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Heterogeneous derivatives of catalysts discovered by Ziegler and Natta are important for the industrial production of polyolefin plastics. However, the interaction between precatalysts, alkylaluminum activators, and oxide supports to form catalytically active materials is poorly understood. This is in contrast to homogeneous or model heterogeneous catalysts that contain resolved molecular structures that relate to activity and selectivity in polymerization reactions. This study describes the reactivity of triisobutylaluminum with high surface area aluminum oxide and a zirconocene precatalyst. Triisobutylaluminum reacts with the zirconocene precatalyst to form hydrides and passivates −OH sites on the alumina surface. The combination of passivated alumina and zirconium hydrides formed in this mixture generates ion pairs that polymerize ethylene., A zirconium precatalyst, alkylaluminum, and oxide support interact to form catalytic sites.

A full elucidation of chemisorbed donor behavior is of fundamental importance for tailoring the active species but has not yet been achieved for Ziegler–Natta catalysts. Herein, by exploiting the s...

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...

Herein, we study comparatively melt-memory effects on recrystallization of two sets of linear low-density polyethylenes (LLDPE) synthesized with Ziegler–Natta (ZN-LLDPE) and with metallocene cataly...

The catalytic activity and stereospecificity of olefin polymerization by using heterogeneous TiCl4/MgCl2 Ziegler-Natta (Z-N) catalysts are determined by the structure and nature of active centers, which are mysterious and fairly controversial. In this work, the propylene polymerization kinetics under different polymerization temperatures by using Z-N catalysts were investigated through monitoring the concentration of active centers [C*] with different tacticity. SEM was applied to characterize the catalyst morphologies and growing polypropylene (PP) particles. The lamellar thickness and crystallizability of PP obtained under different polymerization conditions were analyzed by DSC and SAXS. The PP fractions and active centers with different tacticity were obtained with solvent extraction fractionation method. The catalytic activity, active centers with different tacticity and propagation rate constant kp, fragmentation of the catalyst, crystalline structure of PP are correlated with temperature and time for propylene polymerizations. The polymerization temperature and time show complex influences on the propylene polymerization. The higher polymerization temperature (60 °C) resulted higher activity, kp and lower [C*], and the isotactic active centers Ci* as the majority ones producing the highest isotactic polypropylene (iPP) components showed much higher kp when compared with the active centers with lower stereoselectivity. Appropriate polymerization time provided full fragmentation of the catalyst and minimum diffusion limitation. This work aims to elucidate the formation and evolution of active centers with different tacticity under different polymerization temperature and time and its relations with the fragmentation of the PP/catalyst particles, and provide the solutions to the improvement of catalyst activity and isotacticity of PP.

In the field of Ziegler–Natta catalysis for olefin polymerization, carbon monoxide (CO) is used in the industrial practice to quench the reaction when it proceeds too fast, approaching critical levels for the plant safety. The quenching effect is explained as due to the reversible coordination of CO to the titanium active sites, but no direct evidence has been ever reported. In this work, we designed a series of experiments to monitor CO adsorption at variable temperatures on a model Ziegler–Natta catalyst by means of FT-IR spectroscopy. For the first time, we have been able to spectroscopically detect CO coordinated to alkylated Ti3+ sites and the Ti–acyl species formed upon the subsequent insertion of CO into the Ti3+–alkyl bond, both in the absence and in the presence of the olefin monomer. In perspective, this has important implications for the characterization of the active sites in industrial Ziegler–Natta catalysts, even under working conditions.

1,9-decadiene/propylene copolymerization is assessed as a way for Ziegler-Natta catalysts to access long chain-branched polypropylene. A MgCl2/9,9-bis-(methoxymethyl)fluorine/TiCl4 catalyst with tr...

