This paper will discuss aspects of (co)polymerization of acrylates with reversible addition-fragmentation chain transfer (RAFT). An explanation for bimodal molecular weight distributions observed when making high molecular weight acrylic polymers with narrow molecular weight distributions (M̄./M̄. <1.1) at high conversion involves copolymerization of the macromonomer formed by backbiting-β-scission. Evidence for this mechanism is provided. RAFT copolymerization is illustrated by the synthesis of novel copolymer intercalants/ exfoliants/dispersants for unmodified layered silicates (sodium montmorillonite) in polypropylene (PP) nanocomposites. Block and gradient copolymers were prepared based on a long chain acrylate (e.g. octadecyl acrylate, ODA) and various polar comonomers (e.g. acrylic acid, dimethylaminoethyl acrylate, maleic anhydride, methacrylic acid, N-vinyl pyrrolidone).