Influence of the synthetic procedure on the properties of three Ziegler-Natta catalysts with the same 1,3-diether internal donor

Being the main responsible for the huge production of polyolefins, heterogeneous Ziegler-Natta catalysts are among the most important catalysts in the chemical industry and they have been optimized over the years since their discovery in 1953 crossing many different generations. Lastly, catalysts of the 5th generation are characterized by the introduction in the pre-catalyst of 1,3-diether compounds as internal electron donors, which are stable in the presence of AlR3 activators and do not require the further addition of external donors during the following steps of the catalytic process to control the activity and selectivity. In this work, we synthetized and systematically investigated by a multi-technique approach three Ziegler-Natta catalysts characterized by the same 1,3-diether donor, but differing in the synthesis route. We found that the synthetic route influences the MgCl2 particle size, as well as the properties of the Ti species. In particular, the reprecipitation method brings the smallest MgCl2 particles and the most positive Ti4+ sites in the pre-catalyst, but also the largest amount of accessible Ti3+ sites after TEAl activation. These structural and spectroscopic data correlate pretty well with the kinetic of gas-phase propylene polymerization in very mild conditions.