• Title/Summary/Keyword: polymerization reaction

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Characteristics and Ring-Opening Isomerization Polymerization of 2-(1,3,3-Trimethyl-6-azabicyclo[3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline (TAO) (2-(1,3,3-Trimethyl-6-azabicyclo[3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline(TAO)의 개환이성화중합과 특성평가)

  • Lee, Chan-Woo;Chung, Jin-Do
    • Polymer(Korea)
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    • v.36 no.3
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    • pp.262-267
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    • 2012
  • 2-(1,3,3-Trimethyl-6-azabicyclo [3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline (TAO) was polymerized at several conditions to clarify the influence of initiators, alkyl halide ($PhCH_2Br$, $PhCH_2Cl$, MeI) and sulfonate (MeOTf). The reactions were conducted at $100^{\circ}C$ for 24 h. The resultant polymer forms several kinds of structures with different combination of initiators. The sole MeOTf initiator caused chain transfer reaction to form the one-order structure for which the resultant polymer exclusively formed pendant structure, while alkyl halide and MeOTf formed two kinds of structures, pendant and main chain, which is caused by partly-proceeded double isomerization polymerization by highly reactive nucleophilic counter anion of halogen. Merrifield polymer was also utilized as an intiator and copolymerized with TAO, which produced a graft structure.

Improving Power Conversion Efficiency and Long-term Stability Using a Multifunctional Network Polymer Membrane Electrolyte; A Novel Quasi-solid State Dye-sensitized Solar Cell

  • Gang, Gyeong-Ho;Gwon, Yeong-Su;Song, In-Yeong;Park, Seong-Hae;Park, Tae-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.484.2-484.2
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    • 2014
  • There are many efforts to improving the power conversion efficiencies (PCEs) of dye-sensitized solar cells (DSCs). Although DSCs have a low production cost, their low PCE and low thermal stability have limited commercial applications. This study describes the preparation of a novel multifunctional polymer gel electrolyte in which a cross-linking polymerization reaction is used to encapsulate $TiO_2$ nanoparticles toward improving the power conversion efficiency and long-term stability of a quasi-solid state DSC. A series of liquid junction dye-sensitized solar cells (DSCs) was fabricated based on polymer membrane encapsulated dye-sensitized $TiO_2$ nanoparticles, prepared using a surface-induced cross-linking polymerization reaction, to investigate the dependence of the solar cell performance on the encapsulating membrane layer thickness. The ion conductivity decreased as the membrane thickness increased; however, the long term-stability of the devices improved with increasing membrane thickness. Nanoparticles encapsulated in a thick membrane (ca. 37 nm), obtained using a 90 min polymerization time, exhibited excellent pore filling among $TiO_2$ particles. This nanoparticle layer was used to fabricate a thin-layered, quasi-solid state DSC. The thick membrane prevented short-circuit paths from forming between the counter and the $TiO_2$ electrode, thereby reducing the minimum necessary electrode separation distance. The quasi-solid state DSC yielded a high power conversion efficiency (7.6/8.1%) and excellent stability during heating at $65^{\circ}C$ over 30 days. These performance characteristics were superior to those obtained from a conventional DSC (7.5/3.5%) prepared using a $TiO_2$ active layer with the same thickness. The reduced electrode separation distance shortened the charge transport pathways, which compensated for the reduced ion conductivity in the polymer gel electrolyte. Excellent pore filling on the $TiO_2$ particles minimized the exposure of the dye to the liquid and reduced dye detachment.

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Theoretical Studies on the Cationic Polymerization Mechanism of Cyclic Acetals (산 촉매하의 Cyclic Acetals 공중합반응에 관한 분자궤도론적 연구)

  • Young-Gu Cheun;Jae-Kyung Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.197-204
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    • 1992
  • The cationic polymerization of cyclic acetals are investigated theoretically using the semiempirical MINDO/3, MNDO, and $AM_1$, methods. The nucleophilicity and basicity of cyclic acetals can be explained by the negative charge on oxygen atom of cyclic acetals. The reactivity of propagation in the polymerization of cyclic acetals can be represented by the positive charge on $C_2$ atom and the low LUMO energy of active species of cyclic acetals. The reactivity of 2-buthyl-1,3-dioxepane(2-Bu-DOP) of cyclic oxonium and opening carbenium ion form is expected computational stability of the oxonium ion by 5${\sim}$7kcal/mole favoring the carbenium ion. Owing to the rapid equilibrium of these cation forms and the reaction coordinate based on calculation that the reaction coordinate based on calculation that the chain growth $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.

