• Title/Summary/Keyword: Type of solvent

Search Result 559, Processing Time 0.021 seconds

Michael-type Reactions of 1-(X-substituted phenyl)-2-propyn-1-ones with Alicyclic Secondary Amines in MeCN and H2O: Effect of Medium on Reactivity and Transition-State Structure

  • Kim, Song-I;Hwang, So-Jeong;Park, Yoon-Min;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
    • /
    • v.31 no.5
    • /
    • pp.1199-1203
    • /
    • 2010
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for Michael-type reactions of 1-(X-substituted phenyl)-2-propyn-1-ones (2a-f) with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ value increases as the incoming amine becomes more basic and the substituent X changes form an electron-donating group (EDG) to an electron-withdrawing group (EWG). The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.48 - 0.51. The Hammett plots for the reactions of 2a-f exhibit poor correlations but the corresponding Yukawa-Tsuno plots result in much better linear correlations with ${\rho}$ = 1.57 and r = 0.46 for the reactions with piperidine while ${\rho}$ = 1.72 and r = 0.39 for those with morpholine. The amines employed in this study are less reactive in MeCN than in water for reactions with substrates possessing an EDG, although they are ca. 8 pKa units more basic in the aprotic solvent. This indicates that the transition state (TS) is significantly more destabilized than the ground state (GS) in the aprotic solvent. It has been concluded that the reactions proceed through a stepwise mechanism with a partially charged TS, since such TS would be destabilized in the aprotic solvent due to the electronic repulsion between the negative-dipole end of MeCN and the negative charge of the TS. The fact that primary deuterium kinetic effect is absent supports a stepwise mechanism in which proton transfer occurs after the rate-determining step.

Acquired Color Vision Impairment among Solvent-Exposed Workers in Petrochemical industry (석유화학단지에서의 유기용제 노출에 의한 후천적 색각이상)

  • Lee, Eun-Hee;Cho, Sung-Il;Cheong, Hae-Kwan;Atchison, David A.;Paek, Do-Myung
    • Journal of Korean Ophthalmic Optics Society
    • /
    • v.9 no.2
    • /
    • pp.257-267
    • /
    • 2004
  • Our study investigated the association between solvent exposure and acquired color vision loss using the Lanthony D-15 desaturated panel in petrochemical industry. Since neurotoxic effects associated with chronic solvent exposure, subjects with more than 6 months of exposure were included. Exposure assesment was estimated mean, maximum and cumulative 8hr TWA from individual 8-hour sampling. Exposure status were classified into two groups, occupationally exposed group to solvent and a non-exposed group. The results showed that CCI was positively related for age. According to the results of qualitative analysis, there was no significant difference in the prevalence of specific Type of dyschromatopsia the two examined group. However, the prevalence showed a higher proportion of dyschromatopsia to solvent exposure. It was affect with acquired dyschromatopsia(Type II, III and Complex) in exposed worker group(5.9%,7.86%,14.99%, respectively) than in the nonexposed group(6.16%,7.55%,13.71%, respectively). After each variable was adjusted for age, alcohol and tobacco consumption, a relationship between acquired dyschromatopsia and exposure showed an increase in the Odds ratio as compared to the nonexposed group at only left. The results showed that acquired dyschromatopsia was positively related to age (p<0.001). The results showed that solvent exposure, although not significant, could cause the acquired dyschromatopsia and visual system can serve important information on early neurotoxic effects in generally. Therefore, we need to concerns about eye health in workers.

  • PDF

Adhesion Properties of Low VOC-type Primer Containing Acrylic Modified Tackifier Resin (Acrylic Modified Hydrocarbone Resin을 포함하는 저독성 프라이머의 제조 및 특성)

  • Jeong, Boo-Young;Cheon, Jung-Mi;Oh, Sang-Taek;Chun, Jea-Hwan;Jo, Nam-Ju
    • Journal of Adhesion and Interface
    • /
    • v.12 no.1
    • /
    • pp.11-15
    • /
    • 2011
  • In this study we synthesized low VOC-solvent soluble thermo plastic polyurethane, The effect of chain extender and NCO/OH ratio for properties of thermoplastic polyurethane was investigated. Also, we prepared low VOC-type primer by TPU and acrylic modified tackifier resin. When NCO/OH ratio was 2 or more, TPU was insoluble in low VOC solvent. And peel strength was higher value using polar type tackifier than non-ploar type tackifier.

