• 제목/요약/키워드: Aprotic

검색결과 131건 처리시간 0.019초

Synthesis and Thermal Properties of Poly(benzoxazole)s Based on Pendants

  • Jang, Hyewon;Lee, Seulbi;Choi, Jae Kon
    • Elastomers and Composites
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    • 제50권2호
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    • pp.138-145
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    • 2015
  • A series of wholly aromatic poly(hydroxyamide)s(PHAs), containing varying amounts of 2,6-dimethylphenoxy group and quinoxaline ring in the main chain, were synthesized by a direct polycondensation method. The inherent viscosities of the PHAs in either DMAc or DMAc/LiCl solution at $35^{\circ}C$ were found to be in the range of 1.02~1.90 dL/g. In the solubility study, we observed that PHA 1, PHA 2, and PHA 3 were dissolved in aprotic solvents such as DMAc, NMP, DMF, and DMSO with LiCl on heating; however, PHA 4, PHA 5, and PHA 6 could be dissolved in aprotic solvents on heating without LiCl. For poly(benzoxazole)s(PBOs), the 10% and maximum weight loss temperatures were in the range of $582{\sim}622^{\circ}C$ and $630{\sim}659^{\circ}C$, respectively. Residues of PBOs at $900^{\circ}C$ were found to be relatively high, which were in the range of 65.3~70.8%.

Stoichiometric Solvent Effect on SN1 Solvolytic Reactivity Accounting for Phenomenon of Maximum Rates in Methanol-Nitromethane Mixtures

  • Ryu, Zoon-Ha;Choi, Su-Han;Lim, Gui-Taek;Sung, Dea-Dong;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • 제25권9호
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    • pp.1346-1350
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    • 2004
  • Pseudo-first order rate constants $(k_{obs})$ are reported for the following solvolyses in approximately isodielectric mixtures: 3- and 4-methoxybenzyl chloride, bromo- and chlorodiphenylmethane, and 4-chloro-, 4,4'-dichloro and 4-methyl-chlorodiphenylmethane in 0-80% v/v nitromethane-methanol mixtures; and bromo- and chlorodiphenylmethane and 4-methyl-chlorodiphenylmethane in various acetonitrile-methanol mixtures (in the range 0-50% v/v) at$25^{\circ}C.$ These data, and literature data for t-butyl halides (Cl, Br, and I), and for p-methoxybenzoyl chloride, show rate maxima in solvent compositions of ca. 30% aprotic cosolvent, explained by a stoichiometric solvent effect on electrophilic solvation. Linear relationships are observed between $(k_{obs})/[MeOH]^2$ and [AP]/[MeOH], where [AP] refers to the molar concentration of aprotic cosolvent. The results are consistent with competing third order contributions to $k_{obs}$, $k_{MM}[MeOH]^2$ with hydrogen-bonded methanol as electrophile, and $k_{MAP}[MeOH][AP]$ with hydrogen-bonding disrupted by the aprotic solvent.

물과 극성 비양자성 용매 혼합 계를 이용한 4-도데카노일옥시벤젠술폰산 나트륨의 효율적인 합성 및 표백활성화제로의 응용 (Mild and Efficient Synthesis of Sodium Dodecanoyl-4-oxybenzenesulfonate using Water and Polar Aprotic Solvent Mixed System and Its Application as a Bleach Activator)

  • 곽상운;차경온;정국인;김영호
    • 공업화학
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    • 제32권5호
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    • pp.532-540
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    • 2021
  • 4-도데카노일옥시벤젠술폰산나트륨(sodium dodecanoyl-4-oxybenzenesulfonate; DOBS) 염은 저온에서도 효과적인 표백력과 살균력을 나타내는 물질이다. 본 연구에서는 물(W)-극성 비양자성 용매 계를 사용하는 알칼리 조건하에서 dodecanoyl chloride와 sodium 4-hydroxybenzene sulfonate로부터 DOBS의 온화하고 효율적인 합성방법을 조사하였다. 먼저 물만을 용매로 사용하고 온도 또는 시간을 변화시키며 반응한 결과, 수율은 30 ℃와 1 h 이상의 반응 조건에서 대부분 약 5% 정도로 낮게 나타났다. 효율적인 용매 계를 발견하기 위하여 극성 비양자성 용매의 종류를 변화시키며 물과 혼합하여 제조한 다양한 용매계에서 수율에 미치는 영향을 평가하였다. 수율은 아세톤(acetone; AC)과 물을 혼합한 용매 계에서 가장 우수하였으며, 온화한 반응조건(30 ℃, 1 h 및 상압)의 반응에서 약 82%의 높은 값을 나타냈다. 제조한 DOBS는 높은 표백력 및 살균력을 보여 표백활성화제로서 활용이 가능함을 확인하였다.

Electrochemical Studies on the Reaction of Superoxide Ion with Halocarbons in Aprotic Media

  • Jeon, Seungwon;Choi, Yong-Kook
    • 분석과학
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    • 제8권4호
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    • pp.649-654
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    • 1995
  • The reactivity of superoxide ion($O{_2}^{-.}$) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by $O{_2}^{-.}$. The reaction rates of halogenonitriles with $O{_2}^{-.}$ vary according to the leaving-group propensity of halide (Br>Cl>F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN> $C(O)NH_2$ >Ph, $CH_2CN$). The reaction of $O{_2}^{-.}$ with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and $O{_2}^{-.}$, and the relative rates of cyclization depend on the number of methylenic carbons {$Br(CH_2)_nBr$, [n=1<2<3>4>5]}. Mechanisms are proposed for the reaction of $O{_2}^{-.}$ with halogenated substrates.

