• Restorative Dentistry and Endodontics
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• v.26 no.1
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• pp.86-94
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• 2001

기존의 광중합기는 높은 광강도를 제공함으로써 광중합 복합레진을 최대한 단축된 시간내의 중합을 목표로 하였다. 이러한 높은 광강도는 복합레진의 중합깊이, 중합률면에서는 우수하나 중합 반응속도가 빠름으로 인해 중합시 응력 발생이 높아진다는 일련의 보고가 있다. 최근에는 광중합 속도를 늦춤으로써 변연적합도 및 중합시 응력 발생을 낮추는 새로운 중합방법들이 제시되고 있다. 이에 본 실험에서는 광조사 강도의 변화가 광중합 복합레진의 중합반응 과정에 미치는 영향 및 중합된 복합레진의 중합률에 대한 영향을 분석하고자 하였다. 5개의 혼합형 광중합 복합레진 (Z-100, Spectrum, Z-250, Clearfil AP-X, P-60)을 사용하였으며 중합시 적용된 광조사 강도에 따라 6개의 실험군으로 정의하였다. 실험군과 이에 따른 광조사 방법은 다음과 같다. 1군은 110mW/$\textrm{cm}^2$로 40초 중합, 2군 210mW/$\textrm{cm}^2$로 40초 중합, 3군 410mW/$\textrm{cm}^2$로 40초 중합, 4군 620mW/$\textrm{cm}^2$로 40초 중합, 5군 110mW/$\textrm{cm}^2$로 10초 중합 후 1분 뒤 620mW/$\textrm{cm}^2$로 30초 중합, 6군 210mW/$\textrm{cm}^2$로 10초 중합 후 1분 뒤 410mW/$\textrm{cm}^2$로 30초 중합하였다. 광중합시 중합 반응 양상에 관한 분석은 시차주사 열계량기를 이용하여 37$^{\circ}C$ 항온상태에서 10분간의 열흐름곡선을 기록하였다. 기록된 열흐름곡선에서 중합 반응시 나타나는 중합열 및 최대 중합열에 이르는 시간을 기록하여 중합반응 속도를 측정하였다. 중합된 복합레진의 중합률은 Fourier Transform Infrared Spectrometer(FTIR)를 이용하였으며 2mm 두께의 복합레진 하방에서의 중합률을 측정하였다. 측정된 결과는 ANOVA 및 Student-Newman-Keuls 방법을 이용하여 유의성을 검증하였다. 실험결과 다음과 같은 결론을 얻었다. 1. 광중합 복합레진 중합시 광조사 강도가 증가할수록 중합열은 증가하였으나 통계적 유의성은 보이지 않았다 (p>0.05). 2. 최대 중합열에 이르는 시간은 광조사 강도가 증가할수록 단축되었다. 이단계 중합방법을 사용한 경우 중합반응 속도를 감소시킬 수 있음을 보였다. 3. 광조사 강도가 증가할수록 중합률은 증가하였다. 이단계 중합방법을 사용한 경우 연속적인 고광강도를 사용한 경우와 유사한 높은 중합률을 보였다. 4. 중합률면에서 광중합복합레진의 중합시 400mW/$\textrm{cm}^2$ 이상의 광강도가 필요한 것으로 나타났다.

• Polymer(Korea)
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• v.27 no.5
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• pp.421-428
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• 2003

The kinetics of photoinitiated polymerization of reactive oligomer methacrylates and oligomer methacrylate/SBS blends have been studied to characterize the diffusion-controlled reaction using Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (ATR-FTIR). The polymerization rates of reactive oligomer methacrylates and oligomer methacrylate/SBS blends were autocatalytic in nature at the initial stage and then a retardation of the reaction conversion occurred gradually as the polymer matrix became vitrified, and finally the reaction became diffusion controlled. Photopolymerization behavior of methacrylate/SBS blends was well predicted using the diffusion-controlled reaction model. N-Vinyl-2-pyrrolidinone (NVP) as a reactive solvent was used to incorporate SBS into methacrylate to form semi-IPN via photopolymerization. Due to the high reactivity of NVP, polymerization rate increased with the increase of NVP content. As the content of NVP-SBS in the blends increased up to 10 phr, the reaction conversion maintained almost constant. But above 20 phr of NVP-SBS in the blends, the reaction conversion gradually decreased since the increase of viscosity affected on the photopolymerization rate. The semi-IPN films of methacrylate/SBS blends were transparent at room temperature as well as at increased temperature and were able to be applied to surface coating.