The scientific and technical advances in the field of polymer science has been abundant in recent years. Amongst the various polymeric materials available in market, synthesis of polyolefins has been in the forefront since decades. A major challenge in this domain remains in attaining stereoregular polyolefins especially polypropylene (PP) and significant efforts were carried out by synthesizing various internal donors (ID) aiding the catalysts involved in producing them. This short review gives an overview of i) various generations of Ziegler–Natta (ZN) catalyst systems ii) general classes of ID that has been demonstrated by the researchers over the past decades iii) their influence on PP isotacticity and polymer properties. The coordination modes of different donor classes on supported ZN system and comparative study especially between phthalate and diether ID classes were also addressed here. This review also presents the studies carried out on phthalate catalyst structure analysis, detailed comparison study on phthalate and diether IDs in terms of PP isotacticity, regioselectivity, hydrogen response, and also their cross combination study and competitive behavior. Further a brief description on other structurally varied IDs like malonates, maleates, silyl diol esters, bifunctional donors, multi ether donors demonstrated for isotactic PP were also presented. Studies conducted on compatibility of incorporation of two different classes of IDs on a single supported ZN system for the fundamental understanding of the catalyst behavior; and also on how mixed donor approach enables in tuning the catalyst for polymer properties were also presented. This review also provides an opportunity to the young minds and the basic researchers from academic point of view by and large to create new polymeric materials with useful properties or modify the existing materials for new applications by incorporating new IDs for further improvisation of the stereo regularity in obtaining the polymers. Graphic Abstract

Two series of polypropylene samples (PP) were prepared with two MgCl2/TiCl4-type catalysts with diisobutyl phthalate and 9,9-bis(methoxymethyl)fluorine as internal donors (named as cat1 and cat2), ...

MgCl2 supported Ziegler–Natta (Z–N) catalysts have emerged as the most exciting chemical process for polyolefin technology, which is responsible for the production of ∼150 million tons of polyolefin (polyethylene and polypropylene) per annum. However, fundamental chemistry of Z–N catalysts is not fully understood yet due to their multi-component nature as well as heterogeneous systems. Therefore, in this review, we have highlighted the chronological development of a heterogeneous Z–N catalyst and its polymerization (ethylene, propylene and 1-butene) process including termination steps. Then, we have discussed different structural and chemical aspects of the catalyst support, catalytically active sites, cocatalyst, internal/external electron donors and their different combinations. In the last two decades, density functional theory (DFT) has been employed in Z–N systems to strengthen the experimental work as well as to understand mechanistic aspects of Z–N systems. Future directions of Z–N catalysts have also been discussed.

The crystallization behavior of butene-ethylene random isotactic copolymers prepared with a Ziegler-Natta catalyst, in particular the surprising crystallization of form II of isotactic polybutene in samples with a high ethylene concentration, provides novel evidence of the long-debated blocky molecular structure of these "random" copolymers.

Advanced High Throughput Experimentation (HTE) methods were applied to quantify the regioselectivity and the so-called "hydrogen response" in propene polymerization of four Ziegler-Natta catalysts representative of the three latest industrial generations (i.e., modified with a dialkyl phthalate, 1,3-dimethoxypropane or dialkyl succinate Internal Donor), used in combination with AlEt3 and a library of eight alkoxysilane External Donors with large structural diversity. At odds with stereoselectivity, regioselectivity turned out to be only modestly impacted by the chemical structure of the electron donors used as surface modifiers. A clear and simple relationship between regioselectivity and "hydrogen response", and, therefore, polymer molecular weight modulation was highlighted.

A new multidentate carbonate (3,3,3′,3′-tetramethyl-2,2′,3,3′-tetrahydro-1,1′-spirobiindane-5,5′,6,6′-tetracarbonate) is studied as a potential internal electron donor for Ziegler–Natta (Z–N) catal...

This paper introduces a high throughput experimentation method for fast and accurate evaluations of regioselectivity in Ziegler–Natta (ZN) propene polymerizations. With a simple protocol, the (very low) fraction of regio-irregular 2,1 monomeric units in the polymers can be quantitated by means of 13C NMR chain-end analyses on single H2-terminated polypropylene samples. The method, that was successfully validated for three representative ZN catalyst systems, also provides information on catalyst “dormancy” and propensity to undergo chain hydrogenolysis. This opens the door to the rapid and accurate implementation of quantitative structure–activity relationship (QSAR) databases of regioselectivity and “hydrogen response” in this important industrial catalysis.

