Kinetics of fullerene (C_(60)) inhibition in polymerization of methyl acrylate using bismuthonium ylide and bismuthonium ylide-mercuric chloride complex as initiators

摘要

The effect of fullerene (C_(60)) on the radical polymerization of methyl acrylate (MA), in dioxane, was studied kinetically, where triphenyl bismuthonium 1,2,3,4 tetra phenyl cyclopentadiene ylide and ylide-mercuric chloride {ylide-HgCl_2} complex were used as initiators. Rp, at low fullerene concentration, may be expressed as Rp ∝ [Ylide]~(0.5) [MA]~(1.0) [Full]~(-0.5) on the basis of the results at 60°C. The {ylide-HgCl_2} complex has been found to be more efficient initiator than ylide for the polymerization. The polymer has been characterized by FTIR, ~1H-NMR and ~(13)C-NMR spectroscopic analysis. A mechanism for polymerization, involving the reactions of free radical produced by decomposition of ylide or ylide-complex (initiator) with MA and C_(60) in initiation steps, has been proposed. Fullerene competes with MA for free radicals and acts as a free radical inhibitor that can also be incorporated into the final polymer to produce fullerene terminated polymeric structures.