• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.270-273
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• 2009

A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoro-ethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (1H-NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA and the -COOH groups of IDA. Upon doping with phosphoric acid ($H_3PO_4$) to form imidazole-$H_3PO_4$ complexes, the proton conductivity of the membranes continuously increased with increasing $H_3PO_4$ content. A maximum proton conductivity of 0.015 S/cm was achieved at $120^{\circ}C$ under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/$H_3PO_4$ membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to $250^{\circ}C$, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively.

• Membrane Journal
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• v.20 no.1
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• pp.55-61
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• 2010

A diblock copolymer of polystyrene-b-poly(oxyethylene methacrylate) (PS-b-POEM) was synthesized via atom transfer radical polymerization (ATRP), as revealed by FT-IR spectroscopy. The self-assembled block copolymer membrane was prepared and used to template the growth of silver nanoparticles in the solid state by the introduction of $AgCF_3SO_3$ precursor and UV irradiation process. Transmission electron microscopy (TEM) and UV-visible spectroscopy confirmed the in situ formation of silver nanoparticles within the block copolymer membranes, and the size of nanoparticles were controlled by adjusting the moiety of hydrophilic POEM domains. PS-b-POEM block copolymer with a lower POEM content was effective in generating smaller size of metal nanoparticles.

• Membrane Journal
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• v.20 no.3
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• pp.203-209
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• 2010

Amphiphilic graft copolymers based on poly(epichlorohydrine) (PECH) were synthesized using atom transfer radical polymerization (ATRP). Successful graft polymerization of poly(methyl methacrylate)(PMMA) and poly(butyl methacrylate) (PBMA) from PECH was confirmed by nuclear magnetic resonance ($^1H$ NMR) and FT-IR spectroscopy. Upon the introduction of KI or LiI to the graft copolymers, the ether stretching bands were shifted to a lower wavenumber due to coordinative interactions. Ionic conductivities of PECH-g-PBMA complexes were always higher than those of PECH-g-PMMA complexes, resulting from higher mobility of rubbery PBMA chains. The maximum ionic conductivity of $2.7{\times}10^{-5}\;S/cm$ was obtained at 10 wt% of KI for PECH-g-PBMA electrolytes.

• 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.

• Membrane Journal
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• v.20 no.1
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• pp.1-7
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• 2010

A graft copolymer, i.e. poly(vinylidene fluoride-co-chlorotrifluoroethylene )-g-poly(styrene sulfonic acid) (P(VDF-co-CTFE)-g-PSSA) with 47 wt% of PSSA was synthesized via atom transfer radical polymerization (ATRP). This copolymer was combined with titanium isopropoxide (TTIP) to produce graft copolymer/$TiO_2$ nanocomposite membranes via sol-gel process. $TiO_2$ precursor (TTIP) was selectively incorporated into the hydrophilic PSSA domains of the graft copolymer and grown to form $TiO_2$ nanoparticles, as confirmed by FT-IR and UV-visible spectroscopy. Water uptake and ion exchange capacity (IEC) decreased with TTIP contents due to the decrease in number of sulfonic acid in the membranes. At 5 wt% of TTIP, the mechanical properties of membranes increased while maintaining the proton conductivity.

• 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.

• Membrane Journal
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• v.19 no.2
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• pp.89-95
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• 2009

A comb-like copolymer consisting of a poly(vinyl chloride) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. PVC-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP). This comb-like copolymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA in the graft copolymer and the -COOH groups of IDA. Upon doping with phosphoric acid (PA, $H_3PO_4$) to form imidazole-PA complexes, the proton conductivity of the membranes continuously increased with increasing PA content. A maximum proton conductivity of 0.011 S/cm was achieved at $100^{\circ}C$ under anhydrous conditions. The PVC-g-PHEA/IDA/PA complex membranes exhibited good mechanical properties, i.e. 575 MPa of Young's modulus, as determined by a universal testing machine (UTM). Thermal gravimetric analysis (TGA) shows that the membranes were thermally stable up to $200^{\circ}C$.

• 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.

• Membrane Journal
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• v.18 no.4
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• pp.261-267
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• 2008

A graft copolymer consisting of poly(vinyl chloride) (PVC) backbone and poly(hydroxyethyl acrylate) (PHEA) side chains was synthesized via atom transfer radical polymerization (ATRP). Direct initiation of the secondary chlorines of PVC facilitates grafting of hydrophilic PHEA monomer. This graft copolymer, i.e. PVC-g-PHEA was cross-linked with sulfosuccinic acid (SA) via the esterification reaction between -OH of the graft copolymer and -COOH of SA, as confirmed by FT-IR spectroscopy. Ion exchange capacity (IEC) continuously increased to 0.87meq/g with increasing concentrations of SA, due to the increasing portion of charged groups in the membrane. However, the water uptake increased up to 20.0wt% of SA concentration above which it decreased monotonically. The membrane also exhibited a maximum proton conductivity of 0.025 S/cm at 20.0 wt% of SA concentration, which is presumably due to competitive effect between the increase of ionic sites and the crosslinking reaction.