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4‑Dimensional Modeling Strategy for an Improved Understanding of Miniemulsion NMP of Acrylates Initiated by SG1-Macroinitiator

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journal contribution
posted on 25.11.2014, 00:00 authored by Paul H. M. Van Steenberge, Dagmar R. D’hooge, Marie-Françoise Reyniers, Guy B. Marin, Michael F. Cunningham
For the first time, a kinetic model considering four-dimensional Smith–Ewart equations is presented to simultaneously calculate the time evolution of the conversion, number-average chain length, dispersity, end-group functionality (EGF), and short chain branching (SCB) content for the miniemulsion NMP of n-butyl acrylate (nBuA), initiated by poly­(nBuA)-(N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) at 393 K ([nBuA]0:[poly(nBuA)-SG1]0 = 300). On the basis of literature kinetic and diffusion parameters, model analysis reveals that backbiting cannot be neglected for an accurate description of the NMP characteristics, despite the low number of SCBs formed per chain (ca. 2) and that the small loss of EGF at low conversions is mainly caused by chain transfer to monomer. SG1 partitioning (partitioning coefficient Γ = 50) between the organic and aqueous phase increases the dispersity and polymerization rate at low particle diameters (dp < ca. 50 nm) with a limited effect on the EGF profile. However, the extent of these increases is very sensitive to the Γ value, highlighting the relevance of its accurate experimental determination in future studies.