• Macromolecular Research
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• 제15권1호
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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.

• 대한화학회지
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• 제22권6호
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• pp.423-430
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• 1978

트리옥산을 니트로벤젠 용매중에서 Ti$Cl_4$로서 중합시킬때 개시 반응기구를 연구하였다. 중합반응속도를 측정한결과 미량의 물이나 메탄올을 첨가하면 반응속도가 급격히 감소하였으며 중합을 개시하는 데는 조촉매로서 다른 물질이 필요 없음이 알려졌다. 유전상수 측정결과에 의하면 중합과정중 양성이온이 생기지 않으며 중합제나 개시제 용액의 전기전도도를 측정한 결과 개시 반응은 니트로벤젠 용매중에서 개시제가 동종간 주고 받기반응에 의하여 생긴 Ti$Cl_3^+$ 양이온에 의하여 일어난다는 것이 판명되었다.

• 한국잠사곤충학회지
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• 제34권1호
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• pp.49-56
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• 1992

반응개시제로 potassium persulfate를 사용하여 견섬유에 MAA를 처리하였을 때의 반응 mechanism을 구명하기 위하여, 열분석과 일련의 기구분석을 행하였으며, 이 중 열분석에 의해 얻어진 결과는 다음과 같다. Differential scanning calorimeter 관찰로부터는 metharcrylamide에 의한 가공견섬유는 견 fibroin과 methacrylamide polymer의 열분석에 의한 peak가 뚜렷하게 분리되어 나타났으며, 가공율이 증가함에 따라 두 peak가 모두 고온측으로 이동하는 것으로 나타났다. 가공견섬유의 흡습율은 가공율이 증가함에 따라 증가하였다.

• 한국잠사곤충학회지
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• 제34권2호
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• pp.32-40
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• 1992

반응개시제로 potassium persulfate를 사용한 MAA 가공견섬유에 대하여 열분석, IR spectrum, 아미노산 분석, 전자현미경 등의 기기분석을 통하여 반응 mechanism에 대하여 구명하고자 하였다. IR spectroscopy 분석에서 가공견섬유의 peak은 미가공견섬유와 MAA polymer의 peak을 모두 가지고 있으며, 특이한 peak의 변화는 관찰할 수 없었다. 아미노산 분석에서는 vinyl monomer가 graft된다는 종래의 특정 아미노산의 함량에 있어서, 가공률의 증가에 따른 변화를 관찰할 수 없었으며, MAA 가공견섬유의 중합 mechanism은 styrene 및 MMA의 graft 가공에서와는 일치하지 않는 것으로 나타났는데, 이는 monomer, 개시제, 반응조건에 따라 반응에 관여하는 아미노산이 다른 것으로 추정된다. SEM 관찰에서는 가공률이 낮은 경우의 섬유표면은 미가공견섬유의 표면과 그 차이를 인정할 수 없었으나, 가공률이 증가함에 따라 섬유표면에 섬유축방향으로 줄무늬가 형성되는 것을 관찰할 수 있었다. 이상의 관찰과 앞서 발표한 열분석 결과를 종합하면, potassium persulfate를 반응개시제로한 MAA 가공견의 중합기구에 대해서는 DSC나 IR spectroscopy에 의한 관찰로는 중합기구를 정성정량적으로 분석하기는 힘든 것으로 나타났으며, 아미노산 분석결과로부터 이미 styrene이나 MMA 가공견의 grafting site로 알려 져 있는 Gly, Ala, Ser, Tyr, Thr, Met 및 염기성 아미노산 등의 특정 아미노산에 선택적으로 graft되는 경향을 인정할 수 없으므로 이는 graft 중합에 의해 결합되는 것이라기보다 단지 섬유내부중합에 의해 polymer가 섬유내부에 형성되는 것으로 추정된다. 현미경관찰에서도 polymer는 주로 섬유내에 형성되며, 무게증가율이 큰 경우에는 섬유의 표면에 MAA에 의한 특징적인 줄무늬의 형성을 관찰할 수 있었다.

