• Textile Coloration and Finishing
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• v.24 no.1
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• pp.33-38
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• 2012

In this study, to increase flame retardation of poly(ethylene terephthalate) (PET) in burning, bisphenol A bis(diphenyl phosphate) (BDP), a well known flame retardant containing phosphorous, was reacted on end groups of PET by radical pathway. End-capping mechanism of PET with BDP was suggested and confirmed by spectroscopic and thermal analysis. From 400 MHz $^{31}P$ solid state FT-NMR spectrum of end-capped PET (PET-BDP), phosphorus spectra peak in BDP was found at ca. -20 ppm. Furthermore, P-C bond stretching vibration peaks were found ca. $600cm^{-1}$ in FT-IR spectrums of PET-BDP. These results showed that BDP can be chemically added on end groups of PET by our method. Thermal characteristics of pure PET (pPET) and PET-BDP were measured and evaluated by TGA analysis. There was not significant changes in thermal characteristics of PET-BDP compared to that of pPET.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.517-522
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• 1992

The reaction of ${\beta}$-picoline with substituted benzoyl chlorides has been studied by means of conductometry under various pressures in acetonitrile. From the values of pseudo-first order and second order rate constants, the activation parameters (${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$, ${\Delta}H{\neq}$, ${\Delta}S{\neq}$ and ${\Delta}G{\neq}$) and the pressure dependence of Hammett ${\rho}$ value were studied. The activation volume, the activation compressibility coefficient and the activation entropy were all negative. By increasing pressure the rate constant and Hammett ${\rho}$ value were increased, and the reaction mechanism was proceed in bond formation favored.

• Magazine of the Korean Society of Agricultural Engineers
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• v.29 no.4
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• pp.124-131
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• 1987

The aims of this study was to determine the mechanical properties of steel-fiber reinforced concrete under direct tensile loading, and also to insestigate the mechanism fiber reinforcement in order to improve the possible applications of steel-fiber reinforced concrete. In this study the major variables of experimental investigation were fiber conntents, and the lengths and diameters of fibers. The major results obtained are summarized as follows : 1. The strength, elastic modulus and energy absorption capability of steel-fiber reinforced concrete under direct tensile loading were improved as increasing of fiber contents. 2. The direct tensile strength of steel-fiber reinforced concrete was not influenced by the lengths of fiber, but was decreased as increasing of fiber diameters. 3. The direct tensile strength of steel-fiber reinforced concrete was not influenced by the fiber aspect-ratio, but this was because the fiber contents were below the critical value of fiber content. 4. The correlation of direct tensile strength and combined parameter, Vf l/d, was not good. 5. Mutiple cracking and post-crack resistance were investigated at stress-strain curves in direct tensile test. 6. The effect of fiber reinforcement can be influenced by fiber orientation and the bond strength between fiber and matrix. 7. The improvement of mechanical properties of steel-fiber reinforced concrete under direct tensile loading can be theoretically explained by the concept of composite materials.

• Journal of the Korean Chemical Society
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• v.16 no.6
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• pp.334-340
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• 1972

CNDO/2 calculations have been carried out on methyl chloro-thiol-, methyl chloro-thiono-, and methyl chloro-dithio-formates. Results show that the trans is the stable configuration for these compounds. It was found that sulfur atom has much less tendency to use its lone pair electrons for ${\pi}$ bond formation compared with oxygen, and that thiolformates are stabilized by hyperconjugation of methyl hydrogens. The order of solvolytic reactivity was found to follow the order of cation stability, which is consistent with the $S_N1$ mechanism proposed for these compounds.

• Journal of the Korean Chemical Society
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• v.29 no.6
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• pp.623-628
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• 1985

Rate constants for complexing with thiocyanate after ring opening of molybdenum-oxalate in acid media were obtained spectrophotometrically at 460nm. The acid-assisted dissociation of molybdenum-oxalate and the reaction of thiocyanate with oxalatooxomolybdenum (V) complex in acid media were investigated with thiocyanate and hydrogen ion concentration. The kinetic data indicate that molybdenum-oxalate is protonated to a limited extent in acid media and the protonated complex is responsible for an increase in rate for the reaction of thiocyanate with oxalatooxomolybdenum (V) complex. Replacement of an oxalate ligand in acid media has been interpreted in terms of dissociative mechanism involving bond-breaking of the oxygen trans to the yl oxygen.

