PROPERTIES OF NANOSTRUCTURED COMPOSITES OF POLY(VINYLIDENE FLUORIDE) WITH DOPED POLY(3-METHYLTHIOPHENE)

Abstract

The combination of properties of intrinsically conducting polymers (ICPs) and functional nanostructured template materials opens up prospects for their use in various fields, ranging from bioelectronics to sensors and energy conversion. Successful combinations solve one of the important drawbacks of many ICPs, created by their insolubility and infusibility, and help to achieve their full potential in thermally processable materials. When developing such hybrid materials, it is necessary to take into account the sensitivity of ICP properties to interphase interactions due to extended π-conjugation in these polymers. However, this aspect of ICP-based nanocomposites has not been sufficiently studied yet. In this paper we investigate the effect of template submicron poly(vinylidene fluoride) (PVDF) particles and the nature of the dopant on properties of poly(3-methylthiophene) (P3MT) precipitated as the shell at the PVDF core surface in the course of the 3MT oxidative polymerization. For this purpose, we compare the properties of P3MT phase of the composites with the properties of the neat P3MT doped with dodecylbenzenesulfonate (DBS), perfluorooctanoate (PFO) and chloride anions. In the formed composite core-shell particles the P3MT is in the form of asymmetric nanoparticles which are localized almost exclusively at the surface of PVDF particles. According to the conjugation length, neat polymers form the following series: P3MT-Cl > P3MT-DBS > P3MT-PFO as evidenced by the IR spectral analysis. In their composites the conjugation length of P3MT doped with Cl- does not change noticeably, while for the DBS and PFO anions cases it increases and for the DBS case it exceeds that of Cl- case. X-ray phase analysis showed an increase in the degree of crystallinity of P3MT-Cl and P3MT-DBS phases in the composition of composites by 1.4 and 1.3 times relative to the corresponding values for the neat doped P3MTs. Such an increase can be caused by the influence of the local electric field of the dipoles of the electroactive part of the crystalline phase of PVDF (β- and γ-phase) on the spatial arrangement of charged P3MT macromolecules formed on the surface of PVDF. Thermogravimetric studies show an increase in the thermal stability of the doped P3MT phase of nanocomposites while conductivity measurements reveal a significant effect of the nature of the dopant anion.