• Journal of the Korean Chemical Society
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• v.57 no.3
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• pp.335-340
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• 2013

A chemical reaction of PBDEs was implemented using the polyethylene glycols (PEGs) and KOH, along with different reaction conditions such as temperatures and times. Removal efficiencies of PBDEs before and after chemical reaction were examined by difference of concentration. PBDEs was not removed at lower temperatures of 25 and $50^{\circ}C$. However, under the increased temperature, removal efficiency of PBDEs in ${\sigma}$-xylene was gradually increased, showing completely removal of PBDEs containing 5-6 bromines on biphenyl frame. When increasing the reaction conditions to 4 hours and $150^{\circ}C$, removal efficiency of PBDEs reached almost 100%. In studying the reaction of PEGs with PBDEs, it confirmed that the PBDEs led to less brominated by PEGs through a stepwise process with the successive elimination of bromines.

• Elastomers and Composites
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• v.41 no.3
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• pp.172-181
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• 2006

Flame retardant synergism of phyllite was studied in ABS resins containing brominated flame retardant(tetrabromobisphenol A(TBBA) or brominated epoxy oligomer(BEO)) and antimony trioxide($Sb_2O_3)$. Talc was used for the comparison purpose. ABS compounds were manufactured by a twin-screw co-rotating extruder and subsequently injection molded into several specimen for mechanical and thermal properties. Flame retardancy of ABS compounds measured by UL 94 vertical test with 1.6 mm thick bar specimen was enhanced by the replacement of antimony trioxide into phyllite or talc in the range of 12.5%(0.5 wt%) to 37.5%(1.5 wt%). Phyllite showed better synergistic effect comparing with talc especially for BEO. Only phyllite enhanced the flowability of ABS compounds. Notched Izod impact strength decreased with the proportion of phyllite or talc content. Phyllite could replace the antimony trioxide up to the content of 25%(1 wt%) to give better flame retardancy and flowability without darkening problem.

• Bulletin of the Korean Chemical Society
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• v.2 no.2
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• pp.71-75
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• 1981

Vacuum ultraviolet photolysis of ethyl bromide was studied at 104.8-106.7 nm (11.4-11.6 eV) in the pressure range of 0.2-18.6 torr at $25^{\circ}$ using an argon resonance lamp with and without additives, i.e., NO and He. Since the ionization potential of $CH_3CH_2Br$ is lower than the photon energy, the competitive processes between the photoionization and the photodecomposition were also investigated. The observations indicated that 50% of absorbed light leads to the former process and the rest to the latter one. In the absence of NO the principal reaction products for the latter process were found to be $CH_4, C_2H_2, C_2H_4, C_2H_6, and C_3H_8$. The product quantum yields of these reaction products showed two strikingly different phenomena with an increase in reactant pressure. The major products, $C_2H_4$ and $C_2H_6$, showed positive effects with pressure whereas the effects on minor products were negative in both cases, i.e., He and reactant pressures. Addition of NO completely suppresses the formation of all products except $C_2H_4$ and reduces the $C_2H_4$ quantum yield. These observations are interpreted in view of existence of two different electronically excited states. The initial formation of short-lived Rydberg transition state undergoes HBr molecular elimination and this state can across over by collisional induction to a second excited state which decomposes exclusively by carbon-bromine bond fission. The estimated lifetime of the initial excited state was ${\sim}4{\times}10^{-10}$ sec. The extinction coefficient for $CH_3CH_2Br$ at 104.8-106.7 nm and $25{\circ}$ was determined to be ${varepsilon} = (1/PL)ln(I_0/I_t) = 2061{\pm}160atm^{-1}cm6{-1}$ with 95% confidence level.

