Retardation of the TiCl3·1/3 AlCl3/AlEt2Cl catalyzed propylene polymerization by allene and its relevance to the determination of the number of active centers

The retardation of the TiCl3/AlEt2Cl catalyzed propylene polymerization by allene was studied. On the basis of the results, a mechanism of the competitive chemisorption on active centers was proposed. A non‐linear dependence of the polymerization rate on the amount of allene consumed can be describe...

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Bibliographic Details
Published in:Die Makromolekulare Chemie 1987-08, Vol.188 (8), p.1781-1794
Main Authors: KRATOCHVILA, J, MEJZLIK, J
Format: Article
Language:English
Subjects:
Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
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Summary:The retardation of the TiCl3/AlEt2Cl catalyzed propylene polymerization by allene was studied. On the basis of the results, a mechanism of the competitive chemisorption on active centers was proposed. A non‐linear dependence of the polymerization rate on the amount of allene consumed can be described in terms of the existence of two types of active centers, their numbers being 2 and 20 mmol·mol −1Ti, respectively, differing very substantially in the adsorption coefficients. Copolymerization of propylene with allene was investigated, using the above catalytic system. Assuming identical active centers, the following copolymerization parameters were obtained: r1 = 0,66 ± 0,66 and r2 = 40 ± 30. Based on these results, the consumption of allene by copolymerization during the retardation of propylene polymerization was described in quantitative terms.
ISSN:0025-116X
0025-116X
DOI:10.1002/macp.1987.021880802