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

• Published in: European polymer journal Vol. 198; p. 112410
• Main Authors: Hamzehlou, Shaghayegh, Barquero, Aitor, Agirre, Amaia, Ruipérez, Fernando, Ramon Leiza, Jose
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 17.10.2023
• Subjects: Bio-based acrylate monomers; DFT calculations; Emulsion polymerization; Monte Carlo simulation; Polymer microstructure; Bio-based acrylate monomers; Polymer microstructure; Emulsion polymerization; Monte Carlo simulation; DFT calculations
• ISSN: 0014-3057; 1873-1945
• DOI: 10.1016/j.eurpolymj.2023.112410

[Display omitted] •Different microstructure for bio-based and oil-based C8 alkyl polyacrylates.•Microstructural differences attributed to the chain transfer to polymer reaction.•Higher overall chain transfer to polymer for 2-OA homopolymer compared to 2-EHA.•2-OA showed predominant chain transfer to polymer reaction in the side chain.•Monte Carlo model fits well the experimental data on kinetics and microstructure. 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.