Propylene polymerization with two TiCl4/MgCl2 catalysts (Cat-1: Ti 0.1%; Cat-2: Ti 1.0%) showed different responses to (cyclo-C5H9)2Si(OCH3)2 (De) addition. Cat-1 was deactivated more than Cat-2 by De. Amount of three groups of active centers producing atactic, medium isotactic and isotactic polypropylene chains were all reduced by De addition, but those of Cat-1 were reduced more. Reactivity of the isospecific active centers (kpi) was enhanced by De, but kpi of Cat-2 was changed more sensitively than Cat-1. The lower stereoselectivity of Cat-1 than Cat-2 are attributable to weaker De adsorption on its surface Mg, and the more sparsely dispersed Ti species on Cat-1 is responsible for weak De adsorption.

This chapter presents fascinating insights into the research that earned its investigators Nobel Prizes in the field of organometallic chemistry: Karl Ziegler and Giulio Natta for olefin polymerization catalysts (1963), Ernst Otto Fischer and Geoffrey Wilkinson for sandwich compounds (1973), Alan J. Heeger, Alan G. MacDiarmid, and Hideki Shirakawa for electrically conductive polymers (2000), William S. Knowles, Ryoji Noyori and K. Barry Sharpless for asymmetric catalysis (2001), Yves Chauvin, Robert H. Grubbs and Richard R. Schrock for olefin metathesis (2005), and Richard F. Heck, Eiichi Negishi and Akira Suzuki for Pd-catalyzed cross-coupling reactions (2010).

By combining the elementary reactions described in Chapter 6, transformations catalyzed by organometallic complexes can be constructed. This chapter introduces representative reaction systems catalyzed by organometallic complexes, and outlines the reactions occurring. Ziegler catalysts, prepared from tetrachlorotitanium (TiCl4) and alkylaluminium reagents (AlEt3 or AlEt2Cl), and Natta catalysts, prepared from crystalline TiCl3 and alkylaluminium, are very effective for olefin and propylene polymerization, respectively. This development was a paradigm shift, and Ziegler and Natta received the Nobel Prize in Chemistry in 1963 for their discoveries in the field of the chemistry and technology of high polymers. Transition metal complexes serve as catalysts and are used industrially, such as in olefin isomerization, olefin hydroformylation, the production of acetaldehyde by ethylene oxidation (the Wacker process) and the production of acetic acid from methanol and carbon monoxide (the Monsanto process). These catalytic systems successfully apply the elementary organometallic chemistry reactions described in this book and the basis of the catalytic action in these reactions is explained.

The innovation of Ziegler-Natta (Z-N) catalysts opened a novel aspect of chemistry in terms of polyolefin formation. Significant progress of more than fifty years in catalytic olefin polymerization simplified polyolefin production by optimizing the reaction conditions and internal donors. In this review, we particularly emphasized on recent development on different internal donor based Z-N catalyst systems, the role of external electron donors and co-catalyst chemistry. Furthermore, the Ziegler-Natta catalyst system, polymerization reaction, and polymer process technologies gradually upgrading to produce different polyolefin products. In particular, polyolefin fibers, composites, foam, blends and polyolefin-based 3D-printing products targeted in this review for substantial benefits of both society and highly diversified industries.

International audience; Despite decades of extensive studies, the atomic-scale structure of the active sites in heterogeneous Ziegler–Natta (ZN) catalysts, one of the most important processes of the chemical industry, remains elusive and a matter of debate. In the present work, the structure of active sites of ZN catalysts in the absence of ethylene, referred to as dormant active sites, is elucidated from magnetic resonance experiments carried out on samples reacted with increasing amounts of BCl3 so as to enhance the concentration of active sites and observe clear spectroscopic signatures. Using electron paramagnetic resonance (EPR) and NMR spectroscopies, in particular 2D HYSCORE experiments complemented by density functional theory (DFT) calculations, we show that the activated ZN catalysts contain bimetallic alkyl-Ti(III),Al species whose amount is directly linked to the polymerization activity of MgCl2-supported Ziegler–Natta catalysts. This connects those spectroscopic signatures to the active species formed in the presence of ethylene and enables us to propose an ethylene polymerization mechanism on the observed bimetallic alkyl-Ti(III),Al species based on DFT computations.

