• Transactions of the Korean hydrogen and new energy society
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• v.29 no.4
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• pp.331-338
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• 2018

In this study, sulfonated PAES block copolymers have been synthesized via nucleophilic substitution reaction. Hydrophobic oligomer was prepared using 2,6-dihydroxynaphthalene and bis(4-chlorophenyl) sulfone, whereas hydrophilic oligomer was prepared using sulfonated bis(4-chlorophenyl) sulfone and bis(4-hydroxyphenyl) sulfone. The chemical structure of polymers was analyzed by $^1H$ NMR, FT-IR and GPC. The thermal properties of polymers were measured by TGA and DSC. The oxidative stability of membranes was investigated by Fenton's test. Furthermore, the proton conductivity of membrane was found to be 26 mS/cm at $90^{\circ}C$. All physiochemical properties suggest that fabricated membrane have a great potential for applications in PEMFC.

• Membrane Journal
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• v.18 no.4
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• pp.274-281
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• 2008

Covalent-crosslinked sulfonated poly(arylene ether sulfone) (SPAES) copolymers were synthesized copolymerization technique and additionally crosslinked with divinylbenzene (DVB). To optimize the reaction condition, a concentration of crosslinking agent and a reaction time were varied in the ranges of $30{\sim}90\;v/v%$ and $30{\sim}720\;min$. The properties of the crosslinked membranes were investigated by SEM, TGA and the measurement of proton conductivity. It was found that the proton conductivity of crosslinked membranes decreased depending on a degree of crosslinking while water uptake and methanol permeability reduced.

• Membrane Journal
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• v.24 no.4
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• pp.292-300
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• 2014

Chlorine-resistant sulfonated poly(arylene ether sulfone) random copolymer (SPAES)-thin film composite (TFC) membranes for desalination are prepared using monoglyme as a selective solvent, which dissolves SPAES, but should be inert to porous polysulfone layer (e.g., Udel$^{(R)}$). Different from formic acid and diethylene glycol used as other selective solvents, monoglyme is environmentally friendly and has much lower boiling temperature. After a pretreatment of Udel$^{(R)}$ support film in isopropyl alcohol-glycerine mixture to minimize pore penetration leading to fairly reduced water flux, coating of SPAES solution in monoglyme onto the support and stepwise drying processes are conducted for defect-free TFC formation. The transport behavior through SPAES-TFC membranes is observed, correlating with the effects of sulfonation level, protonation, and physical and chemical crosslinking of SPAES selective layers.

• Transactions of the Korean hydrogen and new energy society
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• v.23 no.5
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• pp.461-467
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• 2012

Multi-block sulfonated poly (arylene ether sulfone) (SPES) membranes were synthesized by post-sulfonation and its properties characterized. Two types of oligomers, F-terminated and OH-terminated telechelic oligomers, were synthesized by controlling the feed ratio of dihydroxyl- and difluoro-monomers. Their number of repeating unit (X and Y) was analyzed by GPC and $^1H$ NMR. Copolymerization with F-terminated and OH-terminated telechelic oligomers via nucleophilic aromatic substitution, gave high-molecular-weight multi-block PESs. Each block length was controlled to have different values with X5Y10, X10Y10, X20Y10 and X20Y20. Successful polymerization and its successful sulfonation was confirmed by GPC and $^1H$ NMR. RH dependence of proton conductivity of multi-block SPES membranes was comparable to that of Nafion 212 at high RH conditions.

• Korean Chemical Engineering Research
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• v.53 no.6
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• pp.690-694
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• 2015

Recently, direct formic acid fuel cells (DFAFC) among direct liquid fuel cells is studied actively. Economical hydrocarbon membranes alternative to fluorinated membranes for DFAFC's membrane are receiving attention. In this study, characteristics of sulfonated poly(ether ether ketone, sPEEK) and sulfonated poly(arylene ether sulfone, PAES) membranes were compared with Nafion membrane at DFAFC operation condition. Formic acid crossover current density of hydrocarbon membranes were lower than that of Nafion 211 fluorinated membrane. I-V performance of sPEEK MEA(Membrane and Electrode Assembly) was similar to that of Nafion 211 MEA due to similar membrane resistance each other. sPEEK MEA with low formic acid crossover showed higher stability compared with Nafion 211 MEA.

