The potential of spectroscopic methods applied to heterogeneous catalysts for olefinpolymerization

Heterogeneous Ziegler–Natta and Phillips-type olefin polymerization catalysts have the monopoly of isotactic polypropylene production and a large share in the market of high density polyethylene, respectively. Their high industrial impact and the relatively mild conditions under which they work explain why both catalysts have been the subject of an intense research. The industrially adopted strategy to improve catalyst's formulation is still based on a trial-and-error procedure; however, a rational design of new and more efficient catalysts (which is the key to produce polyolefins having a specific architecture) necessarily implies to achieve a detailed understanding of the structure of the active sites at a molecular level. Herein, it is shown that spectroscopic methods have this potential, especially when several complementary techniques are adopted and coupled with theoretical calculations. This is valid for both Phillips-type and Ziegler–Natta catalysts, because most of the problems encountered in their characterization and understanding are common, although for decades they were not considered to be closely related. The main advantages and disadvantages of several spectroscopies in the investigation of both categories of catalysts are critically analyzed, by discussing many examples taken from the recent literature.