• 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.

• 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.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1763-1770
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• 2013

A series of the block copolymers were successfully synthesized from post-sulfonated hydrophilic and hydrophobic macromers via three-step copolymerization. The degrees of sulfonation (DS) of the copolymers (10%, 30%, or 50%) were controlled by changing the molar ratio of the hydrophilic and hydrophobic parts. The resulting block copolymers were characterized by $^1H$ NMR and other technologies. The membranes were successfully cast using dimethyl sulfoxide (DMSO) solution at $100^{\circ}C$. The copolymers were characterized to confirm chemical structure by $^1H$ NMR and FT-IR. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) demonstrated that all sulfonated block copolymers exhibited good thermal stability with an initial weight loss at temperatures above $240^{\circ}C$. The membranes showed acceptable ion exchange capacity (IEC) and water uptake values in accordance with DS. The maximum proton conductivity was 184 mS $cm^{-1}$ in block copolymer-50 at $60^{\circ}C$ and 100% relative humidity, while the conductivity of Nifion-115 was 160 mS $cm^{-1}$ under the same measurement conditions. AFM images of the block copolymer membranes showed well separated the hydrophilic and hydrophobic domains. From the observed results it is that the prepared block membranes can be considered as suitable polymer electrolyte membranes for the application of polymer electrolyte membrane fuel cells (PEMFC).

• Polymer(Korea)
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• v.34 no.2
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• pp.137-143
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• 2010

A series of partially fluorinated, sulfonated poly(biphenylene-co-sulfone)ether containing perfluorocyclobutane(PFCB) groups were prepared for fuel cell applications through three synthetic steps: synthesis of trifluorovinylether-terminated monomers, thermal cycloaddition and post-sulfonation. Two kinds of trifluorovinylether-terminated monomers were synthesized and statistically copolymerized via thermal cycloaddition to obtain a series of polymers containing 20-60 mol% of biphenyl units(PBS-X). The post-sulfonation of PBS-X was carried out using chlorosulfonic acid(CSA) to obtain copolymers with various sulfonation levels(SPBS-X). All the synthesized compounds, monomers and polymers were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR. It was confirmed that the ion exchange capacity(IEC), water uptake and ion conductivity of SPBS-X increased with the increment of sulfonated biphenyl units. Particularly, SPBS-60 showed higher ion conductivity compared to Nafion$^{(R)}$-115 at 25~80 $^{\circ}C$.

• 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 ($25{\sim}80^{\circ}C$).

• Journal of Hydrogen and New Energy
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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.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.58-59
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• 2006

Less than a decade ago, most alternate membrane materials for fuel cells relied upon a post-sulfonation process to generate ionic groups capable of transporting protons from the anode to the cathode. These random post sulfonations showed some promise, but in general they produced materials that were not sufficiently stable or protonically conductive at ion exchange capacities where aqueous swelling could be restricted. Our group began to synthesize disulfonated monomers that could be used to incorporate into random copolymer proton exchange membranes. The expected limitation was that the aromatic polymers might not be stable enough to withstand fuel cell conditions. However, this was mostly based upon an accelerated test known was the Fenton's Reagent Test, which did not seem to this author as being a reliable predictor of performance. A much better approach has been to evaluate the open circuit voltage (OCV) for alternate membranes, as well as the benchmark perfluorosulfonic acid systems. When this is done, the aromatic ionomers of this study, primarily based upon disulfonated polyarylene ether sulfones, show up quite well. Real time 3000 hours DMFC results have also been generated. Obtaining conductive materials at low humidities is another major issue where alternate membranes have not been particularly successful. In order to address this problem, multiblock copolymers with relatively high water diffusion coefficients have been designed, which show promise for conductivity at lowered humidity.

• 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.21 no.1
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• pp.1-12
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• 2011

Partially fluorinated poly(arylene ether sulfone) block ionomer membranes with different branch degree for fuel cell applications were investigated. A sulfonable monomer, a non-sulfonable monomer and a trifunctional branching agent were synthesized and the sulfonable monomer was oligomerized to obtain block structures. The oligomer was then further polymerized with the non-sulfonable monomer and the branching agent. The mole ratio of oligomer : non-sulfonable monomer was fixed at 4:6 and the content of the branching agent was varied from 0 to 2 mol% (BBC-40Bx). Post-sulfonation of BBC-40Bx was carried out using chlorosulfonic acid (CSA) (SBBC-40Bx). All the synthesized compounds were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR. It was confirmed that the ion exchange capacity (IEC), water uptake and ion conductivity of SBBC-40Bx increased with the increment of branching agent content.

• Membrane Journal
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• v.22 no.3
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• pp.191-200
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• 2012

New composite membranes were manufactured by impregnating post-sulfonated poly(arylene ether sulfone)s containing perfluorocyclobutane (PFCB) groups into porous polytetrafluoroethylene (PTFE) films. Two kinds of post-sulfonated poly(arylene ether sulfone)s with two different monomer ratios (sulfonable biphenylene monomer : non-sulfonable sulfonyl monomer = 6 : 4, 4 : 6) were first prepared through three synthetic steps: synthesis of trifluorovinylether-terminated monomers, thermal cycloaddition polymerization and post-sulfonation using chlorosulfonic acid (CSA). The composite membranes were then prepared by adjusting the concentrations (5~20 wt%) of the resulting copolymers impregnated in the PTFE films. The water uptake, ion exchange capacity (IEC) and ion conductivity of the composite membranes were characterized and compared with their unreinforced dense membranes and Nafion. All the synthesized compounds, monomers and polymers were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR and the composite membranes were observed with scanning electron micrographs (SEM).