• Title/Summary/Keyword: ATRP

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Synthesis of Copoly(amide-imide)s Based on Silica Nano Particles-polyacrylamide

  • Min, Jun Ho;Park, Chan Young;Min, Seong Kee
    • Elastomers and Composites
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    • v.51 no.2
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    • pp.138-146
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    • 2016
  • It is an inconvenience for silica nano-particles to dry again when using it in that they cohere each other through moisture in the air. Acrylamide groups were introduced to improve such inconvenience and copolymerized with silica nano-particles and then we copolymerized again with polyamic acid in order to increase thermal characteristic. Amide block copolymers were prepared using silica and (3-mercaptopropyl) trimethoxysilane (MPTMS) with a siloxane group, using 2,6-Lutidine as a catalyst. Amide block polymers and copolymers were synthesized via ATRP after brominating pyromellitic dianhydride (PMDA) and polyamic acid of methylene diphenyl diamine (MDA), using ${\alpha}$-bromo isobutyryl bromide. Characteristic peaks of copolymer with amide and imide groups and patterns of amorphous polymers were researched by FT-IR and XRD analyses and the analysis of surface characteristic groups was conducted via XPS. A change in thermal properties was examined through DSC and TGA and solubility for solvents was also researched.

Encapsulation of Nanomaterials within Intermediary Layer Cross-linked Micelles Using a Photo-Cross-linking Agent

  • Kim, Jin-Sook;Youk, Ji-Ho
    • Macromolecular Research
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    • v.17 no.11
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    • pp.926-930
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    • 2009
  • A new method for encapsulating nanomaterials within intermediary layer cross-linked (ILCL) polymeric micelles using a bifunctional photo-cross-linking agent was developed. For ILCL polymeric micelles, an amphiphilic triblock copolymer of poly(ethylene glycol)-b-poly(2-hydroxyethyl methacrylate)-b-poly(methyl methacrylate) (PEG-PHEMA-PMMA) was synthesized via consecutive atom transfer radical polymerization (ATRP), Di(4-hydroxyl benzophenone) dodecanedioate (BPD) was used as a bifunctional photo-cross-linking agent. The PMMA-tethered Au nanoparticles and BPD, or pyrene and BPD were encapsulated in the PEG-PHEMA-PMMA micelles, and their intermediary layers were photo-cross-linked by UV irradiation for 1 h. The HEMA units donated labile hydrogens to the excited-state benzophenone groups in BPD, and they were subsequently cross-linked by BPD through radical-radical combination. The spherical structures of the PEG-PHEMA-PMMA micelles containing the Au nanoparticles or pyrene were unaffected by the photo-cross-linking process.

Current Research Trends on Surface Modification of Pressure-driven Membranes for Fouling Mitigation (압력 구동 기반 분리막의 막 오염 저감을 위한 표면 개질 방법 최신 연구 동향)

  • Jun, Byung-Moon;Lee, Hyung Kae;Kim, Woo Jeong;Park, Jihun;Kim, Jong Hyeok;Kwon, Young-Nam
    • Membrane Journal
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    • v.28 no.1
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    • pp.1-20
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    • 2018
  • Fresh water is an important resource for humans, and pressure-driven membrane technology has been widely known as an energy-efficient method to obtain water resource. However, membrane fouling phenomenon, which is one of the major issue during operation, deteriorates membrane permeability. These fouling is usually affected by interaction between surface of membrane and various foulants, therefore, modification of membrane's surface is one of the methods to improve fouling-resistance. This review focuses on the method to modify surface of pressure-driven membranes such as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO). Specifically, there are two different surface modification methods: (1) adsorption and coating as the physical modification methods, (2) cross-linker, free radical polymerization (FRP), atom transfer radical polymerization (ATRP), plasma/UV-induced polymerization as the chemical modification methods. This review introduces the physico - chemical surface modification methods reported in recent papers and suggests research directions for membrane separation which can increase membrane fouling resistance.

