Copolymerization on Selective Substrates: Experimental Test and Computer Simulations.

We explore the influence of a selective substrate on the composition and sequence statistics during the free radical copolymerization. In particular, we study the radical copolymerization of styrene and acrylic acid in bulk and in silica pores of different sizes. We show that the substrate affects both polymer composition and sequence statistics. We use dissipative particle dynamics simulations to study the polymerization process in detail, trying to pinpoint the parameters responsible for the observed differences in the polymer chain composition and sequences. The magnitude of the observed effect depends on the fraction of adsorbed monomer units, which cannot be described in the framework of the copolymerization theories based on the terminal unit model.