• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.64.1-64.1
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• 2010

The morphology of mesoporous $TiO_2$ films plays an important role in the operation of a DSSC. For example, the energy conversion efficiency of DSSCs with well-organized mesoporous $TiO_2$ films is much higher than those with traditional films possessing a random morphology. In previous research, well-organized mesoporous $TiO_2$ films have mainly been synthesized using an amphiphilic block copolymer, e.g., a poly(ethylene oxide) (PEO)-based template. A graft copolymer is more attractive than a block copolymer due to its low cost and the ease with which it can be synthesized. In this work, we provide the first report on the successful synthesis of well-organized mesoporous $TiO_2$ films templated by an organized graft copolymer as a structure directing agent. Well-organized mesoporous $TiO_2$ films with excellent channel connectivities were developed via the sol gel processusing an organized PVC-g-POEM graft copolymer synthesized by one-pot ATRP. The careful adjustment of copolymer composition and solvent affinity using a THF/$H_2O$/HCl mixture was used to systematically vary the material structure. The influence of the material structure on solar cell performance was then investigated. A solid-state DSSC employing both the graft copolymer templated organized 700 nm-thick $TiO_2$ films and graft copolymer electrolytes exhibited a solar conversion efficiency of 2.2% at 100 $mW/cm^2$. This value was approximately two-fold higher than that attained from a DSSC employing a random mesoporous $TiO_2$ film. The solar cell performance was maximized at 4.6% when the film thickness was increased to $2.5{\mu}m$. We believe that this graft copolymer-directed approach introduces a new and simple route toward the synthesis of well-organized metal oxide films as an alternative to a conventional block copolymer-based template.

• Macromolecular Research
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• v.15 no.6
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• pp.553-559
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• 2007

Nanocomposite films were prepared by sol-gel synthesis from vanadium triisopropoxide with $poly((oxyethylene)_9$ methacrylate)-graft-poly(dimethyl siloxane), POEM-g-PDMS, producing in situ growth of vanadium oxide within the continuous ion-conducting POEM domains of micro phase-separated graft copolymer. The formation of vanadium oxide was confirmed by wide angle x-ray scattering (WAXS) and Fourier transform infrared (FT-IR) spectroscopy. Small angle x-ray scattering (SAXS) revealed the spatially-selective incorporation of vanadium oxide in the POEM domains. Upon the incorporation of vanadium oxide, the domain periodicity of the graft copolymer monotonously increased from 17.2 to 21.0 nm at a vanadium content 14 v%, above which it remained almost invariant. The selective interaction of vanadium oxide with POEM was further verified by differential scanning calorimetry (DSC) and FT-IR spectroscopy. The nanocomposite films exhibited excellent mechanical properties $(l0^{-5}-10^{-7}dyne/cm^2)$, mostly due to the confinement of vanadium oxide in the POEM chains as well as the interfaces created by the microphase separation of the graft copolymer.

• 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.

• Applied Chemistry for Engineering
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• v.7 no.4
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• pp.757-767
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• 1996

Poly(alkyl acrylate-g-caprolactone) graft copolymers were prepared, and they were applied as compatibilizing agents for polycarbonate (PC) / poly(acrylonitrile-butadiene-styrene) (ABS) blends. The incompatible poly(alkyl acrylate) segment was incorporated into the graft copolymer in order to localize the copolymer at the PC/ABS interface. The blend containing 1 phr of the copolymer showed remarkable improvement in impact strength as well as in elongation at break. Impact improvement was more pronounced with a thinner test specimens of 1/8 inch thickness. Morphological study showed that the presence of the graft copolymer led to a smoother PC/ABS interface due to the interfacial enrichment of the graft copolymer.

• 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.

• Macromolecular Research
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• v.17 no.5
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• pp.301-306
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• 2009

This work has demonstrated that a novel amphiphilic poly(epichlorohydrine)-graft-polystyrene (PECH-g-PS) copolymer at 34:66 wt% was synthesized via atom transfer radical polymerization (ATRP) of styrene using PECH as a macroinitiator. The structure of the graft copolymer was characterized by nuclear magnetic resonance ($^1H$ NMR) and FTIR spectroscopy, demonstrating that the "grafting from" method using ATRP was successful. The self-assembled graft copolymer was used as a template film for the in-situ growth of silver nanoparticles from $AgCF_3SO_3$ precursor under UV irradiation. The in situ formation of silver nanoparticles with 6-8 nm in average size in the solid state template film was confirmed by transmission electron microscopy (TEM), UV-visible spectroscopy and wide angle X-ray scattering (WAXS). Differential scanning calorimetry (DSC) also displayed the selective incorporation and the in situ formation of silver nanoparticles within the hydrophilic PECH domains, probably due to stronger interaction of the silvers with the ether oxygens of PECH backbone than that with hydrophobic PS side chains.

