• 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.

• 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.

• Macromolecular Research
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• v.17 no.5
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• pp.325-331
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• 2009

The synthesis and the characterization of crosslinked ABC triblock copolymer, i.e. polystyrene-b-poly (hydroxyethyl methacrylate)-b-poly(styrene sulfonic acid), (PS-b-PHEMA-b-PSSA) is reported. PS-b-PHEMA-b-PSSA triblock copolymer at 20:10:70 wt% was sequentially synthesized via atom transfer radical polymerization (ATRP). The middle block was crosslinked by sulfosuccinic acid (SA) via the esterification reaction between -OH of PHEMA and -COOH of SA, as demonstrated by FTIR spectroscopy. As increasing amounts of SA, ion exchange capacity (IEC) continuously increased from 2.13 to 2.82 meq/g but water uptake decreased from 181.8 to 82.7%, resulting from the competitive effect between crosslinked structure and the increasing concentration of sulfonic acid group. A maximum proton conductivity of crosslinked triblock copolymer membrane at room temperature reached up to 0.198 S/cm at 3.8 w% of SA, which was more than two-fold higher than that of Nafion 117(0.08 S/cm). Transmission electron microscopy (TEM) analysis clearly showed that the PS-b-PHEMA-b-PSSA triblock copolymer is microphase-separated with a nanometer range and well developed to provide the connectivity of ionic PSSA domains. The membranes exhibited the good thermal properties up to $250^{\circ}C$ presumably resulting from the microphase-separated and crosslinked structure of the membranes, as revealed by thermal gravimetric analysis (TGA).

• Macromolecular Research
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• v.16 no.6
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• pp.549-554
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• 2008

Proton conducting crosslinked membranes were prepared using polymer blends of polystyrene-b-poly(hydroxyethyl acrylate)-b-poly(styrene sulfonic acid) (PS-b-PHEA-b-PSSA) and poly(vinyl alcohol) (PVA). PS-b-PHEA-b-PSSA triblock copolymer at 28:21:51 wt% was synthesized sequentially using atom transfer radical polymerization (ATRP). FT-IR spectroscopy showed that after thermal ($120^{\circ}C$, 2 h) and chemical (sulfosuccinic acid, SA) treatments of the membranes, the middle PHEA block of the triblock copolymer was crosslinked with PVA through an esterification reaction between the -OH group of the membrane and the -COOH group of SA. The ion exchange capacity (IEC) decreased from 1.56 to 0.61 meq/g with increasing amount of PVA. Therefore, the proton conductivity at room temperature decreased from 0.044 to 0.018 S/cm. However, the introduction of PVA resulted in a decrease in water uptake from 87.0 to 44.3%, providing good mechanical properties applicable to the membrane electrode assembly (MEA) of fuel cells. Transmission electron microscopy (TEM) showed that the membrane was microphase-separated with a nanometer range with good connectivity of the $SO_3H$ ionic aggregates. The power density of a single $H_2/O_2$ fuel cell system using the membrane with 50 wt% PVA was $230\;mW/cm^2$ at $70^{\circ}C$ with a relative humidity of 100%. Thermogravimetric analysis (TGA) also showed a decrease in the thermal stability of the membranes with increasing PVA concentration.

• Membrane Journal
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• v.27 no.2
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• pp.182-188
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• 2017

Sulfonated poly(arylene ether sulfone) (SPAES)-3-mercaptopropyl silica gel (3MPTSG) composite membranes with improved oxidative stability were prepared for polymer electrolyte fuel cell application. It has been reported that ether part of main chain of aromatic hydrocarbon based membranes were weak to radical attack to decrease membrane durability. In this study, the hydrophilic inorganic particles were introduced by minimizing a decrease in ion conductivity and increasing an oxidative stability. The composite membranes were investigated in terms of ionic conductivity, ion exchange capacity (IEC), FT-IR, TGA and contact angle, etc. As a result, increasing amount of the 3MPTSG resulted in decrease in proton conductivities and water uptakes at 100% R.H. but enhanced thermal and oxidative stabilities.

• Membrane Journal
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• v.19 no.3
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• pp.228-236
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• 2009

ABA type triblock copolymer of poly(hydroxyl ethyl acrylate )-b-polystyrene-b-poly(hydroxyl ethyl acrylate), i.e. PHEA-b-PS-b-PHEA, was synthesized throughatom transfer radical polymerization (ATRP). This block copolymer was thermally crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification between the -OH groups of PHEA in block copolymer and the -COOH groups of IDA. Upon doping with ${H_3}{PO_4}$ to form imidazole-${H_3}{PO_4}$ complexes, the proton conductivity of membranes continuously increased with increasing ${H_3}{PO_4}$ content. The PHEA-b-PS-b-PHEA/IDA/${H_3}{PO_4}$ polymer membrane with [HEA]:[IDA]:[${H_3}{PO_4}$]=3:4:4 exhibited a maximum proton conductivity of 0.01 S/cm at $100^{\circ}C$ under anhydrous conditions. Thermal gravimetric analysis (TGA) shows that the PHEA-b-PS-b-PHEA/IDA/${H_3}{PO_4}$ complex membranes were thermally stable up to $350^{\circ}C$, indicating their applicability in fuel cells.

