Porous versus novel compact Ziegler–Natta catalyst particles and their fragmentation during the early stages of bulk propylene polymerization

The effect of the porosity of Ziegler–Natta catalyst particles on early fragmentation, nascent polymer morphology, and activity were studied. The bulk polymerization of propylene was carried out with three different heterogeneous Ziegler–Natta catalysts under industrial conditions at low temperatures, that is, with a novel self‐supported catalyst (A), a SiO₂‐supported catalyst (B), and a MgCl₂‐supported catalyst (C), with triethyl aluminum as a cocatalyst and dicyclopentyl dimethoxy silane as an external donor. The compact catalyst A exhibited no measurable porosity and a very low surface area (<5 m²/g) by Brunauer–Emmet–Teller analysis, whereas catalysts B and C showed surface areas of 63 and 250 m²/g, respectively. The surface and cross‐sectional morphologies of the resulting polymer particles at different stages of particle growth were analyzed by scanning electron microscopy and transmission electron microscopy. The compact catalyst A showed homogeneous and instantaneous fragmentation already in the very early stages of polymerization, which is typically observed for porous MgCl₂‐supported Ziegler–Natta catalysts. Moreover, the compact catalyst particles gave rise to almost perfectly spherical polymer particles with a smooth surface. In contrast, the silica‐supported catalyst B gave rise to particles having a cauliflower morphology, and the second reference catalyst C produced fairly spherical polymer particles with a rough surface. All of the three catalysts exhibited similar activities of 450 g of polypropylene/g of catalyst after 30 min of polymerization, and most interestingly, the comparative kinetic data presented indicated that the reaction rates were not influenced by the porosity of the catalyst. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Polymer-supported heterogeneous titanium-based Ziegler-Natta catalyst for ethylene polymerization

Reported here in, is the synthesis of polystyrene (PS)-supported Ziegler–Natta catalyst (PS-TiCl₄) by the reaction of PS and titanium tetrachloride (TiCl₄). PS was synthesized by emulsion polymerization using super critical CO₂ (sc-CO₂) as a medium. Three catalysts were synthesized by varying the TiCl₄/PS weight ratio in hexane medium. The resulting catalysts were characterized by Fourier transformed-infrared spectroscopy, UV–visible spectroscopy, scanning electron microscope and energy dispersive X-ray detector, X-ray diffraction analysis. The acidity of the catalysts in an acetone/water solution was measured by pH meter. The thermogravimetric analysis reveals that catalysts are stable upto 150–180°C. Due to their higher degree of thermal stability these catalysts may potentially be used as a support in conventional Ziegler–Natta catalyst for ethylene polymerization. These catalysts also showed good storability and its overall catalytic productivity are found to be 3720 g PE/g Ti. The productivity of the catalysts also depended on the titanium concentration in the polymer matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Kinetic and morphological study of a magnesium ethoxide‐based Ziegler–Natta catalyst for propylene polymerization

BACKGROUND: Kinetic and morphological aspects of slurry propylene polymerization using a MgCl₂‐supported Ziegler–Natta catalyst synthesized from a Mg(OEt)₂ precursor are investigated in comparison with a ball‐milled Ziegler–Natta catalyst. RESULTS: The two types of catalyst show completely different polymerization profiles: mild activation and long‐standing activity with good replication of the catalyst particles for the Mg(OEt)₂‐based catalyst, and rapid activation and deactivation with severe fragmentation of the catalyst particles for the ball‐milled catalyst. The observed differences are discussed in relation to spatial distribution of TiCl₄ on the outermost part and inside of the catalyst particles. CONCLUSION: The Mg(OEt)₂‐based Ziegler–Natta catalyst is believed to show highly stable polymerization activity and good replication because of the uniform titanium distribution all over the catalyst particles. Copyright © 2008 Society of Chemical Industry     

Ethylene polymerization using a novel MgCl2/SiO2‐supported Ziegler–Natta catalyst

