• Title/Summary/Keyword: polymerization mechanism

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The Kinetics of Radical Polymerization of Styrene with Tricaprylymethylammonium Chloride as a Phase-Transfer Catalyst (상이동촉매인 트리카프릴메틸암모니움 클로라이드를 사용한 스티렌 라디칼중합의 동력학적 연구)

  • Park, Sang-Wook;Sohn, In-Joe;Park, Sang-Bo
    • Journal of Adhesion and Interface
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    • v.2 no.2
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    • pp.11-19
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    • 2001
  • The phase-transfer catalyzed radical polymerization of styrene was carried out using tricaprylylmethylammonium chloride as a phase-transfer catalyst in a two-phase system of an aqueous $Na_2S_2O_8$ solution and toluene at $60^{\circ}C$ under nitrogen atmosphere. The initial rate of radical polymerization was expressed as the combined terms of concentrations of quaternary onium cation and peroxydisulfate anion in the aqueous phase rather than the fed concentrations of catalyst and $Na_2S_2O_8$. The observed initial rate of radical polymerization was used to analyze the radical polymerization mechanism with a cycle phase-transfer initiation step in the heterogeneous liquid-liquid system. The viscosity average molecular weight of polystyrene was inversely proportional to concentration of $Na_2S_2O_8$ expressed as $[Q^+]([S_2O{_8}^{2-}]{\alpha}_2)^{1/2}$ derived by the radical polymerization mechanism.

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Formaton of Macrozwitterions in the Cationic Polymerization of Propylene Sulfide Initiated with o-Sulfobenzoic Anhydride (o-Sulfobenzoic Anhydride로 개시된 Propylene Sulfide의 양이온중합시 고분자양성이온의 생성)

  • Man Jung Han
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.173-183
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    • 1978
  • Bulk polymerization of propylene sulfide with o-sulfobenzoic anhydride as initiator was carried out and the polymerization proceeded by a zwitterionic mechanism. Chemical and spectroscopic investigation of the purified polymer revealed that the polymer contained two end groups-thiolester of benzoic acid o-sulfonate anions and acyclic tert-sulfonium ions which were formed by termination of episulfonium ions with sulfide groups in the polymer chains. The concentration of sulfonate anions was nearly the same as the concentration of acyclic tert-sulfonium ions, as expected for macrozwitterions. The cocatalysis mechanism by a trace of water was excluded and the other possible mechanisms were discussed on the basis of end group analysis.

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Diacetylene Polymerize in Amorphous State? Free Radical Initiated Polymerization of Aromatic Diacetylenes.

  • Beristain Miriam F.;Ogawa Takeshi
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.321-321
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    • 2006
  • Aromatic diacetylenes form stable oligomeric diradicals when irradiated with UV light or heated at temperatures above their melting points. In this paper, the formation of stable diradicals is discussed, and the mechanism of polymerization in the presence of peroxide in solution, is discussed. The diphenyldiacetylene undergoes polymerization through coupling of diradicals, and not by the successive addition of radical species.

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The Application of the Pseudo Molecular Complex to Thermal Polymerization (Ⅰ). Proposal of A New Initiation Mechanism (의사분자 착물의 응용 (제1보). 열중합 개시기구 제안)

  • Byung Kack Park
    • Journal of the Korean Chemical Society
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    • v.18 no.6
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    • pp.447-452
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    • 1974
  • A mechanistic possibility for the initiation of the thermal polymerization reactions are envisaged theoretically. As result of the considerations, it is assumed that the thermal polymerization reactions take place via the pseudo molecular complex which has been supposed to be an intermediate in the transition state of Diels-Alder reactions.

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Retention Mechanism of Caffeine and Tryptophan in Macroporous Poly[Methacrylic Acid-co-Ethylene Glycol Dimenthacrylate] Rods (매크로 다공성 Poly[Methacrylic Acid-co-Ethylene Glycol Dimenthacrylate] 막대에서 Caffeine과 Tryptophan의 체류 메카니즘)

  • Jin, Longmei;Yan, Hongyuan;Zheng, Jinzhu;Row, Kyung-Ho
    • KSBB Journal
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    • v.21 no.5
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    • pp.401-404
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    • 2006
  • Macroporous Poly(Methacrylic acid-co-Ethylene Glycol Dimethacrylate) Rods were in situ thermal initialized within a empty column($3.9{\times}150mm$) by free radical polymerization. The polymerization mixture was consisted of monomer, cross-linking monomer, porogenic solvent, initiator and control the ratio of these materials, column efficiency could be developed. Caffeine and tryptophan as separation substances and the retention mechanism of this kind of monolithic column was mainly hydrogen bond function.

