Kinetic Monte Carlo Simulations as a Tool for Unraveling the Impact of Solvent and Temperature on Polymer Topology for Self‐Initiated Butyl Acrylate Radical Polymerizations at High Temperatures.

Mätzig, Jonas; Drache, Marco; Drache, Georg; Beuermann, Sabine

High‐temperature butyl acrylate polymerizations in bulk and in solution are investigated experimentally and by kinetic Monte Carlo (kMC) simulations. The experimental data comprise conversion‐time data, molar mass distributions, and branching levels per polymer chain derived from size‐exclusion chromatography with a multiangle laser light scattering detector. A kMC model is established, which allows for the description of the impact of solvent and temperature on molar mass distribution as well as type and content of macromonomers. Within the study kinetic coefficients for transfer to solvent and the thermal self‐initiation of the monomer are determined according to the Metropolis Hastings algorithm. The kMC simulations provide information, which are otherwise not accessible, for example, the number of branch points per molecule as a function of molar mass or the molar mass distribution of various macromonomer species. Moreover, molar ratios of mid‐chain and chain‐end radicals are at hand for temperatures up to 160°C, which are important for the interpretation of the experimentally and via simulation‐derived polymer topology as a function of molar masses.

MONTE Carlo method; RADICALS (Chemistry); HIGH temperatures; MOLAR mass; PHOTODETECTORS; POLYMERS; COORDINATION polymers

Macromolecular Theory & Simulations, 2023, Vol 32, Issue 4, p1

1022-1344

Academic Journal

10.1002/mats.202300007