• Title/Summary/Keyword: Substitution reaction

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Study on the Development of CVD Precursors I-Synthesis and Properties of New Titanium β-Diketonates

  • 홍성택;임종태;이중철;Ming Xue;이익모
    • Bulletin of the Korean Chemical Society
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    • v.17 no.7
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    • pp.637-642
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    • 1996
  • Preparation and properties of potential CVD (Chemical Vapor Deposition) precursors for the TiO2, a major component of the perovskite materials such as PT, PLT, PZT, and PLZT were investigated. Reactions between β-diketones and TiMe3, formed in situ failed to produce stable Ti(β-diketonate)3 complexes but a stable purple solid, characterized as (OTi(BPP)2)2 (BPP=1,3-biphenyl-1,3-propanedione) was obtained when BPP was used. Several new Ti(Oi-Pr)2(β-diketonate)2 complexes with aromatic or ring substituents were synthesized by the substitution reaction of Ti(OiPr)4by β-diketones and characterized with 1H NMR, IR, ICP, and TGA. Solid complexes such as Ti(Oi-Pr)2(BAC)2 (BAC=1.-phenyl-2,4-pentanedione), Ti(Oi-Pr)2(BPP)2, Ti(Oi-Pr)2(1-HAN)2 (1-HAN=2-hydroxy-1-acetonaphthone), Ti(Oi-Pr)2(2-HAN)2 (2-HAN=1-hydroxy-2-acetonaphthone), Ti(Oi-Pr)2(ACCP)2 (ACCP=2-acetylcyclopentanone), and Ti(Oi-Pr)2(HBP)2 (HBP=2-hydroxybenzophenone) were found to be stable toward moisture and air. Ti(Oi-Pr)2(ACCP)2 and Ti(Oi-Pr)2(HBP)2 were proved to have lower melting points and higher decomposition temperatures. However, these complexes are thermally stable and pyrolysis under an inert atmosphere resulted in incomplete decomposition. Ti(Oi-Pr)2(DPM)2 (DPM=dipivaloylmethane) and Ti(Oi-Pr)2(HFAA)2 (HFAA=hexafluoroacetylacetone) were sublimed substantially during the thermal decomposition. Pyrolysis mechanism of these complexes are dependent on type of β-diketone but removal of Oi-Pr ligands occurs before the decomposition of β-diketonate ligands.

Evaluation of Strength and Durability of Mortar using Ferronickel Slag Powder and Admixtures (페로니켈슬래그 미분말 및 혼화재의 복합사용에 따른 모르타르의 강도 및 내구성 평가)

  • Jo, Seol-Ah;Yoo, Jeong-Hwan;Park, Sang-Soon
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.7 no.3
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    • pp.262-270
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    • 2019
  • Ferronickel slag, which is an industrial byproduct, is activated by mechanochemical reaction as a nonferrous metal and can be used as an admixture. Therefore, ferronickel slag is used as a substitute resource of admixture. In this study, to evaluate the effect of mixed of ferronickel slag powder and admixture, a mortar using a mixture of ferronickel slag powder, quicklime, gypsum and calcium chloride was fabricated by vibrated and rolled manufacturing method. Strength were evaluated by flexural and compressive strength tests, and durability was evaluated by performing chlorine ion penetration resistance and chemical resistance test. When the substitution ratio of ferronickel slag powder is constant, it is considered that the mixed use of quicklime, gypsum and calcium chloride as admixtures increases the performance.

A new efficient route for synthesis of R,R- and S,S-hexamethylpropyleneamine oxime for labeling with technetium-99m

  • Vinay Kumar Banka;Young Ju Kim;Yun-Sang Lee;Jae Min Jeong
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.6 no.2
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    • pp.75-91
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    • 2020
  • [99mTc]Tc-Hexamethylpropylene amine oxime (HMPAO) is currently used as a regional cerebral blood flow imaging agent for single photon emission computed tomography (SPECT). The HMPAO ligand exists in two isomeric forms: d,l and meso showing different properties in vivo. Later studies indicated that brain uptake patterns of 99mTc-complexes formed from separated enantiomers differed. Separation of enantiomers is difficult by fractional crystallizations method. Usually, the substance is obtained in low chemical yield in a time-consuming procedure. Furthermore, the final product still contains some impurity. So we have developed new efficient route for synthesis of R,R- and S,S-HMPAO enantiomeric compounds in 6-steps. Nucleophilic substitution (SN2) reactions of 2,2-dimethylpropane-1,3-diamine either with S- (1a) or R-methyl2-chloropropanoate (1b) were performed to produce compounds R,R- (2a) or S,S-isomer (2b) derivatives protected with benzylchloroformate (Cbz), respectively. And then Weinreb amide and methylation reaction using Grignard reagent, oxime formation with ketone group and deprotectiion of Cbz group by hydrogenolysis gave S,S- (7a) or R,R-HMPAO (7b), respectively. Entaniomeric compounds were synthesied with high yield and purity without any undesired product. The 7a or 7b kits containing 10 ㎍ SnCl2-2H2O were labeled with 99mTc with high radiolabeling yield (90%).

