Initiation, propagation and termination in fluid phase free-radical polymerization

Free-radical polymerizations are carried out in extended ranges of temperat ure, pressure, and conversion. The precise knowledge of individual rate coe fficients of initiation, propagation, termination, and chain-transfer is es sential for the modelling and optimization of monomer conversion and of pol ymer microstructure in technical polymerizations. In addition to the applic ation-oriented interest, this data is of fundamental importance for the det ailed understanding of reaction mechanisms of such free-radical-molecule, f ree-radical-free-radical, and unimolecular decomposition processes. Even fo r the polymerization of rather common monomers at moderate temperatures and ambient pressure such information is scarce. The present paper illustrates some recent advances in measuring, within wide ranges of pressure and temp erature; propagation and termination rate coefficients of free-radical homo - and copolymerizations and also peroxyester decomposition rate coefficient s.