Proton Conducting Composite Membranes Consisting of PVC-g-PSSA Graft Copolymer and Heteropolyacid (PVC-g-PSSA가지형 공중합체와 헤테로폴리산을 이용한 수소이온 전도성 복합 전해질막)

  • Kim, Jong-Hak;Koh, Jong-Kwan;Choi, Jin-Kyu;Yeon, Seung-Hyeon;Ahn, Ik-Sung;Park, Jin-Won
    • Membrane Journal
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    • v.19 no.2
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    • pp.96-103
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    • 2009
  • A series of organic-inorganic composite membranes from poly(vinyl chloride) (PVC) graft copolymer electrolyte and heteropolyacid (HPA) were prepared for proton conducting membranes. First, poly(vinyl chloride)-g-poly(styrene sulfonic acid) (PVC-g-PSSA) was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. HPA nanoparticles were then incorporated into the PVC-g-PSSA graft copolymer though the hydrogen bonding interactions, as confirmed by FT-IR spectroscopy. The proton conductivity of the composite membranes increased from 0.049 to 0.068 S/cm at room temperature with HPA contents up to 0.3 weight traction of HPA, presumably due to both the intrinsic conductivity of HPA particles and the enhanced acidity of the sulfonic acid of the graft copolymer. The water uptake decreased from 130 to 84% with the increase of HPA contents up to 0.45 of HPA weight traction, resulting from the decrease in number of water absorption sites due to hydrogen bonding interaction between the HPA particles and the polymer matrix. Thermal gravimetric analysis (TGA) demonstrated the enhancement of thermal stabilities of the composite membranes with increasing concentration of HPA.

Synthesis and Characterization of Proton Conducting Graft Copolymer Membranes (수소이온 전도성 가지형 공중합체 전해질막 제조 및 분석)

  • Roh, Dong Kyu;Koh, Jong Kwan;Seo, Jin Ah;Kim, Jong Hak
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.126.2-126.2
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    • 2010
  • The "grafting from" technology to prepare the well-defined microphase-separated structure of polymer using atom transfer radical polymerization (ATRP) will be introduced in this presentation. Various amphiphilic comb copolymers were synthesized through this approach using poly (vinylidene fluoride) (PVDF), poly (vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE) and poly(vinyl chloride) (PVC) as a macroinitiator. Hydrophilic side chains such as poly (styrene sulfonic acid) (PSSA) or poly (sulfopropyl methacrylate) (PSPMA) were grafted from the mains chains using direct initiation of the chlorine atoms. The structure of mass transport channels has been controlled and fixed by crosslinking the hydrophobic domains, which also provides the greater mechanical properties of membranes. Successful synthesis and microphase-separated structure of the polymer were confirmed by $^1H$ NMR, FT-IR spectroscopy and TEM. The grafted/crosslinked membranes exhibited good mechanical properties (400 MPa of Young's modulus) and high thermal stability (up to $300^{\circ}C$), as determined by a universal testing machine (UTM) and TGA, respectively.

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Preparation of Porous TiO2 Thin Films by Poly(vinyl chloride)-graft-poly(N-vinyl pyrrolidone) and Their Applications to Dye-sensitized Solar Cells

  • Yeon, Seung-Hyeon;Patel, Rajkumar;Koh, Jong-Kwan;Ahn, Sung-Hoon;Kim, Jong-Hak
    • Journal of the Korean Electrochemical Society
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    • v.14 no.2
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    • pp.83-91
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    • 2011
  • Mesoporous titanium dioxide ($TiO_2$) thin films were prepared using poly(vinyl chloride)-graft-poly(N-vinyl pyrrolidone) (PVC-g-PVP) as a templating agent via sol-gel process. Grafting of PVC chains from PVC backbone was done by atom transfer radical polymerization (ATRP) technique. The successful grafting of PVP to synthesize PVC-g-PVP was checked by fourier-transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The carbonyl group interaction of PVC-g-PVP graft copolymer with $TiO_2$ was confirmed by FT-IR. The porous morphologies of the $TiO_2$ films genereated after calcination at $450^{\circ}C$ was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The mesoporous $TiO_2$ films with 580 nm in thickness were used as a photoelectrode for solid state dye sensitized solar cell (DSSC) and showed an energy conversion efficiency of 1.05% at 100 $mW/cm^2$.

Bioconjugation of Poly(poly(ethylene glycol) methacrylate)-Coated Iron Oxide Magnetic Nanoparticles for Magnetic Capture of Target Proteins

  • Kang, Sung-Min;Choi, In-Sung S.;Lee, Kyung-Bok;Kim, Yong-Seong
    • Macromolecular Research
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    • v.17 no.4
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    • pp.259-264
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    • 2009
  • Chemical modification of magnetic nanoparticles(MNPs) with functional polymers has recently gained a great deal of attention because of the potential application of MNPs to in vivo and in vitro biotechnology. The potential use of MNPs as capturing agents and sensitive biosensors has been intensively investigated because MNPs exhibit good separation-capability and binding-specificity for biomolecules after suitable surface functionalization processes. In this work, we demonstrate an efficient method for the surface modification of MNPs, by combining surface-initiated polymerization and the subsequent conjugation of the biologically active molecules. The polymeric shells of non-biofouling poly(poly(ethylene glycol) methacrylate)(pPEGMA) were introduced onto the surface of MNPs by surface-initiated, atom transfer radical polymerization(SI-ATRP). With biotin as a model of biologically active compounds, the polymeric shells underwent successful post-functionalization via activation of the polymeric shells and bioconjugation of biotin. The resulting MNP hybrids showed a biospecific binding property for streptavidin and could be separated by magnet capture.

