• 제어로봇시스템학회:학술대회논문집
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• 1994.10a
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• pp.207-212
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• 1994

A mathematical model is developed for a batch reactor in which the free radical bulk copolymerization of styrene and acrylonitrile takes place. In this model, we introduce the free volume theory to quantify the diffusion controlled termination and propagation reactions, and develop a model for the chain length dependent termination reaction in the context of the pseudo kinetic rate constant method(PKRCM). The simulation results from this model are found to be in good agreement with experimental data under different copolymerization conditions. The present model can predict both the copolymer composition and the number and weight average molecular weights. These kinetic approaches provide greater insight into the performance of the batch reactor used for the free radical bulk copolymerization of styrene and acrylonitirle.

• Fibers and Polymers
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• v.3 no.2
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• pp.49-54
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• 2002

Radical copolymerization behavior of 4'-vinylbenzo-15-crown-5, a vinyl monomer having a pendant 15-membared crown ether unit (VCE) with di(ethylene glycol) ethyl ether acrylate (DEGEEA) was carried out in toluene solution using 2,2-azobisisobutyronitrile (AIBN) as an initiator. The copolymers were characterized by means of FT-IR, $^1{H-NMR}$, and $^{13}{C-NMR}$ . The reactivity ratio of VCE and DEGEEA, determined by Fineman-Ross and Kelen-Tudos method, gave values 0.55 for VCE, and 0.11 for DEGEEA respectively.

• Macromolecular Research
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• v.15 no.2
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• pp.134-141
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• 2007

The direct chromatographic separation of enantiomers by chiral stationary phases (CSPs) has been extensively developed over the past two decades, and has now become the most popular method for the analytical and preparative separations of enantiomers. Polysaccharide derivatives coated onto silica gel, as CSPs, playa significantly important role in the enantioseparations of a wide range of chiral compounds using high-performance liquid chromatography (HPLC). Unfortunately, the strict solvent limitation of the mobile phases is the main defect in the method developments of these types of coated CSPs. Therefore, the immobilization of polysaccharide derivatives onto silica gel, via chemical bonding, to obtain a new generation of CSPs compatible with the universal solvents used in HPLC is increasingly important. In this article, our recent studies on the immobilization of polysaccharide derivatives onto the silica gel, as CSPs, through radical copolymerization with various vinyl monomers are reported. Polysaccharide derivatives, with low vinyl content, can be efficiently fixed onto silica gel with high chiral recognition.

• Macromolecular Research
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• v.15 no.4
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• pp.324-329
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• 2007

An octa-functional alkoxyamine initiator, with the 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO) free radical, was synthesized based on resorcinarene, with its efficiency to initiate the nitroxide-mediated free radical copolymerization of styrene and methyl methacrylate (MMA) described. A difunctional analogue of this initiator was also synthesized, using resorcinol as the core molecule. The structures of the resulting initiators were confirmed by homolysis studies based on electron spin resonance spectroscopy and molecular modeling. The polymerization behavior and characteristics of the polymers obtained using these two initiators were also compared. Well-defined star-shaped and linear random copolymers, with low polydispersities and controlled molecular weights, were prepared. The efficiencies of these initiators towards copolymerization, as well as the parameters permitting the formation of well-defined polymers, were also investigated. The reactivity ratios were $r_a=0.42(a=styrene)\;and\;r_b=0.33(b=MMA)$ for the octa-functional initiator system and $r_a=0.45\;and\;r_b=0.39$ for the difunctional initiator system.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.324-324
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• 2006

In copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) with various ratios of MA to MMA and $[CuCl]/[PMDETA]/[PVAc-CCl_{3}]$ catalyst system in bulk at $80^{\circ}C$ via ATRP, several terpolymer with different copolymer composition, were synthesized. The atom transfer radical copolymerization of MA and MMA with macroinitiator, is very sensitive to molecular weight and its distribution. In this work it was possible to calculate the molecular weight of the terpolymers and show that it is close to the experimentally determined number average molecular weight from GPC.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.80-85
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• 1980

