• 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.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.196-197
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• 2006

Among various polymerization methods to graft polymers on the surface of CNTs, Atom Transfer Radical Polymerization (ATRP) has several advantages, such as a wide range of polymerizable monomers and superb control in molecular structure and weights. Several research groups including us have showed that ATRP is an efficient and versatile method to modify the surface of CNTs. Here, two independent approaches for the covalent attachment of polymers based on ATRP graft-from and graft-onto methods will be discussed.

• 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.

• 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.

• 폴리머
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• 제35권5호
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• pp.395-401
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• 2011

원자이동 라디칼중합(atom transfer radical polymerization: ATRP) 반응을 이용하여 poly(methyl methacrylate)(PMMA)와 poly((2-dimethyl amino)ethyl methacrylate)(PDMAEMA) 등의 아크릴계 고분자가 각각 multi-walled carbon nanotube(MWNT) 표면에 그래프팅된 MWNT/PMMA 및 MWNT/PDMAEMA 나노복합체를 제조하였다. FTIR과 XRD 분석을 통하여 나노복합체에 존재하는 아크릴계 고분자의 특성피크를 확인하였으며 열중량분석법(TGA) 가열감량 곡선 분석을 통하여 ATRP 반응의 라디칼 리빙성이 유지됨을 확인하였다. 투과전자현미경(TEM)분석을 통하여 아크릴계 고분자가 MWNT에 그래프팅된 나노복합체의 형태(morphology)를 확인하였으며 Raman 분광분석을 수행함으로써 MWNT/PMMA 및 MWNT/PDMAEMA 나노복합체에서 고분자와 MWNT 사이에 공유결합이 형성되어 나타나는 스펙트럼 상의 D 밴드 및 G 밴드의 위치 및 세기 변화를 확인하였다.

• Korean Chemical Engineering Research
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• 제49권5호
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• pp.676-680
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• 2011

스티렌과 메틸아크릴레이트(methyl acrylate, MA)를 원자라디칼이동 중합(atom radical transfer polymerization, ATRP)에서 주요한 중합공정 조건인 투입되는 MA 몰분율, 중합 온도, 중합 시간이 미치는 영향을 조사하였다. MA 몰분율이 증가할수록 분자량은 증가하고 중합시간이 3시간일 때 중합용액의 초기 모노머 몰 비와 생성되는 고분자의 조성비가 거의 선형 관계를 갖는다. 중합시간이 증가함에 따라 공중합체의 분자량은 증가하고, 공중합체의 MA 조성비가 감소함을 알 수 있다. 이를 통해 스티렌-MA 공중도 ATRP의 리빙 라디칼 중합 특징을 보이고 있음을 알 수 있다. 중합온도가 증가함에 따라 공중합체의 분자량은 크게 증가하고, 특히 $110^{\circ}C$의 고온에서 공중합체 내에 MA 조성비가 크게 증가함을 볼 수 있다.

• Macromolecular Research
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• 제17권4호
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• pp.240-244
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• 2009

High molecular weight(MW), 3-arm star poly(methyl methacrylate)(PMMA) with a narrow MW distribution($M_n$=570,000 g/mol, PDI=1.36) was successfully synthesized by activators regenerated by electron transfer(ARGET) atom transfer radical polymerization(ATRP). The polymerization was carried out with a trifunctional initiator/$CuBr_2$/N,N,N',N",N"-pentamethyldiethy lenetriamine(PMDETA) initiator/catalyst system in the presence of a tin(II) 2-ethylhexanoate [$Sn(EH)_2$] reducing agent at $90^{\circ}C$. The concentration of the copper catalyst was as low as 30 ppm, and a high initiation efficiency of the initiating sites was obtained. The chain-end functionality of the high MW, 3-arm star PMMA was confirmed by a chain extension experiment with styrene via ARGET ATRP, using the same catalyst system.

• 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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• 제16권3호
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• pp.238-246
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• 2008

A new strategy using protection-deprotection chemistry was used to prepare branched polymers using the ATRP method only. Among the several monomers with different protecting groups, vinyl benzyl t-butyloxy carbonate (VBt-BOC) and 4-methyl styrene (4-MeSt) could be polymerized successfully to form backbones using the ATRP method in a controlled fashion. The protected groups in the backbones were converted to alkyl bromides and used as initiating sites for branch formation. The benzyl t-butyloxy carbonate groups in the backbones containing VBt-BOC units were first deprotected to benzyl alcohol by trifluoroacetic acid, then converted to benzyl bromide by reacting them with triphenylphosphine/carbon tetrabromide. The benzyl bromide groups in the backbones containing 4-MeSt units could be generated by bromination of the methyl groups using N-bromosuccinimide/benzoyl peroxide. The structures of the prepared polymers were well-controlled, as evidenced by the controlled molecular weight as well as the narrow and unimodal molecular weight distribution.