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Preparation of Monodisperse Poly(Acrylic acid) with a Water-Soluble Initiator by Solution Polymerization in Aqueous Phase (수용액 내에서 수용성개시제를 이용한 단분산성 폴리아크릴산의 용액중합)

  • Park, Moonsoo;Kim, Yeji
    • Elastomers and Composites
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    • v.49 no.3
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    • pp.232-238
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    • 2014
  • Solution polymerization was conducted with water-soluble acrylic acid (AA) as a monomer and potassium persulfate (KPS) as an initiator at a selected temperature between $60^{\circ}C$ and $90^{\circ}C$ with water as a reaction medium. When the ratio between AA and water was reduced or initiator concentration increased, molecular weights decreased. An increase in the reaction temperature produced lower molecular weights. The polydispersity index was close to 1.5 in most of the reactions. An increase in the stirring speed up to 400 rpm led to a progressive increase in molecular weights. When the stirring speed reached 800 rpm, however, we found that both the number and weight average molecular weights decreased. The glass transition temperature was nearly independent of moelcular weights and determined to be between $113^{\circ}C$ and $116^{\circ}C$.

Preparations and Electrochemical Characteristics of Polypyrrole by Constant Potential Electroplymerization (정전위 전해 중합법에 의한 폴리피롤 제조 및 전기화학적 특성)

  • Cho, Seung-Koo;Sim, Chol-Ho
    • Journal of the Korean Electrochemical Society
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    • v.8 no.2
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    • pp.99-105
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    • 2005
  • In this study, the $PPy/CLO_4$ and PPy/PVS composite electrodes were prepared at various polymerization potential by incorporating electrolyte anions of different anion size during constant potential polymerization. The reulting Polypyrrole surfaces were inspected by SEM, and their electrochemical Properties were investigated with CV and ac impedance method. The results of electrochemical analysis were suggested that anion for $PPy/CLO_4$ electrode and cation fir PPy/PVS electrode were transferred during redox reaction. As constant potential of polymerization was increased, the charge transfer resistance of $PPy/CLO_4$ and PPy/PVS was decreased and the electric double layer capacitances of $PPy/CLO_4$ was higher than that of PPy/PVS. The change of PPy/PVS surface was relatively smaller than that of $PPy/CLO_4$ according to electropolymerization potential.

In vitro Polymerization and Copolymerization of Poly-3-hydroxypropionyl-CoA with the PHB Synthase from Ralstonia eutropha

  • Song, Jae-Jun;Goodwin, Steve;Lenz, Robert W.
    • 한국생물공학회:학술대회논문집
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    • 2000.11a
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    • pp.48-51
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    • 2000
  • The poly(3-hydroxybutyrate) (PHB) synthase of Ralstonia. eutropha, which was produced by a recombinant strain E. coli and purified in one-step with a methyl-HIC column to a purity of more than 90%, was used to polymerize 3-hydroxypropionyl-CoA (3HPCoA) and to copolymerize 3HPCoA with 3-hydroxybutyryl-CoA (3HBCoA) in vitro. A $K_m$ of $189\;{\mu}M$ and a $k_{cat}$ of $10\;sec^{-1}$ were determined for the activity of the enzyme in the polymerization reaction of 3HPCoA based on the assumption that the dimer form of PHB synthase was the active form. Free coenzyme A was found to be a very effective competitive inhibitor for the polymerization of 3HPCoA with a $K_i$ of $85\;{\mu}M$. The maximum degree of conversion of 3HPCoA to polymer was less than 40 %. In the simultaneous copolymerization reactions of these two monomers, both the turnover number for the copolymerization reaction and the maximum degree of conversion of 3HPCoA and 3HBCoA to copolymers increased with an increase in the amount of 3HBCoA in the monomer mixture. However, the maximum conversion of 3HPCoA to a copolymer was less than 35 % regardless of the ratio of 3HPCoA to 3HBCoA. Block copolymers were obtained by the sequential copolymerization of the two monomers and these copolymers had a much narrower molecular weight distribution than those obtained by the simultaneous copolymerization of the same molar ratio of 3HPCoA and 3HBCoA.

