• Title/Summary/Keyword: Step-reaction polymerization.

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Graft Polymerization of Methyl Methacrylate onto Cotton Fiber -Comparison of two step graft polymerization and emulsion graft polymerization- (면섬유에 Methyl Methacrylate의 그라프트중합 - 이단계 그라프트중합과 유화 그라프트중합의 비교 -)

  • Bae Hyun-Sook;Kim Sung-Reon
    • Journal of the Korean Society of Clothing and Textiles
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    • v.13 no.1 s.29
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    • pp.89-97
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    • 1989
  • Graft polymerization of MMA onto cotton fiber was carried out in two ways, two step graft polymerization and one step emulsion graft polymerization, using tetravalent cerium ion as an initiator. At two step graft polymerization, the first step was the pretreatment of cotton fiber with an aqueous initiator solution and the second was the grafting pretreated cotton fiber in the monomer solution. In case of one step emulsion graft polymerization, MMA was emulsified with SLS in initiator solution. Under the various graft polymerization conditions, graft yield, graft efficiency and from the Arrhenius plot the apparent activation energy were compared. The results of this study were as follows: 1. Graft yield and graft efficiency of emulsion graft polymerization were higher than those of two step graft polymerization. 2. In case of two step graft polymerization, graft yield was affected by the pretreatment time of cotton fiber with an aqueous initiator solution. And graft yield of emulsion graft polymerization was increased with the concentration of emulsifier below cmc of SLS and was decreased thereafter. 3. Elevation of temperature resulted increase in graft yield for both grafting methods. The apparent activation energy of emulsion graft pelymerzation was lower than that of two step graft polymerization. 4. Increased reaction time increased in graft yield, but decreased in graft efficiency. 5. Moisture regain of grafted cotton was decreased with graft yield.

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Titanium Complexes: A Possible Catalyst for Controlled Radical Polymerization

  • Kwark, Young-Je;Kim, Jeong-Han;Novak Bruce M.
    • Macromolecular Research
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    • v.15 no.1
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    • pp.31-38
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    • 2007
  • Pentamethylcyclopentadienyltitanium trichloride, bis(cyclopentadienyl)titanium dichloride ($Cp_2TiCl_2$), and bis(pentamethylcyclopentadienyl)titanium dichloride were used in the polymerization of styrene without the aid of Group I-III cocatalysts. The properties of the resulting polymer indicated that polymerization was more controlled than in thermal polymerization. The kinetic studies indicated that a lower level of termination is present and that the polymer chain can be extended by adding an additional monomer. To elucidate the mechanism of polymerization, a series of experiments was performed. All results supported the involvement of a radical mechanism in the polymerization using $Cp_2TiCl_2$. The possibility of atom transfer radical polymerization (ATRP) mechanism was investigated by isolating the intermediate species. We could confirm the activation step from the reaction of 1-PEC1 with $Cp_2TiCl$ by detecting the coupling product of the generated active radicals. However, the reversible deactivation reaction competes with other side reactions, and it detection was difficult with our model system.

Controlling the Size and Surface Morphology of Carboxylated Polystyrene Latex Particles by Ammonium Hydroxide in Emulsifier-free Polymerization

  • Dong, Hyun-Bae;Lee, Sang-Yup;Yi, Gi-Ra
    • Macromolecular Research
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    • v.17 no.6
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    • pp.397-402
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    • 2009
  • In emulsifier-free, emulsion polymerization with ionizable comonomer, the ionization of the comonomer is critical in determining the size of the final polymerie particles at sub-micrometer scale. In this study, polystyrene latex beads with carboxylates on the surface were synthesized using acrylic acid as a comonomer. Specifically, ammonium hydroxide was added to the emulsifier-free polymerization system to promote the ionization of acrylic acid by increasing pH. Smaller polystyrene latex particles were produced by increasing the ammonium hydroxide concentration in the reaction system, due to the enhanced stability promoted by the ionization of acrylic acid during the nucleation step. In addition, the surface morphology of the polystyrene latex particles was controlled by the concentration of acrylic acid, the dissociation of which was influenced by the ammonium hydroxide concentration.

Effects of pressure during the synthesis of petroleum pitch precursors in open and closed systems

  • Choi, Jong-Eun;Ko, Seunghyun;Kim, Jong Gu;Jeon, Young-Pyo
    • Carbon letters
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    • v.25
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    • pp.95-102
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    • 2018
  • We examined the pressure effects on petroleum pitch synthesis by using open and closed reaction systems. The pressure effects that occur during the pitch synthesis were investigated in three pressure systems: a closed system of high pressure and two open systems under either an atmosphere or vacuum. A thermal reaction in the closed system led to the high product yield of a pitch by suppressing the release of light components in pyrolysis fuel oil. Atmospheric treatment mainly enhanced the polymerization degree of the pitch via condensation and a polymerization reaction. Vacuum treatment results in a softening point increase due to the removal of components with low molecular weights. To utilize such characteristic effects of system pressure during pitch preparations, we proposed a method for synthesizing cost-competitive pitch precursors for carbon materials. The first step is to increase product yield by using a closed system; the second step is to increase the degree of polymerization toward the desired molecular distribution, followed by the use of vacuum treatment to adjust softening points. Thus, we obtained an experimental quinoline insolubles-free pitch of product yield over 45% with softening points of approximately $130^{\circ}C$. The proposed method shows the possibility to prepare cost-competitive pitch precursors for carbon materials by enhancing product yield and other properties.

