Effect of cocatalyst on the chemical composition distribution and microstructure of ethylene-hexene copolymer produced by a metallocene/Ziegler-Natta hybrid catalyst

A silica-magnesium bisupport (SMB) was prepared by a sol-gel method for use as a support for metallocene/Ziegler-Natta hybrid catalyst. The SMB was treated with methylaluminoxane (MAO) prior to the immobilization of TiCl₄ and rac-Et(Ind)₂ZrCl₂. The prepared rac-Et(Ind)₂ZrCl₂/TiCl₄/MAO/SMB catalyst was applied to the ethylenehexene copolymerization with a variation of cocatalyst species (polymerization run 1: triisobutylaluminum (TIBAL) and methylaluminoxane (MAO), polymerization run 2: triethylaluminum (TEA) and methylaluminoxane (MAO)). The effect of cocatalysts on the chemical composition distributions (CCDs) and microstructures of ethylene-hexene copolymers was examined. It was found that the catalytic activity in polymerization run 1 was a little higher than that in polymerization run 2, because of the enhanced catalytic activity at the initial stage in polymerization run 1. The chemical composition distributions (CCDs) in the two copolymers showed six peaks and exhibited a similar trend. However, the lamellas in the ethylene-hexene copolymer produced in polymerization run 1 were distributed over smaller sizes than those in the copolymer produced in polymerization run 2. It was also revealed that the rac-Et(Ind)₂ZrCl₂/TiCl₄/MAO/SMB catalyst preferably produced the ethylene-hexene copolymer with non-blocky sequence when TEA and MAO were used as cocatalysts.     

Comparison of ethylene-propylene copolymers obtained with Ti,V and Zr catalyst systems

Summary Ethylene and propylene were copolymerized in n-heptane in the presence of high activity heterogeneous MgCl₂/TiCl₄ catalyst and homogeneous VOCl₃ and Cp₂ZrCl₂ catalysts to study the effect on the catalyst to the microstructure and molecular weight distribution of the copolymer. The copolymer obtained with the zirconium catalyst was much more random in structure than that obtained with the vanadium and titanium catalysts and the molecular weight distribution was very narrow. Ethylene and propylene were also copolymerized in liquid propylene with MgCl₂/TiCl₄ and VOCl₃ catalyst systems. These copolymers were column fractionated and the fractions were analysed by NMR spectroscopy and DSC. The fractions of the copolymer obtained with the titanium catalyst was found to have broader distribution in composition than the copolymer obtained with the vanadium catalyst. This probably explains the traces of crystallinity in the copolymer prepared with the titanium catalyst. However, no effect was seen on the glass transition temperature.     

Functionalization of polyethylene using borane reagents and metallocene catalysts

A new method to prepare functionalized polyethylene involving borane intermediates and transition metal catalysts is described. Two processes, direct and post polymerizations, were employed to prepare borane-containing polyethylene (PE-B), which can be transformed to functionalized polyethylene (LLDPE-f) with various functional groups, such as ? BR₂, ? OH, ? NH₂, ? OSi(CH₃)₃. In the direct process, the PE-B copolymers were prepared in one step by copolymerization of ethylene with a borane monomer (ω-borane-α-olefin). The post polymerization process requires two steps: copolymerization of ethylene and 1,4-hexadiene, and subsequential hydroboration reaction of unsaturated PE. Three transition metal catalysts, including two homogeneous metallocene (Cp₂ZrCl₂ [bis(cyclopentadienyl) zirconium dichloride] and Et(Ind)₂ZrCl₂ [1,1′-ethylenedi-η⁵-indenyl-zirconium dichloride] with MAO (methylaluminoxane)) and one heterogeneous (TiCl₃·AA/Et₂AlCl) ones, were studied in the copolymerization reactions. The single site Et(Ind)₂ZrCl₂/MAO homogeneous catalyst, with a strained ligand geometry and opened active site, is by far the most effective system in the incorporation of high olefins into polyethylene structures.     

