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Pressure dependence of propagation rate coefficients in free‐radical homopolymerizations of methyl acrylate and dodecyl acrylate
Author(s) -
Buback Michael,
Kurz Caroline H.,
Schmaltz Claudia
Publication year - 1998
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19980801)199:8<1721::aid-macp1721>3.0.co;2-5
Subject(s) - acrylate , methyl acrylate , polymer chemistry , chemistry , methyl methacrylate , polymerization , methacrylate , radical polymerization , alkyl , organic chemistry , polymer , copolymer
Propagation rate coefficients ( k p ) for the homopolymerization of methyl acrylate (MA) and dodecyl acrylate (DA) were determined by the pulsed laser polymerization (PLP)/size‐exclusion chromatography (SEC) technique at pressures between 100 and 2000 bar. The activation volumes for the propagation step, ΔV # ( k p ), of MA and DA are identical within experimental accuracy, but are clearly different from the previously reported ΔV # ( k p ) of methyl and dodecyl methacrylate. For both the alkyl acrylates and methacrylates a pronounced family‐type behaviour of k p is seen, with k p being slightly enhanced toward larger ester size.