• Title/Summary/Keyword: Interchange reaction

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The Effects of Blend Composition and Blending Time on the Ester Interchange Reaction and Tensile Properties of PLA/LPCL/HPCL Blends

  • Yoon, Cheol-Soo;Ji, Dong-Sun
    • Fibers and Polymers
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    • v.4 no.2
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    • pp.59-65
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    • 2003
  • PLA/LPCL/HPCL blends composed of poly(lactic acid) (PLA), low molecular weight poly($\varepsilon$-caprolactone) (LPCL), and high molecular weight poly($\varepsilon$-caprolactone) (HPCL) were prepared by melt blending for bioabsorbable fila-ment sutures. The effects of blend composition and blending time on the ester interchange reaction by alcoholysis in the PLA/LPCL/HPCL blends were studied. Their thermal properties and the miscibility due to the ester interchange reaction were investigated by $^1{H-NMR}$, DSC, X-ray, and UTM analyses. The hydroxyl group contents of LPCL in the blends decreafed by the ester interchange reaction due to alcoholysis. Thus, the copolymer was formed by the ester interchange reaction at $200^{\circ}C$ for 30-60 minutes. The thermal properties of PLA/LPCL/HPCL blends such as melting temperature and heat of fusion decreased with increasing ester interchange reaction levels. However, the miscibility among the three poly-mers was improved greatly by ester interchange reaction. Tensile strength and modulus of PLA/LPCL/HPCL blend fibers increased with increasing HPCL content, while the elongation at break of the blend fibers increased with increasing LPCL content.

Interchange Reaction Kinetics and Sequence Distribution of Liquid Crystalline Poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate)

  • Rhee, Do-Mook;Ha, Wan-Shik;Youk, Ji-Ho;Yoo, Dong-Il
    • Fibers and Polymers
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    • v.2 no.2
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    • pp.86-91
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    • 2001
  • Liquid crystalline (LC) poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate) [copoly(ET/CPT)] was prepared using poly(ethylene terephthalate) (PET) as a flexible spacer, terephthalic acid (TPA), and chlorohydroquinone diacetate (CHQDA). All reactions involved in the copolymerization were investigated using some model compounds: TAP was used for acidolysis, diphenylethyl terephthalate (DPET) for interchange reaction between PET chains, and 야-o-chlorophenyl terephthalate (DOCT) and di-m-chlorophenyl terephthalate (DMCT) for interchange reaction between PET and rigid rodlike segments. Activation energies obtained for the acidolysis of PET with TPA and for interchange reaction of PET with DPET, DOCT, and DMCT were 19.8 kcal/mol, 26.5 kcal/mole, and 45.9 kcal/mole, respectively. This result supports that the copolymerization proceeds through the acidolysis of PET with TPA first and subsequent polycondensation between carboxyl end group and CHQDA or acetyl end group, which is formed from the reaction of CHQDA and TPA. Also, it was found that ester-interchange reaction can be influenced by the steric hindrance. Copoly(ET/CPT)s obtained has ethylene acetate end groups formed from acetic acid hydroxy ethylene end groups and showed almost the random sequence distribution for all compositions.

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A Study on the Ester Interchange Reaction of Dimethyl Naphthalate with Ethylene Glycol (Dimethyl Naphthalate와 Ethylene Glycol의 에스테르 교환반응에 관한 연구)

  • Sho, Soon-Yong;Cheong, Seong-Ihl
    • Polymer(Korea)
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    • v.25 no.1
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    • pp.25-32
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    • 2001
  • The kinetics of ester interchange reaction of dimethyl naphthalate(DMN) with ethylene glycol(EG) has been studied in the range of 180-200 $^{\circ}C$ using zinc and manganese catalysts. The reaction was performed in a semibatch reactor under nonisothermal condition and the degree of reaction was calculated from experimental data of methanol removal rate and reaction temperature. As a reaction model, both the functional group model and the molecular species model were applied and analysed. In case of zinc catalyst, the ratio of reaction rate of methyl hydroxyethyl naphthalate(MHEN) with EG on that of DMN with EG is about 1.4, whereas in case of manganese catalyst the ratio is about 4.3, which implies that the reaction rate is quite dependent on the type of catalyst. In case of zinc catalyst, the reaction order of catalyst concentration on either DMN or MHEN and EG is less than 1, whereas in case of manganese catalyst, the reaction order is larger than 1. The activation energy for zinc and manganese catalyst, irrespective of the type of molecular species, e.g., DMN and MHEN, were found to be 25000 and 28750 cal/mol, respectively. As a result of comparing two reaction model, the molecular species model fits well for the experimental data.