• Bulletin of the Korean Chemical Society
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• v.11 no.5
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• pp.391-395
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• 1990

The kinetics of thermnal cis-trans isomerization reaction of 1-bromopropene(1-BP) was studied at temperatures from 620.8 to 753.15 K over the pressure range 0.17-50.3 Torr. Both the inhibition effect by cyclohexene or propene and the catalytic effect by HBr showed a radical process as the main mechanism of the isomerization. In the suppression of the radical process by the inhibitors, the molecular process also contributed to overall reaction rate. The reactions demonstrated the first order kinetics under both uninhibited and inhibited conditions and could be represented by the expressions (R = 1.987 cal/mol/K) $k_{un}/s^{-1} = (3.45{\pm}1.50){\times}10^{11}$exp$[(- 48100{\pm}2000)/RT]\;k_{ink}/s^{-1} = (2.98{\pm}1.40){\times}10^{12}$exp$[(- 55800{\pm}1800)/RT]$> where $k_{un}$ is the observed rate constant of cis-1-bromopropene(1-B$P_c$) to trans-1-bromopropene(1-B$P_t$) under uninhibited condition at initial pressure of 50 Torr and $k_{ink}$ is the rate constant under maximal inhibition by cyclohexene. The ratio of rate constants for bromine atom elimination from the allylic hydrogen of reactant(1-BP) and from the inhibitors, propene and cyclohexene, were measured from the observed rates of the uninhibited and inhibited reactions. The inhibition efficiencies of cyclohexene and propene were compared kinetically from the rate constants and shown to give good agreement with the previous results reported from other alkyl bromide pyrolyses.

• Nuclear Engineering and Technology
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• v.8 no.4
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• pp.195-201
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• 1976

The present levels for the contents of mercury, arsenic, bromine, copper, manganese and potassium in various groups of foodstuffs are evaluated and compared with data given previously by others. On the basis of the data for the levels, the average daily intakes have teen estimated to be 2.0$\times$10$^1$$\mu\textrm{g}$ for Hg, 3.2$\times$10$^2$$\mu\textrm{g}$ for As, 2.3$\times$10$^3$$\mu\textrm{g}$ for Br, 2.5$\times$10$^3$$\mu\textrm{g}$ for Cu, 6.8$\times$10$^3$$\mu\textrm{g}$ for Mn and 2.1$\times$10$^{6}$ $\mu\textrm{g}$ for K. For this purpose, the data reported as a result of the 1974 National Nutrition Survey have been used.

• Composites Research
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• v.35 no.6
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• pp.412-418
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• 2022

Flame-retardant vinyl ester (VE) resin films were developed from the mixtures of brominated and non-brominated epoxy resins via esterification with methacrylic acid without reactive diluents. The films were used to fabricate carbon fiber (CF) prepregs via a hot melt impregnation process. The viscosity of VE resins suitable for film production was optimized by mixing low-viscosity bisphenol-A and high-viscosity brominated bisphenol-A epoxy precursors. Increasing the bromine content of the cured VE resin further increased the limited oxygen index (LOI) (39%), storage modulus (2.4 GPa) at 25℃ and residual carbonization (16.1%) values compared to non-brominated VE. Manual layup of as-prepared VE prepregs with subsequent curing led to the successful fabrication of CF-reinforced composites with high tensile and flexural strength. The results from the study hold high promise for a styrene-free, environmentally friendly VE composite process in the future.

• Applied Biological Chemistry
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• v.22 no.4
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• pp.198-209
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• 1979