A novel MgCl₂/SiO₂‐supported Ziegler–Natta catalyst was prepared using a new one‐pot ball milling method. Using this catalyst, polyethylenes with different molecular weight distributions were synthesized. The effects of the [Si]/[Mg] ratio, polymerization temperature and [Al]/[Ti] ratio on the catalytic activity, the kinetic behaviour and the molecular weight and the polydispersity of the resultant polymer were studied. It was found that the polydispersity index of the polymer could be adjusted over a wide range of 5–30 through regulating the [Si]/[Mg] ratio and polymerization temperature, and especially when the [Si]/[Mg] ratio was 1.70, the polydispersity index could reach over 25. This novel bi‐supported Ziegler–Natta catalyst is thus useful for preparing polyethylene with a required molecular weight distribution using current equipment and technological processes. Copyright © 2005 Society of Chemical Industry     

Preparation and properties of isotactic polypropylene obtained from MgCl2-supported TiCl4 catalyst bearing bifunctional internal donor

In this research, a novel MgCl₂-supported TiCl₄ catalyst in conjunction with bifunctional internal donor was synthesized. The effects of internal donor on propylene polymerization behaviors and polymer properties (morphology, M _w and MWD) were investigated. It was found that the activity of novel catalyst was higher than that of the traditional DIBP-based Ziegler–Natta catalyst, while the catalyst activity was less influenced by the ether group length of the bifunctional internal donor. It was also observed that the MWD of PP obtained by bifunctional internal donor-based catalyst was broader than that of PP made by DIBP-based Ziegler–Natta catalyst.     

Polymerization of ethylene and ethylene/1-hexene over Ziegler–Natta/metallocene hybrid catalysts supported on MgCl2 prepared by a recrystallization method

MgCl₂ for use as a catalyst support was prepared by dissolution in methanol and recrystallization in n-decane, followed by vacuum-drying at 2,000 rpm. The prepared support was modified by treatment with alkylaluminum compounds. The activity profile of ethylene over the supported catalysts persisted for periods up to 1 h during the polymerization. The prepared Ziegler–Natta/metallocene hybrid catalysts exhibited the characteristics of both metallocene and Ziegler–Natta catalysts. The polymer produced by the hybrid catalysts gave bimodal peaks in differential scanning calorimetry analysis for ethylene and ethylene/1-hexene polymerization, suggesting that the polymer was composed of two different lamellar structures that were polymerized by each catalyst. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1707–1715, 1998     

Stereospecific polymerization of olefins with supported Ziegler − Natta catalysts

The discovery of Ziegler ? Natta catalysts has been one of the greatest developments in technology for the synthesis of stereoregular polymers in both academy and industry since the 1950s. In particular, the development of the fourth generation Ziegler ? Natta catalyst with MgCl₂ as support brings a revolutionary improvement to the properties of manufactured polyolefins and stimulates people to explore the stereospecific polymerization of α‐olefin and diene monomers, which supplies the power to synthesize a new type of polyolefin materials. Although research on single‐site catalysts has attracted a lot of attention in recent years, the ‘old’ and conventional Ziegler ? Natta catalysts are still being developed vigorously due to their unique industrial advantages such as low cost, high catalytic efficiency and high stereospecificity. In this mini‐review, we mainly summarize the development of the conventional supported Ziegler ? Natta catalyst system and the stereoregular polyolefins synthesized with supported Ziegler ? Natta catalysts. © 2013 Society of Chemical Industry     

Particle morphology and morphogenesis of nascent polyethylene produced with a spherical MgCl2‐supported Ziegler–Natta catalyst in slurry process

Ethylene polymerizations were conducted in slurry process with a spherical MgCl₂‐supported Ziegler–Natta catalyst activated by triethylaluminum, and the morphology of nascent polymer particles was observed by scanning electron microscope. Three kinds of typical microscale morphologies: nodular and rope‐like structures on the external particle surface, and nodular structures in the bulk of the particle were observed. These structures are composed of polyethylene lamellae and amorphous phase filling the space between the lamellae. There is close relation between the polymerization activity and microporosity of the particles. When the activity was higher than 1500 g PE/g Cat, large number of tiny pores appeared in the particles, and rope‐like structures appeared on their surface. Formation of the morphologies can be reasonably explained by models based on multiscale solid structure of the catalyst particle and dynamic interactions among the growing polymer phases. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45679.     

