• Journal of the Korean Chemical Society
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• v.53 no.3
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• pp.345-354
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• 2009

Sulfonated poly(ether sulfone)s (PESs) with a network structure were prepared by heat-induced crosslinking of the allyl-terminated telechelic sulfone polymers using a bisazide and their structure was analyzed by $^1H$ NMR. Having both uniform distribution of the hydrophilic conductive sites and controlled hydrophobic nature by minimized crosslinking, the crosslinked polymer (PES-60) membrane offered excellent proton conductivity at high temperature with a good thermal stability. In addition, selectivity of the crosslinked membrane (PES-60) was more than three times than that of Nafion$^{(R)}$.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.195-196
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• 2009

술폰화 폴리아릴렌에테르술폰 공중합체를 기본구조로 한, 6F OH를 알코올 단량체로 사용하여 블록 공중합체를 직접 중합법으로 합성하였다. 이때 각각의 소수성-친수성 소중합체들은 동일한 분자량을 이용하여 합성했으며 그때의 두 소중합체의 몰비는 1:1로 하여 블록 공중합체의 술폰화도를 50%로 고정하였다. N-메틸-2피롤리돈(NMP) 용매 상에서 연료전지용 고분자 전해질 막을 제조하여 이온전도도 및 메탄올 투과도등의 측정을 통하여 최종 블록 공중합체 전해질 막의 기본 특성을 파악했다. 소수성-친수성 소중합체의 분자량을 조절함에 따라 최종 전해질 막의 이온 전도도를 향상시킬 수 있음이 확인되었고, 연료전지 성능 테스트 결과에서도 나피온(Nafion 115)과 비슷한 성능을 보였다.

• Membrane Journal
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• v.19 no.4
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• pp.291-301
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• 2009

Double-layered polymer electrolyte membranes were prepared from two different sulfonated poly(aryl ether sulfone) copolymers by the two-step solution casting method for direct methanol fuel cells (DMFC). Sulfonation degrees were adjusted 10% (SPAES-10) and 50% (SPAES-50) by controlling monomer ratios, and the weight ratios of SPAES-10 copolymer were varied in the range of 5~20% to investigate the effect of thickness of coating layers on the membranes. Proton conducting layers were fabricated from SPAES-50 solutions of N-methyl-2-pyrrolidone (NMP) by a solution casting technique, and coating layers formed on the semiliquid surface of the conducting layer by pouring of SPAES-10-NMP solutions onto. It was found that double-layered polymer electrolyte membrane could significantly reduce the methanol crossover through the membrane and maintain high proton conductivities being comparable to single-layered SPAES-50 membrane. The maximum power density of membrane-electrolyte assembly (MEA) at the condition of $60^{\circ}C$ and 2 M methanol-air was $134.01\;mW/cm^2$ for the membrane prepared in the 5 wt-% of SPAES-10 copolymer, and it was corresponding to the 105.5% of the performance of the commercial Nafion 115 membrane.

• 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.

• Journal of the Korean Electrochemical Society
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• v.19 no.2
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• pp.45-49
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• 2016

In order to mitigate oxidative degradation of polymer membrane during fuel cell operation, an organic radical quencher was introduced. Rutin was selected as a radical quencher and mixed with sulfonated poly(arylene ether sulfone) to prepare composite membrane. Physicochemical properties of the composite membranes such as water uptake and proton conductivity were characterized. Hydrogen peroxide exposure experiment, which can mimic accelerated oxidative stability test during fuel cell operation, was adopted to evaluate the oxidative stability of the membranes. The composite membranes containing Rutin showed similar proton conductivity and enhanced oxidative stability compared to pristine ones.

• Membrane Journal
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• v.16 no.3
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• pp.221-229
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• 2006

This study is about the preparation and characterization of sulfonated random copolymer membranes containing perfluorocyclobutane (PFCB), fluorenyl, and sulfonyl units. The polymers were prepared through three synthetic steps, that is, the synthesis of a trofluorovinylether-terminated monomer, its thermal polymerization, and post-sulfonation using chlorosulfonic acid. A series of sulfonated random copolymers with different ion exchange capacity (IEC) were prepared by changing contents of fluorenyl uints in polymers with fixed molar ratio of chlorosulfonic acid during the post-sulfonation reaction. All the synthesized compounds were characterized by FT-lR, $^1H-NMR$, $^{19}F-NMR$, and Mass spectroscopy. As the content of sulfonated fluorenyl units increased, the IEC, water uptake, and ion conductivity of the sulfonated random copolymer membranes increased. The sulfonated random copolymer S-1 and S-2 showed higher values of ion conductivity than the Nafion-115 in a wide range of temperatures ($25{\sim}80^{\circ}C$).

• 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.

• Journal of Hydrogen and New Energy
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• v.21 no.4
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• pp.307-312
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• 2010

Poly (ether sulfone)s with Bisphenol-TP and Bisphenol-AF were prepared with Bisphenol-TP <4,4-dihydroxy tetraphenyl methane>, 4-Fluorophenyl sulfone, and Bisphenol-AF <4,4-(hexafluoroisopropylidene) diphenol> using Potassium carbonate in Sulfolane at $210^{\circ}C$. Sulfonated PBTP-AF were obtained by reaction of Chlorosulfuric acid with copolymers. A series of copolymers were studied by $^1H$-NMR spectroscopy, Differential Scanning Calorimeter (DSC), and Thermo Gravimetric Analysis (TGA). Sorption experiments were conducted to observe the interaction of polymers with water and methanol.

• Membrane Journal
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• v.16 no.1
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• pp.16-24
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• 2006

We report on the preparation and characterization of sulfonated polymer membranes containing perfluorocyclobutane (PFCB) units and fluorene units. The polymers were prepared through three synthetic steps, that is, the synthesis of a trifluorovinylether-terminated monomer, its thermal polymerization, and post-sulfonation using chlorosulfonic acid. A series of sulfonated polymers with different ion exchange capacity (IEC) were prepared by changing the content of chlorosulfonic acid during the post-sulfonation reaction. All the synthesized compounds were characterized by FT-IR, $^{1}H-NMR,\;^{19}F-NMR$, and Mass spectroscopy. As the content of chlorosulfonic acid increased, the SD, IEC, water uptake, and ion conductivity of the sulfonated polymer membranes increased. The sulfonated polymer 4 showed higher values of ion conductivity than the Nafion-$115^{\circledR}$ in a wide range of temperatures ($25{\sim}80^{\circ}C$).

• Membrane Journal
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• v.26 no.6
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• pp.458-462
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• 2016

Saline water electrolysis, known as chlor-alkali (CA) membrane process, is an electrochemical process to generate valued chemicals such as chlorine, hydrogen and sodium hydroxide with high purities higher than 99%, using an electrolytic cell composed of cation exchange membrane, anode and cathode. It is necessary to reduce energy consumption per a unit chemical production. This issue can be solved by decreasing intrinsic resistance of the membrane and the electrodes and/or by reducing their interfacial resistance. In this study, the electron radiation grafting of a $Na^+$ ion-selective polymer was conducted onto a hydrocarbon sulfonated ionomer membrane with high chemical resistance. This approach was effective in improving electrochemical efficiency via the synergistic effect of relatively fast $Na^+$ ion conduction and reduced interfacial resistance.