• Title/Summary/Keyword: ATRP

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Well-Defined Thermoresponsive Copolymers with Tunable LCST and UCST in Water

  • Jung, Seo-Hyun;Lee, Hyung-Il
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.501-504
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    • 2014
  • A thermoresponsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), was successfully synthesized by atom transfer radical polymerization (ATRP). Different amounts of 1,3-propanesultone were used as quaternization agent to transit the PDMAEMA into partially modified poly(zwitterions), resulting in p[DMAEMA-co-3-dimethyl(methacryloyloxyethyl)ammonium propanesulfonate] (PDMAEMA-co-PDMAPS). Molecular weight, molecular weight distribution, and degree of quarternization were determined by gel permeation chromatography (GPC) and 1H NMR spectroscopy. The transmission spectra of the 1.0 wt % aqueous solutions of the resulting polymers at 650 nm were measured as a function of temperature. Results showed that the lower critical solution temperature (LCST) and the upper critical solution temperature (UCST) could be easily controlled by the different composition of dimethylamino and zwitterion groups. The effect of partial quaternization on thermoresponsive properties was also studied by dynamic light scattering (DLS) with the same aqueous concentration (1.0 wt %) as employed for turbidimetry studies. The LCST and UCST values measured by DLS correlated well with those determined by turbidimetry.

Atom Transfer Radical Polymerization of Hexadecyl Acrylate Using CuSCN as the Catalyst

  • Xu, Wenjian;Zhu, Xiulin;Cheng, Zhenping;Chen, Jianying;Lu, Jianmei
    • Macromolecular Research
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    • v.12 no.1
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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.

Preparation of Branched Polystyrene Using Atom Transfer Radical Polymerization Techniques and Protection-Deprotection Chemistry

  • Kwark, Young-Je
    • Macromolecular Research
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    • v.16 no.3
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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.

Preparation of Poly(vinyl chloride)-graft-poly(styrene sulfonic acid) Composite Nanofiltration Membranes (폴리비닐클로라이드-그래프트-폴리스티렌 술폰산 복합 나노막 제조)

  • Kim, Jong-Hak;Park, Jung-Tae;Koh, Joo-Hwan;Roh, Dong-Kyu;Seo, Jin-Ah
    • Membrane Journal
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    • v.18 no.2
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    • pp.132-137
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    • 2008
  • Nanofiltration membranes were prepared based on coating a sulfonated comb-like copolymer layer on top of a poly(vinylidene fluoride) (PVDF) support. The comb-like copolymer comprising poly(vinyl chloride) backbone and poly(styrene sulfonic acid) side chains, i.e. PVC-g-PSSA was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. The successful synthesis of graft copolymers were confirmed by nuclear magnetic resonance ($^1H$-NMR), FT-IR spectroscopy and wide angle X-ray scattering (WAXS). Composite nanofiltration membranes consisting PVC-g-PSSA as a top layer exhibited the increase of both rejections and solution flux with increasing PSSA concentration. This performance enhancement is presumably due to the increase of SO3H groups and membrane hydrophilicity. The rejections of composite membranes containing 71 wt% of PSSA were 88% for $Na_2SO_4$ and 33% for NaCl, and the solution flux were 26 and $34L/m^2h$, respectively, at 0.3 MPa pressure.

4-Arm Star Shaped and Linear Block Copolymers for Copper Phthalocyanine Dispersion (4-Arm 스타형과 선형 블록 공중합체의 구리 프탈로시아닌 분산 연구)

  • Kim, Byoungjae;Jeong, Jonghwa;Jung, Ji-Hye;Kim, Bong-Soo;Jung, Ki-Suck;Paik, Hyun-Jong
    • Polymer(Korea)
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    • v.38 no.5
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    • pp.671-675
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    • 2014
  • Well-defined star shaped and linear block copolymers were synthesized to study the dispersion stability of copper phthalocyanine (CuPc). We synthesized dispersants using (2-dimethylamino) ethyl methacrylate (DMAEMA) and poly(ethylene glycol) methyl ether methacrylate) (PEGMA) by activators generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). pDMAEMA-b-pPEGMA copolymers were characterized by GPC and NMR. Furthermore, we studied the effect of the dispersion stability of copper phthalocyanine by controlling the degree of polymerization of PEGMA as a stabilizing group. The 4-arm star shaped polymeric dispersant showed better dispersion stability of CuPc at $25^{\circ}C$ for 7 days.

Preparation of Ag Nanoparticles by Templating Poly(vinyl chloride)-g-poly(styrene sulfonic acid) Graft Copolymer Membrane (Poly(vinyl chloride)-g-poly(styrene sulfonic acid) 가지형 공중합체막을 이용한 은 나노입자 제조)

  • Byun, Su-Jin;Seo, Jin-Ah;Chi, Won-Seok;Shul, Yong-Gun;Kim, Jong-Hak
    • Membrane Journal
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    • v.21 no.1
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    • pp.39-45
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    • 2011
  • An amphiphilic graft copolymer consisting of a poly(vinyl chloride) (PVC) backbone and poly(styrene sulfonic acid) (PSSA) side chains (PVC-g-PSSA) was synthesized via atom transfer radical polymerization (ATRP). This polymer electrolyte membrane was ion-exchanged to Ag ions by immersing in 10 wt% $AgNO_3$ aqueous solution and templated the growth of Ag nanoparticles by a reducing agent. The formation of Ag nanoparticles was confirmed using UV-visible spectroscopy and X-ray diffraction (XRD). Transmission electron microscopy (TEM) revealed that utilization of $NaBH_4$ was the most effective in the formation of Ag nanoparticles with 10~15 nm in size. The formation of Ag nanoparticles was also strongly affected by the concentration of reducing agent and reduction time.

Use of Amphiphilic Graft Copolymer as Dispersant for Carbon Nanotubes (양친성 그래프트 공중합체의 탄소나노튜브 분산제로의 이용)

  • Jeon, Ha-Rim;Ahn, Sung-Hoon;Chi, Won-Seok;Kim, Jong-Hak
    • Polymer(Korea)
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    • v.35 no.6
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    • pp.615-618
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    • 2011
  • Carbon nanotubes (CNTs) draw attention as promising materials due to their excellent electrical and mechanical properties. However, the intrinsic strong interaction between CNTs presents a challenge to their use in various applications. Here, we present a facile method to disperse single-walled carbon nanotubes (SWCNTs) in a polar solution using a graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate), PVC-g-POEM. The graft copolymer was synthesized via atom transfer radical polymerization (ATRP), as confirmed by gel permeation chromatography (GPC) and $^1H$ NMR spectroscopy. The SWCNTs were uniformly dispersed in a polar solvent such as dimethylsiloxane (DMSO) using PVC-g-POEM as a dispersant, due to interaction between CNT and the graft copolymer, as revealed by transmission electron microscopy (TEM) analysis. Upon removal of the solvent, free standing nanocomposite films with good homogeneity were obtained.

Syntheses of Cellulosic Graft Copolymers

  • Ikeda, Isao;Maeda, Yasushi
    • Proceedings of the Korean Fiber Society Conference
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    • 2003.10a
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    • pp.13-14
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    • 2003
  • Cellulosic graft copolymers were synthesized to use them as the functional materials. Three methods containing atom transfer radical polymerization (ATRP), macro-azo-initiator (MAI) method, and the polymerization catalyzed by tetrabutylammonium fluoride (TBAF) were performed in this work.

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