A disentangled state using TiCl<Subscript>4</Subscript>/MgCl<Subscript>2</Subscript> catalyst: a case study of polyethylene

Fully entangled morphology which is usually expected for polyethylene produced using Ziegler–Natta (ZN) catalyst is due to the presence of active sites crowded on catalyst’s support surface as well as within its volume. In this research, the feasibility of producing disentangled, more precisely less entangled, polyethylene using a heterogeneous ZN catalyst supported on magnesium chloride, TiCl₄/MgCl₂, is introduced. Polymerization was carried out at rather low temperature and pressure, and the nascent polymer was characterized to investigate its entanglement state. The rheological measurements, at small amplitude oscillating in the time sweep mode, exhibited a rather good modulus build-up, demonstrating the nascent polymer in its dis(less)-entangled state. Tape and film samples were prepared from the synthesized polyethylene below its melting point to keep the morphology untapped. The solid-state drawability test was performed on the samples at 100 °C showing its improved drawability. Thus, it could be concluded that the polyethylene synthesized at rather low temperature of 0 °C and longer polymerization time was in disentangled state. Furthermore, a rheometrical analysis in frequency mode was used to estimate the molecular weight and molecular weight distribution of the synthesized polyethylene qualitatively. From X-ray diffraction patterns the existence of a small amount of hexagonal phase in the nascent polymer could be detected, which may be due to the formation of extended chains during polymerization.     

Study of propylene polymerization catalyzed by a spherical MgCl2‐supported Ziegler–Natta catalyst system: The effects of external donors

Spherical MgCl₂‐supported Ziegler–Natta catalysts containing internal donors, such as diethyl phthalate, diisobutyl phthalate, and di‐n‐octyl phthalate, have been prepared. The effects of external donors, phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxylsilane, on the propylene polymerization catalyzed by these catalysts were studied. The results indicate that the external donors not only led to an increase in the isotactic index, but also affected the morphology of resultant polymer particles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 738–742, 2005     

Higher aluminum trialkyls and magnesium aluminum alkyls as components of zioegler–natta catalysts

Magnesium aluminum alkyls containing higher (C₄–C₁₀) radical swere studied as components of Ziegler–Natta catalysts in styrene polymerization. The effects of alkyl radical length and MgR² contents in the components mentioned on the degree of TiCl₄ reduction and sterospecific activity of the catalysts were investigated. The components studied exdhibited high reducing (for TiCl4) and catalytic a tivities. Moleculear weight of the synthesized isotactic polystyrene was abnormally high.     

An improved phase‐inversion process for the preparation of silica/poly[styrene‐co‐(acrylic acid)] core–shell microspheres: synthesis and application in the field of polyolefin catalysis

Spherical and well‐dispersed silica/poly[styrene‐co‐(acrylic acid)] (SiO₂/PSA) core–shell particles have been synthesized using an improved phase‐inversion process. The resulting particles were successfully used as supports for polyolefin catalysts in the production of polyethylene with broad molecular weight distribution. Through the vapor phase, instead of the liquid phase in the traditional process, a non‐solvent was introduced into a mixture of micrometer‐sized SiO₂ and PSA solution. The core–shell structure of the resulting SiO₂/PSA microspheres was confirmed using optical microscopy, scanning electron microscopy, Fourier transfer infrared spectrometry, thermogravimetric analysis and measurement of nitrogen adsorption/desorption isotherms. In order to avoid agglomeration of particles and to obtain a good dispersion of the SiO₂/PSA core–shell microspheres, the non‐solvent was added slowly. As the concentration of PSA solution increased, the surface morphology of the core–shell particles became looser and more irregular. However, the surface area and the pore volume remained the same under varying PSA concentrations. The SiO₂/PSA core‐shell microspheres obtained were used as a catalyst carrier system in which the core supported (n‐BuCp)₂ZrCl₂ and the shell supported TiCl₄. Ethylene/1‐hexene copolymerization results indicated that the zirconocene and titanium‐based Ziegler–Natta catalysts were compatible in the hybrid catalyst, showing high activities. The resulting polyethylene had high molecular weight and broad molecular weight distribution. Copyright © 2010 Society of Chemical Industry     

Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3

Ti‐based Ziegler–Natta catalysts supported on MgCl₂ doped with AlCl₃ were prepared by the reaction of MgCl₂/AlCl₃–ethanol adduct with TiCl₄. No AlCl₃ crystallites were found in the AlCl₃‐doped catalysts by WAXD analysis, suggesting that AlCl₃/MgCl₂ solid solution was formed. The effect of doping on the catalyst performance in ethylene polymerization was investigated. The results showed that the catalysts based on AlCl₃‐doped MgCl₂ support exhibited a slightly higher activity than did the MgCl₂‐supported catalyst and the molecular weight distribution (MWD) of polyethylene (PE) markedly increased (from 10.8 to 47.9) with the increase of AlCl₃ content in catalysts. The changes in catalyst's active center distribution were studied based on nonlinear fitting of the polymer GPC curves by multiple Flory functions. It was found that increase of types of active centers by introducing AlCl₃ into the support should be responsible for the broadening of MWD of PE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1768–1772, 2006     

Bi-supported Ziegler–Natta TiCl4/MCM-41/MgCl2 (ethoxide type) catalyst preparation and comprehensive investigations of produced polyethylene characteristics

Bi-supported Ziegler–Natta catalysts (TiCl₄/MCM-41/MgCl₂ (ethoxide type)) were synthesized to improve the morphology and the properties of polyethylene. The morphology control is a crucial issue in polymerization process, while tailoring the properties of polymers is needed for specific applications. The catalysts were synthesized in different ratios of two supports with impregnation method. The polymerization process was carried out in atmospheric slurry reactor. The catalysts were characterized with scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM–EDX), inductively coupled plasma, Fourier transform infrared spectrometry (FTIR), and Brunauer-Emmett-Teller (BET) methods. The polymers were analyzed with scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry, FTIR, and tensile-strength analyses. Ubbelohde viscometer and frequency sweep measurements showed that the synthesized polymers are ultra-high-molecular-weight polyethylene. Mechanical properties of polymers showed higher Young's modulus in samples containing MCM-41, having higher thermal stability supported by TGA analysis. SEM images of bi-supported catalyst showed a controlled spherical morphology with uniform size distribution. SEM analysis support that the polymers replicate their morphology from catalyst, improving their morphology comparing to MgCl₂-supported catalyst. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48553.     

An experimental study on the early stages of gas‐phase olefin polymerizations using supported Ziegler–Natta and metallocene catalysts

The initial stages of gas‐phase polymerizations of propylene and ethylene are analyzed using a fixed bed stopped flow reactor. The very early development of particle morphology and polymer properties is analyzed for three different commercial catalyst systems: MgCl₂‐ and SiO₂‐supported Ziegler–Natta and SiO₂‐supported metallocene. It is shown that, depending on the operating conditions, distinct nonuniform catalyst fragmentation patterns can develop, confirming different scenarios described by published fragmentation models. In addition, it is shown that the molecular weight distributions and polymer yields obtained during the very early stages of the polymerization suggest the existence of significant temperature gradients inside the growing polymer particles. Finally, it is shown that the ratio of catalyst to glass beads in the bed can have a pronounced effect on the evolution of the polymerization reaction. This can be interpreted in terms of the significant temperature difference between the polymer particles and the gaseous monomer stream. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Effects of chemical structure of phenolic antioxidants on Ziegler–Natta catalyst performance during propylene polymerization

Present work studied the synthesis of in-reactor stabilization of polypropylene via introducing antioxidant into polymerization media. Special attention was dedicated to assess the efficiency of antioxidant in catalyst deactivation. Three different types of antioxidants (Irganox 1076, Irganox 1010 and Irganox 1330) which contain ester and/or phenolic OH functional groups were chosen to investigate their impact on Ziegler–Natta catalyst performance during slurry propylene polymerization. Our Results indicated that not only phenolic OH groups but also esteric bond of antioxidants are capable of interacting with active center of catalyst and consequently decreasing the catalyst activity. Our propylene polymerization results showed that determining factors such as antioxidant chemical structures and its steric hindrance effect and the number of functional groups (phenolic and esteric groups) affected on the Ziegler–Natta catalyst performance. Therefore, effects of these three types of antioxidants on polymer characteristics such as particle size distribution, morphology, T _m , T _c , X _c , and isotacticity were evaluated. Morphological analysis using scanning electron microscopy (SEM) showed that introducing antioxidant during propylene polymerization did not destroy the spherical morphology of the polypropylene particles. Conclusively, due to the negative effect of esteric bond of antioxidant on Ziegler–Natta catalyst performance, the use of antioxidant without ester groups (Irganox 1330) is more recommended during propylene polymerization.     