Adsorption of uranium(VI), calcium(II), and samarium(III) ions on synthetic resin adsorbent with styrene hazardous materials (스타이렌 위험물을 포함한 합성수지 흡착제에 의한 U(VI), Ca(II), Sm(III) 이온들의 흡착)

  • Kim, Joon-Tae
    • Analytical Science and Technology
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    • v.22 no.1
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    • pp.92-100
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    • 2009
  • Azacrown resins were synthesized by mixing 1-aza-12-crown-4 macrocyclic ligand into styrene (2th petroleum in 4th class hazardous materials) divinylbenzene (DVB) copolymer with crosslinkage of 1%, 2%, 5% and 10% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, thermogravimetric analysis (TGA), surface area (BET), and IR-spectroscopy. The effects of pH, time, crosslinkage of resins and dielectric constant of solvent on adsorption of metal ions by resin adsorbent were investigated. Metal ions showed a great adsorption over pH 3 and adsorption equilibrium of metal ions was about two hours. In addition, adsorptive selectivity of metals on the resin in ethanol solvent was increased in the order of ${UO_2}^{2+}$ > $Ca^{2+}$ > $Sm^{3+}$ ion and adsorption of uranium ion was decreased with increase of crosslinkage such as 1%, 2%, 5% and 10% and was inversely proportional to the order of dielectric constant of solvents.

Adsorption of uranium(VI) ion on the nitrogen-donor macrocyclic synthetic resin adsorbent (질소-주게 거대고리 합성수지 흡착제에 의한 우라늄(VI) 이온의 흡착)

  • Kim, Joon-Tae
    • Analytical Science and Technology
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    • v.21 no.2
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    • pp.109-116
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    • 2008
  • Resins were synthesized by mixing 1-aza-18-crown-6 macrocyclic ligand into styrene(dangerous matter) divinylbenzene(DVB) copolymer with crosslink of 1%, 2%, 6% and 12% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, elemental analysis, thermogravimetric analysis, electron microscopy, and IR. The effects of pH, time, crosslink of resins and dielectric constant of solvent on adsorption of uranium ion by resin adsorbent were investigated. Uranium ion showed a great adsorption above pH 3 and adsorption equilibrium of metal ions was established in about two hours. In addition, adsorptive selectivity of resin in ethanol solvent was $UO{_2}^{2+}$ > $Zn^{2+}$ > $Lu^{3+}$ ion and adsorption of uranium ion increased with the increase of the degree of crosslinking (1%~12%) and was inversely in proportional to the order of dielectric constant of solvents.

Properties of Iron Powder and Activated Carbon mixed Matrix for the Improvement of Cold Weather Concrete (한중콘크리트 개선을 위한 철가루와 활성탄 혼입 경화체 기초연구)

  • Kim, Won-Jong;Kim, Won-Sik;Kim, Gyu-Yong;Lee, Sang-Soo
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2022.11a
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    • pp.175-176
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    • 2022
  • By studying the characteristics of matrix insulated through heat generated through oxidation of iron powder, the basic research results on the possibility of buffering and applicability of Cold weather concrete as a curing method are presented. In order to prevent freezing due to a sharp decrease in temperature in the initial stage of curing, iron powder (Fe), powder activated carbon, which is a small amount of porous carbonaceous adsorbent, and salt (NaCl) as an oxidizing agent are replaced with iron powder admixture. As the curing temperature increases, the strength tends to increase, and when replacing the admixture at the same curing temperature, the strength slightly decreases. This is determined as a result of generating iron oxide through an oxidation reaction of iron powder, activated carbon, and NaCl generating a large amount of pores in the matrix. In addition, the internal temperature tends to increase as the mixing substitution rate increases, and it is judged that the oxidation heat of the iron powder mixture affects the increase of the internal temperature during curing. The higher the replacement rate of the iron powder mixture, the slightly lower the strength, but it is determined that freezing and melting that may occur in the early stage of curing can be prevented due to an increase in the initial internal temperature.

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Mechanical Properties of PHC Pile Concrete using Alpha-type Hemihydrate Gypsum (알파형 반수석고를 활용한 PHC 파일 콘크리트의 역학적 특성)

  • Hong-Seop Kim;Kyoung-Su Shin;Do-Gyeum Kim
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.12 no.1
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    • pp.25-32
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    • 2024
  • In this study, the mechanical properties of PHC pile concrete using alpha-type hemihydrate gypsum were evaluated. As the replacement ratio of alpha-type hemihydrate gypsum increased, the setting time rapidly accelerated. In particular, when replacement ratio exceeded 20 %, the setting time was shortened due to rapid hydration reaction, making it impossible to secure working time. As the replacement ratio of alpha-type hemihydrate gypsum increased, the ettringite and gypsum peaks tended to increase, and it is believed that the shrinkage of concrete decreased due to the increase in the ettringite peak. At a As the replacement ratio of 5 to 15 % for alpha-type hemihydrate gypsum, the compressive strength increased or was found to be equivalent to that of OPC. But at 20 % substitution, workability deteriorated due to rapid setting, so use of the 5 to 15 % range is considered appropriate.

