• Macromolecular Research
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• v.17 no.1
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• pp.14-18
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• 2009

The acceleration effect of various organic acids, such as methanesulfonic acid (MSA), ethanesulfonic acid (ESA), 4,4'-sulfonyldibenzoic acid (SDA), diphenylacetic acid (DPAA), and $\rho$-toluenesulfonic acid (TSA), on the rate of styrene bulk polymerization with 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) and benzoyl peroxide (BPO) was investigated. The addition of organic acids significantly accelerated the rate. Among these organic acids, DPAA showed an efficient rate-accelerating effect with living nature of polymerization. When DPAA was used as a rate-accelerating additive for TEMPO-mediated living free radical polymerization (LFRP), the rate of polymerization was dramatically enhanced, the linearity of reaction kinetics was successfully maintained, and the polydispersity was effectively controlled.

• Restorative Dentistry and Endodontics
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• v.27 no.2
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• pp.135-141
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• 2002

Objectives : The aim of this study is to evaluate the effect of light intensity variation on the polymerization rate of composite resin using IB system (the experimental equipment designed by Dr. IB Lee) by which real-time volumetric change of composite can be measured. Methods : Three commercial composite resins [Z100(Z1), AeliteFil(AF), SureFil(SF)] were photopolymerized with Variable Intensity Polymerizer unit (Bisco, U.S.A.) under the variable light intensity (75/150/225/300/375/450mW$^2$) during 20 sec. Polymerization shrinkage of samples was detected continuously by IB system during 110 sec and the rate of polymerization shrinkage was obtained by its shrinkage data. Peak time(P.T.) showing the maximum rate of polymerization shrinkage was used to compare the polymerization rate. Results : Peak time decreased with increasing light intensity(p<0.05). Maximum rate of polymerization shrinkage increased with increasing light intensity(p<0.05). Statistical analysis revealed a significant positive correlation between peak time and inverse square root of the light intensity (AF:R=0.965, Zl:R=0.974, SF:R=0.927). Statistical analysis revealed a significant negative correlation between the maximum rate of polymerization shrinkage and peak time(AF:R=-0.933, Zl:R=-0.892, SF:R=-0.883), and a significant positive correlation between the maximum rate of polymerization shrinkage and square root of the light intensity (AF:R=0.988, Zl:R=0.974, SF:R=0.946). Discussion and Conclusions : The polymerization rate of composite resins used in this study was proportional to the square root of light intensity Maximum rate of polymerization shrinkage as well as peak time can be used to compare the polymerization rate. Real-time volume method using IB system can be a simple alternative method to obtain the polymerization rate of composite resins.

• 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.

• Proceedings of the Korea Crystallographic Association Conference
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• 2002.11a
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• pp.53-53
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• 2002

Alkali-soluble random copolymer (ASR) was used as a functional resin in the emulsion polymerization of styrene to prepare structured nanoparticles. The calorimetric technique was applied to study the kinetics of emulsion polymerization of styrene using ASR and conventional ionic emulsifier, sodium dodecyl benzene sulfonate (SDBS). ASR could form aggregates like micelles and the solubilization ability of the aggregates was dependent on the neutralization degree of ASR. The rate of polymerization in ASR system was lower than that in SDBS system. This result can be explained by the creation of a hairy ASR layer around the particle surface, which decreases the diffusion rate of free radicals through this region. Although a decrease in particle size was observed, the rate of polymerization decreased with increasing ASR concentration. The higher the concentration of ASR is, the thicker and denser ASR layer may be, and the more difficult it would therefore be for radicals to reach the particle through this layer of ASR. The rate of polymerization decreased with increasing the neutralization degree of ASR. The aggregates with high neutralization of ASR are less efficient in solubilizing the monomer and capturing initiator radicals than that of the lower neutralization degree, which leads to decrease in rate of polymerization.

• Journal of the Korean Chemical Society
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• v.62 no.3
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• pp.191-202
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• 2018

The aim of this work is to study Monte Carlo simulation of ethylene (co)polymerization over Ziegler-Natta catalyst as investigated by Chen et al. The results revealed that the Monte Carlo simulation was similar to sum square error (SSE) model to prediction of stage II and III of polymerization. In the case of activation stage (stage I) both model had slightly deviation from experimental results. The modeling results demonstrated that in homopolymerization, SSE was superior to predict polymerization rate in current stage while for copolymerization, Monte Carlo had preferable prediction. The Monte Carlo simulation approved the SSE results to determine role of each site in total polymerization rate and revealed that homopolymerization rate changed from site to site and order of center was different compared to copolymerization. The polymer yield was reduced by addition of hydrogen amount however there was no specific effect on uptake curve which was predicted by Monte Carlo simulation with good accuracy. In the case of copolymerization it was evolved that monomer chain length and monomer concentration influenced the rate of polymerization as rate of polymerization reduced from 1-hexene to 1-octene and increased when monomer concentration proliferate.

• 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.

