Transfer Reactions in Phenyl Carbamate Ethyl Acrylate Polymerizations

Abstract

The transfer reactions occurring during polymerization of 2-(phenylcarbamoyloxy)ethyl acrylate (PhCEA) were studied by a detailed product mapping with electrospray ionization mass spectrometry (ESI-MS). Unlike postulated before, PhCEA exhibits the same characteristic transfer reactions as other acrylic monomers at elevated temperatures, resulting in vinyl-terminated and saturated products. Transfer to monomer via abstraction of a hydrogen atom from the ester side chain as suggested before is not observed. When polymerized in a poly(ethylene glycol) (PEG) matrix to increase viscosity, transfer into matrix products are observed in minor amounts, demonstrating that PEG can be employed as a solvent to further increase the overall rate of polymerization without interference from side reactions.