• Applied Chemistry for Engineering
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• v.16 no.4
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• pp.533-541
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• 2005

Non-aqueous cleaning agents were formulated with 2,2,2-trifluoroethanol (TFEA) and hydrofluoroether (HFE), and their physical properties and cleaning abilities were examined. TFEA-based aqueous cleaning agents were also formulated with nonionic surfactants, hydrotropes and builders, and their cleaning abilities were compared. Possibilities of these cleaning agents as substitutes for CFC-113 and 1,1,1-TCE were finally evaluated. In this work, fluxes, cutting oils, greases, and fluoric oils were selected as model contaminants for cleaning experiments. These contaminants have different properties of water-solubility or hydrophilicity, and fat-solubility or lypophilicity. Cleaning abilities of TFEA-based cleaning agents were analyzed and compared through the measurement of contaminant weight changes as a function of cleaning time, and their possibilities as alternative cleaning agents were evaluated. As a result, it was shown that TFEA and HFE-based non-aqueous cleaning agents have quite a good cleaning power for fluxes and fluorine soils but low one for greases. And TFEA-based agueous cleaning agents which consisted of nonionic surfactants, hydrotrope, and builders were very effective for cleaning fluxes and greases under certain formulation conditions. Thus, it was revealed that the TFEA-based cleaning agents were very effective for cleaning specific contaminants and can be used as substitutes for CFC-113 and 1,1,1-TCE in some industrial applications.

• Membrane Journal
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• v.14 no.2
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• pp.166-172
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• 2004

As a preliminary study for esterification membrane reactor used to produce 2,2,2-trifluoroethylmetacrylate (TFEMA), Pervaporation behaviors with crosslinked Poly(vinyl alcohol) composite membranes were investigated for aqueous TFEA (2,2,2-trifluoroethanol) feed solutions. In this study, crosslinked PVA composite membranes were prepared by reacting PVA with glutaraldehyde (CA)/acid catalyst onto porous polyethersulfone (PES) supports. SEH images (scanning electron microscopy) showed the thicknesses of selective coating layer was about 2-3 ${\mu}{\textrm}{m}$. The swelling tests showed the dogree of crosslinking decreased as content of the crosslinking agent, GA, increased. Total permeation flux decreased while separation factor increased as the CA content increased. As operating temperature increased, total permeation flux remarkably increased in the range of 85-95 wt% TFEA aqueous solutions. Interestingly, however, separation factor decreased in 85-90 wt% with operating temperature, while that increased in 95 wt%. In case of 90 wt% TFEA concentration and operating temperature 8$0^{\circ}C$, the PVA composite membrane crosslinked with 0.1 mol GA per PVA repeating unit showed high permeation flux of 1.5 kg/$m^2$hr and separation factor of 320. These results confirmed the applicability of the PVA composite membranes for the esterification membrane reactor of TFEMA.

• Membrane Journal
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• v.15 no.3
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• pp.206-212
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• 2005

Acid-resistant poly(vinyl alcohol) (PVA) membranes connected with ethylene and ether groups were prepared via a thermal crosslinking reaction by varying the ratio of PVA to ethylene glycol diglycidyl ether (EGDE). The crosslinked membranes were characterized using FT-IR and swelling tests, respectively. Pervaporation behaviors with the PVA membranes were investigated for aqueous TFEA (2,2,2-trifluoroethanol) as a function of EGDE content and operating temperature. The pervaporation properties far MA (methacrylic acid)/water mixture were also carried out with the optimized PVA membrane. The PVA membranes prepared with EGDE showed more excellent acid-resistance than those crosslinked with gluaraldehyde. The membranes showed high permeation fluxes of 0.1 and $0.3\;km^2h$ and high separation factors of 100 and 900 in the $96\;wt\%$ TFEA and MA aqueous fred mixtures at high temperature above $80^{\circ}C$, respectively. These confirmed theses membranes could be used in esterification membrane reactor process for the production of 2,2,2-trifluoroethylmetacrylate (TFEMA).

• BMB Reports
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• v.28 no.6
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• pp.546-551
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• 1995

The conformation studies of myelin P2 protein and two of its major peptides were carried out using circular dichroism and fluorescence spectroscopy in water and in lipid environments. Significant conformational changes occur when the protein or peptides were bound to gangliosides. Similar effects were also found in trifluoroethanol solutions. The conformational features of P2 protein and its major peptides were discussed in relation to the environmental changes and the disease-inducing effects.