• Bulletin of the Korean Chemical Society
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• v.23 no.10
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• pp.1459-1462
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• 2002

The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3607-3617
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• 2012

In this paper, the study of various ortho- and meta-substituted Magnolol derivatives is presented. The reaction enthalpies related to three antioxidant action mechanisms HAT, SET-PT and SPLET for substituted Magnolols have been calculated using DFT/B3LYP method in gas-phase and water. Calculated results show that electron-withdrawing substituents increase the bond dissociation enthalpy (BDE), ionization potential (IP) and oxidation/reduction enthalpy (O/RE), while electron-donating ones cause a rise in the proton dissociation enthalpy (PDE) and proton affinity (PA). In ortho- position, substituents show larger effect on reaction enthalpies than in meta-position. In comparison to gas-phase, water attenuates the substituent effect on all reaction enthalpies. In gas-phase, BDEs are lower than PAs and IPs, i.e. HAT represents the thermodynamically preferred pathway. On the other hand, SPLET mechanism represents the thermodynamically favored process in water. Results show that calculated enthalpies can be successfully correlated with Hammett constants (${\sigma}_m$) of the substituted Magnolols. Furthermore, calculated IP and PA values for substituted Magnolols show linear dependence on the energy of the highest occupied molecular orbital ($E_{HOMO}$).

• Journal of the Korean Chemical Society
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• v.55 no.6
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• pp.940-951
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• 2011

Reaction of 1-methylpyrimidine-(1H,3H,5H)-2,4,6-trione (1-MBA 1) as an unsymmetrical barbituric acid with cyanogen bromide and various aldehydes in the presence of triethylamine and/or pyridine afforded diastereomeric mixtures of new class of heterocyclic stable 5-aryl-1,1'-dimethyl- and 5-aryl-3,1'-dimethyl-1H,1'H-spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidine]2,2',4,4',6'(3H,3'H,5H)-pentaones which are dimeric forms of 1-methyl barbiturate at the range of $0^{\circ}C$ to room temperature. In the reaction of some aldehydes with 1-MBA and BrCN were afforded a mixture of diastereomers. Another two aldehydes such as 4-cyano- and 2-hydroxybenzaldehydes gave exclusively two diastereomers in which binded to the salt of triethylammonium hydrobromide by intermolecular H-bond in ratio of 1:1. 4-Hydroxybenzaldehyde and 2-pyridinecarbaldehyde gave exclusively one diastereomer under the same condition. Aldehydes possessing strong electron-donor were produced exclusively two geometric isomers of Knoevenagel adduct (E- and Z-isomers). The structures of compounds were deduced by $^1H$ NMR, $^{13}C$ NMR and FT-IR spectroscopy. Mechanism of the formation is discussed.

• Steel and Composite Structures
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• v.11 no.6
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• pp.469-488
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• 2011

This paper consists of two parts; the first part describes the laboratory work concerning the behavior of lightweight aggregate concrete filled steel tubes (LACFT). Based on eccentricity tests, fifty-four specimens with different slenderness ratios (L/D= 3, 7, and 14) were tested. The main parameters varied in the test are: load eccentricity; steel ratio; and slenderness ratio. The standard load-strain curves of LACFT columns under eccentric loading were summarized and significant parameters affecting LACFT column's bearing capacity, failure mechanism and failure mode such as confinement effect and bond strength were all studied and analyzed through the comparison with predicted strength of concrete filled steel tube columns (CFT) using the existing codes such as AISC-LRFD (1999), CHN DBJ 13-51-2003 (2003) and CHN CECS 28:90 (1990). The second part of this paper presents the results of parametric study and introduces a practical and accurate method for determination of the maximum compressive strength of confined concrete core ($f_{max}$), In addition to, the study of the effect of aspect-ratio and length-width ratio on the yield stress of steel tubes ( $f_{sy}$) under biaxial state of stress in CFT columns and the effect of these two factors on the ultimate load carrying capacity of axially loaded CFT/LACFT columns.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2003-2008
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.