In this contribution, novel bio-derived rosin acid ester compounds have been developed and used as internal electron donors to prepare MgCl2 supported titanium catalysts for propylene polymerization. The results of the polymerization showed that tri-n-amyl maleate, triiso-amyl maleate and tri-n-heptyl maleate as internal electron donors in Ziegler-Natta catalysts all have high polymerization activity and stereoregularity. In particular, the Ziegler-Natta catalyst with tri-n-amyl maleate as the internal electron donor has the highest activity (up to 33.4 kgPP·gCat−1·h−1) for propylene polymerization and the isotacticity of polypropylene is as high as 96.8% determined by 13C NMR. Simultaneously, the obtained polypropylene with a relatively broad molecular weight distribution of 9.0 and melt flow rate of 160.3 g/10 min, which is beneficial to processing and has practical industrial application value when used as the basic material of melt blown cloth for medical mask.

Despite decades of extensive studies, the atomic-scale structure of the active sites in heterogeneous Ziegler-Natta (ZN) catalysts, one of the most important processes of the chemical industry, remains elusive and a matter of debate. In the present work, the structure of “active sites” of ZN catalysts in the absence of ethylene, referred to as “dormant active sites”, is elucidated from magnetic resonance experiments, carried out on samples reacted with increasing amounts of BCl3 so as to enhance the concentration of active sites and observe clear spectroscopic signatures. Using EPR and NMR spectroscopies, in particular 2D HYSCORE experiments complemented by DFT calculations, we show that the activated ZN catalysts contain bimetallic alkyl-Ti(III),Al species whose amount is directly linked to the polymerization activity of MgCl2-supported Ziegler-Natta catalysts. This connects those spectroscopic signatures to the active species formed in the presence of ethylene, and enables us propose an ethylene polymerization mechanism on the observed bimetallic alkyl-Ti(III),Al species based on DFT computations

Copolymerization of 1,3-butadiene with four 1-substituted 1,3-diene comonomers bearing amino and alkyoxy groups by a Ziegler–Natta iron(III) catalytic system to access in-chain functionalized syndiotactic 1,2-polybutadiene is reported herein. The polar comonomer content can be easily regulated by varying the comonomer loadings or polymerization conditions, affording functionalized syndiotactic 1,2-polybutadiene with different amounts of functionalities. The incorporation of a polar comonomer showed little influence on the 1,2-content and stereoregularity of the resulting polymers, giving a 1,2-structure as high as ∼85% and an rrrr pentad of 81.0%. Significantly improved surface properties of the polymers was obtained after incorporation of polar comonomer, as revealed from the remarkably decreased water contact angles.

Two MgCl2-supported Ziegler-Natta model catalysts were prepared by contacting activated MgCl2 with deficient or excess amount of TiCl4. Ethylene/1-hexene copolymerization with the catalysts was conducted under different 1-hexene feed, and active center concentration of the reaction system was determined by quench-labeling method using thiophene-2-carbonyl chloride as the quencher. The catalytic activity was only moderately enhanced (increment

We report on the synthesis of three perylene-tagged electron donors representing three major types – phthalates, diethers, and alkoxysilanes – which are of importance for the subsequent studies of MgCl2-supported Ziegler–Natta catalysts by means of laser scanning confocal fluorescence microscopy. The obtained products were unambiguously characterized, including by X-ray crystal structure analysis; their photophysical properties (absorption and emission spectra) were investigated as well. Additionally, a reliable and convenient protocol for the multigram synthesis of the required starting material – 3-bromo­perylene (PerBr) – was developed. The key step of this method was synthesis of trialkylsilyl-substituted perylenes, which were further separated by means of flash chromatography followed by conversion of the isolated 3-trialkylsilyl-substituted product to PerBr.

More than 50 years have passed since Ziegler and Natta shared the Nobel Prize in Chemistry for their discovery of olefin polymerization catalysts. The field of metal-catalysed polymerization has since matured, in no small part owing to the development of several high-performance catalysts. Although polymerization research has in many ways been driven by catalyst development, this has often occurred as a result of trial and error discovery of a promising motif, followed by extensive tuning of the steric and electronic properties of the ligand(s) present in the lead complex. Recently, some alternative design strategies have emerged that afforded new classes of olefin polymerization catalysts. This Perspective highlights recently designed catalyst motifs and the novel reactivity patterns they enable. Special attention is given to methods specifically designed for the copolymerization of ethylene with polar-functionalized co-monomers — challenging reactions that showcase these creatively designed catalyst motifs. The development of high-performance olefin polymerization catalysts is a major driving force in polyolefin studies. This Perspective discusses some alternative strategies for catalyst design — strategies in which existing systems are tuned beyond merely modifying the electronic and steric properties.

