Department of Engineering and Materials Chemistry, Centro de Investigación en Materiales Avanzados, S.C., Miguel de Cervantes No. 120, Complejo Industrial Chihuahua, Chihuahua 31136, Mexico.
Facultad de Ciencias Químicas, Universidad Autónoma de Chihuahua, Chihuahua 31125, Mexico.
Int J Mol Sci. 2022 Jul 22;23(15):8085. doi: 10.3390/ijms23158085.
In this research, a brush-like polyaniline (poly(2-acrylamide-2-methyl-1-propanesulfonate)--polyaniline)--poly(-vinylcarbazole) (BL PAni) was developed as a strategy to overcome the limited processability and dedoping above pH 4 of conventional polyaniline (PAni). For the BL PAni synthesis, RAFT polymerization (homopolymer), RAFT-mediated surfactant-free emulsion polymerization (block copolymer), and interfacial oxidative polymerization were applied to graft the PAni chains. NMR and FT-IR spectroscopies were performed to confirm the structural elucidation of the reaction pathways, while the thermal properties were analyzed by TGA and DSC. Notably, the BL PAni presents absorption throughout the visible region and up to the near-infrared, showing dedoping resistance at up to 80 °C and at a neutral pH. The absorption range of the BL PAni, block copolymer, and homopolymer were studied by UV-Vis spectroscopy in solid-state and dispersion/solution, highlighting BL PAni and poly(anilinium 2-acrylamide-2-methyl-1-propanesulfonate)--poly(-vinylcarbazole) (PAAMP--PVK) due to the π-stacking between the anilinium and carbazole groups. The cyclic voltammetry confirmed the persistence of electroactivity at a pH near 7.
在这项研究中,开发了一种刷状聚[2-丙烯酰胺-2-甲基-1-丙磺酸(poly(2-acrylamide-2-methyl-1-propanesulfonate)--聚(苯胺)]--聚(-乙烯基咔唑)(BL PAni),作为克服常规聚(苯胺)(PAni)加工性能有限和 pH 值高于 4 时去掺杂的策略。对于 BL PAni 的合成,应用 RAFT 聚合(均聚物)、RAFT 介导的无表面活性剂乳液聚合(嵌段共聚物)和界面氧化聚合来接枝 PAni 链。通过 NMR 和 FT-IR 光谱对反应途径进行了结构阐明的确认,而热性能则通过 TGA 和 DSC 进行了分析。值得注意的是,BL PAni 在整个可见区域到近红外区域都有吸收,在高达 80°C 和中性 pH 值下具有抗去掺杂性。通过固态和分散体/溶液中的 UV-Vis 光谱研究了 BL PAni、嵌段共聚物和均聚物的吸收范围,突出了 BL PAni 和聚(苯胺 2-丙烯酰胺-2-甲基-1-丙磺酸--聚(-乙烯基咔唑)(PAAMP--PVK),因为苯胺基和咔唑基之间存在π-堆积。循环伏安法证实了在接近 7 的 pH 值下的电活性的持久性。