By P. C. Barbe
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Additional info for Catalytical and Radical Polymerization
This explanation, however, obviously cannot be applied to those catalysts in which an increase of the Al-alkyl concentration results in an increase of the isotacticity (see Refs. 48,1o9) and Fig. 34). Moreover, this does not take into consideration the possible effect of the inside base. In fact, as demonstrated by Galli 81), there seems to be a clear connection between the decrease of isotacticity and the progressive decrease of the amount o f base present in the catalyst following its interaction with the Al-alkyl.
29. The instantaneous rate of polymerization during a 3 h experiment at different concentrations of aluminum triethyl. 06 mmol dm -3 9s) By permission of Hiithig & Wepf Verlag. t 0 "5 0,.. 1 2 3 Time (h) With the same type of catalyst Zakharov 92), on the other hand, observed decay-type kinetics without an induction period, where the Al-alkyl first increases the rate and slows down the decay and, thereafter, lowers the rate steadily without modifying the kinetics. With similar catalysts, Duck lo6) reported that the activity increases linearly with the Al-alkyl concentration up to 5 mmoles/1.
By permission of Hiithig & Wepf Verlag. interaction (alkylation) with the metal-alkyl. Nonetheless, in order to explain the observed linear activity vs. Al-alkyl concentration relationship, Duck 1o6) speculated t h a t the metal-alkyl forms a complex with the olefin, which is the "true m o n o m e r " upon which the polymerization rate depends. A similar hypothesis was also expressed by Simon 110) to explain the greater activity obtained with T E A in comparison to DEAC. The kinetic stabilization can be explained, according to some authors 92,97,98), by the need to have a minimum o f Al-alkyl in solution in order to avoid contamination by poisons or to stabilize the polymerization centers if a bimetallic mechanism is accepted.
Catalytical and Radical Polymerization by P. C. Barbe