TiCl4 immobilized on a composite support SiO2/MgCl2·x(1,4-butanediol)/poly[styrene-co-(acrylic acid)] for ethylene polymerization: The barrier effect of poly[styrene-co-(acrylic acid)]

By immobilizing titanium-based Ziegler–Natta catalyst on composite support, SiO₂/MgCl₂·x(1,4-butanediol)/poly[styrene-co-(acrylic acid)] (SiO₂/MgCl₂·xBD/PSA) and SiO₂/MgCl₂·xBD/PSA/TiCl₄ (SMPT) were synthesized for ethylene polymerization. SiO₂/MgCl₂·xBD/TiCl₄ without PSA was also prepared for comparison. The results of energy-dispersive X-ray analysis, SEM, and thermogravimetric analysis demonstrated that SMPT had a unique core-mantle-shell structure. The PSA layer can be considered as a barrier for the mass-transfer of reactants based on the results of self-diffusion measurement by pulsed field gradient NMR and ethylene polymerization. The polyethylene produced by SMPT showed high molecular weight (MW) and broad molecular weight distribution (MWD). The influences of PSA content, hydrogen, and comonomer on the ethylene polymerization behavior were also investigated. The results further demonstrated that the PSA layer in the composite support had different diffusion capabilities to the reactants. The physical properties of the produced polyethylene implied the possibility to control the MW and MWD of polyethylene by the manipulation of PSA layer. The catalyst fragmentation during ethylene polymerization was also affected by the PSA shell due to its barrier effect. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Organic/inorganic support for immobilizing (n‐BuCp)2ZrCl2/TiCl3 hybrid catalyst for use in the preparation of polymer blends

Reactor blends of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and low‐molecular‐weight polyethylene (LMWPE) were synthesized by two‐step polymerization using a hybrid catalyst. To prepare the hybrid catalyst, styrene acrylic copolymer (PSA) was first coated onto SiO₂/MgCl₂‐supported TiCl₃; then, (n‐BuCp)₂ZrCl₂ was immobilized onto the exterior PSA. UHMWPE was produced in the first polymerization stage with the presence of 1‐hexene and modified methylaluminoxane (MMAO), and the LMWPE was prepared with the presence of hydrogen and triethylaluminium in the second polymerization stage. The activity of the hybrid catalyst was considerable (6.5 × 10⁶ g PE (mol Zr)^?1 h^?1), and was maintained for longer than 8 h during the two‐step polymerization. The barrier property of PSA to the co‐catalyst was verified using ethylene polymerization experiments. The appearance of a lag phase in the kinetic curve during the first‐stage polymerization implied that the exterior catalyst ((n‐BuCp)₂ZrCl₂) could be activated prior to the interior catalyst (M‐1). Furthermore, the melting temperature, crystallinity, degree of branching, molecular weight and molecular‐weight distribution of polyethylene obtained at various polymerization times showed that the M‐1 catalyst began to be activated by MMAO after 40 min of the reaction. The activation of M‐1 catalyst led to a decrease in the molecular weight of UHMWPE. Finally, the thermal behaviors of polyethylene blends were investigated using differential scanning calorimetry. Copyright © 2011 Society of Chemical Industry     

Hybrid titanium catalyst supported on core‐shell silica/poly(styrene‐co‐acrylic acid) carrier

Hybrid titanium catalysts supported on silica/poly(styrene‐co‐acrylic acid) (SiO₂/PSA) core‐shell carrier were prepared and studied. The resulting catalysts were characterized by Fourier transform infrared (FTIR) spectroscopy, laser scattering particle analyzer and scanning electronic microscope (SEM). The hybrid catalyst (TiCl₃/MgCl₂/THF/SiO₂·TiCl₄/MgCl₂/PSA) showed core‐shell structure and the thickness of the PSA layer in the two different hybrid catalysts was 2.0 μm and 5.0 μm, respectively. The activities of the hybrid catalysts were comparable to the conventional titanium‐based Ziegler‐Natta catalyst (TiCl₃/MgCl₂/THF/SiO₂). The hybrid catalysts showed lower initial polymerization rate and longer polymerization life time compared with TiCl₃/MgCl₂/THF/SiO₂. The activities of the hybrid catalysts were enhanced firstly and then decreased with increasing P/P. Higher molecular weight and broader molecular weight distribution (MWD) of polyethylene produced by the core‐shell hybrid catalysts were obtained. Particularly, the hybrid catalyst with a PSA layer of 5.0 μm obtained the longest polymerization life time with the highest activity (2071 kg PE mol^?1 Ti h^?1) and the resulting polyethylene had the broadest MWD (polydispersity index = 11.5) under our experimental conditions. The morphology of the polyethylene particles produced by the hybrid catalysts was spherical, but with irregular subparticles due to the influence of PSA layer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and activity of zirconocene catalysts supported on silica-type sol-gel carrier for ethylene polymerization

