Hybrid Nanocomposites Based on Poly(2,5-dichloro-3,6-bis(phenylamino)-p-benzoquinone) and MWCNTs: Synthesis, Structure, and the Role of ZnO

For the first time, hybrid nanocomposites based on poly(2,5-dichloro-3,6-bis(phenylamino)-p-benzoquinone) (PCPAB) and multi-walled carbon nanotubes (MWCNTs) were obtained and the influence of the preparation method on their structure and functional properties was demonstrated. The nanocomposites were obtained both by ultrasonic mixing of PCPAB and MWCNTs, and via in situ oxidative polymerization of CPAB in the presence of MWCNTs or MWCNTs with the addition of ZnO. The formation of hybrid nanocomposites occurs due to non-covalent interaction (π-stacking) between the graphene structures of the MWCNT surface and the phenyl rings of PCPAB. It was found that during the in situ oxidative polymerization of CPAB in the presence of MWCNTs, the growth of polymer chains occurred in close proximity to the filler surface, which led to the formation of a polymer coating. ZnO particles, localized on MWCNTs, on the one hand, prevent their aggregation, and on the other hand, create additional polymerization reaction centers due to the coordination of the Zn-O bond at the H and O atoms of the monomer. An increase in the concentration of reaction centers as a result led to a 2–2.5-fold reduction in the induction polymerization period. According to SEM data, in this case, a more ordered and denser polymer layer is formed due to intermolecular complexation between the main and side chains of the growing polymer with the participation of Zn2+ ions formed as a result of the transformation of ZnO to ZnCl2 in the acidic reaction medium of polymerization. The results of the study of the frequency dependences of conductivity indicate a hopping mechanism of conductivity of nanocomposites. The electrical conductivity of nanocomposites depends on their production method and the MWCNT content and varies between 0.5 and 1.1 S∙cm−1, which is 6–12 times higher than the conductivity of the original polymer. Thermogravimetric analysis revealed that the nanocomposites exhibit enhanced thermal stability compared to PCPAB. The best results were shown by nanocomposites with a higher content of MWCNTs, for which the residual mass at 450 °C was 51–53%.