Impact of the Synthesis Method on the Solid-State Charge Transport of Radical Polymers.
Impact of the Synthesis Method on the Solid-State Charge Transport of Radical Polymers.
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DOI：
10.1039/c7tc04645f
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发表时间：
2018-01-07
期刊：
影响因子：
--
通讯作者：
Ober CK
中科院分区：
文献类型：
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作者：
Zhang Y;Park A;Cintora A;McMillan SR;Harmon NJ;Moehle A;Flatté ME;Fuchs GD;Ober CK
聚（2，2，6，6-四甲基哌啶基氧基甲基丙烯酸酯）（PTMA）是一种氧化还原活性聚合物，其自由基悬挂在绝缘主链上，但其室温电导率的报道相互矛盾。为了了解文献和合成方法中发现的变化，我们使用三种活性方法制备PTMA-阴离子，ATRP和RAFT聚合。我们发现，所有这三种合成方法生产PTMA自由基产率为70 - 80%，控制分子量，和低分散性。此外，我们使用片上EPR来探测在环境空气和光下固体膜中自由基含量的稳健性，并且发现自由基含量随时间的变化可以忽略不计。在电学上，我们发现PTMA是高度绝缘的-电导率在10− S/cm范围内-无论制备的合成方法如何。这些发现为PTMA在储能领域的潜在应用提供了更清晰的信息。虽然聚（2，2，6，6-四甲基哌啶氧基甲基丙烯酸酯）（PTMA）被报道是导电的，但仔细的测量表明其绝缘性质与合成方法无关，这对其在有机电子学中的应用具有意义。
There are conflicting reports in the literature about the presence of room temperature conductivity in poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA), a redox active polymer with radical groups pendent to an insulating backbone. To understand the variability in the findings across the literature and synthetic methods, we prepared PTMA using three living methods – anionic, ATRP and RAFT polymerization. We find that all three synthetic methods produce PTMA with radical yields of 70 – 80%, controlled molecular weight, and low dispersity. Additionally, we used on-chip EPR to probe the robustness of radical content in solid films under ambient air and light, and found negligible change in the radical content over time. Electrically, we found that PTMA is highly insulating – conductivity in the range 10− S/cm – regardless of the synthetic method of preparation. These findings provide greater clarity for potential applications of PTMA in energy storage. Though poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA) was reported to be conductive, careful measurements indicate its insulating nature regardless of synthesis method, which have implication for its application in organic electronics.