Summary Synthesis and activity of bis(cyclopentadienyl)zirconium dichloride catalyst supported on unconventional silica-type material obtained in sol-gel process and activated by organoaluminium co-catalyst were studied. The effect of support modification conditions (thermal dehydration and/or modification by organoaluminium compound) and a type of co-catalyst on an activity of the catalytic system in ethylene polymerization and properties of resulting polymers were investigated and compared with results obtained earlier for vanadium catalysts supported on mentioned sol-gel carrier. The most appropriate method of the sol-gel silica-type support preparation is thermal pre-treating (200°C) followed by modification with AlEt₂Cl. Metallocene catalyst supported on such sol-gel product and activated by MAO appeared to be most active among studied systems. Studied Cp₂ZrCl₂/MAO supported on silica-type sol-gel carrier allow to obtain polyethylene (at 50°C polymerization temperature) with yield up to 30·10⁶ g/(mol_Zr·h), molecular weight below 300 000 and MWD=2−4. Received: 4 September 2000/Revised version: 3 January 2001/Accepted: 3 January 2001     

Structure and properties of multi‐walled carbon nanotubes/polyethylene nanocomposites synthesized by in situ polymerization with supported Cp2ZrCl2 catalyst

Multi‐walled carbon nanotubes (MWCNTs)/polyethylene (PE) nanocomposites were prepared via in situ polymerization with MWCNTs supported Bis‐ (cyclopentadienyl) zirconium dichloride (Cp₂ZrCl₂) catalyst. X‐ray photoelectron spectroscopy (XPS) and field emission scanning electron microscope (FESEM) results implied that Cp₂ZrCl₂ catalyst was immobilized in the surface of the MWCNTs supports via a bridge of methylaluminoxane (MAO). The efficient dispersion of MWCNTs in PE matrix and the strong compressive forces associated with PE on the MWCNTs were demonstrated by means of transmission electron microscope (TEM), FESEM and Raman spectra. With introducing 0.2 wt% MWCNTs, both the tensile strength and elongation of MWCNTs/PE nanocomposite were improved by factors of 1.6 (from 29 to 45 MPa) and 1.5 (from 909% to 1360%) comparing with the pure PE, respectively. Morphology observation of fractured surface revealed that the PE firmly adhered to the nanotubes, which was responsible for the significant improvement of the mechanical properties of nanocomposites. Thermal stabilities of the nanocomposites were significantly improved. In addition, the MWCNTs/PE nanocomposites showed very high ultraviolet (UV) shielding property, which could increase photooxidative stability of the PE. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Control of molecular weight distribution in propylene polymerization with Ziegler–Natta/metallocene catalyst mixtures

Propylene polymerization was investigated with a sequential addition of Ziegler–Natta and metallocene catalysts. From the fact that the molecular weights of polypropylene (PP) produced with Ziegler–Natta and with metallocene catalysts differ, it was possible to control the molecular weight distribution (MWD) of PP with a sequential addition of methylaluminoxane and rac-ethylenebis(indenyl)zirconium dichloride followed by triethylaluminum and magnesium dichloride-supported titanium tetrachloride catalyst. The obtained PP exhibited a wide MWD curve with shoulder peak. The position and height of each peak was controlled with the variation of polymerization time for each catalyst as well as the amount of each catalyst. The MWD of PP prepared with sequential addition of catalysts was much wider than that of PP obtained from each catalyst. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2213–2222, 1998     

Influence of process parameters on ethylene-norbornene copolymers made by using [2,2′-methylenebis(1,3-dimethylcyclopentadienyl)]-zirconium dichloride and MAO

Ethylene-norbornene copolymerization was investigated by using metallocene catalysts, [2,2′-methylenebis( 1,3-dimethylcyclopentadienyl)]zirconium dichloride(2,2′-CH₂ (1,3-Me₂Cp)₂ZrCl₂, Catalyst A) and racemicethylenebis( indenly)zirconium dichloride (rac-Et(Ind)₂ ZrCl₂, Catalyst B), in the presence of methylaluminoxane as a cocatalyst. The influences of different process parameters such as polymerization temperature and ethylene pressure were studied by using a 56 wt% norbornene solution in toluene. The results show that Catalyst A has a higher activity in copolymerization than Catalyst B. Catalyst A also has a superior norbornene insertion performance to Catalyst B, resulting in polymers with higher glass transition temperatures, by approximately 70 ‡C, at similar polymerization conditions, indicative of a great commercial potential of Catalyst A.     

