Synthesis and phase transition behavior of well-defined Poly(arylene ether sulfone)s by chain growth condensation polymerization in organic media

Lee, Jinhee,Lee, Byungyong,Park, Jeyoung,Oh, Jaehoon,Kim, Taehyoung,Seo, Myungeun,Kim, Sang Youl Elsevier 2018 Polymer Vol.153 No.-

<P><B>Abstract</B></P> <P>A series of well-defined poly(arylene ether sulfone)s (PESs) as a rod-type block was synthesized by chain-growth condensation polymerization from a diphenyl sulfone-type initiator containing a fluorine leaving group and an allyl moiety. Interestingly, these oligomeric PESs exhibited lower critical solution temperature (LCST)-type phase transition behavior in organic solvents, i.e., 1,2-dimethoxyethane (DME) and chloroform. The clouding point temperature was affected by the molecular weight and concentration of the polymers. The cloud temperature decreased as the molecular weight polymers and the concentration of polymer solution increased. And also two series of rod-coil type poly(arylene ether sulfone)-<I>b</I>-polylactides were synthesized by controlled ring-opening esterification polymerization of <SMALL>DL</SMALL>-lactide with a PES-derived macroinitiator in which the allyl group was transformed into an aliphatic hydroxyl group by a thiol-ene click reaction. These diblock copolymers also exhibited LCST behavior in DME, and the nanoscale size of the aggregates increased upon heating.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Well-controlled rod-type poly(ethersulfone)s were synthesized. </LI> <LI> The poly(ethersulfone)s exhibited thermos-responsive properties in organic solvents. </LI> <LI> This phase transition behavior was also observed with diblock copolymers. </LI> <LI> Their cloud points were affected by the molecular weight and the concentration. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Ionic Aggregation Characterization of Sulfonated PEEK Ionomers Using by X-Ray and DMA Techniques

노영창,송주명,신준화,손준용 한국고분자학회 2012 Macromolecular Research Vol.20 No.5

Commercial Victrex® poly(ether ether ketone) was dissolved and sulfonated using sulfonic acid at an elevated temperature of 55-70 oC. Various techniques such as thermogravimetric analysis, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and small-angle X-ray scattering (SAXS) were employed to investigate the mechanical properties and morphology of sulfonated poly(ether ether ketone) (SPEEK) film. Sulfonation temperatures were shown to have a direct effect on the degree of sulfonation. The DMA study showed that welldeveloped α-relaxation peaks related to chain relaxation in the ionic regions shifted to higher temperatures as sulfonation degree increased. However, the β- and γ-relaxation peaks showed that the peaks related to chain relaxation in the crystalline regions shifted to lower temperatures as sulfonation degree increased. These DMA results suggest that the sulfonic acid groups act as very effective plasticizers for the intercrystalline regions. DSC thermograms showed that the glass transition shifted systematically to higher temperatures as the sulfonation degree increased. In the SAXS study, an ionic domain peak was observed and the peak position shifted to a slightly higher angle as sulfonation degree increased, implying that the number of ionic aggregates increased.

고분자 전해질 연료전지용 Poly(arylene ether sulfone) copolymer의 합성

정은아(Eun-A Jung),이인자(In-Ja Lee),윤소남(So-Nam Yun),서정균(Jeong-Kyun Seo) 한국자동차공학회 2010 한국자동차공학회 부문종합 학술대회 Vol.2010 No.5

