• Title/Summary/Keyword: equilibrium polymerization

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Anionic Polymerization of 2-Pyrrolidone by $SO_2/KOH$ Catalyst ($SO_2/KOH$ 촉매에 의한 2-Pyrrolidone의 음이온 중합에 관한 연구)

  • Huh, Dong-Sub;Lee, Jung-Keun
    • Elastomers and Composites
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    • v.14 no.4
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    • pp.231-252
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    • 1979
  • Polymerization of 2-pyrrolidone was carried out through anionic mechanism using $SO_2/KOH$ as catalyst. The effects of KOH concentration, $SO_2/KOH$ mole ratio and temperature on polymerization were investigated. The conversion and viscosity of polymers were measured at various polymerization conditions. It was observed that as the concentration of KOH was increased, equilibrium conversion was also increased. It was, however, found that after the concentration of KOH was reached above 8 mole percent, the equilibrium conversion was decreased. The highest rate of polymerization and maximum conversion were obtained when $SO_2/KOH$ mole ratio was around 0.5. It was also found that the rate of polymerization and the equilibrium conversion were higher at $50^{\circ}C$. than at $30^{\circ}C$. but the viscosity of polymer solution at $50^{\circ}C$. was not so high as expected. The rate constant, $K_p$ of polymerization, was determined by least square method: the value of $K_p$ was observed as 16 liter/mole hour at $50^{\circ}C$. and 2.6 liter/mole hour at $30^{\circ}C$., respectively. The mechanism of polymerization was also discussed.

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The Synthesis of Pyrrolidone-N-sulfonyl Chloride and Its Catalytic Effect in Anionic Polymerization of Pyrrolidone (Pyrrolidone-N-sulfonyl Chloride의 합성 및 Pyrrolidone-N-sulfonyl Chloride / KOH 촉매작용에 의한 Pyrrolidone의 음이온 중합)

  • W.J. Chung;S.K. Choi
    • Journal of the Korean Chemical Society
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    • v.23 no.6
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    • pp.402-411
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    • 1979
  • The synthesis of pyrrolidone-N-sulfonyl chloride has been carried out by the reaction of pyrrolidone with sulfuryl chloride in benzene. It was attempted to study the catalytic effect of pyrroldone-N-sulfonyl chloride as an initiator for anionic polymerization of pyrrolidone. It was found that as a concentration of initiator decreased, inherent viscosity of the resulting polymer increased up to 1.8 dl/g. The highest rate of polymerization and equilibrium conversion was observed when mole ratio of PNSC to KOH was 0.25. In general, the observed value of polymerization and equilibrium conversion in circumstances using PNSC/KOH catalysis system were higher than using $CO_2$/KOH catalysis system.

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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.

Rediscovery of a Broad Array of Lewis Acids for Living Cationic Polymerization in the Presence of an Added Base

  • Kanaoka, Shokyoku;Kanazawa, Arihiro;Aoshima, Sadahito
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.325-325
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    • 2006
  • Cationic polymerization of isobutyl vinyl ether using various metal halides was examined in toluene in the presence of an added base at $0^{\circ}C$. In conjunction with an appropriate weak base such as ethyl acetate or 1,4-dioxane, all metal halides but $FeBr_{3}\;and\;GaCl_{3}$ led to living cationic polymerization. The polymerization rates varied as follows: $FeBr_{3},\;GaCl_{3}\;>\;FeCl_{3}\;>\;SnCl_{4}\;>\;InCl_{3}\;>\;ZnCl_{2}\;>>\;AlCl_{3},\;HfCl_{4},\;ZrCl_{4}\;>\;EtAlCl_{2},\;BiCl_{3},\;TiCl4\;>>\;SiCl_{4}\;>\;GeCl_{4}$. This order partially corresponds to that of the equilibrium constant in the formation of a carbocation from a chloroalkane in the presence of a carbonyl compound. With extremely active Lewis acids, such as $FeBr_{3}\;and\;GaCl_{3}$, the use of a stronger base, THF, was required to achieve living polymerization.

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Afterpolymerization and Depolymerization of Poly-${\varepsilon}$-caproamide in Solid State (고체상태에서 Poly-${\varepsilon}$-caproamide의 후중합 및 해중합에 관한 연구)

  • Jung-Ji Moon;Dong-ho Lee;Tae-oan Ahn
    • Journal of the Korean Chemical Society
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    • v.17 no.6
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    • pp.450-454
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    • 1973
  • The afterpolymerization and depolymerization of poly-${\varepsilon}$-caproamide in solid state have been studied under two different reaction conditions, nitrogen flow and sealed state. The degree of polymerization ($\bar{P}$) of nylon 6 increased with the increase in reaction time and temperature, and then reacted finally an equilibrium. In the presence of oxygen, $\bar{P}$ decreased by increasing the reaction time due to the oxidation reaction. Under certain reaction condition, the change of $\bar{P}$ for different initial degree of polymerization ($\bar{P}_0$) tendered toward unity in equilibrium.