Elastomeric properties of ethylene/propylene copolymers prepared by zirconocene/methylaluminoxane catalysts

Ethylene/propylene copolymers (EPM) have been prepared by a liquid propylene suspension process, using homogeneous catalysts based on nonbridged zirconocenes and methylaluminoxane (MAO). When bis(η⁵-cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂), bis(η⁵-cyclopentadienyl) dimethyl zirconium (Cp₂ZrMe₂) and bis(η⁵-cyclopentadienyl), dibenzyl zirconium (Cp₂ZrBz₂) were used as catalyst components, EPM having low average molecular weight (MW) were in general obtained in low yield. On the contrary, a very large improvement of productivity and MW was observed when bis(η⁵-indenyl)zirconium dichloride (Ind₂ZrCl₂) and bis(η⁵-indenyl) dimethyl zirconium (Ind₂ZrMe₂) as well as bis(η⁵-tetrahydroindenyl)zirconium dichloride [(IndH₄)₂ZrCI₂] were employed in combination with MAO. In particular, this last catalytic system allowed one to obtain EPM with a narrower distribution of MW in addition to the above characteristics. Better performances, in terms of rheological and elastomeric properties, were also found for the crude and vulcanized samples prepared by (IndH₄)₂ZrCl₂/MAO catalyst.     

Propylene polymerisations with novel heterogeneous combination metallocene catalyst systems

Propylene was polymerised with novel combination metallocene catalyst systems prepared by an emulsion-based heterogenisation method in liquid monomer conditions. The catalyst combinations investigated were rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride/rac-[ethylenebis(2-(tert-butyldimethylsiloxy)indenyl)]zirconium dichloride/methylaluminoxane (MAO) (1 + 2) and rac-dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride/rac-dimethylsilanylbis(2-isopropyl-4-[3,5-dimethylphenyl]indenyl)zirconium dichloride/MAO (1 + 3). The effects of polymerisation temperature and hydrogen on catalyst performance and polymer properties, as well as copolymerisation with hexene and ethylene were investigated. Depending on the polymerisation conditions, M_w of polypropylene varied from 144 to 286 kg/mol for 1 + 2 and from 200 to 390 kg/mol for 1 + 3. Combination 1 + 2 produced broader molecular weight distribution (MWD) than 1 + 3, and a bimodal MWD with clearly separated low- and high-M_w polymer fractions was observed with 1 + 2. The two catalyst systems showed similar hydrogen and hexene responses. Each metallocene precursor showed individual response towards the polymerisation conditions, especially polymerisation temperature, suggesting that interaction between the catalyst active sites was negligible in the studied systems.     

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     

Preparation of bimodal polypropylene in two‐step polymerization

Polymerization of propylene was carried out by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system in n‐heptane, where MgCl₂, EtOH, TiCl₄, DIBP (diisobutyl phthalate), TEA (triethyl aluminum), and cHMDMS (cyclohexyl methyl dimethoxy silane) were support, ethanol for alcoholation, catalyst, external donor, cocatalyst (activator), and internal donor, respectively. The catalyst activity and polymer isotacticity were studied by measuring the produced polymer and its solubility in boiling n‐heptane, respectively. The molecular weight and molecular weight distribution of the polymers were evaluated by gel permeation chromatography. Hydrogen was used for controlling the molecular weight. For producing the bimodal polypropylene, the polymerization was carried out in two steps (i.e., in the presence and absence of hydrogen). It was found that the catalyst showed high activity and stereoselectivity, on the other hand, bimodal polymer could simply be produced in two‐step polymerization by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system. Meanwhile, the effect of the step of the hydrogen adding on propylene polymerization was investigated. It was shown that the addition of hydrogen in the second step was more suitable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1456–1462, 2006     

Plausible guard effect on the active sites of heterogeneous Ziegler–Natta catalyst by coordinating monomers and growing polymer chains in the initial stage of propene polymerization

Investigation of propene polymerization by a modified stopped‐flow technique using TiCl₄/ethylbenzoate(EB)/MgCl₂ Ziegler–Natta catalyst with or without pretreating the catalyst with triethylaluminium (TEA) within an ultra‐short period (ca 1 s) was conducted to gain new understanding of the nature of active sites related to TEA in the early stage of polymerization. When the catalyst was pretreated by a cocatalyst, deactivation behaviour was clearly observed, even within an extremely short pretreatment period. In contrast, without pretreatment, the deactivation of active sites can be neglected within the polymerization period indicating that the activated Ti species might be protected from deactivation by TEA when monomer is present in the system. A plausible guard effect on the active sites by coordinating monomer and growing polymer chains in the initial stage of polymerization is proposed to account for this phenomenon. Copyright © 2004 Society of Chemical Industry     