The free radical copolymeriaztion of N-vinylurea(VU) with vinyl acetate (VAc) was carried out at $60^{\circ}C$ in three solvents. VU-vinyl alcohol(VA) copolymers were prepared by the methanolysis of the VU-VAc copolymers. From the nitrogen content measurements of VU-VA copolymers, the monomer reactivity ratios for the VU-VAc copolymerization and the values of Alfrey-Price's Q and e for VU were determined. These Q and $\varrho$ values obtained in the cases of using methanol and methanol-dioxane as the polymerization solvents are comparable with those found for other monomers which have > NCO-pendent groups. The $\varrho$ value indicates that the urea group of VU is a electron-donating group. The copolymerization parameter of VU shows a strong effect of the solvents. These results are interpreted to be that VU is in equilibrium with its tautomer at the polymerization temperature.

• 제어로봇시스템학회:학술대회논문집
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• 1997.10a
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• pp.309-312
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• 1997

The dynamic characteristics of a continuous MMA/MA free-radical solution copolymerization reactor were studied. A mathematical model was developed and kinetic parameters which had been estimated in the previous work were used. With this model, bifurcation diagrams were constructed with various parameters as the bifurcation parameter to predict the region of stable operating conditions and to enhance the controller performance. It was shown that the steady-state multiplicity existed over wide ranges of residence time and jacket inlet temperature. Periodic solution branches were found to emanated from Hopf bifurcation points. Under certain conditions isola was also observed, which would result in poor performance of feedback controllers.

• Elastomers and Composites
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• v.28 no.3
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• pp.183-190
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• 1993

The radical copolymerization with propagation and depropagation is presented in order to estimate reactivity rate of monomers and $K_{11}$(the equilibrium constant for propagation and depropagation) in the copolymerization of ${\alpha}-methylstyrene-co-methylmethacrylate$ and ${\alpha}-methylstyrene-acrylonitrile$. The value of ${\alpha}-methylstyrene$ and methylmethacrylate and $K_{11}$ are found to be 0.48, 0.47 and 5.0 respectively. The value of ${\alpha}-methylstyrene$ and acrylonitrile and the $K_{11}$ are found to be 0.1251, 0.0577 and 23.8 respectively. The treatment rate constant of ${\alpha}-methylstyrene-co-methylmethacrylate$ and ${\alpha}-methylstyrene-co-acrylonitrile$ in the copolymerization is estimated to be 2.5, 80.72 regardless of monomer feed composition.

• Journal of Integrative Natural Science
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• v.5 no.2
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• pp.127-130
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• 2012

Polymerization of vinyl monomers is promoted by thianthrene cation radical as a part of our research concerning the reactions of various agents with readily isolable, yet highly reactive species and elucidate the biological activity. Thianthrene cation radical initiated the homopolymerization and copolymerization of styrene and ethyl vinyl ether. The polymerization yields decreased as the concentration of phenylacetylene or diphenylethylene increased. Such polymereization by cationic thianthrene radical could provide some clues for the reaction in living animals. Comments on possible polymerization mechanisms were suggested.

• Journal of the Korean Chemical Society
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• v.26 no.6
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• pp.421-426
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• 1982

Free radical-initiated copolymerization of diethyl isopropenyl phosphate (DEIPA) with vinyl acetate (VAc) and acrylonitrile (AN) was studied. The monomer reactivity ratios for the monomer pairs, determined at $60^{\cric}C$ using benzoyl peroxide as an initiator, are: ${\gamma}_1$(VAc) = 1.56, ${\gamma}_2$(DEIPA) = 0.44: ${\gamma}_1$(AN) = 15.2, ${\gamma}_2$(DEIPA) = 0.031. The values of the Alfrey-Price constants, Q and e, for DEIPA were calculated to be 0.015 and 0.39, respectively, from the VAc system, and 0.014 and 0.34, respectively, from AN/DEIPA pair. These results indicate that ${\alpha}$-methyl substituent of vinyl phosphate monomer decreases the general reactivity in free radical copolymerization. The intrinsic viscosity and number-average molecular weight of copolymers decreased as their content of DEIPA units increased, indicating a high degree of chain transfer caused by DEIPA, as previously learned in DEVPA system.