This paper deals with a Poly(arylene ether sulfone)copolymer which is a kind of component of the Fuel Cell and is a key element of the PEMFC. 3,3′-Sulfonated-4,4′dichlorodiphenyl sulfone (SDCDPS) is composited by 4, 4′-Dichlorodiphenyl sulfone (DCDPS) and Fuming sulfuric acid whose ratio is 1 : 3.3 and is derived from Elec trophilic Sulfonation. Also, purified 3,3′-Sulfonated-4,4′-dichlorodiphenyl sulfone (SDCDPS) is gotten by recrystallization procedure of Isopropanol-H2O. Sulfonated Poly(arylene ether sulfone) (SPAES) is synthesiszed from 3,3′-Sulfonated-4,4′-dichlorodiphenyl sulfone (SDCDPS), 4,4′-Dichlorodiphenyl sulfone (DCDPS) and 4,4′ -Biphenol, and is called Aromatic Substituton and Condensation Polymerization. Poly(arylene ether sulfone) copolymer which has a very high viscosity is synthesised through direct polymerization using Potassium carbonate to catalyst. The result of synthesis are confirmed by methods such as FT-IR Spectrum and 1H-NMR Spectrum.

Organic-inorganic Nano Composite Membranes of Sulfonated Poly(Ether Sulfone-ketone) Copolymer and for Fuel Cell Application

Lee Dong-Hoon,Park Hye-Suk,Seo Dong-Wan,Kim Whan-Gi 한국분말야금학회 2006 한국분말야금학회 학술대회논문집 Vol.2006 No.1

Novel bisphenol-based wholly aromatic poly(ether sulfone-ketone) copolymer containing pendant sulfonate groups were prepared by direct aromatic nucleophilic substitution polycondensation of 4,4-difluorobenzophenone, 2,2'-disodiumsulfonyl-4,4'-fluorophenylsulfone (40mole% of bisphenol A) and bisphenol A. Polymerization proceeded quantitatively to high molecular weight in N-methyl-2-pyrrolidinone at . Organic-inorganic composite membranes were obtained by mixing organic polymers with hydrophilic (ca. 20nm) obtained by sol-gel process. The polymer and a series of composite membranes were studied by FT-IR, , differential scanning calorimetry (DSC) and thermal stability. The proton conductivity as a function of temperature decreased as content increased, but methanol permeability decreased. The nano composite membranes were found to posse all requisite properties; Ion exchange capacity (1.2meq./g), glass transition temperatures , and low affinity towards methanol .

직접 불소화에 의해 표면 개질된 SPEEK/APSf, SPEEK/APEI 바이폴라막을 이용한

김가영,정성일,임지원 한국막학회 2015 멤브레인 Vol.25 No.5

약: 본 연구에서는 Polysulfone (PSf), Polyetherimide (PEI)를 각각 비율을 달리하여 아민화하였고, Polyether ether ketone (PEEK)을 설폰화하였다. 합성한 두 이온교환고분자를 더블캐스팅방법으로 SPEEK (sulfonated PEEK)/APSf (aminated PSf) 및 SPEEK/APEI (aminated PEI) 바이폴라막을 제조하였다. 각각의 막 표면을 불소화하고, 아민화 비율에 따라 차아염소산 나트륨발생량을 비교하였다. 아민화 비율이 증가할수록 차아염소산나트륨 발생 농도 또한 증가하였다. SPEEK/APSf 3 : 1 막의 경우 불소화 전의 차아염소산나트륨 농도와 총 운전시간은 61.0 ppm, 220 min이고, 불소화한 막의 경우 58.6 ppm, 570 min이 다. 또한 SPEEK/APEI 3 : 1 막에서 역시 불소화 전후의 차아염소산나트륨 농도는 각각 60.1 ppm, 58.3 ppm이고, 총 운전시간 은 150 min에서 440 min으로 내구성이 크게 향상되었다. 따라서 표면 불소화가 막의 내구성에 중요한 역할을 한다고 사료된다. In this study, Polysulfone (PSf) and polyetherimide (PEI) as the anion exchange polymers were aminated in the different ratio whereas the polyether ether ketone (PEEK) as the cation exchange polymer was sulfonated. The bipolar membranes of SPEEK (sulfonated PEEK)/APSf (aminated PSf) and SPEEK/APEI (aminated PEI) were prepared by the double- casting method. The surfaces of bipolar membranes were fluorinated in accordance with the amination ratio and applied to produce the hypochlorite. As the amination increased, the hypochlorite concentration is also increased. Typically, for SPEEK/APSf 3 : 1 membrane, the produced hypochlorite concentration was 61.0 ppm and its durability was 220 min for the non-fluorinated membrane while for the fluorinated membrane, the concentration of 58.6 ppm and its durability lasted 570 min. Also for SPEEK/APEI 3 : 1 membrane, the hypochlorite concentrations of 60.1 ppm and 58.3 ppm for before- and after-fluorination, respectively were observed whereas the durability was remarkably developed from 150 min to 440 min. Therefore, the surface fluorination takes an important role for the development of the membrane durability.