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Immobilization of Homogeneous Catalyst on Functionalized Carbon Nanotube via 1,3-Dipolar Cycloaddition Reaction and its Ethylene Polymerization (1,3-Dipolar cycloaddition 반응을 통해 기능화된 carbon nanotube 표면 위에 균일계 촉매 담지 및 에틸렌 중합)

  • Lee, Jeong Suk;Lee, Se Young;Lee, Jin Woo;Ko, Young Soo
    • Korean Chemical Engineering Research
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    • v.54 no.4
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    • pp.574-581
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    • 2016
  • In this study, CNT functionalized with pyrrolidine ring via 1,3-dipolar cycloaddition reaction with various amino acid and aldehyde was synthesized. Metallocene was subsequently immobilized on the functionalized CNT and CNT/polyethylene composite was prepared via in-situ ethylene polymerization. The polymerization activities of metallocene supported on CNT functionalized with glycine and benzaldehyde (Gly+BA-CNT) were similar to those of metallocene supported on CNT functionalized with N-benzyloxycarbonylglycine and paraformaldehyde (Z-Gly+PFA-CNT) although its Zr content was lower than that of Z-Gly+PFA-CNT. In the case of metallocene supported on Z-Gly+PFA-CNT, the even distribution of active sites hindered the diffusion of ethylene monomer and cocatalyst MAO due to steric hindrance during ethylene polymerization. Compared to polyethylene produced from homogeneous metallocene catalysts, CNT/PE composites had a higher initial degradation temperature ($T_{onset}$) and maximum mass loss temperature ($T_{max}$). It suggests that pyrrolidine functionalized CNT is uniformly dispersed and strongly interacted with the PE matrix, enhancing the thermal stability of PE.

A Study on the Alkali-Silica Reaction of Geopolymer Mortar (지오폴리머 모르타르의 알칼리-실리카반응에 관한 연구)

  • Kim, Sung-Hoon;Kim, Young-Soo
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2015.11a
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    • pp.7-8
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    • 2015
  • The purpose of this study is to investigate the expansion of alkali-activated geopolymer mortar containing reactive aggregate due to alkali-silica reaction. In addition, this study is particularly concerned with the behavior of these alkaline materials in the presence of reactive aggregates. The test method included expansion measurement of the mortar bar specimens and geopolymer compressive strength test. Major results that alkali-activated geopolymer mortars showed expansion due to the alkali-silica reaction. geopolymer mortars is safety for the expansion exhibited less than 0.2% at 14 day.

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Development of pH-Responsive Core-Shell Microcapsule Reactor

  • Akamatsu, Kazuki;Yamaguchi, Takeo
    • Proceedings of the Membrane Society of Korea Conference
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    • 2004.05a
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    • pp.191-194
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    • 2004
  • A novel type of intelligent microcapsule reactor system was prepared. The reactor can recognize pH change in the medea and control reaction rate by itself. For the reactor system, acrylic acid (AA), N-isopropylacrylamide (NIPAM), and glucose oxidase (GOD) were selected as a pH-responsive device, a gating device according and a reaction device, respectively. Poly(NIPAM-co-AA) (P-NIPAM-co-AA) are known to change its hydrophilicity-hydrophobicity due to pH change. They were integrated in a core-shell microcapsule space. GOD was loaded inside the core space and the pores in the outside shell layer were filled with P-NIPAM-co-AA linear grafted chains as pH-responsive gates by plasma graft filling polymerization method. When P-NIPAM-co-AA gates are hydrophilic at high pH value, this microcapsule permits glucose penetration into the core space and GOD reaction proceeds. However, when P-NIPAM-co-AA gates are hydrophobic at low pH value, this microcapsule forbids glucose penetration and GOD reaction will not occur. The accuracy of this concept was examined.

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The Effects of the Heavy Metal Ions on the Hydration and Microstructure of the Cement Paste (중금속이온이 시멘트의 수화 및 미세구조에 미치는 영향)

  • 김창은;이승규
    • Journal of the Korean Ceramic Society
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    • v.30 no.11
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    • pp.967-973
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    • 1993
  • The effect on the hydration of cement was that Cu and Pb reacted with alkali to form soluble hydrates at theinitial stage and then there followed a slow reaction forming insoluble metal hydroxides. These hydroxides were deposited on the surface of cement particles providing a barrier against further hydration. But as a slow reaction continued, the insoluble layers were eventually destroyed and the hydration reaction resumed. Thereafter, another retardation occured by restricting the polymerization of silicates, shown by FT-IR spectroscopy analysis. In the case of Cr, as its reaction with cement caused H2O, the coordinator of Cr complex, to replace or polymerize with OH-, the formation of Cr complex promoted the leakage of OH- and increased the heat of dissolution. So the total heat evolution during hydration was larger than that in the case of Pb or Cu. The retarding effect of heavy metal ions was in the order Pb>Cu>Cr.

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