• Proceedings of the Membrane Society of Korea Conference
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• 1999.07a
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• pp.23-26
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• 1999

Urethane block copolymers, containing soft segments such as polydimethylsiloxane (PDMS), polytertramethylene glycol(PTMG) and PEO-PPO-PEO (Poloxamer) block copolymer, were synthesized and examined for th vapor- phase separation of toluene from nitrogen stream by using vapor permeation equipment. Generally permeabilities of PTMG and PDMS based urethane membranes were higher than those of Poloxamer based urethane membranes. Organic vapor permeability in the PDMS and PTMG soft segment urethane membranes were greater than those measured in the Poloxamer films, due to more polymer swelling. The membranes performed best with toluene, with toluene/dry N2 seletivities ranging from 120~200 and permeablilities as high as 23$\times$10-9 mol/m2sPa for saturated toluene feeds at 23$^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.375-376
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• 2012

• Journal of Hydrogen and New Energy
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• v.27 no.6
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• pp.660-669
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• 2016

A fluorinated-sulfonated, hydrophobic-hydrophilic copolymer was planed subsequently synthesized using typical nucleophilic substitution polycondensation reaction. A novel AB and ABA (or BAB) block copolymers were synthesized using sBCPSBP (sulfonated 4,4'-bis[4-chlorophenyl)sulfonyl]-1,1'-biphenyl), DHN (1,5-dihydroxynaphthalene), DFBP (decafluorobiphenyl) and HFIP (4,4'-hexafluoroisopropylidenediphenol). All block copolymers were easily cast and made into clear films. The structure and synthesized copolymers and corresponding membranes were analyzed using GPC (gel permeation chromatography), $^1H$-NMR ($^1H$ nuclear magnetic resonance) and FT-IR (Fourier transform infrared). TGA (Thermogravimetric analysis) and DSC (differential scanning calorimetry) analysis showed that the prepared membranes were thermally stable, so that elevated temperature fuel cell operation would be possible. Hydrophobic/hydrophilic phase separation and clear ionic aggregate block morpology was confirmed in both triblock and diblock copolymer in AFM (atomic force microscopy), which may be highly related to their proton transport ability. A sulfonated BAB triblock copolymer membrane with an ion-exchange capacity (IEC) of 0.6 meq/g has a maximum ion conductivity of 40.3 mS/cm at $90^{\circ}C$ and 100% relative humidity.

• Proceedings of the Membrane Society of Korea Conference
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• 2003.11a
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• pp.51-54
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• 2003

• 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).

• 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).

• Membrane Journal
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• v.29 no.1
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• pp.44-50
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• 2019

In this paper, we developed mixed matrix membranes (MMMs) consisting of SBS-g-POEM block-graft copolymer, ionic liquid (EMIMTFSI) and ZIF-8 nanoparticles to separate a $CO_2/N_2$ gas pair. The SBS-g-POEM is a rubbery block-graft copolymer synthesized through low-cost free-radical polymerization. The EMIMTFSI was dissolved into the SBS-g-POEM matrix and solution synthesized ZIF-8 nanoparticles were also dispersed into the copolymer matrix. The physico-chemical properties of manufactured membranes were characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffraction (XRD), which showed that the components were compatible with each other. The gas separation performance was confirmed by time-lag measurements showing $CO_2$ permeability of 537.0 barrer and $CO_2/N_2$ selectivity of 15.2. The result represents the EMIMTFSI and ZIF-8 nanoparticles improves the gas permeability more than two-times, without significantly sacrificing the $CO_2/N_2$ selectivity.

• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.75-80
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• 2015

Multi-block sulfonated poly(arylene ether sulfone) (SPAES) copolymer was synthesized via nucleophilic aromatic substitution reaction for proton exchange membrane fuel cell application. After synthesizing the hydrophilic and hydrophobic precursor oligomers having different end-groups (F-terminated or OH-terminated), the effect of end group on the molecular weight was investigated. Hydrophilic oligomers with hydroquinone showed better performance as fuel cell membranes. SPAES membranes showed comparable proton conductivity to that of Nafion at $80^{\circ}C$ and above 70% RH. In particular, SPAES 9 with hydroquinone showed higher proton conductivity than SPAES 10 in the whole RH range studied. Increased local concentration of sulfonic acids within hydrophilic block might develop the hydrophilic-hydrophobic phase separation in the block copolymers.

• 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.