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Understanding the kinetics of olefin polymerization with Ziegler–Natta and related catalysts means identifying the main kinetic parameters such as kp and concentration of active sites. The high-pressure quenched-flow technique could be an absolute method for counting active sites and for activation studies of molecular catalysts. A kinetic study of metallocene catalysts and a phenoxy-imine titanium catalyst in the first instants of polymerization is presented in this paper. [ABSTRACT FROM AUTHOR]