Polymerization of butadiene with tii4‐Al(i‐Bu)3 catalyst: Part I: Kinetic study

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Abstract
A kinetic study on the polymerization of butadiene in toluene with TiI4‐Al(i‐Bu)3 catalyst has been carried out in a batch reactor. The effects of catalyst concentration, Al/Ti ratio, initial monomer concentration and temperature on the polymerization rate and the molecular weight distribution were investigated. It was found that the rate of propagation which is first order with respect to monomer concentration is a function of Al/Ti ratio, having a maximum rate at a ratio of 1.5 and decreasing rapidly as ratio increases. The number of active sites which is directly proportional to the concentration of Til4, is the prime determinant of the molecular weight of the polymer, yet the growth of the living polymer molecules is regulated by the chain transfer reaction to aluminum alkyls. The termination reaction was found significant only at Al/Ti ratio where the catalyst is most reactive.
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