• Title/Summary/Keyword: $[C_5(CH_3)_5]_2TiCl_2$

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Cycloolefins Oxidation Reaction Catalyzed by Ga(III)-, In(III)- and TI(III)-Porphyrin Derivatives (Ga(III)-, In(III)-, TI(III)-porphyrin 유도체를 촉매제로 한 고리성 올레핀의 산화반응)

  • Na, Hun-Gil
    • Journal of the Korean Applied Science and Technology
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    • v.21 no.1
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    • pp.76-88
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    • 2004
  • The catalytic oxidation reaction of several cycloolefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin(M = Ga(III), In(III) and TI(III) complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)$TPP, $(p-CH_3)$TPP, TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})$TPP (TPP=5,10,15,20-tetraphenyl-21H,23H-porphyrin) and olefins were cyclopentene, cyclohexene, cycloheptene and cyclooctene, The substrate conversion yield(%) was investigated according to the radius effect of non-redox metal ion, substituent effect and hindrance effect of metalloporphyrin. The conversion yield of cycloolefin was in the following order : $C_5$ < $C_6$ < $C_7$ = $C_8$.

The Crystallographic Properties of TiC Deposited on Different Substrate Steel by Chemical VaporDeposition (화학증착법에 의한 여러 가지 강들위에 증착된 TiC의 결정학적 특성)

  • 윤순길;김호기
    • Journal of the Korean Ceramic Society
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    • v.24 no.6
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    • pp.519-526
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    • 1987
  • TiC was deposited onto several substrate steels by the Chemical Vapor Deposition technique from TiCl4-CH4-H2 gas mixtures in the horizontal resistance furnace. Deposition rates and morphologies of the coatings were investigated with the carbon contents. Deposition thickness increased linearly with the deposition time in the Presence of CH4 gas. The various interlayers of coating by EDS and X-ray Diffraction were proved as Cr7C3 and Fe3C. Chromium contents did not affect the preferred orientation of TiC deposit. The deposition was controlled by a mass transport and a surface reaction in case of 1 wt% C-5.25 wt% Cr steel irrespective of deposition temperature.

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Preparation of Polymethylene-bridged Half-Titanocenes and Investigation of Their Styrene Polymerization Properties (폴리메틸렌 다리를 가진 Dinuclear Half-Titanocene 합성과 이에 의한 스티렌 중합 연구)

  • 태원태;김상현;노석균;김태학;이동호
    • Polymer(Korea)
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    • v.24 no.2
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    • pp.159-167
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    • 2000
  • The polymethylene-bridged dinuclear half-titanocenes [(CH$_2$)$_{n}$(C$_{5}$ H$_4$)$_2$][TiCl$_3$]$_2$ (n=5(10), 7(11), 9(12)) have been synthesized by treating the distannylated derivatives of the ligands with two equivalents of TiCl$_4$ in toluene. All complexes are characterized by IR, $^1$H NMR, $^{13}$ C NMR and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has been conducted in the presence of MMAO. From the polymerization experiments it was found that ( i ) all the prepared complexes 10-12 produced syndiotactic polystyrenes, ( ii ) the complex 12 holding the longest bridging ligand exhibited the highest activity but produced a polymer having the smallest molecular weight among the polymethylene-bridged dinuclear half-titanocenes. This behavior was attributed to the influence of electron-donating caused by the polymethylene bridge between two active centers as well as the effect of steric congestion around metal center caused by the proximal distance between two active sites.s.

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Polymerization of Ethylene Initiated with Trisiloxane-bridged Heterometallic Dinuclear Metallocene