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Copper(II) Oxyanion Complexes Derived from Sparteine Copper(II) Dinitrate: Synthesis and Characterization of 4- and 5-Coordinate Copper(II) Complexes

  • Lee, Yong-Min;Kim, Yong-Kyu;Jung, Hee-Cheul;Kim, Young-Inn;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.23 no.3
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    • pp.404-412
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    • 2002
  • Nine copper(Ⅱ) oxyanion, and mixed oxyanion complexes that have four- or five-coordinate geometries around copper(Ⅱ) centers were derived from sparteine copper(Ⅱ) dinitrate precursor [Cu($C_{15}$$H_{26}$N2)(NO3)2]. The precursor complex undergoes an anion exchange with various oxyanions, and an interchange reaction with other sparteine copper(Ⅱ) complexes. The [Cu($C_{15}$$H_{26}$N2)(CH3CO2)2] also undergoes "halogen atom abstraction" reaction with CCl4 to produce the mixed anion complex [Cu($C_{15}$$H_{26}$N2)(CH3CO2)Cl]. The whole set of prepared complexes has been used for the comparative electrochemical and spectroscopic studies.

Thermal Properties of Poly(trimethylene terephthalate)/ Poly(ethylene terephthalate) Melt Blends

  • Son, Tae Won;Kim, Kwang Il;Kim, Nam Hun;Jeong, Min Gi;Kim, Young Hun
    • Fibers and Polymers
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    • v.4 no.1
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    • pp.20-26
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    • 2003
  • The thermal behavior, morphology, ester-interchange reaction of Poly(trimethylene terephthalate) (PTT)/poly(ethylene terephthalate) (PET) melt blends were investigated over the whole composition range(xPTT/(1-x)PET) using a twinscrew Brabender. The melt blends were analyzed by differential scanning calorimetry (DSC), nuclear magnetic resonance spectroscopy ($^{13}{C-NMR}$), and scanning electron microscopy (SEM). Single glass transition temperature ($T_g$) and cold crystallization temperature ($T_cc$) were observed in all melt blends. Melt blends were found to be due to the ester-interchange reaction in PTT/PET blend. Also the randomness of copolymer increases because transesterification between PT and PET increases with increasing blending time This reaction increases homogeneity of the blends and decreases the degree of crystallinity of the melt blends. In PTT-rich blends, mechanical properties decrease with increase of PET content compared with that of pure PTT. And, in PET-rich blends, tensile modulus decreases with increase of PTT content, but tensile strength and elongation is similar to that of pure PET.

Synthesis of $TiO_2$ Powders by the Hydrolysis of Titanium n-Butoxide and Reaction Mechanism (Titanium n-Butoxide의 가수분해에 의한 $TiO_2$ 분말 합성과 반응 메커니즘)

  • Park, J.K.;Myung, J.J.;Chung, Y.S.;Kyong, J.B.;Kim, H.K.
    • Journal of the Korean Chemical Society
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    • v.43 no.5
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    • pp.505-510
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    • 1999
  • $TiO_2$ powders were prepared via hydrolysis of titanium n-butoxide in n-butanol and hydrolysis mechanism of titanium n-butoxide was studied using UV-Vis spectrometer. Hydrolysis reactions were controlled to proceed to pseudo-first order reaction in the presence of excess water. The phases of $TiO_2$ powders, prepared under the these conditions, were identified by XRD and reaction rates were calculated by Gugggenheim method. Prepared powders were noncrystalline states in their initial stage of formation but transformed to crystalline rutile structure by heating. Reaction mechanism of titanium n-butoxide was proposed as Interchange-Associative(Ia) mechanism, based on the data of n-value and termodynamic parameters which were determined from the rate constants.

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Simplified analysis method for anti-overturning of single-column pier girder bridge

  • Liang Cao;Hailei Zhou;Zhichao Ren
    • Structural Engineering and Mechanics
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    • v.91 no.4
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    • pp.403-416
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    • 2024
  • The single-column pier girder bridge, due to its low engineering cost, small footprint, and aesthetic appearance, is extensively employed in urban viaducts and interchange ramps. However, its structural design makes it susceptible to eccentric loads, flexural-torsional coupling effects, and centrifugal forces, among others. To evaluate its anti-overturning performance reasonably, it is crucial to determine the reaction force of the support for the single-column pier girder bridge. However, due to the interaction between vehicle and bridge and the complexity of vibration modes, it poses a significant challenge to analyze the theory or finite element method of single-column pier girder bridges. The unit load bearing reaction coefficient method is proposed in this study to facilitate the static analysis. Numerous parameter analyses have been conducted to account for the dynamic amplification effect. The results of these analyses reveal that the dynamic amplification factor is independent of road surface roughness but is influenced by factors such as the position of the support. Based on parameter analysis, the formula of the dynamic amplification factor is derived by fitting.