Preparation of Al@Fe2O3 Core-Shell Composites Using Amphiphilic Graft Copolymer Template

  • Patel, Rajkumar;Kim, Sang Jin;Kim, Jin Kyu;Park, Jung Su;Kim, Jong Hak
    • Korean Chemical Engineering Research
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    • v.52 no.2
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    • pp.209-213
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    • 2014
  • A graft copolymer of poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) was synthesized via atom transfer radical polymerization (ATRP) and used as a structure-directing agent to prepare $Al@Fe_2O_3$ core-shell nanocomposites through a sol-gel process. The amphiphilic property of PVC-g-POEM allows for good dispersion of Al particles and leads to specific interaction with iron ethoxide, a precursor of $Fe_2O_3$. Secondary bonding interaction in the sol-gel composites was characterized by Fourier transform-infrared (FT-IR) spectroscopy. The well-organized morphology of $Al@Fe_2O_3$ core-shell nanocomposites was observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Energy dispersive X-ray (EDX) and X-ray diffraction (XRD) were used to analyze the elemental composition and crystallization structure of the composites.

Preparation and Characterization of Proton Conducting Composite Membranes From P(VDF-CTFE)-g-PSPMA Graft Copolymer and Heteropolyacid

  • Seo, Jin-Ah;Roh, Dong-Kyu;Koh, Jong-Kwan;Kim, Jong-Hak
    • Korean Membrane Journal
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    • v.10 no.1
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    • pp.20-25
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    • 2008
  • Proton conducting composite membranes were prepared by solution blending of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(sulfopropyl methacrylate) (P(VDF-CTFE)-g-PSPMA) graft copolymer and heteropolyacid (HPA). The P(VDF-CTFE)-g-PSPMA graft copolymer was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of P(VDF-CTFE). FT-IR spectroscopy revealed that HPA nanoparticles were incorporated into the graft copolymer via hydrogen bonding interactions. The water uptake of membranes continuously decreased with increasing HP A concentration up to 45wt%, after which it slightly increased. It is presumably due to the decrease in number of water absorption sites due to hydrogen bonding interaction between the HP A particles and the polymer matrix. The proton conductivity of membranes increased with increasing HPA concentration up to 45wt%, resulting from both the intrinsic conductivity of HP A particles and the enhanced acidity of the sulfonic acid of the graft copolymer.

Thermosensitive Block Copolymers Consisting of Poly(N-isopropylacrylamide) and Star Shape Oligo(ethylene oxide)

  • Lee, Seung-Cheol;Chang, Ji-Young
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1521-1525
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    • 2009
  • Thermosensitive block copolymers of ethylene oxide and N-isopropylacrylamide (NIPAM) were synthesized. A five armed star shape oligo(ethylene oxide) initiator with a cyclotriphosphazene core was prepared and used for the atom transfer radical polymerization (ATRP) of NIPAM. The lower critical solution temperatures (LCSTs) of the copolymers were 36 to 46 ${^{\circ}C}$, higher than that of PNIPAM (32 ${^{\circ}C}$), depending on their molecular weights. The copolymers were soluble in water below the LCSTs but formed micelles above the LCSTs. The thermosensitive micellization behaviors of the polymers were investigated by fluorescence spectroscopy. With increasing the temperature of an aqueous solution of P2 and pyrene above the LCST, the peak of 333 nm red-shifted to appear around 339 nm and its intensity increased significantly, indicating the micelle formation. The transfer of pyrene into the micelles was also confirmed by a confocal laser scanning microscope. The fluorescence image obtained from P2 in an aqueous pyrene solution exhibited a green emission resulting from the pyrene transferred into the micelles. Salt effects on the solubility of the copolymers in an aqueous solution were investigated. The LCST of P2 decreased sharply as the concentration of sodium chloride increased, while decreased slowly with potassium chloride.