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Inorganic halide additives can act as dopants and/or chlorine-donating species in Ziegler–Natta recipes.

In this study, commercially available, milled, and heat-treated Mg(OEt)2 were used as the precursors in the synthesis procedure of industrially-favorable supported Ziegler–Natta catalysts. The effects of milling and heat-treatment of the support were completely investigated during the catalyst synthesis and polymerization using SEM, PSD, BET, DCS, and XRD techniques. It was found that despite the support treatments had no significant effect on the elemental analysis results of the catalysts, the morphology of the catalyst pores was very sensitive to support manipulation, and bottleneck-type pores were predominated in the catalysts which were made using the non-manipulated supports. On the other hand, the catalysts which were made using the milled and not-milled supports showed a clear difference between the activity, particle size, and particle size distribution of the catalysts. Also, a high level of stacking disorder and high grain size was observed in the crystal structure of the catalyst made using the commercially available support. In the following, competition between fragmentation and replication was investigated in the synthesized samples, and an attempt was made to link the stacking disorder (in the catalyst structure) to the ease of the fragmentation process. Finally, using practical observation, a mechanism was proposed to justify the changes in the morphology of the catalysts during synthesis procedures. We claimed that milling and especially heat-treating of the support leads to the ordering of the MgCl2 stacking structure.

Although Ziegler-Natta catalysts were discovered more than four decades ago, many aspects of their characteristics are not fully understood. The effect of the support particle size on the final pro...

Many researchers have studied the effects of donors, promoters and alkyl aluminum compounds on the polymerization catalysts, the polymerization process and the final properties of polymers. Neverth...

Due to the important role of cocatalyst in the polymerization process employing industrially favored Ziegler–Natta catalysts, its effect on kinetic behavior, catalyst activity, and polymer properties is discussed. In this paper, triethyl aluminum (TEA) and triisobutyl aluminum (TIBA) have been used as the main cocatalyst ingredient with 10–20 mol percent of diethyl aluminum chloride (DEAC) and ethyl aluminum dichloride (EADC) cocatalysts, being neat TEA the cocatalysts with the highest activity. Moreover, TEA-DEAC and TEA-EADC cocatalysts revealed a built-up kinetic profile, while TIBA-DEAC and TIBA-EADC show a decay-type kinetic curve. According to melt flow index results, no considerable change in flowability was detected in the synthesized polyethylenes (PE). On the other hand, the ethylene insertion and chain termination mechanisms were investigated by means of density functional calculations using Ti active center located in (110) and (104) facets of the MgCl2 surface. To shed light on the bulkiness level of employed cocatalysts, buried volume (VBur) together with the two-dimensional map of cocatalyst systems were considered. Higher VBur of TIBA complex can explain its lower activity and decay type kinetic profile obtained by experimental studies Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. S.P.P thank the Spanish Ministerio de Ciencia e Innovacion for Juan de la Cierva Formacion fellowship (FJC2019-039623-I )

The effects of the type and concentration of comonomers 1-hexene and 1-octene in the copolymerization of ethylene were investigated using pre polymerized Ziegler-Natta (catalyst a) and without pre polymerized (catalyst b) catalysts in the presence of hydrogen as a chain transfer agent. The properties of produced polymers were characterized by a set of techniques: (SEM), (EDX), (DSC), (GPC). TIBA and DEAC were used as co catalysts. The results of microscopic and SEM images showed the morphology and structure of catalysts (a) and (b) and the obtained spherical polymers. In the presence of 1-hexene, activity of catalyst (a) was at its maximum. The comonomer 1-octene at 32 mmol presented its activity (1.7 × 103 g polymer/(g cat.h)) and after that, the activities decreased. Copolymerization of ethylene and 1-hexene by catalyst (b) showed higher activity (1.6 × 103 g polymer/ polymer/(g cat.h)) at 40 mmol concentration of 1-hexene in comparison to catalyst (a).