A comparative study of tetraisobutyldialuminoxane and methylaluminoxane as cocatalysts for Cp2ZrCl2 catalyzed ethylene polymerization

Summary The effect of [A1]/[Zr] mol ratio and temperature on the cocatalytic effects of tetraisobutyldialuminoxane (TIBDAO) and methylaluminoxane (MAO) for ethylene polymerization using Cp₂ZrCl₂ catalyst were studied. The decay type kinetic profile was observed for both TIBDAO and MAO cocatalyzed ethylene polymerizations. Catalytic activity and rate of polymerization were found to be low for TIBDAO cocatalyzed ethylene polymerization when compared to MAO cocatalyzed ethylene polymerization. The differences in catalytic activity and rate of polymerization for ethylene polymerization catalyzed by Cp₂ZrCl₂-TIBDAO and Cp₂ZrCl₂-MAO were discussed with respect to the structures of MAO and TIBDAO. An active species for Cp₂ZrCl₂-MAO and Cp₂ZrCl₂-TIBDAO catalyzed ethylene polymerizations was also discussed. The polyethylene was characterized by intrinsic viscosity measurements.     

Polymerization of styrene by diphenylzinc-additive systems

Summary Styrene was polymerized using combined systems of diphenylzinc, Ph₂Zn, and metallocene compounds activated by methylaluminoxane, MAO. From the various metallocenes employed bis (indenyl) zirconium dichloride, Ind₂ZrCl₂, [isopropyl (cyclopentadienyl) (1-fluorenyl)] zirconiumdichloride, i-Pr (Flu) (Cp) ZrCl₂, and bis (cyclopentadienyl) titanium dichloride, Cp₂TiCl₂, produced the larger amounts of polymer. Ph₂Zn-Cp₂TiCl₂-MAO system gave polystyrene, PSt, whose DSC analysis indicated a major endotherm peak at 256°C. A butanone insoluble fraction of the polymer was separated from the crude PSt. The proportion of insoluble polymer depends on the metallocene employed and on the conversion to polymer.Partly presented at MakroAkron '94, Akron, Ohio, USA. July 1994. Part 3: cf. [13]     

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.     

Easy one-pot method to control the morphology of polyethylene/carbon nanotube nanocomposites using metallocene catalysts

An easy one pot method is demonstrated for the controlled periodical surface coating of polyethylene over multiwalled carbon nanotubes (MWCNT) by insitu polymerization of ethylene using highly active metallocene catalysts (Cp₂ZrCl₂ and Cp₂TiCl₂) in combination with methylalumoxane. The crystallinity of the nanocomposite was increased and its morphology could be tuned from “sausage” like to “shish-kebab” in the presence of CNT depending on the experimental condition and choice of metal atom.     

Ethylene polymerization with hybrid nickel diimine/Cp2TiCl2 catalyst: a new method to prepare blends of linear and branched polyethylene

Blends of linear polyethylene (LPE) and branched polyethylene (BPE) display very good mechanic properties that can be beneficial for various applications such as shear thinning and melt elasticity. LPE, BPE and amorphous polyethylene can be produced using nickel diimine (DMN) catalyst under various polymerization conditions, while LPE can be obtained using metallocene catalyst. Thus, LPE/BPE blends can be achieved by in situ polymerization using a hybrid DMN/metallocene catalyst. A novel hybrid catalyst made of DMN and Cp₂TiCl₂ was designed and used for ethylene polymerization. A synergistic effect of the two active sites in the hybrid DMN/metallocene catalyst was observed. Blends of linear and low branched polyethylene were synthesized when polymerization was conducted at low temperature (0 °C), while blends of linear and highly branched polyethylene were obtained at high temperature (50 °C). However, the miscibility of the polymers obtained at 50 °C was dramatically reduced as compared to those obtained at 0 °C. Mesoporous particles (MCM‐41) consisting of aluminosilicate with cylindrical pores were used to support the hybrid catalyst, in which MCM‐41 provides sufficient nanoscale pores to facilitate the polymerization in well‐controlled confined spaces. Blends of LPE and BPE were synthesized by in situ polymerization without adding comonomer and characterized. The miscibility of the polymer blends can be improved by supporting the hybrid catalyst on MCM‐41. Copyright © 2009 Society of Chemical Industry