Investigation of Free-Radical Copolymerization Propagation Kinetics of Vinyl Acetate and Methyl Methacrylate

Investigation of Free-Radical Copolymerization Propagation Kinetics of Vinyl Acetate and Methyl Methacrylate

The free-radical copolymerization propagation kinetics of vinyl acetate (VAc) and methyl methacrylate (MMA) at 50 °C were investigated through an experimental study combined with a computational analysis based on quantum chemistry. Copolymer composition data, obtained using pulsed laser polymerizati...

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Veröffentlicht in:The journal of physical chemistry. B 2010-04, Vol.114 (12), p.4213-4222
Hauptverfasser: Dossi, Marco, Liang, Kun, Hutchinson, Robin A, Moscatelli, Davide
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B: Macromolecules, Soft Matter
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container_issue 12
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container_title The journal of physical chemistry. B
container_volume 114
creator Dossi, Marco
Liang, Kun
Hutchinson, Robin A
Moscatelli, Davide
description The free-radical copolymerization propagation kinetics of vinyl acetate (VAc) and methyl methacrylate (MMA) at 50 °C were investigated through an experimental study combined with a computational analysis based on quantum chemistry. Copolymer composition data, obtained using pulsed laser polymerization followed by size exclusion chromatography (PLP-SEC) and proton nuclear magnetic resonance (NMR), were well represented by the terminal model using monomer reactivity ratios obtained with the computational approach (r VAc = 0.001 and r MMA = 27.9). Concerning the composition-averaged copolymerization propagation rate coefficient k p,cop, the differences between the terminal model and the implicit penultimate unit effect (IPUE) model (s MMA = 0.544 and s VAc = 0.173) are small for VAc/MMA, with the terminal model sufficient to describe the experimental k p,cop data measured by PLP-SEC. Monomer and radical charge distributions determined computationally are used to explain the reactivity exhibited by the VAc/MMA system.
doi_str_mv 10.1021/jp1007686
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title Investigation of Free-Radical Copolymerization Propagation Kinetics of Vinyl Acetate and Methyl Methacrylate
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