The majority of EPDM materials are produced by traditional Ziegler–Natta/Vanadium catalyst and process technology. In recent decades, EPDM metallocene catalyst technologies have increased the effic...

The effect of hydrogen on the number of active centers (СР) and the propagation rate constant (kP) at ethylene polymerization over titanium–magnesium catalysts is studied using quenching by radioactive carbon monoxide (14СО). The polymerization rate drops after hydrogen was added to the polymerization medium mainly due to the decrease in the calculated kP value. The changes in the polymerization rate and the experimental kP value observed after hydrogen was added or removed are found to be reversible. The data on the effect of the [H2]/[C2H4] molar ratio in the gas phase within the range of 0.125–1 on polymerization rate and the СР and kP values are obtained. Reduction of the kP value and a small decrease in the number of active centers are observed at the H2/C2H4 molar ratio ≥ 0.5. These findings were used to propose a scheme interpreting the effect of hydrogen on the СР and kP values. The scheme suggests that the decrease in the calculated kP value observed in the presence of hydrogen is related to the reversible formation of temporarily inactive dormant sites containing the titanium–polymer bond.

The name of Natta is entwined inextricably with that of Ziegler, in the famous catalyst systems known by their names and used to make polyethylene and polypropylene. Unlike ethylene, which is achiral, propylene is a prochiral molecule and upon polymerization can lead to interesting stereochemical and regiochemical enchainment sequences. Natta’s prescience in recognizing this unique feature of propylene led to the discovery of crystalline isotactic polypropylene and the beginning of a new industry. The story of how Natta discovered polypropylene is an engrossing one – one of stiff competition amongst contemporaries, Natta’s intimate relationship with the Italian industries, and his unique scientific background. Natta’s identification of isotactic polypropylene as a righthanded three fold ‘single helix’ in March 1954, in quick succession to the discovery of DNA ‘double helix’ by Watson, Crick, and Rosalind Franklin (March 1953), and the coiledcoil motif of ‘triple helix’ of collagen by G N Ramachandran (August 1954), makes this period the ‘golden age of macromolecular crystallography’.

Polyethylenimines, polymers bearing amino functionalities, are studied for the first time as internal electron donors for Ziegler–Natta catalysts. An advantage of polyethylenimines (PEIs) compared to the conventional phthalate electron donors is their relative harmlessness. Interaction of PEI with MgCl2 support was studied using computational (DFT; M06-2X) and experimental (PXRD, DRIFT, CP/MAS 13C NMR) methods. Quantum chemical calculations suggest that the structural variations in PEIs significantly affect their ability to stabilize the catalytically relevant MgCl2 surfaces. Coordination on the (104) surface seems to be favored upon consideration of the layered structure of MgCl2. The surface stabilization energies of branched PEIs are of the same magnitude with a phthalate electron donor reference. Experimental results indicate, in agreement with theoretical results, a strong coordination ability of branched PEI through nitrogen atoms to MgCl2. Based on spectroscopic data, nitrogen atoms of primary, sec...

A series of (SiO2/MgO/ID/MgCl2)·TiCl x Ziegler-Natta catalysts for propylene polymerization has been prepared with a new method. These catalysts were synthesized using soluble Mg-compounds as the Mg-source and the preparation progress was relatively simple. The catalyst could copy the spherical shape of the carrier very well. The propylene polymerization results showed that the catalyst revealed the best activity with 9,9-di(methoxymethyl)fluorene (BMMF) as internal donor at 50 °C with the optimal molar ratio Al/Ti = 5, which was much lower than what the industrial polypropylene catalyst used (at least molar ratio Al/Ti = 100), resulting in great cost saving. Additionally, the polymerization kinetics of the catalyst exhibited very stable property after achieving a relatively high value. These catalysts possessed rather high activity and good hydrogen response. The isotactic index (II.) value of the PP products could be higher than 98% in the presence of both internal and external electron donors. Moreover, temperature rising elution fractionation method was used to understand the influence of donors and H2 on the properties of the PP products.

