• 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.

• Journal of Industrial and Engineering Chemistry
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• 제68권
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• pp.1-5
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• 2018

In this study, we designed and synthesized novel thermal radical initiators of BTAP (1-phenyl-3,3-dipropyltriazene), BTACP (1-(phenyldiazenyl)pyrrolidine), BTACH (1-(phenyldiazenyl)piperidine), and BTACH7 (1-(phenyldiazenyl)azepane) based on a triazene moiety to provide a thermal initiator for radical polymerization. The synthetic method is valuable due to the simplicity. In addition, the synthesized thermal initiator did not affect the color of the polymer. Among the four initiators, the polymerization time for the BTACH of the 6-membered ring decreased by 67%, as opposed to the polymerization time without initiator. Conversion after polymerization was over 92%. DSC experiments also showed that the initiator with hexagonal rings had the lowest peak polymerization temperature of $160^{\circ}C$. Our study suggests a promising new initiator system that is effective for radical polymerization.

• 통합자연과학논문집
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• 제5권2호
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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.

• 접착 및 계면
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• 제2권2호
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• pp.11-19
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• 2001

트리카프릴메틸 암모니움 클로라이드를 상이동촉매로 사용하여 $Na_2S_2O_8$의 수용액과 톨루엔의 이상계에서 질소분위기하에 $60^{\circ}C$에서 스티렌의 라디칼중합을 행하였다. 중합시의 초기 중합속도는 촉매와 $Na_2S_2O_8$의 초기공급 농도보다는 수용액 상에서의 4급 암모늄양이온과 퍼록시디슬페이트 음이온의 농도로 나타낼 수 있었다. 관찰된 초기중합속도를 사용하여 분균일 액-액계에서의 순환 상이동에 의한 개시과정을 포함한 중함메카니즘을 밝힐 수 있었다. 폴리스티렌의 점도평균분자량은 $Na_2S_2O_8$의 농도에 역비례하였는데, 라디칼 중합메카니즘에 의하여 $[Q^+]([S_2O{_8}^{2-}]{\alpha}_2)^{1/2}$로 나타내어졌다.

• Macromolecular Research
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• 제14권5호
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• pp.539-544
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• 2006

2-Furancarboxaldehyde-2-pyridinylhydrazone (FPH) and 5-methyl-2-furancarboxaldehyde-2-pyridinylhydrazone (MFPH) were synthesized and used as tridentate ligands of copper (I) bromide for the atom transfer radical polymerization of methyl methacrylate (MMA) and styrene. The polymerization of methyl methacrylate achieved high conversion and yielded polymers with a good control of molecular weight and low polydispersity (PDI=1.33). Higher PDI were observed in the polymerization of styrene. Using 1-phenyl ethylbromide (PEBr) and ethyl 2-bromoisobutyrate (EBiB) as model compounds for the polymeric chain ends, the activation rate constants of the new catalytic systems were measured. These results were correlated with the polymerization results and compared with another catalytic system previously reported.

• Elastomers and Composites
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• 제39권4호
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• pp.281-285
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• 2004

이 연구는 열분석법을 이용하여 간단하게 자유 라디칼 중합의 활성화 에너지를 결정하는 방법을 부틸 아크릴레이트을 모델로 하여 구했다. 활성화 에너지는 Kissinger, Osawa 및 half-width법인 다수의 주사 속도법 (multiple scanning-rate method)을 이용하여 $1^{\circ}C/min,\;2^{\circ}C/min,\;5^{\circ}C/min$, 그리고 $10^{\circ}C/min$로 측정하였으며 단수 주사 속도법인 Barret 법을 이용하여 구하였다. 열분석법에 의해 구해진 중합반응의 활성화 에너지는 개시반응, 성장반응 및 종결반응의 각각의 활성화 에너지에서 계산된 전체 중합반응에서의 활성화 에너지와 가깝게 접근하였다.

• Macromolecular Research
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• 제15권4호
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• pp.302-307
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• 2007

The living radical polymerization of methyl methacrylate (MMA) by atom transfer radical polymerization, (ATRP) employing a $Fe(II)X_2/diphenyl-2-pyridyl$ phosphine (PyP) catalytic system (X=Cl, Br), was investigated using several initiators and solvents at various temperatures. Most of the polymerizations with the PyP ligand were well controlled, with a linear increase in the number average molecular weights ($M_n$) vs. conversion, with relatively low molecular weight distributions ($M_w/M_n=1.2-1.4$) throughout the reactions. The measured weights matched those of the predicted values. The ethyl-2-bromoisobutyrate (EBriB) initiated ATRP of MMA, with the $Fe(II)X_2/diphenyl-2-pyridyl$ phosphine catalytic system (X=Cl, Br), was better controlled in p-xylene at $80^{\circ}C$ than the other solvents used in this study.

• 한국응용과학기술학회지
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• 제26권3호
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• pp.306-316
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• 2009

In this study, block copolymer of polystyrene and polyethylene glycol methyl ether methacrylate(PEGMA) by ATRP(atom transfer radical polymerization) method was synthesized. 4 arm-molecule which contained halogen atom was synthesized for an initiator. With 4 arm-molecule monodispered polystyrene were synthesized by ATRP method. The molecular change of synthesized monodispersed polystyrene with respect to time was investigated and living polymer characteristic was confirmed. Block copolymer of polystyrene and polyethylene glycol methyl ether methacrylate(PEGMA) was synthesized by ATRP with macroinitiator which was synthesized from the monodispersed polystyrene(Mn=12000). The molecular weight of obtained PS-b-PEGMA was 22,000.

• 통합자연과학논문집
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• 제6권2호
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• pp.71-75
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• 2013

$Bu_3Sn$-endded poly(vinyl)s with biological activity were obtained by the radical polymerization of vinyl monomers using thianthrene cation radical/$^nBu_3H$. Thianthrene cation and stannyl radicals promoted the homopolymerization and copolymerization of styrene and ethyl vinyl ether having number average molecular weights of 2000-3100. Tributyltin hydride functions as a chain transfer agent. Such polymereization by cationic thianthrene and stannyl radicals could provide some clues for the biological reaction in living animals. Plausible polymerization mechanisms were suggested.

• Macromolecular Research
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• 제13권3호
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• pp.236-242
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• 2005

Three dithioester-derived carboxyl acid functionalized RAFT(reversible addition-fragmentation chain transfer) agents, viz. acetic acid dithiobenzoate, butanoic acid dithiobenzoate and 4-toluic acid dithiobenzoate, were used in the RAFT bulk polymerization of styrene, in order to study the effects of the R-group structure on the living nature of the polymerization. By conducting the polymerization with various concentrations of the RAFT agents and at different temperatures, it was found that the R-group structure of the RAFT agents plays an important role in the RAFT polymerization; the bulky structure and radical stabilizing property of the R-group enhances the living nature of the polymerization and allows the polymerization characteristics to be well controlled.