• Title/Summary/Keyword: polymerization reaction

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Laccase-Catalyzed Transformation of Chlorophene (Laccase를 이용한 Chlorophene 산화전이에 관한 연구)

  • Kim, Jong-Oh;Kim, Young-Jin
    • Journal of Environmental Health Sciences
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    • v.33 no.1 s.94
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    • pp.63-67
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    • 2007
  • Laccase catalyzes the oxidation and polymerization of aromatic compounds in the presence of molecular oxygen. The oxidative transformation of chlorophene with laccase was conducted in a closed, temperature controlled system. The optimal pH for transformation of chlorophene was proven to be about 5-6. As the temperature rose up to $55^{\circ}C$, the transformation of chlorophene increased. The chlorophene transformation was not enhanced in the presence of soluble polymers. The toxicity of the reaction mixture was increased two times than that of initial reaction mixture after the enzymatic treatment. ABTS has enhanced chlorophene transformation at 0.1 mM and showed negative linear relationship with residual chlorophene by the reaction.

Photochemistry and Thermochemistry of Picolyl Chlorides

  • Shim, Sang-Chul;Kim, Sung-Sik
    • Bulletin of the Korean Chemical Society
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    • v.3 no.3
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    • pp.110-115
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    • 1982
  • Thermochemistry and photochemistry of picolyl chlorides were studied. The thermal reaction of 2-picolyl chloride in benzene afforded intermolecular condensation product. In the case of 3-picolyl chloride, this type of the reaction did not occur, but polymers were obtained. A cyclic hexamer, suggested by a molecular model, was not formed because of the steric strain and low reactivity. The thermal reaction of 4-picolyl chloride gave a cyclic hexamer as well as a polymer. The cyclic hexamer, identified by NMR spectrum, showed ${\lambda}_{max}$ at 460 nm. The cyclic hexamer was cloven to the linear structure. Photolysis of 2-picolyl chloride at 253.7 nm gave a para-isomer followed by polymerization. When a methyl hydrogen of 2-methylpyridine is substituted by $CH_3O$, iso-PrO, and EtO group, the photoisomerization to the corresponding anilines or para-substituted pyridines did not occur within the range of the time used for 2-picolyl chloride. Thermolysis of picolyl chlorides in an acidic methanol solution did not afford any product.

Hydroxy-Substituted Polyenaminonitrile as a Soluble Precursor for Rigid-Rod Polybenzoxazole

  • Kim, Ji Heung;Lee, Jae Gwan
    • Bulletin of the Korean Chemical Society
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    • v.22 no.9
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    • pp.999-1004
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    • 2001
  • (1-Chloro-2,2-dicyanovinyl)benzene or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene was reacted with 2-amino-phenol to give the model compound, hydroxy enaminonitrile, which was found to undergo thermal cyclization reaction to form the corresponding benzoxazole. This intramolecular cyclization reaction is expected to occur through nucleophilic attack to electropositive enamine carbon by ortho-hydroxy group on the phenyl ring, which is accompanied by the release of neutral malononitrile through rearrangement. From each bifunctional monomer, o-hydroxy substituted polyenaminonitrile was prepared and characterized as a new precursor polymer for well-known aromatic polybenzoxazole. Also the unusual macrocyclic dimer formation from the 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane polymerization reaction system was discussed. The thermal cyclization reactions and the properties of polymers were investigated using FT-IR and thermal analysis (DSC & TGA).