L-Tyrosine, 2-chloro-L-tyrosine, 2-bromo-L-tyrosine, and 2-iodo-L-tyrosine were synthesized by ${\beta}-tyrosinase$ obtained from cells of Escherichia intermedia A-21, through the reversal of the ${\alpha},{\beta}-elimination$ reaction, and their molecular structures were analyzed by element analysis, NMR spectroscopy, mass spectrometry and IR spectroscopy. Rates of synthesis and hydrolysis of halogenated tyrosines by ${\beta}-tyrosinase$, inhibition of the enzyme activity by halogenated phenols, and effects of addition of m-bromophenol on the synthesis of 2-bromotyrosine were determined. The results obtained were as follows: 1) In the synthesis of halogenated tyrosines, the yield of 2-chlorotyrosine from m-chlorophenol were approximately 15 per cent, that of 2-bromotyrosine from m-bromophenol 13.8 per cent, and that of 2-iodotyrosine from m-iodophenol 9.8 per cent. 2) Rate of synthesis of halogenated tyrosines by ${\beta}-tyrosinase$ was slower than that of tyrosine and the rates were decreased in the order of chlorine, bromine and iodine, that is, by increasing the atomic radius. Relative rate of 2-chlorotyrosine synthesis was determined to be 28.2, that of 2-bromotyrosine to be 8.13, and that of 2-iodotyrosine to be 0.98, respectively, against 100 of tyrosine. However 3-iodotyrosine was not synthesized by the enzyme. 3) The relative rate of 2-chlorotyrosine hydrolysis by ${\beta}-tyrosinase$ was 70.7, that of 2-bromotyrosine was 39.0, and that of 2-iodotyrosine was 12.6 against 100 of tyrosine, respectively. The rate of hydrolysis appeared to be decreased in the order of chlorine, bromine and iodine, that is, by increasing the atomic radius or by decreasing the electronegativity. But 3-iodotyrosine was not hydrolyzed by the enzyme. 4) The activity of ${\beta}-tyrosinase$ was inhibited by phenol markedly. Of the halogenated phenols, o-, or m-chlorophenol and o-bromophenol gave marked inhibition on the enzyme action, however inhibition by iodophenol was not strong. Plotting by Lineweaver-Burk method, a mixed-type inhibition by m-chlorophenol was observed and its Ki value was found to be $5.46{\times}10^{-4}M$. 5) During the synthesizing reaction of 2-bromotyrosine by the enzyme, sequential addition of substrate which was m-bromophenol with time intervals and in a small amount resulted in better yield of the product. 6) The halogenated tyrosines which were produced by ${\beta}-tyrosinase$ from pyruvate, ammonia and m-halogenated phenols were analysed to determine their molecular structures by element analysis, NMR spectroscopy, mass spectrometry, and IR spectroscopy. The result indicated that they were 2-chloro-L-tyrosine, 2-bromo-L-tyrosine, and 2-iodo-L-tyrosine, respectively.

• Analytical Science and Technology
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• v.26 no.4
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• pp.235-244
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• 2013

Detection of halogens using laser-induced breakdown spectroscopy (LIBS) in open air is very difficult since their strong atomic emission lines are located in VUV region. In NIR region, there are other emission lines of halogens through electronic transitions between excited states. However, these lines undergo Stark broadening severely. We report the observation of the emission lines of halogens in laser-induced plasma (LIP) spectra in NIR region using a helium gas flow. Particularly, the emission lines of iodine at 804.374 and 905.833 nm from LIPs have been observed for the first time. In the helium ambient gas, Stark broadening of the emission lines and background continuum emission could be suppressed significantly. Variations of the line intensity, plasma temperature, and electron density with the helium flow rate was investigated. Detection of chlorine and bromine in flame retardant of rubbers was demonstrated using this method. Finally, we suggest a pulsed helium gas jet as a practical and ecomonical helium gas source for the LIBS analysis of halogens in open air.

• Journal of the Korean Chemical Society
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• v.25 no.6
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• pp.351-360
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• 1981

Ultraviolet spectrophotometric investigations have been carried out on the system of durene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_2(CH_3)_4{\cdot}X_2$ or $C_6H_2(CH_3)_4{\cdot}IX$(X denotes halogen atoms). The equilibrium constant were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. The thermodynamic parameters, ${\Delta}H,\;{\Delta}G\;and\;{\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the durene complexes at each temperature decrease in the order, $ICl>IBr>I_2>Br_2$. This order may be a measure of their relative acidities toward durene, which is explained in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order; Benzene

• Journal of the Korean Chemical Society
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• v.25 no.2
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• pp.75-84
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• 1981

Ultraviolet spectrophotometric investigations have been carried out on the systems of mesitylene with iodine, bromine, iodine monochloride and iodine monobromide in carbon tetrachloride. The results reveal the formation of the charge transfer complexes of the type, $C_6H_3(CH_3)_3{\cdot}X_2$ or $C_6H_3(CH_3)_3{\cdot}IX$ (X denotes halogen atoms). The equilibrium constants were obtained in consideration of that absorption maxima due to the formation of the charge transfer complexes shift to blue with the increasing temperatures. Thermodynamic parameters, ${\Delta}H$, ${\Delta}G$ and ${\Delta}S$ for the formation of the charge transfer complexes were calculated from these values. These results indicate that the relative stabilities of the mesitylene complexes at each temperature decrease in the order, ICl > IBr > $I_2$ > $Br_2$. This order may be a measure of their relative acidities toward mesitylene, which is explaned in terms of the relative polarizabilities of halogen molecules and the relative electronegativities of halogen atoms. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order Benzene < Toluene < Xylene < Mesitylene Thus, analysis of these findings is discussed.