Abstract
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 ...
Published Version
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