직접 불소화에 의해 표면 개질된 SPEEK/APSf, SPEEK/APEI 바이폴라막을 이용한 차아염소산나트륨 생성

김가영,정성일,임지원 한국막학회 2015 멤브레인 Vol.25 No.5

In this study, Polysulfone (PSf) and polyetherimide (PEI) as the anion exchange polymers were aminated in the different ratio whereas the polyether ether ketone (PEEK) as the cation exchange polymer was sulfonated. The bipolar membranes of SPEEK (sulfonated PEEK)/APSf (aminated PSf) and SPEEK/APEI (aminated PEI) were prepared by the double- casting method. The surfaces of bipolar membranes were fluorinated in accordance with the amination ratio and applied to produce the hypochlorite. As the amination increased, the hypochlorite concentration is also increased. Typically, for SPEEK/APSf 3 : 1 membrane, the produced hypochlorite concentration was 61.0 ppm and its durability was 220 min for the non-fluorinated membrane while for the fluorinated membrane, the concentration of 58.6 ppm and its durability lasted 570 min. Also for SPEEK/APEI 3 : 1 membrane, the hypochlorite concentrations of 60.1 ppm and 58.3 ppm for before- and after-fluorination, respectively were observed whereas the durability was remarkably developed from 150 min to 440 min. Therefore, the surface fluorination takes an important role for the development of the membrane durability. 본 연구에서는 Polysulfone (PSf), Polyetherimide (PEI)를 각각 비율을 달리하여 아민화하였고, Polyether ether ketone (PEEK)을 설폰화하였다. 합성한 두 이온교환고분자를 더블캐스팅방법으로 SPEEK (sulfonated PEEK)/APSf (aminated PSf) 및 SPEEK/APEI (aminated PEI) 바이폴라막을 제조하였다. 각각의 막 표면을 불소화하고, 아민화 비율에 따라 차아염소산나트륨발생량을 비교하였다. 아민화 비율이 증가할수록 차아염소산나트륨 발생 농도 또한 증가하였다. SPEEK/APSf 3 : 1 막의경우 불소화 전의 차아염소산나트륨 농도와 총 운전시간은 61.0 ppm, 220 min이고, 불소화한 막의 경우 58.6 ppm, 570 min이다. 또한 SPEEK/APEI 3 : 1 막에서 역시 불소화 전후의 차아염소산나트륨 농도는 각각 60.1 ppm, 58.3 ppm이고, 총 운전시간은 150 min에서 440 min으로 내구성이 크게 향상되었다. 따라서 표면 불소화가 막의 내구성에 중요한 역할을 한다고 사료된다

Preparation and characterization of sulfonated amine-poly(ether sulfone)s for proton exchange membrane fuel cell

Seo, D.W.,Lim, Y.D.,Lee, S.H.,Jeong, Y.G.,Hong, T.W.,Kim, W.G. Pergamon Press ; Elsevier Science Ltd 2010 International journal of hydrogen energy Vol.35 No.23