  • Lee, Dong-Ho;Lee, Hun-Bong;Kim, Woo-Sik;Min, Kyung-Eun;Park, Lee-Soon;Seo, Kwan-Ho;Kang, Inn-Kyu;Noh, Seok-Kyun;Song, Chang-Keun;Woo, Sang-Sun;Kim, Hyun-Joon
    • Macromolecular Research
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    • v.8 no.5
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    • pp.238-242
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    • 2000
  • The new trisiloxane-bridged heterometallic dinuclear metallocenes, hexamethyltrisiloxanediyl(cyclopentadienyltitanium trichloride) (cyclopentadienylindenyl zirconium dichloride) , $C_3ITi-Cp(CH_3)_2Si-O-Si(CH_3)_2-O-Si(CH_3)_2-Cp-ZrIndCI_2$ (1) and hexamethyltrisiloxanediyl (cyclopentadienylindenylhafnium dichloride) (cyclopentadienylindenyl zirconium dichloride), $C_2IndHf-Cp(CH_3)_2Si-O-Si(CH_3)_2-Cp-ZrIndCl_2$ 2) connecting two dissimilar metallocenes were synthesized and used for ethylene polymerization in the presence of modified methylaluminoxane (MMAO) cocatalyst. The catalytic activity of heterometallic dinuclear metallocenes, 1 and 2 was lower than that of corresponding mononuclear metal-locene as well as two physically mixed catalysts, $CpTiCl_2/Cp_2ZrCl_2 and Cp_2HfCl_2/Cp_2ZrCl_2$. On the tither hand, MWD of PE obtained with 1 and 2 was remarkably broader ($M_w/M_n$) became up to 9.4) than those of PEs prepared with the corresponding mononuclear metallocenes and mixed catalysts. With analysis by GPC and CFC, it was found that PE produced by the heterometallic dinuclear metallocenes exhibited the definite bimodal GPC curves that should cause the broadening of MWD.

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Photodegradation of Halogen Derivatives of Aliphatic Hydrocarbon in Aqueous Photocatalytic Suspensions (지방족 탄화수소의 할로겐 유도체 수용액의 광촉매-광분해)

  • Jun, Jin;Jung, Hak-Jin;Kim, Hae-Jin;Kim, Sam-Hyeok
    • Journal of Environmental Science International
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    • v.6 no.1
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    • pp.75-88
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    • 1997
  • The rates of photodegradation, reactivities, and mechanisms of photooxidation for the aqueous solution containing with halogen derivatives of aliphatic hydrocarbons have been discussed with respect to the kinds of photocatalysts, concentration of photocatalytlc suspensions, strength of radiant power, time of illumination, changes of pH of substrate solution, wavelength of radiation, and pressure of oxygen gas saturated In the solution. These aqueous solutions suspended with 0.5 $gL^{-1}$ $TiO_2$ powder have been photodecomposed in the range of 100 and 93.8% per 1 hour if it is illuminated with wavelength (λ $\geq$ 300nm) produced from Xe-lamp(450W). The photocatalytic abilities have been increased In the order of $Fe_2O_3$ < CdS < $CeO_2$ < Y_2O_3$ <$TiO_2$, and rates of photodegradation for the solution have maldmum values in the condition of pH 6 ~ 8 and 3 psi-$O_2$ gL^{-1}$. These rates for the Photoolddation Per 1 hour were dependent on the size of molecular weight and chemical bonding for organic halogen compounds and the rates of photodegadation were increased in the order of $C_2H_5Br$ < CH_2Br_2$ < C_5H_11Cl C_2H_4Cl_2$ < tracts-$C_2H_2Cl_2$ < cis-C_2H_2Cl_2$ The T_{1/2}$ and t99% for these solutions were 5~21 and 40~90 minutes. respectively, and these values were coincided with Initial reaction kinetics(ro). It was found that reaction of photodegradation has the pseudo first-order kinetics controlled by the amount of $h^+_{VB}$ diffused from a surface of photocatalysts.

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Pyrolytic Conversion of Blended Precursors into Ti-Al-N Ceramic Composites

  • Cheng, Fei;Sugahara, Yoshiyuki;Kuoda, Kazuyuki
    • The Korean Journal of Ceramics
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    • v.6 no.1
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    • pp.32-36
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    • 2000
  • Pyrolytic preparations of Ti-Al-N ceramics from three blended precursors were investigated. The precursors were prepared stirring ($HA1N^{i}Pr_m$ and an aminolysis product of $Ti(NMe_2)_4$ with $MeHNCH_2CH_2$NHMe in $C_6/H_6$ . IR and $^1H\;NMR $analyses suggested that essentially no Ti-N-Al bonds were present in the precursors. Pyrolysis of the precursors under $NH_3-N_2$led to the formation of brown solids with ceramic yields of about 30%, and the Ti-Al ratios in the pyrolyzed products were close to those of the precursors. XRD analysis of the pyrolyzed product from the precursor with Ti:Al=5:1 indicated the formation of a NaCl-type compound as the only crystalline phase. Pyrolysis of the precursor with Ti:Al=2:1 led to the formation of AlN besides the major NaCl-type compound. A ceramic composite containing AlN and the NaCl-type compound was formed by pyrolysis of the precursor with Ti:Al=1:2.

