The photopolymerization of vinyl acrylate has been investigated using real-time MR. The acrylate and vinyl groups exhibit different polymerization kinetics with the acrylate functionality polymerizing at a much faster rate. Vinyl acrylate not only self-initiates its own free-radical polymerization, but also photoinitiates the polymerization of mono- and difunctional acrylates. Kinetic studies using a model monomer system indicate that it is essential for the acrylate and vinyl group to be part of the same molecule in order to function as an effective initiator for acrylate polymerization. (C) 2003 Elsevier Science Ltd. All rights reserved.