Gas-phase polymerization of propylene at low reaction rates: a precise look at catalyst fragmentation

Abstract

In this work, we reported the development of a mini-reactor experimental setup for synthesizing of polypropylene with heterogeneous Ziegler–Natta catalysts in gas-phase. Use of pro-activated 4th generation of Ziegler–Natta catalyst and preheated monomer feed enabled the polymerization reaction to be carried out at constant temperature. Evaluation of monomer consumption with high precision (0.01 bar pressure drop) allowed the detection of polymerization yield at low reaction rates. In this regard, polymerization yield, particle morphology and catalyst fragmentation were studied, as well. The results of melt microscopy showed that catalyst fragmentation was developed during the reaction, and was not restricted to the initial rupture of catalyst particles. The rate determination showed a peak during the polymerization (not necessarily at the initial stage). The results showed that depending on the reaction condition, this peak could be either a consequence of a major catalyst fragmentation or overheating. Low reaction yield, large fragments of catalyst and agglomeration of particles were considered as evidence of particle overheating and polymer local melting. As we imposed the results of melt microscopy for the polymerization conditions, a layer-by-layer fragmentation of the catalyst was found to be the main fragmentation process, at least at the beginning of the polymerization reaction.