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Theoretical Studies on The Cationic Polymerization Mechanism of Oxetanes (산촉매하의 옥세탄 공중합에 관한 분자 궤도론적 연구)

  • Cheun, Young-Gu;Kim, Joon-Tae;Park, Seong-Kyu
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.636-644
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    • 1991
  • The cationic polymerization of substituted oxethanes which have pendant energetic groups such as methoxy, azido, and nitrato are investigated theoretically using the semiempirical MINDO/3, MNDO, and AM1 methods. The nucleophilicity and basicity of substituted oxethanes can be explained by the negative charge on oxygen atom of oxetanes. The reactivity of propagation in the polymerization of oxetanes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxetanes. The reaction of the energetic cyclic oxonium ion forms to the open chain carbenium ion forms is expected by computational stability energy of the oxonium and carbenium ion (about 10~20 kcal/mole) favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on clauclation that the prepolymer propagation step SN1 mechanism will be at least as fast as that for SN2 mechanism.

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

  • Kim, Joon-Tae
    • Applied Chemistry for Engineering
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    • v.20 no.2
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    • pp.159-164
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    • 2009
  • Monomers of oxetane high explosives were theoretically examined in terms of reactivity, reaction mechanism and process of polymerization substituted by azido $(-CH_2N_3)$, nitrato $(-CH_2ONO_2)$ and hydrazino $(-CH_2N_2H_3)$ which belong to the 5th class hazardous materials and have explosiveness under acid catalyst using MINDO/3, MNDO, and AMI methods for formal charge, heat of formation, and energy level. Nucleophilicity and base of oxetane high explosives could be explained by negative charge size of oxetane oxygen atom and reactivity of oxetane in the growth stage of polymerization under acid catalyzer could be expected to be governed by positive charge size of axial carbon atom and low LUMO energy of electrophile. It could be estimated that carbenium ion was more beneficial in the conversion process of oxetane high explosives than that of stabilization energy (13.90~31.02 kcal/mole) of oxonium ion. In addition, concentration of oxonium ion and carbenium ion in equilibrium state influenced mechanism and it was also estimated that $S_N1$ mechanism reacts faster than that of $S_N2$ in prepolymer growth stage considering quick equilibrium based on form and calculation of polymerization under acid catalyzer.

Theoretical Study on Polymerization of Oxepane High Explosives

  • Kim, Joon-Tae
    • Journal of Integrative Natural Science
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    • v.5 no.3
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    • pp.175-181
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    • 2012
  • Oxepane high explosives substituted to explosive group such as azido, nitrato and hydrazino are investigated theoretically the acid catalyzed reaction using the semiempirical MINDO/3, MNDO and AM1 methods to use as the guidelines of high explosives. The nucleophilicity and basicity of oxepane high explosives can be explained by the value of negative charge on oxygen atom of oxepane and the reactivity in propagation step can be represented by the value of positive charge on carbon atom and low electrophile LUMO energy. It was known that carbenium ion was favorable due to the stable energy (19.507~32.101 Kcal/mol) between oxonium ion and carbenium ion in the process of cyclic oxonium ion of oxepane high explosives being converted to open carbenium ion in oxepane high explosives. The value of concentration of cyclic oxonium ion and open carbenium ion in equilibrium status was found to be a major determinant of mechanism, it was expected to react faster in the prepolymer propagation step in SN1 mechanism than in that of $S_N2$.

Viscosity and Thermodynamic Properties of Liquid Sulfur

  • Chang, Man-Chai;Jhon, Mu-Shik
    • Bulletin of the Korean Chemical Society
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    • v.3 no.4
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    • pp.133-139
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    • 1982
  • It has been presumed that the molten sulfur above $159^{\circ}C$ consists of an equilibrium mixture of $S_8$ rings and $S_x$ polymers where the number average degree of polymerization, P, is large. But it is known that admixture of halogens with liquid sulfur greatly reduce the viscosity. Constructing a new equilibrium equation, it is possible to evaluate the viscosity when halogens are added to liquid sulfur. Calculated viscosity is in good agreement with experimental values. Using the proposed model, the thermodynamic properties of liquid sulfur are also calculated over a wide range of temperature which the sulfur exists as the polymer.