期刊
RSC ADVANCES
卷 10, 期 22, 页码 12810-12822出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0ra01816c
关键词
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资金
- New Energy and Industrial Technology Development Organisation (NEDO)
- Ministry of Education, Culture, Sports, Science and Technology, Japan [17H03119]
- Grants-in-Aid for Scientific Research [17H03119] Funding Source: KAKEN
To achieve precise control of sulfonated polymer structures, a series of poly(p-phenylene)-based ionomers with well-controlled ion exchange capacities (IECs) were synthesised via a three-step technique: (1) preceding sulfonation of the monomer with a protecting group, (2) nickel(0) catalysed coupling polymerisation, and (3) cleavage of the protecting group of the polymers. 2,2-Dimethylpropyl-4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonate (NS-DPBP) was synthesised as the preceding sulfonated monomer by treatment with chlorosulfuric acid and neopentyl alcohol. NS-DPBP was readily soluble in various organic solvents and stable during the nickel(0) catalysed coupling reaction. Sulfonated poly(4-phenoxybenzoyl-1,4-phenylene) (S-PPBP) homopolymer and seven types of random copolymers (S-PPBP-co-PPBP) with different IECs were obtained by varying the stoichiometry of NS-DPBP. The IECs and weight average molecular weights (M(w)s) of ionomers were in the range of 0.41-2.84 meq. g(-1) and 143 000-465 000 g mol(-1), respectively. The water uptake, proton conductivities, and water diffusion properties of ionomers exhibited a strong IEC dependence. Upon increasing the IEC of S-PPBP-co-PPBPs from 0.86 to 2.40 meq. g(-1), the conductivities increased from 6.9 x 10(-6) S cm(-1) to 1.8 x 10(-1) S cm(-1) at 90% RH. S-PPBP and S-PPBP-co-PPBP (4 : 1) with IEC values >2.40 meq. g(-1) exhibited fast water diffusion (1.6 x 10(-11) to 8.0 x 10(-10) m(2) s(-1)), and were comparable to commercial perfluorosulfuric acid polymers. When fully hydrated, the maximum power density and the limiting current density of membrane electrode assemblies (MEAs) prepared with S-PPBP-co-PPBP (4 : 1) were 712 mW cm(-2) and 1840 mA cm(-2), respectively.
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