• 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.

• Korean Membrane Journal
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• v.9 no.1
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• pp.57-63
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• 2007

Amphiphilic graft copolymer from poly(vinylidene fluoride) (PVDF) was synthesized using atom transfer radical polymerization (ATRP) for composite nanofiltration membranes. Direct initiation of the secondary fluorinated site of PVDF facilitates grafting of tert-butyl methacrylate (tBMA). Amphiphilic PVDF-g-PMAA graft copolymer with a 51:49 wt ratio was obtained by hydrolyzing poly(tert-butyl methacrylate) (PtBMA) to poly(methacrylic acid) (PMAA). Wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) confirmed the decrease of crystallinity of PVDF upon graft copolymerization. Composite nanofiltration membranes were prepared from PVDF-g-PMAA as a top layer coated onto PVDF ultrafiltration (UF) support membrane. The morphology and hydrophilicity of membranes were characterized using scanning electron microscopy (SEM) and contact angle measurement. The rejections of composite membranes were 80.2% for $Na_2SO_4$ and 28.4% for NaCl, and the solution flux were 9.5 and $14.5\;L/m^2\;h$ at 1.0 MPa pressure.

• Biomaterials and Biomechanics in Bioengineering
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• v.2 no.2
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• pp.97-109
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• 2015

A series of amphiphilic graft copolymers were synthesized by varying the number of graft chains and graft chain lengths. The polarity of the hydrophobic graft chain on the copolymers was varied their solution properties. The glass transition temperature of the copolymers was in the low-temperature region, because of the amorphous nature of poly (trimethylene carbonate) (PTMC). The surface morphology of the lyophilized colloid gel had a bundle structure, which was derived from the combination of poly(N-hydroxyethylacrylamide)( poly(HEAA)) and PTMC. The solution properties were evaluated using dynamic light scattering and fluorescence measurements. The particle size of the graft copolymers was about 30-300 nm. The graft copolymers with a higher number of repeating units attributed to the TMC (trimethylene carbonate) component and with a lower macromonomer ratio showed high thermal stability. The critical association concentration was estimated to be between $2.2{\times}10^{-3}$ and $8.9{\times}10^{-2}mg/mL$, using the pyrene-based fluorescence probe technique. These results showed that the hydrophobic chain of the graft copolymer having a long PTMC segment had a low polarity, dependent on the number of repeating units of TMC and the macromonomer composition ratio. These results demonstrated that a higher number of repeating units of TMC, with a lower macromonomer composition, was preferable for molecular encapsulation.

• 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.

• 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.

• 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.

• Membrane Journal
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• v.20 no.2
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• pp.169-172
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• 2010

Silver ions of poly(vinyl chloride)-g-poly(styrene sulfonic acid) (PVC-g-PSSA) graft copolymer were reduced to form silver nanoparticles under thermal condition ($80^{\circ}C$). We were successful in synthesizing silver nanoparticles with various morphologies by changing reaction time. At short reaction times (~1 h), silver nanoparticles with 5 nm in size were formed without disrupting a microphase-separated structure of graft copolymer. At medium reaction times (~5 h), silver nanoparticles were aggregated to form large clusters ranging 30~50 nm in size. At much longer reaction times (~18 h), hurricane-like silver clusters were observed due to strong particle aggregation.

• 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.

• 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.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.