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Poly(para-phenylene) ionomer membranes: effect of methyl and trifluoromethyl substituents
Polymer Chemistry ( IF 4.1 ) Pub Date : 2021-09-15 , DOI: 10.1039/d1py01141c Fanghua Liu 1 , Jinju Ahn 2 , Junpei Miyake 3 , Kenji Miyatake 3, 4, 5
Polymer Chemistry ( IF 4.1 ) Pub Date : 2021-09-15 , DOI: 10.1039/d1py01141c Fanghua Liu 1 , Jinju Ahn 2 , Junpei Miyake 3 , Kenji Miyatake 3, 4, 5
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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 (lp, index of linearity, distance required for a polymer chain to bend by 90° 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 (Mn = 28–30 kDa and Mw = 88–100 kDa for SPP-BP-CH3 and Mn = 49–149 kDa and Mw = 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.).
中文翻译：
聚（对亚苯基）离聚物膜：甲基和三氟甲基取代基的影响
通过使用甲基和三氟甲基取代基获得了具有高分子量和成膜能力的磺化聚（对亚苯基）。通过引入这些取代基，聚合物主链的线性度降低；2,2'-二甲基-1,1'-联苯 (BP-CH 3 ) 和 2的均聚物的持久长度（l p，线性指数，聚合物链平均弯曲 90° 所需的距离）， 2'-双（三氟甲基）-1,1'-联苯（BP-CF 3）约为。分别为 350.6 nm 和 87.7 nm，通过对骨架构象进行数值平均估计。含磺基对苯撑、SPP-BP-CH 3和 SPP-BP-CF 3 的共聚物，用高分子量得到的（中号Ñ = 28-30 kDa的和中号瓦特= 88-100千道尔顿为SPP-BP-CH 3和中号Ñ = 49-149千道尔顿和中号瓦特= 161-316 kDa的用于SPP- BP-CF 3，分别）以通过从溶液中浇铸来提供柔性膜。尽管取代基具有更强的疏水性，但 SPP-BP-CF 3膜表现出比具有可比离子交换容量 (IEC) 的SPP-BP-CH 3膜更高的吸水率和质子传导率。SPP-BP-CF 3膜显示出比 SPP-BP-CH 3稍高的最大应变 (2.9–5.2%)膜（1.1-2.1%），正如预期的那样，BP-CF 3均聚物的持续长度较小，从而导致更高的破裂能量。虽然 SPP-BP-CH 3在苛刻的氧化条件下分解，但 SPP-BP-CF 3 的氧化稳定性更高，并且在重量、分子量、分子结构和膜性能（质子传导性、机械性能等）方面的变化可以忽略不计。
更新日期：2021-09-27
中文翻译：
聚（对亚苯基）离聚物膜：甲基和三氟甲基取代基的影响
通过使用甲基和三氟甲基取代基获得了具有高分子量和成膜能力的磺化聚（对亚苯基）。通过引入这些取代基，聚合物主链的线性度降低；2,2'-二甲基-1,1'-联苯 (BP-CH 3 ) 和 2的均聚物的持久长度（l p，线性指数，聚合物链平均弯曲 90° 所需的距离）， 2'-双（三氟甲基）-1,1'-联苯（BP-CF 3）约为。分别为 350.6 nm 和 87.7 nm，通过对骨架构象进行数值平均估计。含磺基对苯撑、SPP-BP-CH 3和 SPP-BP-CF 3 的共聚物，用高分子量得到的（中号Ñ = 28-30 kDa的和中号瓦特= 88-100千道尔顿为SPP-BP-CH 3和中号Ñ = 49-149千道尔顿和中号瓦特= 161-316 kDa的用于SPP- BP-CF 3，分别）以通过从溶液中浇铸来提供柔性膜。尽管取代基具有更强的疏水性，但 SPP-BP-CF 3膜表现出比具有可比离子交换容量 (IEC) 的SPP-BP-CH 3膜更高的吸水率和质子传导率。SPP-BP-CF 3膜显示出比 SPP-BP-CH 3稍高的最大应变 (2.9–5.2%)膜（1.1-2.1%），正如预期的那样，BP-CF 3均聚物的持续长度较小，从而导致更高的破裂能量。虽然 SPP-BP-CH 3在苛刻的氧化条件下分解，但 SPP-BP-CF 3 的氧化稳定性更高，并且在重量、分子量、分子结构和膜性能（质子传导性、机械性能等）方面的变化可以忽略不计。
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