It is now well documented that the radical polymerization of acrylic monomers is heavily influenced by transfer to polymer reactions. In this article we show that transfer to polymer impacts uniquely on the kinetics and microstructure of poly(n-butyl acrylate) synthesized by microemulsion polymerization where the polymer chains are confined to a small volume. Intramolecular transfer to polymer results in a distinctive kinetic profile with a maximum in the rate of conversion at approximate to 25% monomer conversion in batch microemulsion polymerizations, and this effect is explained by development of a mathematical model. Furthermore, the importance of intermolecular transfer to polymer in seeded microemulsion polymerizations is explored. It is shown that intermolecular transfer to polymer followed by termination reactions lead to the majority of chains in each individual particle being linked together. However, because of the small size of the particles formed in microemulsion polymerization, a limit on the maximum molecular weight of the polymer prevents formation of gel, and allows for control over the polymer microstructure. Finally, we show that this control over microstructure can be used to tune the adhesive properties of films cast from the latex dispersions. (C) 2016 Elsevier B.V. All rights reserved.