• Macromolecular Research
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• v.15 no.2
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• pp.160-166
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• 2007

Novel multiblock copolymers, based on segmented sulfonated hydrophilic-hydrophobic blocks, were synthesized and investigated for their application as proton exchange membranes. A series of segmented sulfonated poly(arylene ether sulfone)-b-polyimide multiblock copolymers, with various block lengths, were synthesized via the coupling reaction between the terminal amine moieties on the hydrophilic blocks and naphthalene anhydride functionalized hydrophobic blocks. Successful imidization reactions required a mixed solvent system, comprised of NMP and m-cresol, in the presence of catalysts. Proton conductivity measurements revealed that the proton conductivity improved with increasing hydrophilic and hydrophobic block lengths. The morphological structure of the multiblock copolymers was investigated using tapping mode atomic force microscopy (TM-AFM). The AFM images of the copolymers demonstrated well-defined nanophase separated morphologies, with the changes in the block length having a pronounced effect on the phase separated morphologies of the system. The self diffusion coefficient of water, as measured by $^1H$ NMR, provided a better understanding of the transport process. Thus, the block copolymers showed higher values than Nafion, and comparable proton conductivities in liquid water, as well as under partially hydrated conditions at $80^{\circ}C$. The new materials are strong candidates for use in PEM systems.

• Macromolecular Research
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• v.17 no.11
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• pp.825-828
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• 2009

• New & Renewable Energy
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• v.2 no.4 s.8
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• pp.46-55
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• 2006

본 연구는 불소그룹을 함유한 술폰화된 아릴렌에테르계 블록 공중합체 고분자 전해질막의 제조 및 연료전지 특성에 관한 것이다. 이러한 불소그룹을 함유한 술폰화된 아랄렌에테르계 블록 공중합체를 제조하기 위하여 양말단에 불소계 비닐기를 가지면서, 고분자 전환시 상온에서 술폰화 가능한 biphenyl계 단량체와 술폰화가 불가능한 sulfonyl계 단량체를 각각 합성하였다. Biphenyl계 단량체로 부터 올리고머를 합성한 후 sulfonyl계 단량체와 열적 고리화 부가중합을 하여 다양한 몰조성을 갖는 일련의 perfluorocyclobutane(PFCB)기를 포함하는 블록 공중합체를 제조하였다. 제조된 블록 공중합체를 상온에서 술폰화제인 chlorosulfonic acid(CSA)를 이용하여 후술폰화시켜 강산 이온기인 sulfonic acid를 biphenyl계 올리고머 부분에 선택적으로 도입하였다. 이렇게 제조된 술폰화된 고분자를 제막한 후 연료전지 특성을 Nafion-115와 비교하였다. 술폰화가 되는 올리고머 블록의 비율 증가에 따라 이온교환능력 (IEC)이 증가하였고 , 그에 따른 팽윤도 역시 증가하는 것을 보였다. 술폰화된 고분자들은 건조 및 습윤 상태에서도 기계적 강도가 우수하였다. 최적화된 술폰화 블록 고분자(S-2) 를 대상으로 membrane electrolyte assembly(MEA) 를 제조하여 연료전지 초기성능을 측정한 결과 Nafion-112와 유사한 전기화학적 성능을 나타내었다.

• Membrane Journal
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• v.22 no.5
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• pp.352-358
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• 2012

In this study, we found structure-property relationship for pressure retarded osmosis (PRO) membrane, between BPS-XX and BisA-XX having similar structure but different free volume. And this comparison was subdivided by controlling its sulfonation degree. BPS-XX and BisA-XX were prepared via a polycondensation reaction. The degree of sulfonation were 20 to 60 mol.%. And they were fabricated to membrane. Characteristics were analyzed to verify of free volume. And the results showed that increase of free volume normally lead to increase permeability and decrease selectivity in equivalent molecule structure. Finally, in the permeability-selectivity results, we conclude high permeability and selectivity membrane can be prepared by controlling molecular structure and free volume.

• Membrane Journal
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• v.20 no.4
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• pp.278-289
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• 2010

A series of composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) were prepared via addition of tetraethyl orthosilicate (TEOS) and solution casting method. The morphological structure, water uptake, proton conductivity of the resulting composite membranes were extensively investigated as function of the content of TEOS. By the sol-gel reaction, TEOS molecules were not completely converted to $SiO_2$ particles, but formed only oligomer-type. Also, EDS confirms that the resulting silicon dioxide was homogeneously distributed in the composite membranes. As the content of TEOS increased, the prepared membranes increased water uptake and proton conductivity at high temperature and low relative humidity condition. In particular, considerably high proton conductivity (0.015 S/cm) at $120^{\circ}C$ and 48%RH was demonstrated in the composite membrane containing 200% TEOS, which is 10 times greater than that of unmodified SPAES membrane. Also, the composite membranes were found to have enhanced thermal stability compared to the unmodified membrane.