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We study the effect of dielectric constant of some poly(styrene)-type polymer matrix on the percolation threshold in conductive polymer composites with carbon black (CB). We demonstrate that percolation threshold diminishes with an increment of the dielectric constant of polymer matrix. We chose polystyrene and other three polymers similar in structure and molecular weight but with different chemical nature. The corresponding dielectric constant and critical concentration, Xc,  in volume fraction of carbon black, v/v CB,  were the following: 4MePS (ε=2.43; Xc=0.058), PS (ε=2.60; Xc=0.054), 4BrPS (ε=2.82; Xc=0.051), and 4ClPS (ε=2.77; Xc=0.047). The correlation between both parameters confirms that the percolation threshold decreases while the dielectric constant increases. At microscopic level, this effect is attributed to an enhanced physical interaction of the CB particles with the asymmetric electric density produced by electronegative or inductive atoms/groups. Therefore, by controlling the chemical structure of the polymer matrix, the attraction forces between the polar groups on the carbon black surface particles with those of the polymer matrix can be improved, which in turn induces a better disaggregation and dispersion of those particles into the polymer matrix, allowing the percolation threshold reached at a lower filling fraction

Relationship between Polymer Dielectric Constant and Percolation Threshold in Conductive Poly(styrene)-Type Polymer and Carbon Black Composites