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Number of active centers and propagation rate constants in the propene polymerization on supported Ti–Mg catalysts in the presence of hydrogen
Author(s) -
Bukatov Gennadii D.,
Goncharov Valerii S.,
Zakharov Vladimir A.
Publication year - 1995
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/macp.1995.021960529
Subject(s) - propene , polymerization , chemistry , catalysis , polymer chemistry , steric effects , carbon monoxide , hydrogen , reaction rate constant , photochemistry , polymer , organic chemistry , kinetics , quantum mechanics , physics
Polymerization inhibition with radioactive carbon monoxide was used to determine the number of active centers ( C p ) and the propagation rate constant ( K p ) in the isospecific polymerization of propene with the catalytic system TiCl 4 /diisobutyl phthalate/MgCl 2 —AlEt 3 —PhSi(OEt) 3 . The presence of hydrogen was found to decrease C p (by a factor of ≈ 2) and to increase k p (by a factor of ≈ 4). In the absence of hydrogen a considerable part of the active centers (titanium‐polymer bonds) reacting with 14 CO seems to be inactive in the propene polymerization for steric reasons. Hydrogen is able to transform such centers into an active state. Thus, k p ≈ 2,5 · 10 3 L/(mol · s) at 70°C obtained in propene polymerization in the presence of the hydrogen seems to be correct, since the portion of centers in the active state is maximum. The influence of polymerization time, external and internal donors on C p and k p was studied.