• Journal of the Korean Chemical Society
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• v.22 no.6
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• pp.423-430
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• 1978

The initiation mechanism of trioxane polymerization catalyzed by Ti$Cl_4$ in nitrobenzene was investigated. The kinetic studies revealed that the rate of polymerization was drastically decreased by the addition of a minute amount of water or methanol. A third substance as cocatalyst was not required for the polymerization. Measurements of dielectric constants gave no evidence for the zwitterionic mechanism of the polymerization. The electric conductivity measurements of polymerization system and the initiator solution showed that the initiation was started by Ti$Cl_3^+$ cation, formed by a disproportionation of the initiator in nitrobenzene.

• Journal of the Korean Chemical Society
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• v.25 no.4
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• pp.214-218
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• 1981

Kinetic studies were carried out on urethane polymerization reaction of hydroxyl-terminated polybutadiene with isophorone diisocyanate under presence of Hexogen as solid additive. The rate was found to increase with the amount of Hexogen added. However the rate acceleration was not a catalytic effect but solely due to an increase of activation entropy. The reaction was a good 2nd order process with nearly constant activation energy of 8.4 kcal/mole.

• Journal of the Korean Chemical Society
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• v.22 no.4
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• pp.268-274
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• 1978

The kinetics of the bulk polymerization of propylene sulfide initiated by o-sulfobenzoic anhydride were investigated, which proceeded by a zwitterionic mechanism.The instantaneous concentrations of monomer and initiator were determined by means of ir-and nmr-spectroscopy. The rate constant of propagation was found to be about three order of magnitude higher than that of initiation and this should be caused by a zwitterion mechanism.

• 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.

• 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.

• Applied Chemistry for Engineering
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• v.17 no.1
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• pp.33-36
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• 2006

The kinetics of photopolymerization of urethane-acrylate oligomer which has many applications in photopolymerizable adhesives was analysed to investigate the influence of polymerization temperature and functionality of oligomer using the autocatalytic model. It was revealed that the maximum polymerization rate decreased as the polymerization temperature increased. The reaction rate constant, k, showed little change with the increase in polymerization temperature, while exponents m and n exhibited an increase. These results could be related to the diffusion and mobility restriction of reactive species during the cross-linking reaction. The decrease in photopolymerization rate with increase of temperature was mainly controlled by the reaction order n.

• Applied Chemistry for Engineering
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• v.2 no.3
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• pp.199-208
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• 1991

Carbocationic polymerization is widely applied to prepare polymers from electron-rich monomers. The reaction is usually uncontrollable due to many side reactions and explosively fast rate of polymerization. In a living polymerization, however, the reaction is controlled as designed, and many workers reported many successful cases recently. In this review several ways of living carbocationic polymerization were illustrated, and they were connected together under a basic principle.

• Polymer(Korea)
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• v.24 no.1
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• pp.16-22
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• 2000

Poly(butylene terephthalate- co-oxybenzoate)(PBOT) containing mesogenic oxybenzoate units in the main chain was synthesized through ester exchange reaction by melt mixing of poly(butylene terephthalate)(PBT) and p-acetoxybenzoic acid (ABA). From the kinetics of the copolymerization reaction, the activation energies and the rate constants of homopolymerization and copolymerization, k$_{h}$ and k$_{c}$, could be determined. From the reaction conditions of different compositions, 4/6, 5/5, and 6/4 of PBT/ABA, at 250, 260, and 27$0^{\circ}C$, it was revealed that copolymerization between PBT and ABA proceeds on a pseudo-second order reaction if the ABA content and its conversion are low. In this case, the ratio of rate constants of homopolymerization to copolymerization was in the range from 1.08 to 3.17, indicating that the copolymer with more notable block character was obtained at the higher mole fraction of ABA and at higher temperature.e.e.