A Study on the Polymerization of Energetic Poly(NEO) (에너지를 함유한 선 폴리머인 poly(NEO) 제조 공정 연구)

  • Cheun Young Gu;Kim Jin Seuk
    • Journal of the Korea Institute of Military Science and Technology
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    • v.7 no.2 s.17
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    • pp.109-117
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    • 2004
  • We synthesized energetic prepolymer(2-nitrato ethyl oxirane, NEO) for plastic-bonded explosive and measured its thermodynamic parameters. 2-Nitrato ethyl oxirane(NEO) as a monomer was synthesized from 4-butene-ol, the first-step was preparation of 1-nitrate-3-butene and second-step was synthesized 2-nitrate-ethyl oxirane from 1nitrate-3-butene and then polymerized by cationic ring opening polymerization. The unreacted monomer concentration was measured by GC. The thermodynamic parameters were obtained from the ceiling temperature(Tc) values of 1 mole monomer at each reaction temperature. We varied feed rate of monomer, concentration of initiator and monomer to control molecular weight and polydispersity of perpolymer(NEO). Number average molecular weight(Mn), polydispersity(PD), and glass transition temperature(Tg), viscosity of prepolymer(NEO) were 2000, 1.07, $-55^{\circ}C$ and 300 poise respectively.

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 $S_N2$.

Synthesis and Hydrophilicities of Poly(ethylene 2,6-naphthalate)/ Poly(ethylene glycol) Copolymers

  • Son, Jun-Sik;Ji, Dong-Sun
    • Fibers and Polymers
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    • v.4 no.4
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    • pp.156-160
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    • 2003
  • Poly(ethylene 2,6-naphthalate) (PEN)/Poly(ethylene glycol) (PEG) copolymers were synthesized by two step reaction during the melt copolymerization process. The first step was the esterification reaction of dimethyl-2,6-naphthalenedicarbox-ylate (2,6-NDC) and ethylene glycol (EG). The second step was the condensation polymerization of bishydroxyethylnaphthalate (BHEN) and PEG. The copolymers contained 10 mol% of PEG units with different molecular weights. Structures and thermal properties of the copolymers were studied by using $^1{H-NMR}$, DSC, TGA, etc. Especially, while the intrinsic viscosities of PEN/PEG copolymers increased with increasing molecular weights of PEG, but the glass transition temperature, the cold crystallization temperature, and the weight loss temperature of the copolymers decreased with increasing molecular weights of PEG. Consequently, the hydrophilicities by means of contact angle measurement and moisture content of the copolymer films were found to be significantly improved with increasing molecular weights of PEG.

Multivariable Nonlinear Model Predictive Control of a Continuous Styrene Polymerization Reactor

  • Na, Sang-Seop;Rhee, Hyun-Ku
    • 제어로봇시스템학회:학술대회논문집
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    • 1999.10a
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    • pp.45-48
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    • 1999
  • Model predictive control algorithm requires a relevant model of the system to be controlled. Unfortunately, the first principle model describing a polymerization reaction system has a large number of parameters to be estimated. Thus there is a need for the identification and control of a polymerization reactor system by using available input-output data. In this work, the polynomial auto-regressive moving average (ARMA) models are employed as the input-output model and combined into the nonlinear model predictive control algorithm based on the successive linearization method. Simulations are conducted to identify the continuous styrene polymerization reactor system. The input variables are the jacket inlet temperature and the feed flow rate whereas the output variables are the monomer conversion and the weight-average molecular weight. The polynomial ARMA models obtained by the system identification are used to control the monomer conversion and the weight-average molecular weight in a continuous styrene polymerization reactor It is demonstrated that the nonlinear model predictive controller based on the polynomial ARMA model tracks the step changes in the setpoint satisfactorily. In conclusion, the polynomial ARMA model is proven effective in controlling the continuous styrene polymerization reactor.

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Synthesis of Poly(trimethylene terephthalate) Using an Organic Titanium Compound as a Catalyst (유기티타늄을 촉매로 한 폴리트리메틸렌테레프탈레이트 합성에 관한 연구)

  • Pio Sifuentes;Kim, Kap-Jin
    • Proceedings of the Korean Fiber Society Conference
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    • 2003.04a
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    • pp.335-336
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    • 2003
  • The synthesis of poly(trimethylene terephthalate) (PTT), whose application is being expanded very rapidly to new apparel and carpet materials, was investigated by melt condensation polymerization using 1,3-propanediol (PDO) and terephthalic acid (TPA). No catalyst was used in the 1st step reaction (esterification), but tetrabutyl titanate(TBT) was used as a polyesterification catalyst ranging from 25 to 75 ppm based on the weight of TPA used in the 2nd step reaction (polyesterification). The molar ratio of PDO to TPA was set as 2.2:1. The effect of reaction conditions on the color and intrinsic viscosity of the final product was investigated. (omitted)

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