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Analysis of Fracture Surface of API-X-80 Steel Failed by Hydrogen Induced Cracking (수소유기 균열된 APi-X80 강재의 파면 분석)

  • Kim, Ma-Ro;Gu, Da-Yeong;Choe, Yong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2015.05a
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    • pp.124-124
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    • 2015
  • Acoustic microscopy and scanning electron microscopy were applied to non-destructively evaluate the hydrogen-induced cracking of API X-80 steels and to find the initiation time of the crack. The API X-80 steel had the average grain size of about $4-10{\mu}m$. The hardness was reduced from 240 to 202 [Hv] after exposing in HIC environment for 2-days. Friction coefficient and wear loss were 0.745 and 0.392 mm, respectively. Empirical equation of corrosion potential and corrosion rate of the steel with HIC time in $5%NaCl-0.5%CH_3COOH$ at $25^{\circ}C$ were $Eh\;(up)=0.06^*t[day]+0.2951$, $Eh(down)=0.376^*t[day]+0.5938$, respectively. HIC grew with micro-size after 1-day exposure. The HIC tended to propagate on the surface with Al, Si, Ti, and Mn.

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Syndiotactic Polymerization of Styrene Catalyzed by Dinuclear (Cyclopentadienyl) (Aryloxy) Titanium(IV) Complexes with Polymethylene Bridge (폴리메틸렌 가지로 연결된 이핵 아릴옥시 티타늄 화합물을 이용한 스티렌의 신디오탁틱 중합)

  • Kum Don-Ho;Jung Woosung;Kim Kyungsik;Noh Seok Kyun;Lee Dong-Ho;Lyoo Won Seok
    • Polymer(Korea)
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    • v.30 no.1
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    • pp.64-69
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    • 2006
  • A series of dinuclear half-sandwich titanium complexes with aryloxy substituent at titanium$[(\eta^5-cyclopentadienyl)(aryloxy)TiCl_2]_2[(CH_2)_n]$ (n=3, n=6, n=9) have been successfully synthesized and their styrene polymerization properties have been investigated. All complexes are characterized by $^1H\;NMR,\;^{13}C\;NMR$, elemental analysis, and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has beer conducted in the presence of MMAO. It was found that (i) all the prepared complexes were very effective catalyst for the production of SPS (syndiotactic polystyrene), (ii) the complex with the longest bridge between the two active sites exhibited greatest catalytic activity among the three catalysts, but produced SPS with the smallest molecular weight, (iii) the activities of dinuclear half-titanocens with aryloxy substitution at titanium metal were greater than those of the chloride substituted compounds. These results indicate that not only the nature of the bridge between the two active sites but also the property of substituents at the metal exert a significant influence on the polymerization behaviors of the dinuclear half-titanocene.

Synthesis, Characterization and Haemocompatibility of Poly(styrene-b-isobutylene-b-styrene) Triblock Copolymers (폴리(스티렌-이소부틸렌-스티렌) 삼중블록 공중합체의 합성, 분석 및 혈액적합성)

  • Ren, Ping;Wu, Yi-Bo;Guo, Wen-Ii;Li, Shu-Xin;Mao, Jing;Xiao, Fei;Li, Kang
    • Polymer(Korea)
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    • v.35 no.1
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    • pp.40-46
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    • 2011
  • The synthesis of well-defined poly(styrene-b-isobutylene-b-styrene) (SIBS) triblock copolymers was accomplished by cationic sequential block copolymerization of isobutylene (IB) with styrene (St) using 1,4-di(2-chloro-2-propyl) benzene (DCC) /$TiCl_4$/2,6-di-tert-butylpyridine(DtBP) as an initiating system in methyl chloride ($CH_3Cl$)/methylcyclohexane(MeChx) (50/50 v/v) solvent mixture at $-80^{\circ}C$. The triblock copolymers exhibited excellent thermoplastic and elastomeric characteristics. Tensile strengths and Shore hardness increased with increasing polystyrene (PS) content, while elongation at break decreased. The blood-compatibility of SIBS was assessed by SEM observation of the platelet adhesion, blood clotting time and haemolysis ratio. The haemolysis ratios were below 5% which met the medical materials standard. The platelet adhesion test further indicated that SIBS block copolymers had a good blood compatibility.