• Title/Summary/Keyword: ATRP

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Synthesis of block copolymer of polystyrene and polyethylene glycol methyl ether methacrylate(PEGMA) by ATRP (atom transfer radical polymerization) (ATRP(atom transfer radical polymerization)에 의한 polystyrene과 poly ethylene glycol methyl ether methacrylate(PEGMA)의 블록 공중합체의 합성)

  • Kim, Sang-Hern
    • Journal of the Korean Applied Science and Technology
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    • v.26 no.3
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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.

Atom Transfer Radical Polymerization of [Poly(ethylene glycol)methyl ether] Methacrylate Using an Amide-Based Initiator (아미드기를 가지는 개시제를 이용한 [Poly(ethylene glycol)Methyl Ether] Methacrylate의 원자 이동 라디칼 중합)

  • Lee, Hyo-Kyung;Lee, Sun-Gu;Paik, Hyun-Jong
    • Polymer(Korea)
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    • v.31 no.6
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    • pp.550-554
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    • 2007
  • Atom transfer radical polymerization (ATRP) has been widely used in bioconjugation as it is an efficient and facile method to prepare polymers with pre-designed structures. Quite often, bioconjugation with proteins employs primary amines in proteins as a functional group to attach an initiator. When 2-bromoisobutryl bromide, the most widely used precursor for ATRP initiator, is used, ${\alpha}-halo$ amide initiating groups are formed in the proteins, which are known to exhibit slow initiation behavior in the ATRP process. Here we studied the ATRP of [poly(ethylene glycol)methyl ether] methacrylate (PEGMA) using amide-based initiator. PEGMA differs for both the nature and size of the polymer side branches and shows good solubility in water and a property that made it an ideal candidate for biomaterials. While normal ATRP produced ill-defined p(PEGMA) with amide based initiators, the halogen exchange method and the external additional of deactivator effectively improved the control of ATRP of PEGMA.

Synthesis and Characterization of Low Molecular Weight Poly(methyl acrylate)-b-Polystyrene by a Combination of ATRP and Click Coupling Method

  • Hasneen, Aleya;Kim, Su-Jeong;Paik, Hyun-Jong
    • Macromolecular Research
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    • v.15 no.6
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    • pp.541-546
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    • 2007
  • The combination of atom transfer radical polymerization (ATRP) and click chemistry was employed for the efficient preparation of well-defined block copolymers. Bromo terminated poly(methyl acrylate) (pMA-Br) was prepared by an ATRP initiator, ethyl-2-bromoisobutyrate (EBiB). Subsequently, the bromine chain end of pMA-Br was converted to an azide group by simple nucleophilic substitution reaction. ${\alpha}-Alkyn-{\omega}-bromo-functionalized$ polystyrene was also synthesized by ATRP using the alkyn-functionalized initiator, propargyl-2-bromoisobutyrate (PgBiB). In both cases, the conversion was limited to a low level to ensure a high degree of chain end functionality. Then the coupling reaction between the azide end group in $pMA-N_3$ and alkyn-functionalized PgBiB-pSt was performed by Cu(I)catalysis. This coupling reaction was monitored by gel permeation chromatography (GPC). The synthesized block copolymer was characterized by FT-IR, $^1H-NMR$ spectroscopy and $^1H-^1H$ COSY correlation spectroscopy.

Covalent Functionalization of Carbon Nanotubes using Atom Transfer Radical Polymerization

  • Paik, Hyun-Jong
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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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.

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Effect of Multi-wall Carbon Nanotube Surface Treatment on the Interface and Thermal Conductivity of Carbon Nanotube-based Composites (다중벽탄소나노튜브 복합재료의 계면 및 열전도도에 표면처리 방법이 미치는 영향)

  • Yoo, Gi-Moon;Lee, Sung-Goo;Kim, Sung-Ryong
    • Journal of Adhesion and Interface
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    • v.11 no.4
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    • pp.174-180
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    • 2010
  • The effect of carbon nanotube surface treatment on the interface and thermal conductivity of carbon nanotube-based poly(methylmethacrylate) (PMMA) composites was investigated. Coagulation and atomic-transfer radical polymerization (ATRP) was applied to modify the surface of multi-wall carbon nano-tube. The composite of ATRP method used carbon nanotube showed the higher transparency and thermal conductivities than that of the coagulation method used. In comparison to the thermal conductivity of pure PMMA, 0.21 W/mK, the ATRP carbon nanotube used PMMA/MWNT composite showed a thermal conductivity of 0.38 W/mK. The interface between carbon nanotube and PMMA was observed by scanning electron microscope and uniform dispersion of carbon nanotube was observed without any void in the PMMA matrix. It may be beneficial to transport the phonon without any scattering and it may result in a higher thermal conductivity.

Synthesis of High Molecular Weight 3-Arm Star PMMA by ARGET ATRP

  • Jeon, Hyun-Jeong;Youk, Ji-Ho;Ahn, Sung-Hee;Choi, Jin-Hwan;Cho, Kwang-Soo
    • Macromolecular Research
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    • v.17 no.4
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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.

Investigation on Chain Transfer Reaction of Benzene Sulfonyl Chloride in Styrene Radical Polymerization

  • Li, Cuiping;Fu, Zhifeng;Shi, Yan
    • Macromolecular Research
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    • v.17 no.8
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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.

Effect of Polymerization Condition on Atom Transfer Radical Copolymerization Behaviors of Styrene with Methyl Acrylate (스티렌과 메틸아크릴레이트의 원자 이동 라디칼 공중합에서 중합조건에 따른 중합 특성 연구)

  • Song, Seon-Ja;Ko, Young Soo
    • Korean Chemical Engineering Research
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    • v.49 no.5
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    • pp.676-680
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    • 2011
  • Investigated was the effect of the crucial polymerization conditions such as methyl acrylate(MA) mole fraction in feed, polymerization temperature and time on Atom Radical Transfer Polymerization(ATRP) behavior of styrene and methyl acrylate(MA). As MA mole fraction in feed increased, molecular weight(MW) of the resulting copolymer increased. At polymerization time of 3 hrs the composition of MA in the resulting copolymer was shown to have a linear relationship with the mole fraction of MA in feed. MW was increased and the composition of MA in copolymer was decreased as the polymerization time increased, showing the characteristics of ATRP. MW was also increased as polymerization temperature increased, and the composition of MA in copolymer was shown to be increased drastically at polymerization temperature of $110^{\circ}C$.