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

The behaviors of three different catalyst systems, TiCl₄/MgCl₂, Cp₂ZrCl₂ and Cp₂HfCl₂, were investigated in ethylene/1,5‐hexadiene copolymerization. In the Fourier transform infrared spectra of the copolymers, cyclization and branching were detected for 1,5‐hexadiene insertion in the metallocene and Ziegler–Natta systems, respectively. DSC and viscometry analyses results revealed that copolymers with lower T_m and crystallinity and higher molecular weight were obtained with metallocene catalysts. The sequence length distribution of the copolymers was investigated by using the successive self‐nucleation and annealing thermal fractionation technique. The continuous melting endotherms obtained from successive self‐nucleation and annealing analysis were employed to get information about short‐chain branching, the branching dispersity index, comonomer content and lamella thickness in the synthesized copolymers. The results established that metallocene catalysts were much more effective than Ziegler–Natta catalysts in the incorporation of 1,5‐hexadiene in the polyethylene structure. Metallocene‐based copolymers had higher short‐chain branching and comonomer content, narrower branching dispersity index and thinner lamellae. Finally, the tendency of the employed catalysts in the 1,5‐hexadiene incorporation and cyclization reaction was explored via molecular simulation. The energy results demonstrated that, in comparison to Ziegler–Natta, metallocene catalysts have a much higher tendency to 1,5‐hexadiene incorporation and cyclization. © 2018 Society of Chemical Industry     

Preparation of novel MgCl2‐adduct supported spherical Ziegler–Natta catalyst for α‐olefin polymerization

In this article, preparation of novel MgCl₂‐adduct supported spherical Ziegler–Natta catalyst for α‐olefin polymerization is reported. The factors affecting the particle size (PS) and particle size distribution (PSD) of the prepared support were investigated. In this method, the internal donor added while preparing MgCl₂‐adduct support was supposed to act as a crosslinking agent. Therefore it provided a reasonable way to enhance the morphology and control the PS of the resultant polymer particles. The possible mechanism is discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 945–948, 2006     

Solubility of 1‐hexene in LLDPE synthesized by (2‐MeInd)2ZrCl2/MAO and by Mg(OEt)2/DIBP/TiCl4–TEA

The solubility of 1‐hexene was measured for linear low‐density polyethylenes (LLDPEs) produced over a heterogeneous Ziegler–Natta catalyst, Mg(OEt)₂/DIBP/TiCl₄–TEA (ZN), and over a homogeneous metallocene catalyst, (2‐MeInd)_zZrCl₂–MAO (MT). The 1‐hexene solubility in LLDPEs was well represented by the Flory–Huggins equation with a constant value of χ. ZN–LLDPEs dissolved a larger amount of 1‐hexene and thus showed a lower value of χ compared to MT–LLDPEs. The Flory–Huggins interaction parameter χ, or the solubility of 1‐hexene at a given temperature and pressure, was suggested as a sensitive measure for the composition distribution of LLDPEs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1566–1571, 2002; DOI 10.1002/app.10418     

Kinetics of ethylene polymerization at high temperature with Ziegler–Natta catalysts

A kinetic technique is developed for the study of ethylene polymerization reaction at high temperature with Ziegler–Natta catalysts. The technique is based on the calculation of polymerization rate parameters from the data on ethylene consumption vs. time. It takes into account increase of reaction temperature at the beginning of the reaction. Kinetic data in coordinates “polymerization rate–time” are presented for several pseudohomogeneous catalysts (TiCl₄? AlEt₂Cl, Ti(OiC₃H₇)₄? AlEt₂Cl), heterogeneous catalysts (δ-TiCl₃? AlEt₃, δ-TiCl₃? AlEt₂Cl, TiCl₄/MgCl₂? AlEt₃, TiCl₄/MgCl₂? AlEt₂Cl) and solubilized catalysts (δ-TiCl₃? poly-1-hexene? AlEt₂Cl) at 180°C and reaction pressure 14.6 atm for first 10 min of the reaction. These data are useful for the selection of Ziegler–Natta catalysts for testing in ethylene polymerization reaction in continuous high pressure reactors at short residence times.