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sulfonated polyimideS CONTAINING PYRIDINE GROUPS AS PROTON EXCHANGE MEMBRANE MATERIALS

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Chinese Journal of Polymer Science 2011年第5期29卷 532-539页

作者：高连勋 State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied Chemistry Chinese Academy of Sciences

A series of sulfonated polyimides （SPIs） containing pyridine groups were prepared by direct polycondensation from 1,4,5,8-naphthalenetetracarboxylic dianhydride （NTDA）, 4,4＇-diaminodiphenyl ether-2,2＇-disulfonic acid （ODADS） and 4-（4-methoxy）phenyl-2,6-bis（4-aminophenyl）pyridine （DAM）. The resulting copolymers displayed good solubility in common organic solvents. Flexible, transparent, tough membranes were obtained via solution casting. All the films showed high thermal stability with desulfonation temperature over 300℃. They exhibited prominent mechanical properties with Young＇s modulus around 2.0 GPa. High proton conductivity （0.23 S/cm at 100% RH） was also observed. More importantly, the new materials exhibited low water uptake （30 wt%-75 wt% at 80℃） and improved water stability, which were attributed to the acid-base interaction between sulfonic acid and pyridine functional groups.

关键词： sulfonated polyimide Pyridine Acid-base interaction Proton conductivity. : sulfonated polyimide Pyridine Acid-base interaction Proton conductivity.

sulfonated polyimides Containing 1,2,4-Triazole Groups for Proton Exchange Membranes

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Chinese Journal of Polymer Science 2014年第7期32卷 941-952页

作者： Rui Lei 高连勋 Ri-zhe Jin Xue-peng Qiu Shaanxi Coal and Chemical Technology Institute Co. Ltd. State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied ChemistryChinese Academy of Sciences

A series of sulfonated polyimide copolymers as novel proton exchange materials were synthesized by the polycondensation of 1,4,5,8-naphthalene-tetracarboxylic dianhydride （NTDA）, sulfonated diamine based on pyridine group and diamine containing N-phenyl-1,2,4-triazole moiety. Flexible, transparent and tough membranes with high thermal stability and good mechanical properties were obtained. They exhibited good stability in boiling water and Fenton＇s reagent at 80 ℃. More interestingly, a nonlinear relationship between proton conductivities of the resulting membranes and the degree of sulfonation （DS） was observed. The membrane with 50% DS exhibited the maximum proton conductivity, which was due to the combinational contributions of sulfonic acid and N-pheny-1,2,4-triazole groups. Thus, the N-phenyl-l,2,4- triazole moiety in this study not only can depress water absorption but also increase proton conductivity, especially at low DS.

关键词： Triazole Acid-base interaction sulfonated polyimide Proton exchange membrane.

Synthesis and Characterization of Novel sulfonated polyimides from 4,6-Bis（4-aminophenoxy）-naphthalene-2-sulfonic Acid

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Chemical Research in Chinese Universities 2013年第6期29卷 1225-1228页

作者： LI Yu-han WANG Wei-jian JIN Ri-zhe GAO Lian-xun College of Food Science and Engineering Jilin Business and Technology College Changchun 130062 P.R.China State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied ChemistryChinese Academy of Sciences Changchun 130022 P.R.China

A novel sulfonated diamine monomer, 4,6-bis（4-arninophenoxy）-naphthalene-2-sulfonic acid（BAPNS）, was synthesized. A series of sulfonated polyimide copolymers was prepared from BAPNS, 1,4,5,8-naphthalenetetracarboxylic dianhydride（NTDA） and nonsulfonated diamine 4,4＇-diaminodiphenyl ether（ODA）. Flexible, transparent, and mechanically strong membranes were obtained. The novel sulfonated polyimide（SPI） membranes show higher conductivity, for example, SPI-100 shows a conductivity of 0.0698 S/cm at 80℃（SPI-X： Xrefers to molar fraction of BAPNS）. The membranes exhibit the permeability of methanol from 2.18×10^-7 cm2/s to 2.57×10^-7 cm2/s, which is much lower than that of Nafion（2.00×10 6 cm^2/s）. The copolymers were thermally stable up to 330℃. The sulfonated polyimide copolymers also show reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 100%（molar fraction） BAPNS is 1.35 GPa under high moisture condi- tions. The optimum concentration of BAPNS was found to be 100%（molar fraction） from the view point of proton conductivity, methanol permeability, and membrane stability.

关键词： sulfonated polyimide Proton conductivity Proton-exchange membrane

Synthesis and Characterization of Photosensitive Poly(imide sulfonates) for Fuel Cell Application

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Journal of Wuhan University of Technology(Materials Science) 2013年第4期28卷 635-642页

作者：文璞山 LIU Hui KIM Jae Hoon LI Xiangdan LEE Myong-Hoon Department of Polymer Science and Technology Research Center for Advanced Materials Development Chonbuk National University College of Chemistry and Material Science South-Central University for Nationalities The Graduate School of Flexible and Printable Electronics Chonbuk National University

The novel sulfonated polyimide membranes were successfully synthesized by thermal imidization with monomers of 4,4＇-（hexafluoroisopropylidene）diphthalic anhydride （6FDA）, 4,4＇-diamino- diphenyl ether-2,2＇-disulfonic acid （SODA） and 3,3 ＇-diaminochalcone （3DAC）. Photosensitive chalcone moiety was introduced to the main chain of copolymers, and the photocrosslinking of resulting copolymer in aqueous electrolyte was attempted. A series of sulfonated copolyimide precursors containing chalcone functional groups in the main chain were prepared with different sulfonation degrees by controlling the molar ratio of SODA, 6FDA and 3DAC. The polymer membranes were prepared from these sulfonated aromatic precursors by solution casting and subsequent thermal imidization. The crosslinking with UV irradiation was attempted in the presence or absence of distilled water. The characterizations of the resulting membrane such as the ion-exchange capacity, water absorption and ionic conductivity were performed with respect to the copolymer compositions and the photocrosslinking conditions.

关键词： sulfonated polyimide photosensitive chalcone polymer electrolyte membrane fuel cell

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新型磺化聚酰亚胺的合成与性能研究

新型磺化聚酰亚胺的合成与性能研究