• Elastomers and Composites
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• 제14권4호
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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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• 제8권4호
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• pp.147-152
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• 2000

The activity of periodic acid as an initiator for the polymerization of acrylamide in aqueous medium was investigated. The rate of polymerization was found to be proportional to the monomer concentration to the 1.5th power in the range of 1.41-5.64 mol/L. The reaction order to the periodic acid concentration was 0.49, which indicated a bimolecular mechanism for the termination reaction in the range of 0.5-4.0$\times$10$\^$-2/ mol/L. Propagation rate increased with raising the temperature according to an Arrhenius expression resulting in the exhibition of an apparent activation energy of 87.8 kJ/mol in the temperature range of 60-80$\^{C}$. The addition of hydroquinone as a radical scavenger stopped the polymerization of acrylamide initiated by periodic acid. These results support that the polymerization proceeds via a radical chain mechanism .

• The Korean Journal of Physiology and Pharmacology
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• 제26권3호
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• pp.175-182
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• 2022

Translocation of azurophil granules is pivotal for bactericidal activity of neutrophils, the first-line defense cells against pathogens. Previously, we reported that lysophosphatidylcholine (LPC), an endogenous lipid, enhances bactericidal activity of human neutrophils via increasing translocation of azurophil granules. However, the precise mechanism of LPC-induced azurophil granule translocation was not fully understood. Treatment of neutrophil with LPC significantly increased CD63 (an azurophil granule marker) surface expression. Interestingly, cytochalasin B, an inhibitor of action polymerization, blocked LPC-induced CD63 surface expression. LPC increased F-actin polymerization. LPC-induced CD63 surface expression was inhibited by both a Rho specific inhibitor, Tat-C3 exoenzyme, and a Rho kinase (ROCK) inhibitor, Y27632 which also inhibited LPC-induced F-actin polymerization. LPC induced Rho-GTP activation. NSC23766, a Rac inhibitor, however, did not affect LPC-induced CD63 surface expression. Theses results suggest a novel regulatory mechanism for azurophil granule translocation where LPC induces translocation of azurophil granules via Rho/ROCK/F-actin polymerization pathway.

• 대한전기학회논문지
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• 제36권1호
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• pp.29-35
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• 1987

TPolystyrene thin films are prepared by glow discharge of sytrene monomer vapor th establish the growth mechanism of organic thin films by the plasma polymerization. As the discharge parameters, discharge current(5mA-20mA), frequency (10kHz-50kHz, 13.56MHz), gaspressure (0.2torr-1.5torr), and discharge time(2min-12min)are adopted. Plasma-polymerized filmsof styrene vapor are identified as polystyrene by IR spectra. The thickness of plasma-polymerized films increases with gas pressure, frequency and discharge current in the region of the low frequency and below the allowed gas pressure where the polymerization occurs. It is suggested that the growth mechanism can be explained by ionic reaction in d.c. and low frequency region, and by radical reaction in high frequency region.

• Bulletin of the Korean Chemical Society
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• 제20권11호
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• pp.1269-1276
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• 1999

Metallocenes, whether using a cocatalyst or not, act as catalysts in ethylene polymerization. The positive charge on the transition metal of a metallocene might have an important role in polymerization as an active site in our model approach. Using semiempirical calculations in the absence of cocatalyst, we show one of the possibilities that the positive charge on a metallocene might be more easily transferred through the Cp ring of a ligand to the ethylene than to transfer directly from the transition metal to the ethylene. In these calculations, the charge on titanium in an eight C2H4 system is transferred and a polymer chain is produced. This reaction takes place only when ethylenes are arranged in a particular direction with respect to the ring, but does not take place for ethylenes near Ti or Cl atoms. The same mechanism is shown for a metallocene ligand which is sterically hindered or where the Cp ring is replaced by fluorenyl. These results suggest an entirely new polymerization mechanism in the absence of a cocatalyst in which the Cp ring is the active site.

• Elastomers and Composites
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• 제33권4호
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• pp.255-266
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• 1998

본 연구는 한대의 modular 치합형 동방향회전 이축 압출기에서 음이온 중합 mechanism을 이용하여 Lauryl lactam 단량체의 고분자합성 도중 EPDM을 투입하여 연속적 중합을 수행한 연구이다. PA 12의 반응 도중 EPDM과 반응블렌드(reactive blend)를 하고 기계적블렌드와 그 물성을 비교 측정하였다.