Medium- and high-resolution SEM analysis of several Ti-based MgCl2-supported Ziegler–Natta catalysts and isotactic polypropylene produced with them is carried out. Each catalyst particle, 35–55 μ in size, produces one polymer particle with an average size of 1.5–2 mm, which replicates the shape of the catalyst particle. Polymer particles contain two distinct morphological features. The larger of them are globules with Dav ∼400 nm; from 1 to 2 × 1011 globules per particle. Each globule represents the combined polymer output of a single active center. The globules consist of ∼2500 microglobules with an average size of ∼20 nm. The microglobules contain several folded polymer molecules; they are the smallest thermodynamically stable macromolecular ensembles in propylene polymerization reactions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3832–3841

Titanium-magnesium Ziegler-Natta catalysts are the basis of the modern processes for polypropylene production. These catalysts have been the object of numerous studies for many decades. Nevertheless, the structure of the catalysts remains a significant research focus. One of the major questions to be answered is the nature of the active sites precursor − the titanium compound, its form and structure on the surface of the catalysts. In the present study, the experimental data show that the precursor of the catalyst active site is TiCl 4 , which is weakly bound to the surface of the catalyst. This TiCl 4 is able to migrate outside the catalyst particles and to adsorb on activated MgCl 2 , giving rise to new precursors of the active sites. The quantity of TiCl 4 , which is able to migrate easily, amounts to about half the total amount of titanium compounds in the catalysts. At the same time, the rest of titanium is tightly bound to the catalyst surface and does not produce the active sites.

Isotactic polypropylene (i-PP) is mainly produced with heterogeneous Ziegler-Natta (ZN) catalyst systems. Direct structural information on the active species is very difficult to achieve; as a matter of fact, the 13C NMR microstructure of the polymer has long been used as an indirect "fingerprint". For a long time, however, the intrinsically poor sensitivity of natural abundance 13C NMR spectroscopy hampered a complete evaluation of the microstructure, and many rare albeit important details escaped detection with standard tools and methods. The most prominent case is that of the regiodefects, which are specially important because they dictate ZN catalyst response to molecular hydrogen used as a chain transfer agent. In recent papers we have reported on the quantification of regioirregular 2,1 units in ZN i-PP by means of high-temperature cryoprobe 13C NMR. Here we shift the focus onto the stereochemical environment of such units, which was highlighted by comparing the spectra of suitable ZN PP fractions with those of model PP samples made with molecular catalysts of different structures and symmetries. The results lend support to our three-site model of ZN catalytic species, originally based on the stereochemistry of regioregular PP chains/blocks.

Chemical routes for preparing Ziegler-Natta (ZN) catalysts accompany the formation of by-products that remain in final catalysts in different amounts. In the history of ZN catalysts, much less emphasis has been given to analyze such by-products present in catalysts. Herein, we prepared various Mg(OEt)2-based ZN catalysts and conducted solution-state NMR measurements to characterize and quantify the organic components of these catalysts. It was found that, depending on the molecular structure of the internal donor (ID) and catalyst preparation conditions, an ID can undergo side reactions to produce organic by-products. All the catalysts contained different amounts of titanium alkoxy by-products formed in the reaction between Mg(OEt)2 and TiCl4, which were detrimental for the catalyst activity. These by-products were responsible for increasing the amount of the amorphous fraction in polypropylene and decreasing the highly crystalline fraction's stereoregularity. Possible hypotheses to explain the negative impacts of titanium alkoxy by-products are discussed.

We report a facile coagglomeration method for preparing graphene (G)/MgCl2-supported Ti-based Ziegler-Natta catalysts. The effects of graphene feed ratio on catalyst morphology and ethylene polymerization behavior were examined. The synthesized catalyst exhibited very high activity for ethylene polymerization. The resultant polyethylene (PE)/G nanocomposites showed a layered morphology, and the graphene fillers were well dispersed in the PE matrix. In addition, the thermal stability and mechanical properties of PE were significantly enhanced with the introduction of a very small amount of G fillers (0.05 wt%). This work provides a facile approach to the production of high-performance PE.