• Membrane Journal
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• v.22 no.5
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• pp.342-351
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• 2012

In this study, PTMSP[poly(1-trimethylsilyl-1-propyne)]/PDMS[poly(dimethylsioxane)]-NaY zeolite and PTMSP/PDMS-NaA zeolite composite membranes were made to incorporate zeolite into PTMSP/PDMS graft copolymer in order to improve the selectivity and thermal stability, the drop of permeability by physical aging effect during long period of time for the PTMSP membrane. To investigate the physico-chemical characteristics of composite membranes, the analytical methods such as FT-IR, $^1H$-NMR, TGA, SEM, and GPC have been utilized. The gas permeability and selectivity properties of $H_2$ and $N_2$ were evaluated. The permeability of the PTMSP/PDMS-NaY zeolite and PTMSP/PDMS-NaA zeolite composite membranes than PTMSP/PDMS graft copolymer membrane increased, increased as zeolite content increased. On the contrary, the selectivity ($H_2/N_2$) of the composite membranes decreased as zeolite content increased. PTMSP/PDMS-NaA zeolite composite membrane showed better permeability and separation factor than PTMSP/PDMS-NaY zeolite composite membrane.

• Elastomers and Composites
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• v.11 no.1
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• pp.54-62
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• 1976

It has been studied the graft copolymerization of glycidyl-methacrylate monomer containing two functional groups (vinyl- & epoxyl-) to chloroprene rubber. The reaction occured in the manner of chain transfer mechanism was carried out by means of solution polymerization in toluene in the presence of benzoyl peroxide as the radical initiator. The graft copolymer obtained from this work was analyzed by using IR spectrum, and the physical properties of the polymer such as the thermal behavior were also studied according to TG-DTA methods, and the potency of adhesiveness for the purpose of commercial application was investigated. Experimental results for the graft copolymerization are summarized as follows. 1) A small amount of initiator (0.5%) and 50% of monomer showed the best result for the grafting of monomer to the polymer chain of rubber while the 15% of rubber solution was found to be most suitable to raise either for the grafting ratio or the polymerization ratio. 2) Optimum temperature for better yield of graft copolymer was proved to he at $75^{\circ}C\sim80^{\circ}C$ while those of reaction time was to be $1\sim2$ hours.

• Applied Chemistry for Engineering
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• v.4 no.3
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• pp.627-636
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• 1993

Anionic acrylic resin utilizing macromer(TBMA-g-MMA) copolymer was synthesized by preparing (TBMA) macromer using anionic living polymerization, followed by graft copolymerization with MMA macromer. To control the anionic site content in graft copolymer, the relative composition((TBMA) macromer/MMA ratio) of the graft copolymer was controlled at 7/3, 10/90, 15/85, 20/80, 30/70, 40/60, 50/50 in weight content. In the course of anionic living polymerization of(TBMA) macromer, broad molecular weight distribution (1.4~1.5) was obtained by using n-butyllithium-diphenyethylene initiatior system at $-78^{\circ}C$. To introduce the double bond at the end of chain in termination step, methacryloyl chloride was reacted after insertion of benzaldehyde as capping material. Moreover, TBMA parts in graft copolymer were hydrolyzed in the presence of p-toluenesulfonic acid catalyst, and neutralization of graft copolymer with triethylamine was granted acrylic resin to anionic site. Molecular weight and molecular weight distribution of(TBMA) macromer were determined by GPC, and the hydrolysis of TBMA with neutralization of acrylic resin were determined by IR and NMR. From water dispersion and stability point of view, stable dispersion state appeared at low molecular weight(TBMA) macromer with a small TBMA content as a result of scrutiny about the relation to TBMA content and branch length for(TBMA) macromer molecular weight in graft copolymer.