• Macromolecular Research
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• v.13 no.3
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• pp.187-193
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• 2005

The TEMPO-mediated living free-radical bulk and dispersion polymerization of styrene in the presence of camphorsulfonic acid (CSA) are investigated. In the absence of TEMPO and CSA in the bulk polymerization, a conversion of $93\%$ is achieved within 6 hr of polymerization. When only TEMPO is involved in this polymerization, the pseudo-living free-radical polymerization is well achieved, however, the polymerization rate becomes quite slow. This retardation of the polymerization rate is solved by the addition of a low concentration of CSA. In the TEMPO-mediated dispersion polymerization in the presence of CSA, similar trends in the conversion, kinetics, and PDI are observed as those observed in the case of bulk polymerization. When only TEMPO is used in the dispersion polymerization, the resulting particle size becomes quite broad, due to the prolonged polymerization time. However, when a 1.0 molar ratio of CSA to TEMPO is added to the TEMPO-mediated dispersion polymerization, fairly mono-disperse PS microspheres having an average size of 5.83 $\mu$m and a CV of 3.4$\%$ are successfully obtained, due to the narrow molecular weight distribution of the intermediate oligomers and shortening of the polymerization time. This result indicates that the addition of CSA to the TEMPO-mediated bulk and the use of dispersion polymerization not only shortens the polymerization time, but also greatly improves the uniformity of the microspheres.

• Journal of Technologic Dentistry
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• v.35 no.2
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• pp.127-136
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• 2013

Purpose: In order to find out the impact of changes in polymerization conditions of orthodontic acrylic resin on maximum load. Methods: While maintaining mixing ratio 3:1 of polymer and monomer in spray-on way in the production condition of polymerization temperature $25^{\circ}C$ or $37^{\circ}C$ for 10 minutes or 30 minutes of polymerization time by pressure $3kfg/cm^2$ or $6kfg/cm^2$ in the lab maintaining $25^{\circ}C$ of room temperature, the change in maximum load rise rate was tested by producing 5 acrylic resin specimens for orthodontics per group to meet the standards of $25mm{\times}2mm{\times}2mm$ and using INSTRON with the 3rd bar 2mm in diameter and parallel support bending device of $15{\pm}0.1mm$ as test equipment showing 30.00mm/min of crosshead speed, $50{\pm}16$ N/min of load ratio in the laboratory of $24^{\circ}C$ room temperature and as a result, the following results were obtained. Results: 1. When increasing pressure from $3kfg/cm^2$ to $6kfg/cm^2$, maximum load was lowered by -4.285%. 2. When increasing polymerization time from 10 minutes to 30 minutes, maximum load rose by 3.848%. 3. When increasing polymerization temperature from $27^{\circ}C$ to $37^{\circ}C$, maximum load rose by 5.854%. Conclusion: Considering the above test results that polymerization time and polymerization temperature when polymerizing acrylic resin for orthodontics according to changes in working conditions had an impact on the rate of rise of maximum load values but the rate of rise was lowered when increasing pressure from $3kfg/cm^2$ to $6kfg/cm^2$, we came to a conclusion that high pressure more than necessary does not affect the rate of rise of maximum load.

• Journal of the Korean Chemical Society
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• v.19 no.1
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• pp.53-64
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• 1975

The polymerization of methyl methacrylate initiated by cobalt(II) chloride in tetrahydrofuran has been studied. The conversion was increased liearly with polymerization time at initial stage of 6${\sim}$7% conversion and then the rate of polymerization was slightly reduced, and after that the autoacceleration was observed. The rate of polymerization was increased with the concentration of cobalt(Ⅱ) chloride, but at the concentration of cobalt(II) chloride higher than $3.4{\times}10^{-4}$ mole/l the rate of polymerization was decreased. The rate of polymerization was dependent on the 1.38 power of the concentration of methyl methacrylate. The effect of the radical inhibitor DPPH was observed and the inhibition time was increased with the concentration of DPPH. The apparent overall activation energy was calculated to be 13.2 kcal/mole. In the copolymerization of methyl methacrylate ($M_1$) and styrene ($M_2$), the monomer reactivity ratio was found to be $r_1$ = 2.35, $r_2$ = 0.78. From the above results. the initiation mechanism of polymerization was discussed and it was considered that the polymerization proceeds mainly via diradical mechaism.

• Macromolecular Research
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• v.14 no.3
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• pp.338-342
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• 2006

The kinetic features of polymerization with an active site comprising cobalt dihalides ($CoX_2$, where X=Cl, Br, I) activated by methylaluminoxane (MAO) were investigated in 1,3-butadiene polymerization. The catalytic system exhibited the characteristic features of living polymerization. The initiation ($k_i$) and propagation ($k_p$) rate coefficients were estimated using the kinetic model for slow initiation previously reported by Shiono et al. The energy of activation fur the propagation reaction was calculated to be 27-30 $kJmol^{-1}$. The marked changes in reaction rate observed with different halides could be adequately described in terms of variations in the initiation process, with the same Arrhenius curve fitting propagation rate coeffcients estimated from all three halides, suggesting that the halide does not participate in the growing chain end.