Full quantum chemical calculations, using density functional theory (DFT), have been conducted to explain the effect of donors on the “activation mechanism” in the Ziegler–Natta (Z–N) catalyst system. In the activation mechanism, the inactive TiIVCl4 catalyst converts into the active TiIIICl2Et catalyst with the help of the AlEt3 present in the system. The donors that have been considered in this study are: ethyl benzoate (eb), two representative diether cases, a phthalate donor, and a silyl ester donor. The results indicate that eb and the diether donor cases donor have a negative effect on the barriers for the activation mechanism. However, the eb donor can be displaced from the MgCl2 surface by AlEt3, which matches experimental observations. For the phthalate, silyl ester and TiCl3–OC4H8Cl cases, the results indicate that a significant induction period would be present in Z–N systems employing such donors or having such a catalytic center, before catalysis could commence.

This study focuses on gas-phase polymerization of ethylene using the titanium-based Ziegler–Natta catalysts prepared from different magnesium sources including MgCl2 (Cat A), magnesium powder (Cat B), and Mg(OEt)2 (Cat C). During polymerization, different cocatalysts were also used. It was found that Cat C with triethylaluminum as a cocatalyst exhibited the highest activity. This was likely attributed to optimal distribution of active sites on the catalyst surface. It can be observed by increased temperature in the reactor due to highly exothermic reaction during polymerization. By the way, the morphologies of the polymer obtained from this catalyst were spherical, which is more preferable. Besides the catalytic activity, crystallinity and morphology were also affected by the different magnesium sources used to prepare the catalysts.

The isoprene polymerization kinetics by using TiCl4/MgCl2 type Ziegler-Natta catalysts (TMC) with different titanium contents were studied for better understanding the possible active-specie structures of heterogeneous Ziegler-Natta (Z-N) catalysts for conjugated diene polymerizations. The catalytic features including the catalytic activity (CA), number of active centers ([C*]/[Ti]), rate constant for polymerization (kp), stereoregularity of these TMC catalysts were studied. The low titanium content catalyst TMC-1 (Ti = 0.09 wt.%) with more isolated mononuclear titanium species showed higher CA and yielded cis-1,4-/trans-1,4- mixed microstructure polyisoprene with low molecular weight (Mw) in the initial polymerization stage. The medium high titanium content catalyst TMC-2 (Ti = 2.38 wt.%) with more clustered mononuclear titanium species showed lower CA and yielded cis-1,4-/trans-1,4- mixed microstructure polyisoprene with high Mw in the early stage of polymerization. The high titanium content catalyst TMC-3 (Ti = 3.76 wt.%) presented lowest CA and yielded high trans-1,4- polyisoprene with higher Mw.

The penta-ether compound was synthesized by the reaction of di(trimethylolpropane) with sodium hydride as the strong base and methyl iodide as the alkyl halide. This compound was characterized by NMR, FTIR, and GC techniques. The MgCl2-supported titanium catalysts were incorporated with varying amounts of penta-ether compound as the internal donor and also the catalysts without the internal donor were synthesized. The synthesized catalysts and the conventional Ziegler- Natta catalyst were characterized. The titanium contents were determined by spectrophotometry, magnesium by complexometric titration and chloride by argentometric titration. The effects of the new internal donor on propylene polymerization with the prepared MgCl2-supported Ziegler-Natta catalysts were investigated and then these results were compared to the results obtained using the conventional diisobutyl phthalate-besed-Ziegler-Natta catalyst. The highest crystallinity degree, melting temperature, and isotacticity of polypropylene were obtained using the catalyst with a penta-ether/Mg molar ratio equal to 0.21.

The electron paramagnetic resonance (EPR) method was used to investigate the formation of alkylated Ti(III) species in superactive titanium–magnesium catalysts with a low titanium content during their interaction with an organoaluminum activator (AlMe3), as well as the interaction of alkylated Ti(III) surface species with carbon monoxide. EPR data on the content of alkylated Ti(III) species in these catalysts agree well with the number of Ti–R bonds that are determined after the interaction of radioactive carbon monoxide (14CO) with catalyst activated by triethylaluminum in the absence of monomer. Parameters of EPR spectra of the Ti(III) species having different structure and composition on the surface of titanium–magnesium catalysts were calculated by quantum-chemical simulations. The calculated g-values are consistent with the g-values observed in EPR spectra of the catalysts. Analysis of the literature data and results of our study made it possible to propose the parameters of EPR spectra characterizin...