• 제목/요약/키워드: Substitution reaction

검색결과 580건 처리시간 0.025초

Preparation of Cellulose Acetate Produced from Lignocellulosic Biomass

  • Jo, Jong-Soo;Jung, Ji Young;Byun, Ji-Hye;Lim, Bu-Kug;Yang, Jae-Kyung
    • Journal of the Korean Wood Science and Technology
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    • 제44권2호
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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.

생체적합성과 생분해성을 갖는 Polypeptide Copolymer의 합성과 물성에 관한 연구. (1) 폴리에틸렌 글리콜을 그라프트시킨 폴리펩티드의 합성 (Synthesis and Physical Properties of Biocompatible and Biodegradable Polypeptide Copolymers. (1) Synthesis of Poly(ethylene glycol) grafted Polypeptides)

  • 강인규;권대룡;조종수;성용길
    • 대한화학회지
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    • 제34권2호
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    • pp.197-202
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    • 1990
  • 한쪽 말단에 히드록시 혹은 양말단에 아미노기를 갖는 폴리에틸렌글리콜(PEG)을 이용한 에스테르 교환 혹은 아미노 치환반응을 행하여 (PEG) grafted poly γ-benzyl L-glutamate (PBLG)를 합성했다. 이들의 점도 특성은 진한 용액내에서는 농도 감소에 따라 점도가 감소하다가 어느 이상 묽어지게 되면, 농도 감소에 따라 점도는 다시 증가했다. PEG를 함유하는 폴리펩티드 중합체의 젖음성은 동종 중합체보다도 향상 됐고, 이들 중합체 필름을 아미노에탄올과 표면반응시킨 결과, 물의 접촉각이 대폭적으로 작아져 표면에 수화겔이 형성됨을 알 수 있었다.

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Nucleophilic Substitution Reactions of α-Bromoacetanilides with Benzylamines

  • Adhikary, Keshab Kumar;Kim, Chan-Kyung;Lee, Bon-Su;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제29권1호
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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.

Transition State Variation in the Anilinolysis of O-Aryl Phenyl Phosphonochloridothioates in Acetonitrile

  • Adhikary, Keshab Kumar;Lumbiny, Bilkis Jahan;Dey, Shuchismita;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권8호
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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.

$Pb(Mg_{1/3}Nb_{2/3})O_3-PbTiO_3-BaTiO_3$ 고용체의 미세구조와 유전특성에 관한 연구 (A Study on Microstructures and Dielectric Properties in $Pb(Mg_{1/3}Nb_{2/3})O_3-PbTiO_3-BaTiO_3$ Solid Solution)

  • 박현;이응상
    • 한국세라믹학회지
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    • 제31권10호
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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.

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고분자 전해질형 연료전지용 나프탈렌 부분을 갖는 술폰화된 폴리(아릴렌 이써 설폰) 블록 공중합체의 합성과 특성연구 (Synthesis and Properties of Sulfonated Poly (Arylene Ether Sulfone) Block Copolymers with Naphthalene Moiety for Polymer Electrolyte Fuel Cells)

  • 한다솜;유동진
    • 한국수소및신에너지학회논문집
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    • 제29권4호
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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.

친핵성치환반응에서 압력과 온도변화에 따른 친핵체 효과 (Nucleophile Effects for the Reactions of Nucleophilic Substitution by Pressure and Temperature)

  • 김세경;최성용;고영신
    • 대한화학회지
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    • 제48권5호
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    • pp.461-466
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    • 2004
  • 고진공 및 고압에서 친핵체변화에 따른 반응을 온도변화에 따라 속도론적으로 연구하였다. 유사1차반응속도상수, 2차반응속도상수, 열역학함수 및 Hammett ${\rho}$ 값을 구하였다. ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;및\;{\Delta}S^{\neq}$는 모두 음의 값을 나타내었으며, 모든 압력 조건에서 친핵체의 치환기효과 ${\rho}$x는 음의 값을 나타내었다. 전체적인 반응은 전형적인 $S_N2$ 반응메카니즘을 따르며, 압력과 친핵체 변화에 따라 반응메카니즘에 변화가 생김을 알 수 있다.

Kinetics and Mechanism of the Pyridinolysis of Ethylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권12호
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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.

Synthesis of new Pb-based layered cuprates in (Pb,S)(Sr,La)CuOz compounds

  • Kim, Jin;Lee, Ho Keun
    • 한국초전도ㆍ저온공학회논문지
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    • 제20권3호
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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.

$n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ Heterojunction 태양전지의 제작과 특성 (Fabrication and Characteristics of $n-CdS_{0.69}Se_{0.31}/p-Cu_{2-x}S_{0.69}Se_{0.31}$ Heterojunction Solar Cell)

  • 백승남;홍광준
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2004년도 춘계학술대회 논문집 반도체 재료 센서 박막재료 전자세라믹스
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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.

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