Synthesis and Characterisation of Sulphonated Poly(arylene sulphone) Terpolymers with Triphenylphosphine Oxide Moieties for Proton Exchange Membrane Fuel Cells

被引:9
作者
Titvinidze, G. [1 ]
Kaltbeitzel, A. [1 ]
Manhart, A. [1 ]
Meyer, W. H. [1 ]
机构
[1] Max Planck Inst Polymer Res, D-55128 Mainz, Germany
关键词
Fuel Cells; Ionomer Membranes; Proton Conductivity; Sulphonated Poly(phenylene sulphone) Terpolymers; POLYMER ELECTROLYTE MEMBRANES; POLY(ETHER ETHER KETONE); STATISTICAL COPOLYMERS; MULTIBLOCK COPOLYMERS; ENGINEERING POLYMERS; IONOMER MEMBRANES; PHOSPHINE OXIDE)S; METALATION ROUTE; WATER-UPTAKE; ACID GROUPS;
D O I
10.1002/fuce.200900151
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
For application in fuel cells, a series of sulphonated poly(phenylene sulphone) terpolymers with triphenylphosphine oxide moieties as constitutional units in the polymer backbone have been prepared. The synthesis of the terpolymers represents a two-step process including: (i) an aromatic nucleophilic substitution polycondensation of three difluoro monomers with varying ratios, i.e. 3,3'-disulphonate-4,4'difluorodiphenylsulphone, 4,4'-difluorodiphenylsulphone and bis(4-fluorophenyl)phenyl phosphine oxide (BEPPO), with 4,4'-thiobisbenzenethiol yielding sulphonated poly(phenylene sulphide) terpolymers (sPPSPO) and (ii) their following oxidation with hydrogen peroxide in acidic solution to yield sulphonated poly(phenylene sulphone) terpolymers (sPPSO2PO). The structures and molecular compositions were confirmed by H-1 and C-13 NMR spectroscopy. The ion exchange capacity (IEC) was adjusted at will choosing the appropriate ratio of sulphonated and unsulphonated monomers. Terpolymers with 1.72 <= IEC <= 2.32 have been obtained. Sulphonated poly(arylene) ionomers containing only sulphone (-SO2-) linkages and phosphine oxide (-PO-) units rather than ether or sulphide in the backbone reveal a high thermal and oxidative stability. Membranes were cast either from dimethylformamide (DMF) or from dimethyl sulphoxide (DMSO) solutions. For all terpolymers some general characteristic trends were observed, such as an increase of the proton conductivity with increasing IEC, water uptake and temperature. The series of sPPSO2PO membranes offered high conductivities at high humidification, however, their performance strongly depends on the relative humidity. The mechanical properties of sulphonated poly(phenylene sulphone)s have been considerably improved by means of terpolymerisation with phenylene oxide moieties. Even under high humidification the terpolymers form clear, flexible membranes the stress at break of some membranes exceeds that of Nafion under the same conditions by 40%.
引用
收藏
页码:390 / 400
页数:11
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