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Pyrene-functional PMMAs were prepared via ATRP-controlled polymerization and click reaction, as efficient dispersing agents for the exfoliation of few-layered graphene sheets (GS) in easily processable low boiling point chloroform. In parallel, detailed atomistic simulations showed fine dispersion of the GS/polymer hybrids in good agreement with the experiment. Moreover, the molecular dynamics simulations revealed interesting conformations (bridges, loops, dangling ends, free chains) of GS/polymer hybrids and allowed us to monitor their time evolution both in solution and in the polymer nanocomposite where the solvent molecules were replaced with PMMA chains. Microscopic information about these structures is very important for optimizing mechanical performance. It seems that the combination of atomistic simulation with advanced chemistry constitutes a powerful tool for the design of effective graphene dispersing agents that could be used for the production of graphene-based nanocomposites with tailor-made mechanical properties.

In this work, linear polystyrene-poly(2-vinylpyridine) (PS-b-P2VP) and heteroarm star PS_22P2VP_22 ionizable block copolymers were used as dispersing agents for the liquid-phase exfoliation of pristine graphene. Various strategies such as direct exfoliation, film hydration and phase transfer have been employed and compared. The best strategy involved a two-step process, namely, pre-exfoliation of graphite in polymer/CHCl3 solutions followed by phase transfer to acidified water. High concentrations of stable aqueous suspensions of graphene flakes, highly enriched in monolayer structures, were then obtained by using the star-shaped copolymers as stabilizers. The as-prepared graphene/copolymer hybrids were used as a filler material in order to prepare functional polymer composites for mechanical reinforcement. Such copolymer-modified graphene sheets have proven to be efficient reinforcing agents of PVA, as a significant increase of storage modulus (145% higher than that of neat PVA) was achieved even at a low graphene weight fraction of 0.1 wt%.