4.7 Article

Poly(para-phenylene) ionomer membranes: effect of methyl and trifluoromethyl substituents

期刊

POLYMER CHEMISTRY
卷 12, 期 42, 页码 -

出版社

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1py01141c

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资金

  1. New Energy and Industrial Technology Development Organization (NEDO)
  2. JSPS KAKENHI [18H05515, 21H01650]
  3. Japan Science and Technology (JST) through SICORP [JPMJSC18H8]
  4. JKA promotion funds from AUTORACE
  5. Thermal and Electric Energy Technology Foundation
  6. China Scholarship Council
  7. Grants-in-Aid for Scientific Research [21H01650] Funding Source: KAKEN

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Sulfonated poly(para-phenylene)s with high molecular weight and membrane-forming capability were obtained using methyl and trifluoromethyl substituents. Despite being more hydrophobic, SPP-BP-CF3 membranes exhibited higher water uptake and proton conductivity than SPP-BP-CH3 membranes with comparable ion exchange capacity.
Sulfonated poly(para-phenylene)s with a high molecular weight and membrane forming capability were obtained by using methyl and trifluoromethyl substituents. The linearity of the polymer main chain decreased by introducing these substituents; the persistence length (l(p), index of linearity, distance required for a polymer chain to bend by 90 degrees on average) of homopolymers for 2,2 '-dimethyl-1,1 '-biphenyl (BP-CH3) and 2,2 '-bis(trifluoromethyl)-1,1 '-biphenyl (BP-CF3) was ca.350.6 nm and 87.7 nm, respectively, estimated by numerically averaging backbone conformations. Copolymers with sulfo-para-phenylene, SPP-BP-CH3 and SPP-BP-CF3, were obtained with a high molecular weight (M-n = 28-30 kDa and M-w = 88-100 kDa for SPP-BP-CH3 and M-n = 49-149 kDa and M-w = 161-316 kDa for SPP-BP-CF3, respectively) to provide flexible membranes by casting from the solution. Despite the more hydrophobic nature of the substituents, SPP-BP-CF3 membranes showed higher water uptake and proton conductivity than SPP-BP-CH3 membranes with comparable ion exchange capacity (IEC). SPP-BP-CF3 membranes showed slightly higher maximum strain (2.9-5.2%) than SPP-BP-CH3 membranes (1.1-2.1%), leading to a higher rupture energy as expected from the smaller persistence length of BP-CF3 homopolymers. While SPP-BP-CH3 decomposed under harsh oxidative conditions, SPP-BP-CF3 was more oxidatively stable and exhibited negligible changes in the weight, molecular weight, molecular structure and membrane properties (proton conductivity, mechanical properties, etc.).

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