Propagation mechanisms in ring-opening polymerization of small phosphorus heterocycles: toward free-radical polymerization of phosphines?
The mechanism and kinetics of the propagation step in the radical ring-opening polymerization of methylphosphirane, -phosphetane, and -phospholane, and also phenylphosphetane, were studied via high-level ab initio calculations. It was found that radical ring-opening polymerization should occur via attack of the carbon-centered propagating radical at the phosphorus center of the ring. This is a facile process (with reaction rates of the order of 104-106 L mol-1 s-1 at 298.15 K), driven by the...[Show more]
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