Intracluster Ion/Molecule Reactions within 1,1-Difluoroethylene Homocluster

  • 이선영;최창주;정경훈
    • Bulletin of the Korean Chemical Society
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    • v.18 no.3
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    • pp.296-300
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    • 1997
  • The intracluster ion/molecule reactions within 1,1-difluoroethene homocluster have been studied by electron-impact quadrupole mass spectrometry. When CH2CF2 seeded in helium is expanded and ionized by electron impact, two different types of ion/molecule association (polymerization) reaction products, i.e., (CH2CF2)n+ (n≥l) and (CF2CH2)qX+ (X=fragment species, q≤n), are formed. The higher association products, (CH2CF2)n+ (n=3, 4), have shown stronger intensities over the lower association product, (CH2CF2)2+, in the low electron impact energy region ( < 39 eV). These stronger intensities are interpreted in terms of the stabilization of these ions due to the ring formations over the dimer ion in this energy region. The evidence of ring formation mechanism is on the basis of the intensity distribution of fragments at various electron impact energy. In another typical branched-chain growth reaction of these compounds, the F-shift reaction path is found to be more favorable energetically than the H-shift via the fragment patterns of clusters and semi-empirical calculation.

Synthesis and Photopolymerization Characterization of Propenyl Ether Monomers (프로페닐 에테르 단량체들의 합성과 광중합 특성)

  • Kim, Ki-Sang;Shim, Sang-Yeon
    • Journal of the Korean Applied Science and Technology
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    • v.34 no.2
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    • pp.203-209
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    • 2017
  • The propenyl ether-type monomers which are applicable for cationic photo-polymerization were synthesized by the condensation reaction of mono and di-functional alcohol with allyl bromide. To examine photo-curable reactivity, these monomers were combined with cationic photoinitiator to prepare coating composition. As a result, the initial rate of polymerization of POMB in mono propenyl ether type was 10.2, which was relatively lower than BPOB in di-propenyl ethers type. However, POMB containing 1.5mol% photoinitiator almost quantitatively reacted within 90 seconds. In addition, Sulfonium salt type photo-initiators containing long-alkyl group showed good solubility with monomers and apperaed to have comparatively higher rate of polymerization and conversion ratio when applying DPSA and DPST which have high acidity on all monomers.

h Study on the Preparation of PMMA/PSt Composite Particles by Sequential Emulsion Polymerization (단계중합법에 의한 PMMA/PSt Composite Particle의 제조에 관한 연구)

  • 이선룡;설수덕
    • Polymer(Korea)
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    • v.25 no.5
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    • pp.617-624
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    • 2001
  • The core-shell composite latexes were synthesized by stage emulsion polymerization of methyl methacrylate (MMA) and styrene (St) with ammonium persulfate after preparing monomer pre-emulsion in the presence of anionic surfactant. However, in preparation of core-shell composite latex, several unexpected results are observed, such as, particle coagulation, low degree of polymerization, and formation of new particles during shell polymerization. To solve the disadvantages, We study the effect of initiator concentrations, surfactant concentrations, and reaction temperature on the core-shell structure of polymethyl methacrylate/polystyrene and polystyrene/polymethyl methacrylate. Particle size and particle size distribution were measured using particle size analyzer, and the morphology of the core-shell composite latex was determined using transmission electron microscope. Glass temperature was also measured using differential scanning calorimeter. To identify the core-shell structure, pH of the two composite latex solutions were measured.

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Preparation of Colored Electrophoretic Nanoparticles by Emusifier-Free Emulsion Polymerization and Reactive Dyeing (무유화 에멀젼 공중합법과 반응염법을 이용한 전기영동 고분자 컬러나노입자의 제조)

  • Chon, Jin-A;Ha, Jae-Hee;Lim, Min-Ho;Kwon, Yong-Ku
    • Polymer(Korea)
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    • v.34 no.6
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    • pp.491-494
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    • 2010
  • Colored, electrophoretic polymer nanoparticles of poly (styrene-co-divinylbenzene-co-vinyl acetate)[poly(St-co-DVB-co-VAc)] were prepared by emulsifier-free emulsion co-polymerization and reactive dyeing. The emulsifier-free emulsion polymerization of styrene, divinyl benzene and vinyl acetate was carried out at $70^{\circ}C$ for 20 hrs to obtain monodisperse polymer nanoparticles of poly(St-co-DVB-co-VAc) with an average diameter of 180~200 nm. These nanoparticles were transformed into poly(styrene-co-divinylbenzene-co-vinyl alcohol) [poly(St-co-DVB-co-VA)] nanoparticles through the saponification reaction. The poly(St-co-DVB-co-VA) nanoparticles were treated with reactive dyes to obtain the colored, monodisperse electrophoretic nanoparticles, and their morphology and surface charge were characterized by scanning electron microscopy, differential scanning calorimetry, UV/Vis absorbance and zeta-potentiometry.