Sulfonated amine-poly(ether sulfone)s (S-APES)s were prepared by nitration, reduction and sulfonation of poly(ether sulfone) (ultrason<SUP>(</SUP>R)-S6010). Poly(ether sulfone) was reacted with ammonium nitrate and trifluoroacetic anhydride to produce the nitrated poly(ether sulfone), and was followed by reduction using tin(II)chloride and sodium iodide as reducing agents to give the amino-poly(ether sulfone). The S-APES was obtained by reaction of 1,3-propanesultone and the amino-poly(ether sulfone) (NH<SUB>2</SUB>-PES) with sodium methoxide. The different degrees of nitration and reduction of poly(ether sulfone) were successfully synthesized by an optimized process. The reduction of nitro group to amino was done quantitatively, and this controlled the contents of the sulfonic acid group. The films were converted from salt to acid forms with dilute hydrochloric acid. Different contents of sulfonated unit of the S-APES were studied by FT-IR, <SUP>1</SUP>H NMR spectroscopy, differential scanning calorimetry (DSC), and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion exchange capacity (IEC), a measure of proton conductivity, was evaluated. The S-APES membranes exhibit conductivities (25 <SUP>o</SUP>C) from 1.05 x 10<SUP>-3</SUP> to 4.83 x 10<SUP>-3</SUP> S/cm, water swell from 30.25 to 66.50%, IEC from 0.38 to 0.82 meq/g, and methanol diffusion coefficients from 3.10 x 10<SUP>-7</SUP> to 4.82 x 10<SUP>-7</SUP> cm<SUP>2</SUP>/S at 25 <SUP>o</SUP>C.

Hydrocarbon membranes with high selectivity and enhanced stability for vanadium redox flow battery applications: Comparative study with sulfonated poly(ether sulfone)s and sulfonated poly(thioether ether sulfone)s

Choi, So-Won,Kim, Tae-Ho,Jo, Sang-Woo,Lee, Jang Yong,Cha, Sang-Ho,Hong, Young Taik Elsevier 2018 ELECTROCHIMICA ACTA Vol.259 No.-

<P><B>Abstract</B></P> <P>A series of sulfonated poly(ether sulfone) copolymers (SPES-Xs) with varying degrees of sulfonation were prepared and investigated as ion-exchange membranes for vanadium redox flow battery (VRFB) applications. Sulfonated poly(thioether ether sulfone) copolymers (SPTES-Xs) were initially synthesized via polycondensation, and the SPES-Xs were then obtained by oxidation of the corresponding SPTES-Xs. The SPES-X membranes showed reduced vanadium-ion permeability, low area resistance, and, thereby, much superior selectivity compared with the parent SPTES-X membranes and a Nafion115 membrane. In single-cell VRFB performance tests, a SPES-50 membrane with an ion-exchange capacity of 1.80 meq/g exhibited a higher coulombic efficiency (>99%) and energy efficiency (76–89%) than the Nafion115 membrane over a wide range of current densities from 40 to 100 mA/cm<SUP>2</SUP> and a significantly larger capacity retention (>62%) during 200 charge-discharge cycles. The SPES-X materials, in which every benzene ring is deactivated by the presence of electron-withdrawing sulfone linkages, showed much better chemical stability during <I>ex situ</I> and <I>in situ</I> tests than the SPTES-X materials, which contain an electron-donating thioether linkage in their repeat unit.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Sulfonated poly(ether sulfone) (SPES-X) membranes are investigated for VRFBs. </LI> <LI> SPES-X membranes exhibit much superior proton/vanadium ion selectivity. </LI> <LI> Enhanced <I>ex situ</I> and <I>in situ</I> chemical stability is achieved for SPES-Xs. </LI> <LI> The VRFBs with SPES-X membranes exhibit high performance and good stability. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Nafion/poly(ether(amino sulfone)) 산-염기 블렌드 전해질막을 이용한 디메틸 에테르 직접연료전지 특성연구

박선미,최원춘,남승은,이규호,오세용,이창진,강영구,Park Sun-Mi,Choi Won-Choon,Nam Seung-Eun,Lee Kew-Ho,Oh Se-Young,Lee Chang-Jin,Kang Yong-Ku 한국전기화학회 2006 한국전기화학회지 Vol.9 No.2

