• Journal of the Korean Wood Science and Technology
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• v.44 no.2
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• pp.241-252
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• 2016

Cellulose acetate is one of well-known industrial materials which have various commercial uses. We treated the lignocellulosic biomass using two-step (steam explosion-chemical) reaction followed by acetylation to get the cellulose acetate in this study. The two-step treatment was done to improve the yields of acetylation of the substrates. The yields of the cellulose acetate were about 88.4, 88.1, and 151.7% in barley straw, rice straw, and oak tree, respectively. Also the degree of substitution (DS) of the acetates was 2.1 to 2.5 in the biomass. We found that the biomass were valuable cellulosic sources, including their derivatives, in this study. This means that the biomass can be converted into the high-valued cellulosic stuff.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.197-202
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• 1990

Polyethylene glycol (PEG) grafted poly γ-benzyl L-glutamate (PBLG) were prepared from esterification or substitution reaction of PBLG with PEG having hydroxyl group at one end or primary amino groups at both ends. The viscosity of these polymer solution was decreased with decrease of polymer concentration. But in more dilute solution the viscosity was increased with decrease of polymer concentration. PEG-grafted PBLG polymers showed smaller water contact angles than PBLG homopolymer, and the water contact angles of the surface of PEG-grafted PBLG polymers were largely dropped by reacting with aminoethanol, resulting in hydrogel surfaces.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.191-196
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• 2008

Kinetic studies of the reactions of a-bromoacetanilides [YC6H4NHC(=O)CH2Br] with substituted benzylamines (XC6H4CH2NH2) have been carried out in dimethyl sulfoxide at 35.0 oC. The Hammett plots for substituent (Y) variations in the substrate (log kN vs. sY) are biphasic concave upwards/downwards with breaks at Y = 4-Cl (sY = 0.23). The Hammett coefficients rY and the cross-interaction constant rXY (= +0.16) are positive for sY 0.23, while the rY values are positive/negative [rY > 0 for X = (4-MeO and 4-Me) and rY < 0 for X = (H, 4-Cl and 3-Cl)] and the rXY (= -1.51) value is negative for sY ³ 0.23. Based on these and other results, the benzylaminolyses of a-bromoacetanilides are proposed to proceed through rate-limiting expulsion of the bromide leaving group from a zwitterionic tetrahedral intermediate, T, with a bridged transition state for s Y 0.23, while the reaction proceeds through concerted mechanism with an enolate-like TS in which the nucleophile attacks the a-carbon for s Y ³ 0.23.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2628-2632
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• 2011

The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.

• Journal of the Korean Ceramic Society
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• v.31 no.10
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• pp.1240-1246
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• 1994

While sintering the Pb(Mg1/3Nb2/3)O3-PbTiO3-BaTiO3 system through solid-reaction route, pyrochlore(Pb3Nb4O13) phase while reduces the dielectric constant is inevitably formed. Substitution of Pb(Mg1/3Nb2/3)O3 with PbTiO3 and BaTiO3 can retard the occurrence of pyrochlore phase. The perovskite solid-solution without containing pyrochlore phase can be obtained when we consolidated the materials consisting of PbTiO3 and BaTiO3 at 1200℃ for 2 hours. The sintered body composed of 0.8Pb(Mg1/3Nb2/3)O3-0.1PbTiO3-0.1BaTiO3 composition showed the diffused phase transition(DPT) phenomena and the maximum value of dielectric constant at 0℃ (Tc') with the value of 1.3×104.

• Transactions of the Korean hydrogen and new energy society
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• v.29 no.4
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• pp.331-338
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• 2018

In this study, sulfonated PAES block copolymers have been synthesized via nucleophilic substitution reaction. Hydrophobic oligomer was prepared using 2,6-dihydroxynaphthalene and bis(4-chlorophenyl) sulfone, whereas hydrophilic oligomer was prepared using sulfonated bis(4-chlorophenyl) sulfone and bis(4-hydroxyphenyl) sulfone. The chemical structure of polymers was analyzed by $^1H$ NMR, FT-IR and GPC. The thermal properties of polymers were measured by TGA and DSC. The oxidative stability of membranes was investigated by Fenton's test. Furthermore, the proton conductivity of membrane was found to be 26 mS/cm at $90^{\circ}C$. All physiochemical properties suggest that fabricated membrane have a great potential for applications in PEMFC.

• Journal of the Korean Chemical Society
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• v.48 no.5
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• pp.461-466
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• 2004

Kinetics for the nucleophiles have been studied under high vacuum and high pressures in various temperatures. Pseudo-first order rate constants, second order rate constants, thermodynamic parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;and\;{\Delta}S^{\neq}$are all negative. The Hammett r-values are negative for the nucleophile (${\rho}$x) over the pressure range studied. The results of kinetic studies for pressure and nucleophilet show that these reactions proceed in typical $S_N2$ reaction mechanism and change of mechanism.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4347-4351
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (2) with X-pyridines are investigated kinetically in acetonitrile at $-20.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. Unusual positive ${\rho}_X$ (= +2.49) and negative ${\beta}_X$ (= -0.41) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=6.6^{\circ}C$. The pyridinolysis rate of 2 with a cyclic five-membered ring is forty thousand times faster than its acyclic counterpart (3: diethyl chlorophosphate) because of great positive value of the entropy of activation of 2 (${\Delta}S^{\neq}$ = +49.2 eu) compared to negative value of 3 (${\Delta}S^{\neq}$ = -44.1 eu) over considerably unfavorable enthalpy of activation of 2 (${\Delta}H^{\neq}=28.4\;kcal\;mol^{-1}$) compared to 3 (${\Delta}H^{\neq}=6.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed.

• Progress in Superconductivity and Cryogenics
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• v.20 no.3
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• pp.1-4
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• 2018

The effect of sulfate substitution on the formation of (Pb,S)-1201 type phase was investigated. Polycrystalline samples with nominal compositions of $(Pb_{0.5}B_{0.5-x}S_x)(Sr_{2-y}La_y)CuO_z$, (x = 0 - 0.5, y = 0.7 - 1.0) and $(Pb_{0.5}S_{0.5})(Sr_{2-y}La_y)CuO_z$ (y = 0.5 - 1.0) were prepared by using a solid-state reaction method. The samples were characterized by powder X-ray diffraction (XRD) and resistivity measurements. XRD data revealed that almost-single (Pb,S)-1201 phase samples could be obtained for x = 0.5 and y = 0.9-1.0, judging from the similar results of the XRD patterns between the (Pb,S)-1201 and (Pb,B)-1201 phases. Each of the samples has a crystal structure with tetragonal symmetry. The sample with x = 0.5 and y = 0.9 is found to show an onset of resistivity dropping at over 23 K and zero resistivity at 12 K.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.04b
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• pp.51-55
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• 2004

$CdS_{0.69}Se_{0.31}$ single crystal grown by sublimation method. Hall effect measurement were carried out by the Van der Pauw method. The measurement values under the temperature were found to be carrier density $n=1.95{\times}10^{23}m^{-3}$, Hall coeffcient $RH=3.21{\times}10^{-5}m^3/c$, conductivity ${\sigma}=362.41{\Omega}^{-1}m^{-1}$, and Hall mobility ${\mu}=1.16{\times}10^{-2}m^2/v.s.$ Heterojunction solar cells of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ were fabricated by the substitution reaction. The open-circuit voltage, short-circuit currint density, fill factor and power conversion efficiency of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ heterojunction solar cell under $80mW/cm^2$ illumination were found to be 0.41V, $19.5mA/cm^2$, 0.75 and 9.99%, respectivity.