Phase Transfer Polymerization. Two Phase Polycondensation of Diphenoxides and 1,6-Dibromohexane in the Presence of Tetrabutylammonium Bromide (狀移動重合. Tetrabutylammonium Bromide 존재하에서 Diphenoxides와 1,6-Dibromohexane의 二狀重縮合反應)

  • Jung-Il Jin;Yong-Woon Jung;Kwang-Sup Lee;Keun-Woo Chung
    • Journal of the Korean Chemical Society
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    • v.23 no.4
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    • pp.259-266
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    • 1979
  • Linear polyethers were prepared by the reaction of diphenoxide anions from 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxylphenyl) sulfide, and bis (khydroxyphenyl) sulfone with 1,6-dibromohexane in aqueous/nitrobenzene heterogeneous phases. Tetrabutylammonium bromide was employed as a phase transfer catalyst. The polymerizations were dependent both on stirring speed and catalyst level, but only up to certain maximum values. Distribution studies demonstrated transference of diphenoxide anions from aqueous phase into nitrobenzene in the presence of the catalyst. Some of polymers were characterized with respect to their intrinsic viscosities (0.09-O.16), number average molecular weight (2400-4800)) and thermal properties. The use of a new terminology, 'phase transfer polymerization?, is proposed to differentiate this type of polymerizations from interfacial polycondensations.

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

  • Moon, Jiyeon;Chung, Kyungho;Park, Moonsoo
    • Elastomers and Composites
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    • v.48 no.4
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    • pp.294-299
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    • 2013
  • Solution polymerization was conducted with water-soluble methacrylic acid (MAA) as a monomer and potassium persulfate (KPS) as an initiator at a selected temperature between $70^{\circ}C$ and $90^{\circ}C$. When the ratio between MAA and water was reduced or initiator concentration increased, molecular weights decreased. Molecular weights of poly(methacrylic acid) (PMAA) showed nearly no dependence on reaction temperature. The Weissenberg effect was observed in most polymerization reactions, while its effect weakened at $90^{\circ}C$. The polydispersity index was less than 1.5 in most of the reactions. An increase in the stirring speed produced PMAAs with increasing molecular weights. When the stirring speed reached 800 rpm, we retrieved a monodisperse PMAA with both the number and weight average molecular weights of 791,000 g/mol. The glass transition temperature was found to be $162^{\circ}C$.

A Study Based on Molecular Orbital Theory of Polymerization of Oxolane High Explosives (Oxolane 고폭 화약류의 중합반응에 관한 분자 궤도론적 연구)

  • Kim, Joon-Tae
    • Applied Chemistry for Engineering
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    • v.21 no.3
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    • pp.278-283
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    • 2010
  • The cationic polymerization of oxolane high explosives which have pendant explosive groups such as azido, nitrato and hydrazino is investigated theoretically using the semiempirical MINDO/3, MNDO and AM1 methods. The nucleophilicity and basicity of oxolane high explosives can be explained by the negative charge on oxygen atom of oxolane. The reactivity of propagation in the polymerization of oxolane can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxolane. The reaction of the oxolane high explosives in oxonium ion form to the open chain carbenium ion form is expected by computational stability energy (17.950~30.197 kcal/mol) of the oxonium ion and carbenium ion favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium ion and carbenium ion is found to be a major determinant of mechanism, owing to the rapid equilibrium of these catoinic forms. Based on calculation, in the prepolymer propagation step, $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.