Enhanced Adhesion of Tire Cords via Argon Etching and Acetylene Plasma Polymerization (아르곤 에칭과 아세틸렌 플라즈마 중합에 의한 타이어 코드의 접착성 향상연구)

  • H. M. Kang;Kim, R. K.;T. H. Yoon
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 1999.11a
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    • pp.36-39
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    • 1999
  • Steel tire cords were coated via RF Plasma Polymerization of acetylene in order to enhance adhesion to rubber compounds. Adhesion of tire cords was measured by TACT as a function of plasma polymerization and argon etching conditions such as power, treatment time and chamber pressure. Tested tire cords were analysed by SEM to elucidate the adhesion mechanism. The highest adhesion values were obtained with argon etching condition at 90W, 10min, 30mtorr followed by acetylene plasma polymerization condition at 10W, 30sec., 30mtorr. In SEM analysis, the plasma polymerized tire cord at the optimized condition showed 100% rubber coverage as observed from brass-plated steel tire cords.

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수처리 목적의 대기압플라즈마를 이용한 유사 폴리도파민 필름 증착

  • Mun, Mu-Gyeom;Yeom, Geun-Yeong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.124-124
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    • 2018
  • Polydopamine은 수중 접착력, 친환경 접착제, nanoparticle absorption 등 다양한 특성으로 많이 연구되고 있는 소재이다. 본 연구에서는 dopamine을 이용하여 수중 금속을 흡착시키는 thin film을 제작하였다. 종래의 Polydopamine coating 방법으로 wet coating 이 사용되고 있다. 하지만 wet 방식의 경우 시간이 오래 걸릴 뿐만 아니라 in-line, roll to roll 방식을 적용하는 것이 어렵기 때문에 생산적이지 않다. 이에 본 연구에서는 Atmospheric Pressure Plasma(APP)를 이용 하여 Polydopamine-like film을 coating 하였다. APP의 경우 vacuum system, solution tank가 필요 없고 in-line, roll to roll 방식을 적용 할 수 있기 때문에 더 경제적이고 생산적인 공정이다. 또한 기존의 Plasma polymerization 방법은 Plasma energy가 높기 때문에 source의 분자구조가 바뀌거나 atom 단위로 분해된다. source의 분자구조가 바뀌는 "Atomic polymerization", Neiswender-Rosskamp Mechanism이 적용되면 wet 방식 coating한 film과는 다른 특성을 갖게 된다. 하지만 APP polymerization은 Plasma energy가 vacuum plasma 보다 매우 낮기 때문에 stile polymerization mechanism을 구현 하는데 적합 하다. stile polymerization mechanism은 Plasma 내부에서 polymer source를 분해 성장 시켜서 Polymer film 얻는 것이 아닌 source의 분자구조가 깨지지 않으면서 polymer growing 시키는 방법이다. dopamine source의 분자구조를 최대한 유지하려고 하는 이유는 metal absorption과 같은 특성이 dopamine chemical structure에 영향을 받기 때문이다. 많은 논문들에서 dopamine의 catechol group이 metal absorption, adhesion force에 영향을 주는 주요 인자라고 주장하고 있기 때문이다. 그래서 본 논문에서는 Dopamine source의 형태를 보존하면서 Polymerization 하는 방법으로 APP process를 사용 하여 낮은 전압에서 Polydopamine-like film을 제작 하였다. APP system 의 Plasma 방전부 에 Dopamine source를 유입하기 위하여 본 논문에서는 Piezo Spray 방식을 사용 하였다. Dopamine을 evaporator 하는 것이 어렵고 chemical composition이 유사한 monomer를 사용해서 Plasma Polymerization으로 Dopamine 분자 구조를 재현하는 것도 어렵다. 그래서 본 연구에서는 Dopamine을 water에 immerse 하고 Dopamine solution을 mist 상태로 만들어서 Plasma discharge area에 유입하였다. 이러한 방법으로 만들어진 film은 Polydopamine film은 아니지만 Polydopamine film과 유사한 Chemical composition, chemical structure, metal absorption을 갖는 것을 FT-IR, SEM, XPS을 이용 하여 확인 하였다. Dopamine source의 보존에 대하여 명확하게 확인하기 위하여 FT-IR을 측정 하였다. 전압에 따른 Benzene ring, hydroxyl group의 비율을 확인 하였다. 낮은 전압으로 coating 된 Polydopamine-like film 일수록 hydroxyl group peak($3400{\sim}3000cm^{-1}$)과 비교하여 Benzene ring peak($1600{\sim}1580cm^{-1}$ and $1510{\sim}500cm^{-1}$)이 흡수를 더 많이 하는 것을 확인 할 수 있다. 이것은 Benzene ring이 파괴되지 않고 보존되는 것을 보여준다. Dopamine에서 Benzene ring은 absorption main factor인 catechol에 있는 chemical structure이다. 즉 Benzene ring peak이 높을수록 Catechol이 잘 보존 되었다는 의미 이다. Catechol의 보존은 absorption main factor가 보존 된다는 의미 이다. 이러한 Polydopamine-like film으로 As, Cr, Mg, Cu 200ppm solution에 대한 filtration 능력을 확인 하였다. As, Cr, Cu, Mg 의 제거율이 각각 약25%, 35%, 45%, 65%인 것을 확인 하였다. 이 수치는 시중에 판매되는 제품들과 비교했을 때 300%~500% 향상된 수치 이다.

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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.