Kiseleva Svetlana G, Bondarenko Galina N, Orlov Andrey V, Muratov Dmitriy G, Kozlov Vladimir V, Vasilev Andrey A, Karpacheva Galina P
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky pr., 29, 119991 Moscow, Russia.
Polymers (Basel). 2024 Jun 27;16(13):1832. doi: 10.3390/polym16131832.
Hybrid nanocomposites based on poly(3,6-dianiline-2,5-dichloro-1,4-benzoquinone) (PDACB) in salt form and graphene oxide (GO) have been obtained for the first time, and the significant influence of the preparation method on the composition and structure of nanocomposites and their functional properties has been demonstrated. Nanocomposites were prepared in three ways: via ultrasonic mixing of PDACB and GO; via in situ oxidative polymerization of 3,6-dianiline-2,5-dichloro-1,4-benzoquinone (DACB) in the presence of GO; and by heating a suspension of previously prepared PDACB and GO in DMF with the removal of the solvent. The results of the study of the composition, chemical structure, morphology, thermal stability and electrical properties of nanocomposites obtained via various methods are presented. Nanocomposites obtained by mixing the components in an ultrasonic field demonstrated strong intermolecular interactions between PDACB and GO both due to the formation of hydrogen bonds and π-stacking, as well as through electrostatic interactions. Under oxidative polymerization of DACB in the presence of GO, the latter participated in the oxidative process, being partially reduced. At the same time, a PDACB polymer film was formed on the surface of the GO. Prolonged heating for 4 h at 85 °C of a suspension of PDACB and GO in DMF led to the dedoping of PDACB with the transition of the polymer to the base non-conductive form and the reduction of GO. Regardless of the preparation method, all nanocomposites showed an increase in thermal stability compared to PDACB. All nanocomposites were characterized by a hopping mechanism of conductivity. Direct current (dc) conductivity σ values varied within two orders of magnitude depending on the preparation conditions.
首次制备了基于盐形式的聚（3,6 - 二苯胺 - 2,5 - 二氯 - 1,4 - 苯醌）（PDACB）和氧化石墨烯（GO）的杂化纳米复合材料，并证明了制备方法对纳米复合材料的组成、结构及其功能特性有显著影响。纳米复合材料通过三种方式制备：通过PDACB和GO的超声混合；通过在GO存在下3,6 - 二苯胺 - 2,5 - 二氯 - 1,4 - 苯醌（DACB）的原位氧化聚合；以及通过加热先前制备的PDACB和GO在DMF中的悬浮液并除去溶剂。给出了通过各种方法获得的纳米复合材料的组成、化学结构、形态、热稳定性和电学性质的研究结果。通过在超声场中混合组分获得的纳米复合材料表明，由于氢键和π - 堆积的形成以及静电相互作用，PDACB和GO之间存在强烈的分子间相互作用。在GO存在下DACB的氧化聚合过程中，后者参与氧化过程并部分还原。同时，在GO表面形成了PDACB聚合物膜。将PDACB和GO在DMF中的悬浮液在85°C下长时间加热4小时导致PDACB去掺杂，聚合物转变为非导电的碱形式并使GO还原。无论制备方法如何，与PDACB相比，所有纳米复合材料的热稳定性均有所提高。所有纳米复合材料均以跳跃传导机制为特征。直流（dc）电导率σ值根据制备条件在两个数量级内变化。
