• 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.

• Polymer(Korea)
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• v.26 no.4
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• pp.415-421
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• 2002

A sulfonated PP-g-styrene ion-exchange hollow fiber membrane was prepared by pre-irradiation method with E-beam followed by sulfonation reaction. Degree of grafting increased with the increase of styrene monomer concentration and showed the maximum value of 128% at 80% of styrene monomer composition. Sulfonation yield increased with the degree of grafting. At 100% degree of grafting, sulfonation yield showed the maximum value of 13.4%. Ion exchange capacity of sulfonated HPP-g-styrene of 3.42 meq/g was attained, resulting in the remarkable increase of adsorption ability BET analysis proved that the surface area of sulfonated HPP-g-styrene was 62.54 $m^2/g$ and the mean pore size was 25 $\AA$. From the BSA adsorption experiments, the adsorption amount of BSA was increased with sulfonation. At 13.4% sulfonation yield the adsorption amount of BSA was maximum as 3.8 mg/g. Sulfonated HPP-g-styrene was synthesized successfully and suitable for the adsorption and separation of BSA.

• Membrane Journal
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• v.29 no.5
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• pp.252-262
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• 2019

A sulfonated star branched poly(styrene-b-butadiene-b-styrene) triblock copolymer (SSBS) was synthesized with varying degrees of sulfonation. The effective sulfonation on the butadiene block was confirmed by FT-IR spectroscopy. Ion exchange capacity by titration was used to determine the degree of sulfonation. The synthesized polymer observed enhanced water uptake and proton conductivity. At room temperature, the SSBS with 25 mol% degree of sulfonation showed an outstanding proton conductivity of 0.114 S/cm, similar to that of commercial membrane, Nafion. The effect of temperature at constant relative humidity on conductivity resulted to a remarkable increase in proton conductivity. Methanol permeability studies showed a value lower than Nafion for all the sulfonated membranes. Structural nature observed using AFM showed that the membranes observed microphase separated nanostructures and the connectivity of the interionic channels.

• Korean Chemical Engineering Research
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• v.49 no.2
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• pp.211-217
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• 2011

In this study, ion exchange membranes were prepared using high impact polystyrene(HIPS) with various crosslinking and sulfonation time. Degree of sulfonation(DS) of sulfonated HIPS(SHIPS) membrane was increased with sulfonation time and decreased with crosslinking time. The highest value of DS was 66%. Also, water uptake and ion exchange capacity(IEC) of SHIPS membrane were decreased with degree of crosslinking and increased with sulfonation time. Then their values were 35.2% and 1.55 meq/g, respectively. Electrical resistance and ion conductivity of the membranes were showed more excellent value with sulfonation time. The maximum value of electrical resistance and ion conductivity were $0.4\Omega{\cdot}cm^{2}$ and 0.1 S/cm, respectively. It is indicated that the SHIPS membrane has the higher performance compare with Nafion 117. Durability of SHIPS membranes in a organic solvent was increased with increasing crosslinking time. The surface roughness of HIPS membranes were confirmed with SEM that was become uneven surface with progressing sulfonation.

• Korean Chemical Engineering Research
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• v.49 no.1
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• pp.69-74
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• 2011

In this study, it was prepared for nanofiber with high impact polystyrene(HIPS). HIPS is able to crosslinking after electrospinning with crosslinking agent and it could overcome brittle characteristics of polystyrene(PS). After thermal crosslinking, HIPS nanofiber was sulfonated by sulfuric acid. It was investigated FT-IR, XPS, water uptake, ion exchange capacity(IEC), SEM, and contact angle. According to the result of FT-IR and XPS, it was increased due to introduce the hydrophilic group($SO_3H$) in the HIPS nanofiber. The highest water uptake and IEC were 75.6%, 2.67 meq/ g at 120 min sulfonation time with 7.5 wt% DVB.

