Shedding light on the microstructural differences of polymer latexes synthesized from bio-based and oil-based C8 acrylate isomers

There is a great interest in replacing traditional oil-based monomers with more renewable bio-based ones. However, their replacement in current formulations is not straightforward. Herein, we investigate the origin of the microstructural differences of the homopolymers of 2-octyl acrylate (2-OA, bio-based) and its isomer 2-ethylhexyl acrylate (2-EHA, oil-based) synthesized by emulsion polymerization through Density Functional Theory calculations (DFT) and a kinetic Monte Carlo study. DFT calculations show that hydrogen abstraction from the polymer backbone in 2-EHA homopolymer is predominant comparing to the chain transfer to polymer reaction in the side chain, while this trend is inverse for 2-OA homopolymer. The Monte Carlo model is able to fit well the experimental data of both homopolymerizations, and predicts the microstructural differences between the two systems, namely; higher amount of gel and molar mass of the gel in 2-OA homopolymerization.