Nafion/poly(ether(amino sulfone)) acid-base 블렌드 고분자 전해질 막을 제조하여 이온전도도, 디메틸 에테르(DME) 투과도를 측정하였으며 이를 이용하여 직접 DME 연료전지 특성을 연구하였다. Poly(ether(amino sulfone)) (PEAS)는 아민기의 치환도가 $0.6\sim2.0$인 것을 합성하였다. Nafion/PEAS 블렌드 전해질 막은 Nafion과 PEAS를 DMF에 용해시켜서 캐스팅하는 방법으로 제조하였다. 블렌드 전해질막은 $100^{\circ}C$ 이상에서도 이온전도도가 계속 증가하였다. Nafion/PEAS-0.6(85:15) 블렌드 전해질막은 $50^{\circ}C$ 이상에서의 수소 이온전도도가 recast Nafion보다 더 높게 나타났으며 $120^{\circ}C$에서의 수소 이온전도도는 $1.42\times10^{-1}S/cm$로 측정되었다. PEAS의 아민기가 많이 치환될수록 블렌드 전해질막의 DME 투과도와 이온전도도는 비례적으로 감소하는 것을 확인할 수 있었다. $100^{\circ}C$ 이상 가압 조건에서 Nafion/PEAS 블렌드 전해질막을 사용한 직접 DME 연료전지(DDMEFC)의 최대 전력밀도가 같은 조건에서 Nafion 115를 사용한 것보다 약 50%증가하였다. 이와 같은 DDMEFC의 성능 향상은 블렌드 전해질막이 Nafion과 비교하여 고온에서의 이온전도도가 향상되었고 DME투과도가 감소하였기 때문인것으로 해석된다. Nafion/poly(ether(amino sulfone)) acid-base blend polymer electrolyte membranes were prepared and their proton conductivity and dimethyl ether permeability were investigated. Characteristics of direct dimethyl ether fuel cell (DDMEFC) performance using prepared blend membrane were studied. The increase of amine groups in the base polymer in composite membranes resulted in the decrease in dimethyl ether permeability. The proton conductivity of the blend membranes gradually increased as increasing temperature. The conductivity of Nafion/PEAS-0.6 (85:15) blend membranes was measured to be $1.42\times10^{-2}S/cm\;at\;120^{\circ}C$ which was higher than that of the recast Nafion. The performance of direct dimethyl ether fuel cell (DDMEFC) using the Nafion/PEAS blend membranes was higher than that using $Nafion^(R)115$ membrane. Enhanced performance of direct dimethyl ether fuel cells using Nafion/PEAS blend membrane was explained by reducing dimethyl ether (DME) crossover through the electrolyte membrane and maintenance of the proton conductivity at high temperature.

Nafion-Sulfonated Poly(arylene ether sulfone) Composite Membrane for Direct Methanol Fuel Cell

Choi Jisu,Kim II Tae,Kim Sung Chul,Hong Young Taik The Polymer Society of Korea 2005 Macromolecular Research Vol.13 No.6

Composite membranes of Nafion and sulfonated poly(arylene ether sulfone) were prepared. Sulfonated poly(arylene ether sulfone)s with different degrees of sulfonation were blended with Nafion to reduce the methanol crossover. The morphology, proton conductivity and methanol permeability of the resulting composite membranes were investigated by SEM, EDAX, AC impedance spectroscopy and permeability measuring instrument. The cross­sections of the composite membranes showed a phase separated morphology. The morphology and phase separation mechanism could be controlled by varying the blend ratio and the degree of sulfonation of poly(arylene ether sulfone). These complex morphologies can be applied for reducing methanol crossover. The methanol permeability and proton conductivity of the composite membranes were lower than those of Nafion 117 membrane since the development of an ionic pathway in the blend membrane was more difficult than that in Nafion itself.