Molybdenum-Based Electrocatalysts for Direct Alcohol Fuel Cells: A Critical Review

  • Gaurav Kumar Yogesh;Rungsima Yeetsorn;Waritnan Wanchan;Michael Fowler;Kamlesh Yadav;Pankaj Koinkar
    • Journal of Electrochemical Science and Technology
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    • v.15 no.1
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    • pp.67-95
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    • 2024
  • Direct alcohol fuel cells (DAFCs) have gained much attention as promising energy conversion devices due to their ability to utilize alcohol as a fuel source. In this regard, Molybdenum-based electrocatalysts (Mo-ECs) have emerged as a substitution for expensive Pt and Ru-based co-catalyst electrode materials in DAFCs, owing to their unique electrochemical properties useful for alcohol oxidation. The catalytic activity of Mo-ECs displays an increase in alcohol oxidation current density by several folds to 1000-2000 mA mgPt-1, compared to commercial Pt and PtRu catalysts of 10-100 mA mgPt-1. In addition, the methanol oxidation peak and onset potential have been significantly reduced by 100-200 mV and 0.5-0.6 V, respectively. The performance of Mo-ECs in both acidic and alkaline media has shown the potential to significantly reduce the Pt loading. This review aims to provide a comprehensive overview of the bifunctional mechanism involved in the oxidation of alcohols and factors affecting the electrocatalytic oxidation of alcohol, such as synthesis method, structural properties, and catalytic support materials. Furthermore, the challenges and prospects of Mo-ECs for DAFCs anode materials are discussed. This in-depth review serves as valuable insight toward enhancing the performance and efficiency of DAFC by employing Mo-ECs.

Preparations of Universal, Functionalized Long-Chain Alkylthiol Linkers for Self-assembled Monolayers (자기조립단분자막을 위한 보편적이고 기능화된 긴 사슬 알킬티올 연결자의 제조)

  • Yoo, Dong-Jin;Lee, Kyong-Sub;Kim, Ae-Rhan;Nahm, Kee-Suk
    • Korean Chemical Engineering Research
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    • v.49 no.3
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    • pp.330-337
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    • 2011
  • In this research, the preparation processes for making a series of $\omega$-mercapto alkylamine 1 and $\omega$-mercapto alkanoic acid 2 useful for studying of the self-assembled monolayer(SAM) are described. The preparation methods of the first goal materials, $\omega$-mercapto alkylamines 1 were carried out as follows: First, $\omega$-phthalimide alkanol 3 was synthesized from commercially available potassium phthalimide derivatives and $\omega$-bromoalkanol in DMF at $80{^{\circ}C}$ via substitution reaction. After refluxing $\omega$-phthalimide alkanol 3 with hydrazine hydrate in ethanol followed by treating with c-HCl, $\omega$-aminoalkanol 4 was obtained in 76-98% yield, accompanied with side-product 5. Bromination of hydroxyl moiety of $\omega$-aminoalkanol 4 using aqueous hydrobromic acid furnished $\omega$-bromoamine 6 in 34-97% yields. Substitution reaction 6 with thiourea in 95% ethanol gave $\omega$-aminoalkanthiuronium 7, which was treated with aqueous strong base and aqueous strong sulfuric acid gave desired products, $\omega$-mercapto alkylamines 1 through overall 5 steps. The second target material, $\omega$-mercapto alkanoic acid 2 was prepared via 2 steps. $\omega$-bromo alkanoic acid was reacted with thiourea to give $\omega$-thiourea alkanoic acid 7 in 69-85%, which was treated with aqueous strong base and strong acid to furnish $\omega$-mercapto alkanoic acid 2 in 50-98%. The fabricated long-chain alkylthiol(LCAT) can be used as linkers to immobilize protein, enzyme and various kinds of biomolecules on the surface of metallic materials(Au, Pt, Ti) by SAM, and can be useful chemical tools for the application study on the surface modification of metallic materials.

Synthesis and characterization of thermally stable pink-red inorganic pigment for digital color (디지털 컬러용 pink-red 고온발색 무기안료의 합성 및 특성평가)

  • Lee, Won-Jun;Hwang, Hae-Jin;Kim, Jin-Ho;Cho, Woo-Suk;Han, Kyu-Sung
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.24 no.4
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    • pp.169-175
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    • 2014
  • Digital ink-jet printing system has many advantages such as fast and fine printing of various images, high efficiency and low cost process. Generally digital ink-jet printing requires ceramic pigments of cyan, magenta, yellow and black with thermal and glaze stability above $1000^{\circ}C$ for the application of porcelain product design. In this study, pink-red colored $CaO-SnO_2-Cr_2O_3-SiO_2$ pigment was synthesized using solid state reaction. The synthesis conditions of $Ca(Cr,Sn)SiO_5$ pigment such as annealing temperature, amount of mineralizer and non-stoichiometric composition were optimized. Crystal structure and morphology of the obtained $Ca(Cr,Sn)SiO_5$ pigment were analyzed using XRD, SEM, PSA, FT-IR and effect of Cr substitution on the pigment color was analyzed using Uv-vis. spectrophotometer and CIE $L^*a^*b^*$ measurement.