• Macromolecular Research
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• v.11 no.5
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• pp.311-316
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• 2003

The kinetics of photoinitiated polymerization of dimethacrylate macromonomers have been studied to determine the diffusion-controlled reaction parameters using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). A predicted kinetic rate expression with a diffusion control factor was employed to estimate an effective rate constant and to define the reaction-controlled and diffusion-controlled regimes in the photopolymerization. An effective rate constant, k$_{e}$, can be obtained from the predicted kinetic rate expression. At the earlier stages of polymerization, the average values of kinetic rate constants do not vary during the reaction time. As the reaction conversion, $\alpha$, reaches the critical conversion, $\alpha$$_{c}$, in the predicted kinetic expression, the reaction becomes to be controlled by diffusion due to the restricted mobility of dimethacrylate macromonomers. A drop in value of effective rate constant causes a drastic decrease of reaction rate at the later stages of polymerization. By determining the effective rate constants, the reaction-controlled and diffusion-controlled regimes were properly defined even in the photopolymerization reaction system.m.m.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.325-329
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• 2002

In this study, the dependency of the behavior of propagating front on the reaction condition in frontal polymerization reaction has been studied. We have used some multifunctional acrylates as a monomer and ammonium persulfate as an initiator for the polymerization reactions. In frontal polymerization, a method of producing polymeric materials via a thermal front that propagates through the unreacted monomer/initiator solution, the behavior of self propagating front shows various dynamic patterns depending on the reaction condition. We have obtained some spin modes of propagating front in the number of 'hot spots' or 'spin heads' by changing the reaction condition. The effect of the reactor tube diameter on the mode of propagating front has also been studied by using some reactor tubes with different size of tube diameter and it has been examined in some detail by adopting an experimental method of two-tubes system.

• Journal of the Korean Society of Safety
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• v.26 no.5
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• pp.46-53
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• 2011

The risk assessment of thermal behavior and runaway reaction cased by an exothermic batch process in manufacture of the vinyl acetate resin are described in the present paper. The aim of the study was to evaluate the risk of runaway reaction with operating parameters such as a reaction inhibitor, reaction temperature and a mount of methanol charged in the vinyl acetate polymerization process. The experiments were performed by a sort of calorimetry with the Multimax reactor system as a screening tool to investigate runaway reaction. From the experimental results, it was found that we could occur the auto acceleration for reaction of raw materials with operating parameters over $65^{\circ}C$ of reaction temperature in the vinyl acetate polymerization process.

• Bulletin of the Korean Chemical Society
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• v.18 no.12
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• pp.1288-1291
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• 1997

4-Allylanisole was polymerized with AlCl3 as a catalyst. The polymerization was carried out in nitroethane at various temperatures with changing the ratio of the initiator to the monomer concentration. The weight averge molecular weights measured by gel permeation chromatography in chloroform with polystyrene standards were between 1,500 and 4,700. 1H NMR spectroscopy showed that the polymerization proceeded through a stepwise aromatic electrophilic substitution reaction along with a minor chain-reaction, resulting in a branched polymer. 4-Chloromethylanisole was also polymerized with AlCl3 in nitroethane through an aromatic electrophilic substitution reaction to give a high molecular weight polymer (Mw=88,000).

• 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.

• Journal of the Korean Society of Safety
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• v.17 no.3
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• pp.81-89
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• 2002

The runaway reaction was analyzed experimently and theoretically at the batch styrene suspension polymerization process. In the experiments, the reaction temperature with time was measured at various experimental conditions. According to the experimental results, the risk of the runaway reaction was increased with increasing the ratio of the monomer(styrene, M) to the dispersion medium(water, W), the concentration of the initiator(BPO), and the monomer mass, respectively. And simulation results showed that the runaway reaction was significantly affected by the reaction rate constant of the propagation and that the phenomena of the runaway reaction occurred at about 70% conversion. Also, we found that the runaway reaction did not occur under the operating condition of below 0.5 for M/W, approximate 3 wt% BPO, and below 75$^{\circ}C$ for the cooling temperature.

• Journal of the Korean Institute of Gas
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• v.17 no.4
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• pp.1-8
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• 2013

The aim of this study is to assess thermal hazards of polystyrene polymerization process by bulk polymerization with accelerating rate calorimeter(ARC) and Multimax reactor system(MM). From this study, we found out that the polymerization process should be operated at reaction temperature of $120^{\circ}C{\sim}130^{\circ}C$. At reaction temperature over $130^{\circ}C$, there was a runaway reaction hazard due to the temperature control failure following a viscosity increase of reaction products. With a cooling failure of a reactor in the early stage of process operation at the reaction temperature ($120^{\circ}C{\sim}130^{\circ}C$), there was a high thermal hazard of burst of a reactor's rupture disk or explosion of a reactor caused by the rapid rise of temperature and pressure to $340^{\circ}C$, 5.3 bar respectively within 30 - 50 minutes.

• 제어로봇시스템학회:학술대회논문집
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• 1996.10b
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• pp.1000-1003
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• 1996

Nonlinear unified predictive control(UPC) algorithm was applied to the temperature control of a batch polymerization reactor for polymethylmethacrylate(PMMA). Before the polymerization reaction is initiated, the parameters of the process model are determined by the recursive least squares(RLS) method. During the reaction, nonlinearities due to generation of heat of reaction and variation of heat transfer coefficients are predicted through the nonlinear model developed. These nonlinearities are added to the process output from the linear process model. And then, the predicted process output is used to calculate the control output sequence. The performance of nonlinear control algorithm was verified by simulation and compared with that of the linear unified predictive control algorithm. In the experiment of a batch PMMA polymerization, nonlinear unified predictive control was implemented to regulate the temperature of the reactor, and the validity of the nonlinear model was verified through the experimental results. The performance of the nonlinear controller turned out to be superior to that of the linear controller for tracking abrupt changes in setpoint.

• Polymer(Korea)
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• v.32 no.4
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• pp.385-389
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• 2008

Chain propagation and chain transfer in anionic polymerization of hexafluoropropylene oxide were investigated under various reaction conditions such as the stabilization of reaction temperature, the amount of hexafluoropropylene solvent, and the feeding rate of hexafluoropropylene oxide monomer. Anionic initiator for the polymerization was synthesized from cesium fluoride and hexafluoropropylene oxide in tetraethyleneglycol dimethylether. It was possible to obtain a high molecular weight poly(HFPO) ($M_w$ 14800) using the anionic initiator in conditions of stabilized reaction temperature, and optimized addition of solvent and monomer feeding (HFP/initiator mole ratio=31.5 and HFPO feeding rate=11.67 g/hr). Otherwise, chain transfer reaction in anionic polymerization was increased. From the results of molecular weight in various reaction conditions, it was found that chain propagation and chain transfer in anionic polymerization of HFPO were very sensitive to reaction conditions.

• Analytical Science and Technology
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• v.15 no.4
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• pp.341-345
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• 2002

The extent of UV-curing photo-polymerization reaction was monitored by near-IR spectroscopic method. Acrylates containing quaternary ammonium salts and Darocur 1173 were used as reactive monomer and a photo initiator, respectively. The extent of photo-polymerization reaction was obtained from the conversion ratio of acrylate double bond calculated from the intensities of measured bands at 1615 nm and at 2105 nm. Near-IR spectroscopic methods can be an useful tool for the monitoring of the progress of photo-polymerization.