs and mechanism for thiophosphoryl transfer reactions. The steric effects of the two ligands on reactivity, DKIEs, mechanism, and substituent effects of the nucleophile (X) on the DKIEs are discussed.

• Bulletin of the Korean Chemical Society
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• 제34권4호
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Transactions on Electrical and Electronic Materials
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• 제7권3호
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• pp.112-117
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• 2006

In this paper we present that the effects of polymer adsorption on stabilities and CMP performance of ceria abrasive particles. Characterization of ceria abrasive particles in the presence of poly(vinyl pyrrolidone) (PVP) was performed by the measurements of adsorbed amounts of PVP, average sizes, and the back scattering intensities of the ceria abrasive particles as functions of PVP molecular weight and PVP concentration. The ceria abrasive particles in the presence of PVP were used to polish $SiO_2\;and\;Si_3N_4$ films deposited on Si wafers in order to understand the effect of PVP adsorption on chemical mechanical polishing (CMP) performance, together with ceria abrasive particles without PVP. Adsorption of PVP on the ceria abrasive particles enhanced the stability of ceria abrasive particles due to steric stabilization of the thick adsorbed layer of PVP. Removal rates of the deposited $SiO_2\;and\;Si_3N_4$ films by the ceria abrasive particles in the presence of PVP were much lower than those in the absence of PVP and their magnitudes were decreased with an increase in the concentration of free PVP chains in the dispersion media. This suggests that the CMP performance in the presence of PVP could be mainly controlled by the hydrodynamic interactions between the adsorbed PVP chains and the free ones. Moreover, the molecular weight dependence of PVP on the removal rates of the deposited films was hardly observed. On the other hand, high removal rate selectivity between the deposited films in the presence of PVP was not observed.