Kinetics and Mechanism of Michael-type Reactions of Ethyl Propiolate with Alicyclic Secondary Amines in H2O and MeCN: Solvent Effect on Reactivity and Transition-State Structure

  • Kim, Song-I;Baek, Hye-Won;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
    • /
    • v.30 no.12
    • /
    • pp.2909-2912
    • /
    • 2009
  • The amines studied in this study are less reactive toward ethyl propiolate (3) in MeCN than in H$_2$O although they are 7 to 9 pK$_a$ units more basic in the aprotic solvent. The reactivity of morpholine and deuterated morpholine toward 3 is found to be identical, indicating that proton transfer occurs after rate-determining step (RDS). The fact that kinetic isotope effect is absent excludes a stepwise mechanism in which proton transfer occurs in RDS as well as a concerted mechanism in which nucleophilic attack and proton transfer occur concertedly through a 4-membered cyclic transition state (TS). Thus, the reactions have been concluded to proceed through a stepwise mechanism in which proton transfer occurs after RDS. Brønsted-type plots are linear with small ${\beta}_{nuc}$ values, i.e., ${\beta}_{nuc}$ = 0.29 in H$_2$O and ${\beta}_{nuc}$ = 0.51 in MeCN, indicating that bond formation is not advanced significantly in RDS. The small ${\beta}_{nuc}$ value also supports the conclusion drawn from the study of kinetic isotope effect.

Predispersed Solvent Extraction of Succinic Acid Aqueous Solution by Colloidal Liquid Aphrons in Column

  • Kim Bong Seock;Hong Yeon Ki;Huh Yun Suk;Hong Won Hi
    • Biotechnology and Bioprocess Engineering:BBE
    • /
    • v.9 no.6
    • /
    • pp.454-458
    • /
    • 2004
  • A study of the POSE (predispersed solvent extraction) for succinic acid by colloidalliq­uid aphrons was conducted. The organic phase contaning TOA (tri-n-octylamine) and 1-octanol permits a selective extraction of succinic acid from its aqueous solution. There was no difference of the extractability of POSE and that of conventional mixer-settler type extraction. Taking into account the no mechanical mixing in POSE, it was concluded that the POSE process is more adaptive than the conventional mixer-settler type extraction process. From mass transfer analysis at the various concentration of TOA in counter-current continuous operation, the concentration of TOA had no influence on the mass transfer coefficient. The loading values in continuous POSE were almost same as those in batch operation.

A Study on the Physical Properties of Polyurethane Resin Blended With Liquid Rubber (액상(液狀)고무를 Blend한 Polyurethane 수지(樹脂)의 특성(物性)에 관(關)한 연구(硏究))

  • Park, Seong-Ho;Choi, Sei-Young
    • Elastomers and Composites
    • /
    • v.29 no.3
    • /
    • pp.226-233
    • /
    • 1994
  • The properties of the mixed prepolymer-urethane in the range of 10-40 phr were observed. LBR and LCR have same functional group but different in structure of molecular. The viscosity of mixture depending on content of rubber, adhesive strength, thermal property and compatibility with a diluted solvent are as follows: 1. The viscosity of the mixture was influenced by solubility of the diluent for urethane resin and liquid rubber. 2. Adhesive strength showed the highest value at 30phr rubber, decreased gradually at above 30phr rubber. And LBR revealed better physical property than that of LCR. 3. The most effective factors affecting adhesive strength are molecular structure of rubber, the type of solvent, and volatility. 4. Urethane resin containing LBR showed better compatibility for solvent and faster drying velocity. 5. LBR showed more favorable compatibility and dispersion state than those of LCR by analyzing the results of SEM.

