Reactivity of Methacrylates in Insertion Polymerization

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Journal of the American Chemical Society : JACS. 2010, 132(46), pp. 16623-16630. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja107538r
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Polymerization of ethylene by complexes [{(P^O)PdMe(L)}] (P^O ) κ2-(P,O)-2-(2-MeOC6H4)2-PC6H4SO3)) affords homopolyethylene free of any methyl methacrylate (MMA)-derived units, even in the presence of substantial concentrations of MMA. In stoichiometric studies, reactive {(P^O)Pd(Me)L} fragments generated by halide abstraction from [({(P^O)Pd(Me)Cl}μ-Na)2] insert MMA in a 1,2- as well as 2,1-mode. The 1,2-insertion product forms a stable five-membered chelate by coordination of the carbonyl group.
Thermodynamic parameters for MMA insertion are ΔHq ) 69.0(3.1) kJ mol-1 and ΔSq ) -103(10) J mol-1 K-1 (total average for 1,2- and 2,1-insertion), in comparison to ΔHq ) 48.5(3.0) kJ mol-1 and ΔSq)-138(7) J mol-1 K-1 for methyl acrylate (MA) insertion. These data agree with an observed at least 102-fold preference for MA incorporation vs MMA incorporation (not detected) under polymerization conditions. Copolymerization of ethylene with a bifunctional acrylate-methacrylate monomer yields linear polyethylenes with intact methacrylate substituents. Post-polymerization modification of the latter was exemplified by free-radical thiol addition and by cross-metathesis.

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ISO 690RÜNZI, Thomas, Damien GUIRONNET, Inigo GÖTTKER-SCHNETMANN, Stefan MECKING, 2010. Reactivity of Methacrylates in Insertion Polymerization. In: Journal of the American Chemical Society : JACS. 2010, 132(46), pp. 16623-16630. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja107538r
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@article{Runzi2010React-9639,
  year={2010},
  doi={10.1021/ja107538r},
  title={Reactivity of Methacrylates in Insertion Polymerization},
  number={46},
  volume={132},
  issn={0002-7863},
  journal={Journal of the American Chemical Society : JACS},
  pages={16623--16630},
  author={Rünzi, Thomas and Guironnet, Damien and Göttker-Schnetmann, Inigo and Mecking, Stefan}
}
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