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A Modified Alkaline Hydrolysis of Total Ginsenosides Yielding Genuine Aglycones nad Prosapogenols

  • Im, kwang-Sik;Chang, Eun-Ha;Je, Nam-Gyung
    • Archives of Pharmacal Research
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    • 제18권6호
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    • pp.454-457
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    • 1995
  • To improve the yield of genuine aglycones from glycosides, the conditions of alkaline hydrolysis were investigated, and a modified method was established. The modified method empolyed pyridine as an aprotic solvent. To complete the hydrolysis and obtain 20(S)-protopanaxadiol (1) and 20(S)-protopanaxatriol(2), which are the genuine aglycones of ginsenosides, total ginsenosides were refluxed with sodium methoxide in pyridine. Addition of methanol, a protic polar solvent to the reaction miuxture, led partial hydrolysis yielding a mixture of the genuine prosapogenols. Of the prosapogenols compound 3 and 6 characteristically possessed D-glucopyranosyl moiety attached at the sterically hindered C-20 hydroxyl group. 3 and 6 were not obtaijned by other hydrolysisw methods except by the soil bacterial hydrolysis.

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Dispersions of partially reduced graphene oxide in various organic solvents and polymers

  • Kim, Hye Min;Kim, Seo Gyun;Lee, Heon Sang
    • Carbon letters
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    • 제23권
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    • pp.55-62
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    • 2017
  • We report on the dispersion state of partially reduced graphene oxide (PRGO) in organic solvents, namely methyl ethyl ketone, ethyl acetate, methylene chloride, toluene, and xylene, by controlling the carbon to oxygen (C/O) atomic ratio of the PRGOs. A two-phase solvent exchange method is also proposed to transfer PRGO from water to an aprotic solvent, such as methyl ethyl ketone. We achieve relatively good dispersion in aprotic and non-polar solvents by controlling the C/O atomic ratio of the PRGOs and applying the two-phase solvent exchange method. There is an increase in the glass transition temperatures with the dispersion of PRGOs into amorphous polymers, in particular a $4.4^{\circ}C$ increase for poly(methyl methacrylate) and $3.0^{\circ}C$ increase for polycarbonate. Good dispersion of PRGO in a nonpolar polymer, such as linear low density polyethylene, is also obtained.

Synthesis and Properties of Polybenzoxazole Copolymers Having Non Linear Units

  • Han, So Hee;Lee, Eung Jae;Choi, Jae Kon
    • Elastomers and Composites
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    • 제54권4호
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    • pp.321-329
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    • 2019
  • A series of poly(hyroxyamide)s (PHAs) was prepared by direct polycondensation reaction of 4,4'-(2,3-pyridinedioxy)dibenzoic acid and/or isophthalic acid with 3,3'-dihydroxybenzidine. The yield percentages of the products were high, and the inherent viscosities of the polymer in DMAc solution at 35℃ were 0.31-0.59 dL/g. All PHA polymers were found to be soluble in polar aprotic solvents such as DMAc, DMSO, NMP, and DMF. On the other hand, LiCl was required to dissolve IPHA-1 in aprotic solvents. Poly(benzoxazole)s (PBOs) were partially soluble in conc-H2SO4; IPBO-4, -5, and -6 were partially soluble in NMP only when LiCl was added to the solution, and the solution was heated. The PBO polymers showed a maximum weight loss in the temperature range of 654-680℃, and the char yields at 900℃ under nitrogen atmosphere exceeded 63%.

Preparation and Characterization of Wholly Aromatic Polybenzoxazole Copolymers Bearing Ether and Bulky Units

  • Han, So Hee;Lee, Eung Jae;Choi, Jae Kon
    • Elastomers and Composites
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    • 제55권3호
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    • pp.205-214
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    • 2020
  • A series of wholly aromatic polyhyroxyamide (PHA) copolymers were prepared by direct polycondensation reaction of isophthalic acid and diacids containing bulky units with 3,3'-dihydroxybenzidine. The inherent viscosities of the PHAs measured at 35℃ in DMAc solution were in the range of 0.31-0.56 dL/g. The solubility study revealed that the PHAs were readily soluble in aprotic solvents such as, dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP) at room temperature and in less polar solvent such as pyridine. However, the polybenzoxazole (PBO) copoymers were quite insoluble in all organic solvents except partially soluble in concentrated sulfuric acid and partially soluble in NMP containing LiCl. The PBO copolymers showed maximum weight loss temperature in the range of 593-632℃ and high char yields in the range of 65.0-71.2% at 900℃ in a nitrogen atmosphere.

Intramolecular Hydrogen Bonding Effect on the Excited-State Intramolecular Charge Transfer of p-Aminosalicylic Acid

  • 김양희;윤민중
    • Bulletin of the Korean Chemical Society
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    • 제19권9호
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    • pp.980-985
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    • 1998
  • The excited-state intramolecular proton transfer (ESIPT) emission has been observed for 0.01 mM p-aminosalicylic acid (AS) in nonpolar aprotic solvents as demonstrated by the large Stokes' shifted fluorescence emission around 440 nm in addition to the normal emission at 330 nm. However in aprotic polar solvent such as acetonitrile, the large Stokes' shifted emission band becomes broadened, indicating existence of another emission band originated from intramolecular charge transfer (ICT). It is noteworthy that in protic solvents such as methanol and ethanol the normal and ICT emissions are quenched as the AS concentration decreases, followed by the appearance of new emission at 380 nm. These results are interpreted in terms of ESIPT coupled charge transfer in AS. Being consistent with these steady-state spectroscopic results, the picosecond time-resolved fluorescence study unravelled the decay dynamics of the ESIPT and ICT state ca. 300 ps and ca. 150 ps, respectively with ca. 40 ps for the relaxation time to form the ICT state.