Initiation and termination kinetics in fluid-phase free-radical polymerization up to high pressure

Rate coefficients of peroxyester decomposition in solution of n-heptane have been measured as a function of temperature and pressure. The data is used to determine initiator efficiencies for the ethene high-pressure polymerization. The efficiency strongly depends on the structure of the peroxyester. Free-radical termination rate coefficients of (meth)acrylate systems have been studied up to about 50 % monomer conversion. The reaction is controlled by segmental diffusion in the early period and by reaction diffusion at later stages of the polymerization.