• Membrane Journal
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• v.19 no.4
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• pp.302-309
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• 2009

A block copolymer of polystyrene-b-poly (hydroxyl ethyl methacrylate), PS-b-PHEMA, was synthesized via atom transfer radical polymerization (ATRP) and crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via esterification of the -OH groups of PHEMA in the block copolymer and the -COOH groups of IDA. Upon doping with $H_3PO_4$ to form imidazole-$H_3PO_4$ complexes, the proton conductivity of the membranes continuously increased as the content of $H_3PO_4$ increased. In addition, both the tensile strength and the elongation at break increased with IDA content. A proton conductivity of 0.01 S/cm at $100^{\circ}C$ was obtained for the PS-b-PHEMA/IDA/$H_3PO_4$ membrane with [HEMA]:[IDA]:[$H_3PO_4$] = 3:4:4 under anhydrous conditions. All of the PS-b-PHEMA/IDA/$H_3PO_4$ membranes were thermally stable up to $350^{\circ}C$, as revealed by thermal gravimetric analysis (TGA).

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.611-616
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• 1995

Oxovanadium(IV) complexes with salicylaldoxime, o-vanilline oxime, 2-hydroxy-4-methoxybenzaldoxime, 2-hydroxy-5-methoxybenzaldoxime and 2-hydroxy-5-nitrobenzaldoxime were synthesized. The complexes have been characterized by elemental analysis, electric conductivity measurement, infrared spectrometry, electronic spectrometry, mass spectrometry, and thermal analysis. The results of elemental analysis were well coincided with the theoretical values. The values of molar conductance of the complexes in DMF implicated that the complexes were non-electrolyte. The characteristic stretching frequency of V=O appeared strong band in the range of $980{\pm}20\;cm^{-1}.$ All the complexes showed two d-d transition in visible spectra and two charge transfer transitions in ultraviolet spectra. Results of mass spectrometry of $VO(sal)_2\;and\;VO(van)_2$ indicated two peaks corresponding to vanadium containing ion(I) of 1 : 2(metal to ligand) chelate and a fragment ion(II) of 1 : 1 chelate due to loss of ligand radical from ion(I). The thermal analysis showed the endothermic peak due to the thermal decomposition.

• Carbon letters
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• v.13 no.3
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• pp.173-177
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• 2012

A drug delivery system (DDS) was prepared with a temperature and pH-responsive hydrogel. Poly(vinyl alcohol) (PVA)/poly(acrylic acid) (PAAc)/poly(N-isopropylacrylamide) (PNIPAAm)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by radical polymerization for the temperature and pH-responsive hydrogels. MWCNTs were employed to improve both the thermal conductivity and mechanical properties of the PVA/PAAc/PNIPAAm/MWCNT nanocomposite hydrogels. Various amounts of MWCNTs (0, 0.5, 1 and 3 wt%) were added to the nanocomposite hydrogels. PVA/PAAc/PNIPAAm/MWCNT nanocomposite hydrogels were characterized with a scanning electron microscope. The mechanical properties were measured with a universal testing machine. Swelling and releasing properties of nanocomposite hydrogels were investigated at various temperatures and pHs. Temperature and pH-responsive release behavior was found to be dependent on the content of MWCNTs in nanocomposite hydrogels.

• Bulletin of the Korean Chemical Society
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• v.17 no.5
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• pp.424-428
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• 1996

TlCl2(TCNQ)2.5 and Tl(TCNQ)3 were obtained from the reaction of LiTCNQ (TCNQ=tetracyanoquinodimethane) and TlX3 (X=Cl and NO3). These compounds were characterized by spectroscopic(IR, UV, EPR), electrochemical methods, and electrical conductivity measurements. Thermal analysis (TG, DSC) was also conducted. The room temperature electrical conductivities of these compounds are in the range of semiconductors. Spectroscopic studies indicate that Tl(TCNQ)3 has fully ionized TCNQ- ions in a form of simple salt, whereas TlCl2(TCNQ)2.5 is consisted of TCNQ- and TCNQ0 as a complex salt. EPR values of TCNQ- radical anion are 1.999 in both compounds and the signal attributable to metal ion is not observed, suggesting that any unpaired electrons are localized on TCNQ radicals, and metal atoms have diamagnetic state. Ligand decomposition and reduction process are simultaneously progressed in both compounds above at 200 ℃. The endothermic activation energy of TlCl2(TCNQ)2.5 is shown somewhat larger than that of Tl(TCNQ)3, it may be due to Tl-Cl bond strength. The mid-peak potentials of these compounds are very similar to those of TCNQ and the values of Epa and Epc are almost equal to 1. The wave of thallium ion is not detected in cyclic voltammogram, hence the redox processes of the complexes might be mainly localized to the TCNQ ligand rather than thallium ion.