  • PDF

Water Permeation Flux of Oil-Emulsion through Surface-Modified Polysulfone Membrane (표면개질된 폴리설폰 막에 대한 오일에멀젼의 수투와 플럭스)

  • Song, Kun-Hoo;Kim, Kang-Hee;Cho, Seong-Heon;Lee, Kwang-Rae
    • Journal of Industrial Technology
    • /
    • v.23 no.A
    • /
    • pp.187-191
    • /
    • 2003
  • A hollow-fiber type polysulfone UF membrane was surface-coated with hydroxyethylmethacrylate (HEMA). The effect of various coating parameters on permeation flux, such as concentration ratio of AIBN/HEMA, solvent(water or methanol), and UV irradiation time, was investigated. The water permeation flux of oil-emulsion increased with concentration ratio of AIBN/HEMA, and increased with UV irradiation time. The flux of the membrane coated in solution using methanol as a solvent was greater than that of the membrane coated in solution using water as a solvent. The flux of both the coated and the uncoated membrane declined with the operation. The flux decline means that the membrane fouling by oil-emulsion occurs. However, the fouling of the coated membrane was much less than that of the uncoated membrane.

  • PDF

Comparative Analysis of Dissolution and Refolding Processes for Inclusion Body Protein Renaturation (내포체 단백질 재생을 위한 용해 및 재접힘공정의 비교분석)

  • 김창성;김윤하;이은규
    • KSBB Journal
    • /
    • v.13 no.2
    • /
    • pp.133-140
    • /
    • 1998
  • Using rlFN-$\alpha$ and rhGH as the model proteins, the refolding performances of the published processes were evaluated and compared. Key engineering parameters such as the type of denaturant and this concentration, protein concentration in the refolding buffer, and pH and ionic strength of the buffer were experimentally investigated. Furthermore, the role of a co-solvent of surfactant type in aggregation reduction was also studied. Of the denaturants tested (8M urea, 6M guanidine HCI, 0.5% SDS), SDS at alkaline pH (9.5) and ambient temperature gave the highest recovery yield. The SDS process was effective in the refolding of observed where dissolution proceeded better under lower strength (10 mM) but aggregation was suppressed under higher strength (>50 mM.) When PEG-4000 and/or Tween were added as co-solvent or refolding-enhancing additive, 1.6-2 times higher yield was realized. The‘masking’of the hyrophobic patches located on the surface of the protein with the surfactant molecules was believed to be responsible for the considerable reduction in aggregation during refolding.

  • PDF

Resource Recycling Technology for the PCP-treated Ammunition Box (PCP로 방부 처리된 탄약목상자의 자원순환형 처리기술)

  • Lee, Jong-Chol;Choi, Soo
    • Journal of the Korea Institute of Military Science and Technology
    • /
    • v.9 no.3
    • /
    • pp.123-131
    • /
    • 2006
  • This paper reports the apparatus and method for the safe treatment of pentachlorophenol(PCP)-treated ammunition box by solvent extraction. Experimental variables were chosen as the composition of solvents, types of substance(chips and sawdust), temperatures and sonication to obtain maximum PCP removal from wood samples of the dismantled ammunition box. Up to 99% of PCP in the wood chip was extracted within 2 hours at room temperature when using methanol as the solvent. The extraction volume ratio of methanol per dried sample was about 10. Type of samples, extraction temperature and sonification showed little effects on PCP extraction. Based on this study, a resource recycling system for the treatment of ammunition boxes was recommended.

Large Solvent and Noise Peak Suppression by Combined SVD-Harr Wavelet Transform

  • Kim, Dae-Sung;Kim, Dai-Gyoung;Lee, Yong-Woo;Won, Ho-Shik
    • Bulletin of the Korean Chemical Society
    • /
    • v.24 no.7
    • /
    • pp.971-974
    • /
    • 2003
  • By utilizing singular value decomposition (SVD) and shift averaged Harr wavelet transform (WT) with a set of Daubechies wavelet coefficients (1/2, -1/2), a method that can simultaneously eliminate an unwanted large solvent peak and noise peaks from NMR data has been developed. Noise elimination was accomplished by shift-averaging the time domain NMR data after a large solvent peak was suppressed by SVD. The algorithms took advantage of the WT, giving excellent results for the noise elimination in the Gaussian type NMR spectral lines of NMR data pretreated with SVD, providing superb results in the adjustment of phase and magnitude of the spectrum. SVD and shift averaged Haar wavelet methods were quantitatively evaluated in terms of threshold values and signal to noise (S/N) ratio values.