• Korean Chemical Engineering Research
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• v.48 no.6
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• pp.731-736
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• 2010

In this study, the sulfonated SBS cation-exchange membrane was prepared by post-sulfonation. Degree of sulfonation(DS), water-uptake, ion exchange capacity and electrical resistance and conductivity of sulfonated SBS were investigated as a function of sulfonation time. The DS of sulfonated SBS membrane was increased with increasing the reaction time and concentration of sulfuric acid. The maximum value of DS was 24.0%. And also, the water uptake and ion exchange capacity of the sulfonated SBS membrane were increased as increasing the value of DS. The values of water uptake and IEC were 41.2% and 0.80 meq/g, respectively. The electrical resistance and conductivity of the membrane showed $23.6{\Omega}{\cdot}cm^2$ and $4.24{\times}10^{-4}S/cm$, respectively.

• Membrane Journal
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• v.15 no.4
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• pp.355-362
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• 2005

A PFCB-containing biphenylene ether polymer was synthesized and sulfonated using chlorosulfonic acid and then cast into membranes from their solutions for fuel cell applications. Sulfonation reactions were carried out by changing the molar ratio of chlorosulfonic acid and the PFCB-containing biphenylene ether polymer under fixed time and temperature. The resulting sulfonated polymers showed different sulfonation degree (SD), ion exchange capacity (IEC), and water uptake. With the increment of the content of chlorosulfonic acid, the SD, IEC, water uptake of the sulfonated polymer membranes increased. The ion conductivity of the sulfonated PFCB-containing biphenylene ether polymers was compared with that of Nafion 115.

• Polymer(Korea)
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• v.33 no.6
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• pp.608-614
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• 2009

The cation-exchange membrane which was sulfonated styrene-ethylene/buthlene-styrene(SEBS) block copolymer containing the high impact polystyrene (HIPS) was prepared via post-sulfonation and casting method using the epoxidized polybutadiene and divinylbenzene as crosslinking agents. Post-sulfonation was carried out with sulfuric acid as sulfonating agent and silver sulfate as initiator in the nitrogen atmosphere. The basic properties of membranes, degree of sulfonation (DS), water uptake, ion-exchange capacity (IEC), electrical resistance, and modulus have been examined. DS of membrane increased with increasing the sulfonation time. The maximum DS of membrane containing 10 wt% HIPS was 83.6 %. The water uptake and IEC of membranes gradually increased as increasing the DS. The maximum water uptake and IEC of membranes were 43.8 % and 1.14 meq/g, respectively. The lowest electrical resistance of membrane containing the 20 wt% HIPS was $83\;\Omega{\cdot}cm^2$. The electrical conductivity of membrane containing 10 wt% HIPS was $1.22\times10^{-4}S/cm$. The modulus of membrane increased with increasing DS and these values were 153 and $204\;kgf/cm^2$ before and after sulfonation, respectively.

• Membrane Journal
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• v.16 no.4
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• pp.241-251
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• 2006

In this study, crosslinked copolyimides with random (r-) and block (b-) structure were fabricated using N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid and pentanediol as crosslinkers. Linear r- and b-sulfonated copolyimides were also fabricated for comparison. Ion exchange capacities of r- and b-copolyimides were very similar to each other owing to their strong dependence of sulfonic acid content. The physical crosslinking via dimerization of carboxylic acid groups induced a reduced average interchain distance in b-copolyimide without crosslinkers. Consequently, its water uptake and methanol permeability were lower than those of r-sulfonated copolyimides. Simultaneously, the reduced interchain distance increased the content of fixed-charged ions per unit volume. The high fixed-charged ion density contributed to an enhancement of proton conductivity In the b-sulfonated copolyimide. Crosslinking caused the reduction of average interchain distance between polymer chains irrespective of types of crosslinker and polymer structure, leading to low methanol permeability. On the contrary, their proton conductivity was improved owing to formation of effective hydrophilic channels responsible for proton conduction. In particular, this trend was observed in r-copolyimide containing a fixed charged ion.

• 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.