• 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.

• Macromolecular Research
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• 제12권1호
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• pp.32-37
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• 2004

The atom transfer radical polymerization (ATRP) of hexadecyl acrylate (HDA) was carried out in Ν,Ν-dimethylformamide (DMF) in the presence of CuSCN/Ν,Ν,Ν′,Ν"Ν"-pentamethyldiethylenetriamine (PMDETA). The results indicate that the polymerization is well-controlled: a linear increase of molecular weights occurs with respect to conversion and the polydispersities are relatively low. In particular, the use of CuSCN as the catalyst resulted in faster polymerization rates for hexadecyl acrylate than did those using either CuBr or CuCl; the polydis-persity, however, was larger than those obtained in the cases when CuBr and CuCl were used. In addition, we report the thermodynamic data and activation parameters for the solution ATRP of hexadecyl acrylate.

• 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.

• Macromolecular Research
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• 제17권8호
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• pp.557-562
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• 2009

The free radical polymerization of styrene was initiated with azobis(isobutyronitrile) in the presence of benzene sulfonyl chloride. Analysis of the terminal structures of the obtained polystyrene with $^1H$ NMR spectroscopy revealed the presence of a phenyl sulfonyl group at the ${\alpha}$-end and a chlorine atom at the ${\omega}$-end of each polystyrene chain. The terminal chlorine atom in the polystyrene chains was further confirmed through atom transfer radical polymerization (ATRP) of styrene and methyl acrylate using the obtained polystyrenes as macroinitiators and CuCl/2,2'-bipyridine as the catalyst system. GPC traces of the products obtained in ATRP at different reaction times were clearly shifted to higher molecular weight direction, indicating that nearly all the macroinitiator chains initiated ATRP of the second monomers. In addition, the number-average molecular weights of the polystyrenes increased directly proportional to the monomer conversions, and agreed well with the theoretical ones.

• Bulletin of the Korean Chemical Society
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• 제24권4호
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• pp.521-523
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• 2003

• Macromolecular Research
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• 제10권6호
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• pp.339-344
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• 2002

Poly(vinyl alcohol-b-styrene) (poly(VA-b-St)) diblock copolymer containing high syndiotactic poly (vinyl alcohol) (PVA) was synthesized by the saponification of poly(vinyl pivalate-b-styrene) (poly(VPi-b-St)). For the block copolymer, poly(vinyl pivalate) (PVPi) with trichloromethyl end group was obtained via telomerization of vinyl pivalate with carbon tetrachloride as a telogen and 2,2-azobisisobutyronitrile (AIBN) as an initiator. Then resulting poly(vinyl pivalate) with trichloromethyl end group was used as an effient macroinitiator for the synthesis of poly(VPi-b-St) using atom transfer radical polymerization (ATRP) in the presence of CuCl/2,2'-bipyridine at 130 $^{\circ}C$. The poly(vinyl pivalate) macroinitiator, poly(VPi-b-St), poly(VA-b-St) were characterized by GPC, FT-IR and $^1$H-NMR. And the analysis showed that integrity of the block copolymer was maintained during saponification reaction.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.897-906
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• 1998

A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.324-324
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• 2006

In copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) with various ratios of MA to MMA and $[CuCl]/[PMDETA]/[PVAc-CCl_{3}]$ catalyst system in bulk at $80^{\circ}C$ via ATRP, several terpolymer with different copolymer composition, were synthesized. The atom transfer radical copolymerization of MA and MMA with macroinitiator, is very sensitive to molecular weight and its distribution. In this work it was possible to calculate the molecular weight of the terpolymers and show that it is close to the experimentally determined number average molecular weight from GPC.

• 멤브레인
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• 제18권2호
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• pp.132-137
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• 2008

폴리비닐리덴플로라이드(PVDF) 지지체 위에 빗살모양의 술폰화된 공중합체를 코팅하여 나노 분리막을 제조하였다. 빗살모양의 공중합체는 원자전달 라디칼 중합법(ATRP)에 의해 제조하였으며, 폴리비닐클로라이드의 주사슬과 폴리스티렌 술폰산(PSSA)의 곁사슬로 구성되어 있다. 핵자기 공명법($^1H$-NMR), FT-IR분광학 그리고 WAXS 분석법에 의해 공중합체가 성공적으로 합성되었음을 확인하였다 PVC-g-PSSA로 구성된 복합 나노 분리막은 PSSA의 함량이 증가함에 따라 플럭스와 배제율 모두 증가하였다. 이러한 성능 향상은 분리막의 술폰산의 함량의 증가로써 설명할 수 있다. PSSA가 71wt%첨가된 나노 복합막의 배제율은 $Na_2SO_4$ 88%, NaCl 33%을 나타내었고, 플럭스는 $Na_2SO_4$ 26, NaCl $34L/m^2 h$을 각각 나타내었다.

• 농업과학연구
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• 제11권2호
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• pp.315-321
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• 1984

0.1M tetraethylammoniumperchlorate (TEAP)를 지지전해질로 한 acetonitrile속에서 direct current (DC), differential pulse (DP) polarography 및 cyclo voltammetry (CV) 방법에 의한 Sumithion의 전기화학적 환원반응은 -1.0~-2.50volt vs. Ag-AgCl 범위에서, 제1단계로 P-Oph 결합의 분열에 의하여 dimethylthiophosphonyl radical과 p-nitro-m-cresol이 생성되는 1전자 유사가역반응이 일어나고, 제2단계는 전형적인 1전자 비가역 반응으로 dimethylthiophosphonyl radical이 dimethylthiophosphonate가 되며, 제3단계 반응은 2.7volt vs. Ag-AgCl의 높은 음전위에서 p-nitro-m-cresol은 4전자 비가역반응에 의한 nitro group의 환원으로 p-hydroxy-amino-m-cresol이 생성되는 총 3단계의 비가역적인 electron-transfer chemical reaction (EC) 메카니즘으로 전극반응이 진행됨을 알았다.