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Initiation and termination kinetics in fluid‐phase free‐radical polymerization up to high pressure
Author(s) -
Buback Michael
Publication year - 2002
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/1521-3900(200206)182:1<103::aid-masy103>3.0.co;2-g
Subject(s) - polymerization , radical polymerization , acrylate , heptane , kinetics , monomer , diffusion , polymer chemistry , decomposition , bulk polymerization , materials science , chemistry , thermodynamics , polymer , organic chemistry , physics , quantum mechanics
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.