• Clean Technology
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• v.11 no.3
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• pp.129-139
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• 2005

Fluoride-type cleaning agents such as TFEA (2,2,2-trifluoroethanol) and HFE (hydrofluoroether) are noticed to be next generation cleaning agents alternative to CFCs since they do not destruct ozones in the stratosphere due to no containment of chloride in the molecule, have lower global warming potential compared to HFCs and HCFCs, and are thermally stable compounds. Thus, the physical properties and cleaning agents were measured and compared with those of CFC-113, 1,1,1-TCE and HCFC-141b which are ozone destruction substances. They were also compared and evaluated with those of IPA and methanol which are currently employing as alternative cleaning agents. And TFEA-based cleaning agents consisted of TFEA and alcohols or HFEs were formulated, their physical properties and cleaning abilities were measured and their utilization as alternative cleaning agents was evaluated. As a result, TFEA and HFEs have lower cleaning ability for their removal of various soils compared to chloride-type cleaning agents, but theyshow excellent cleaning ability for Fluoride-type soils. And it is observed that the formulated cleaning agents of TFEA and alcohols or HFEs caused to increase cleaning ability of flux and unsoluble cutting oil more than 100% compared to their individual component. Therefore, the fluoride-type cleaning agents are expected to be utilized for development of environmental-friendly non aqueous cleaning agents with excellent cleaning ability if they are formulated with proper solvents or additives.

• Clean Technology
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• v.14 no.3
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• pp.184-192
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• 2008

Fluoride-type cleaning agents such as 2,2,2-trifluoroethanol (TFEA) and hydrofluoroethers (HFEs) do not destroy ozone in the stratosphere and have low global warming potential compared to hydrofluorocarbons(HFCs) and hydrochlorofluorocarbons (HCFCs). Especially, HFEs which have no flash point are paid attention as next generation type of cleaning agents for chlorofluorocarbons (CFCs) since they are safe in handling and have excellent penetration ability compared to hydrocarbon cleaning agents with low flash point. Here, the physical properties and cleaning abilities of fluoride-type cleaning agents such as TFEA, HFE-7100, HFE-7200, HFE-476mec, HFE-449mec-f, AE-3000 and AE-3100E and silicide-type cleaning agents such as trifluoroetoxytrimethylsilane (TFES) and hexamethyldisilazane (HMDS) were measured and compared with those of ozone destruction substances such as CFC-113 and 1,1,1-trichloroethane. They were also compared with toxic methylene chloride (MC) and isopropyl alcohol (IPA) which are now being used as an alternative cleaning agents. As a result, TFEA and HFEs had lower cleaning ability for removal of various soils compared to chloride-type cleaning agents, but they showed excellent cleaning ability fur fluoride-type soils. TFES and HMDS also showed excellent cleaning ability for silicide-type soils.

• Bulletin of the Korean Chemical Society
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• v.23 no.8
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• pp.1089-1096
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• 2002

Solvolyses rate constants of trimethylacetyl chloride (2), isobutyryl chloride (3), diphenylacetyl chloride (4) and p-methoxyphenylacetyl chloride (5) in 2,2,2-trifluoroethanol (TFE)-water, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)-water and TFE-et hanol solvent systems at $10^{\circ}C$ are determined by a conductimetric method. Kinetic solvent isotope effects (KSIE) are reported from additional kinetic data for methanolyses of various substituted acetylchlorides in methanol According to the results of those reactions analyzed in terms of rate-rate profiles,extended Grunwald-Winstein type correlations, application of a third order reaction model based a general base catalyzed (GBC) and KSIE values. Regardless of the kind of neighboring groups (CH3- or Ph-groups) of reaction center, for aqueous fluorinated alcohol systems, solvolyses of 2, 3, 4, and 5 were exposed to the reaction with the same mechanism (a loose SN2 type mechanism by electrophilic solvation) controlled by a similarity of solvation of the transition sate (TS). Whereas, for TFE-ethanol solvent systems, the reactivity depended on whether substituted acetyl chloride have aromatic rings (Ph-) or alkyl groups (CH3-); the solvations by the predominant stoichiometric effect (third order reaction mechanism by GBC and/or by push-pull type) for Ph- groups (4 and 5) and the same solvation effects as those shown in TFE-water solvent systems for CH3- groups (2 and 3) were exhibited Such phenomena can be interpreted as having relevance to the inductive effect ( $\sigmaI)$ of substituted groups; the plot of log (KSIE) vs. ${\sigma}I$ parameter give an acceptable the linear correlation with r = 0.970 (slope = 0.44 $\pm$ 0.06, n = 5).

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1293-1302
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• 2003

Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.378-382
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• 2009

Rates of solvolyses of benzhydryl chloride ($Ph_2$CHCl, 1) and benzhydryl bromide ($Ph_2$CHBr, 2) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, 2,2,2-trifluoroethanol (TFE) and acetone are reported. Solvolyses were also carried out in TFE-ethanol mixtures. Application of the extended Grunwald-Winstein equation led to l value of 1.19 (1), 1.29 (2) and m value of 1.00 (1), 0.77 (2), correlation coefficient of 0.965 (1) and 0.970 (2). Sensitivities (l = 1.19 (1), 1.29 (2) and m = 1.00 (1), 0.77 (2)) were similar to those obtained for several previously studied solvolyses, in which an $S_N$2 pathway is proposed for the solvolyses of benzhydryl halides ($Ph_2$CHX, X = Cl or Br).

• Journal of the Korean Chemical Society
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• v.63 no.4
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• pp.233-236
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• 2019

In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol-water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ mechanism.