Cocatalytic activities of methylaluminoxane prepared by direct water addition method in ethylene polymerization over Cp2ZrCl2

The characterization of ethylene polymerization behaviors catalyzed over Cp₂ZrCl₂/MAO homogeneous system using methylaluminoxanes prepared by the direct hydrolysis of AlMe₃ (Me=methy1) were reported. The MAO was prepared at the ratio of [H₂O]/[A1]=1 and 0.5 and at three different temperatures, i.e., −40, −60 and −80 °C. The polymerization rate was not decreased with polymerization time when the MAO prepared at the ratio of [H₂O]/[AlMe₃]=l at −60 °C was used as a cocatalyst regardless of the ratio of Al/Zr and the polymerization temperature. The polymerization rate drastically decreased with polymerization time above 60 °C in case of using MAO prepared at the ratio of [H₂O]/[AlMe₃]=l at −80 °C. However, in case of the MAO prepared at the ratio of [H₂O]/ [AlMe₃]=0.5 at −80 °C, the rate continuously increased with polymerization time at the polymerization temperature of 70 °C and 80 °C. The amount of MAO needed to activate Cp₂ZrC1₂ was larger than that of MAO prepared at the ratio of [H₂O]/[A1]=1. The viscosity molecular weight of polyethylene (PE) cocatalyzed with MAO prepared at the ratio of [H₂O]/[Al]=0.5 was lower than that of polyethylene obtained with MAO prepared at the ratio of [H₂O]/[A1]=1.     

Ethylene polymerization over a nano-sized silica supported Cp2ZrCl2/MAO catalyst

Nano-sized and micro-sized silica particles were used to support Cp₂ZrCl₂/MAO catalyst for ethylene polymerization. Nano-sized catalyst exhibited much better ethylene polymerization activity than micro-sized catalyst. At the optimum temperature of 60 °C, nano-sized catalyst’s activity was 4.35 times the micro-sized catalyst’s activity, which was attributed to the large specific external surface area, the absence of internal diffusion resistance, and the better active site dispersion for the nano-sized catalyst. Polymers produced were characterized with SEM, XRD, DSC, and densimeter. SEM indicated that the resulting polymer morphology contained discrete tiny particles and thin long fiberous interlamellar links.     

Kinetic study on copolymerization of ethylene and 1‐hexene catalyzed by Cp2ZrCl2/MAO catalytic system

The kinetics of ethylene and 1‐hexene copolymerization catalyzed by Cp₂ZrCl₂/MAO was studied. A new kinetic mathematical model that takes the reactivation effect of MAO into account has been developed. Applying this model, the good agreement between the experimental data and the fitting profiles was achieved. POLYM. ENG. SCI., 47:540–544, 2007. © 2007 Society of Plastics Engineers     

Synthesis of linear low density polyethylene with a nano-sized silica supported Cp2ZrCl2/MAO catalyst

A nano-sized silica supported Cp₂ZrCl₂/MAO catalyst was used to catalyze the copolymerization of ethylene/1-hexene and ethylene/1-octene to produce linear low-density polyethylene (LLDPE) in a batch reactor. Under identical reaction conditions, the nano-sized catalyst exhibited significantly higher polymerization activity, and produced copolymer with greater molecular weight and smaller polydispersity index than a corresponding micro-sized catalyst, which was ascribed to the much lower internal diffusion resistance of the nano-sized catalyst. Copolymer density decreased with the increase of polymerization temperature, probably due to the decrease of reactivity ratio r ₁ and ethylene solubility with increasing temperature. Polymerization activity of the nano-sized catalyst increased rapidly with increasing comonomer concentration. Ethylene/1-octene exhibited higher polymerization activity and had a stronger comonomer effect than ethylene/1-hexene.     

Ethylene polymerization over MgO‐supported zirconocene catalysts

Supported zirconcene catalysts on a new support, MgO, were prepared and tested in ethylene polymerization. Three types of impregnation methods were employed to find an optimum supporting method for MgO. The direct impregnation of Cp₂ZrCl₂ on MgO showed low metal loading and polymerization activity, while the catalyst had a higher metal loading and polymerization activity when MgO was treated with methylaluminoxane (MAO) before supporting. Treatment of MgO with MAO during the supporting step invoked two types of catalytic sites, which was evidenced by the bimodal molecular weight distribution of the polymer products. MgO is considered to have potential as a support for metallocenes.     

Polymer-supported metallocene catalysts for gas-phase ethylene polymerization

The use of hydroxylated chloromethylated-styrene/divinylbenzene copolymer as a support for three different catalysts, Cp₂ZrCl₂, [Ind]₂ZrCl₂ and (CH₃)₂Si[Ind]₂ZrCl₂ has been examined for the polymerization of ethylene in gas phase. The gas phase polymerization experiments were performed in a horizontal reactor by using Box-Behnken experimental design [Box and Wilson, 1951] to study the effects of temperature, ethylene partial pressure, and MAO cocatalyst level on polymerization. The measured average catalyst activities were empirically correlated with these three factors. Temperature appears to be the most important factor, which shows a first and second order effect on activity and also interacts with pressure and MAO. The kinetic study shows that these supported catalysts might contain two types of active sites, and the deactivation of sites follows a first order kinetic. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Copolymerization of ethylene and 1-octadecene with the Cp2ZrCl2/MAO and Cp2HfCl2/MAO catalyst systems

Summary The comparison of the copolymers obtained with the Cp₂ZrCl₂/MAO and Cp₂HfCl₂/MAO catalyst systems showed that the catalyst having hafnocene was much more reactive towards 1-octadecene than zirconocene. The comonomer concentration had to be three times higher in the zirconocene copolymerization than in the hafnocene copolymerization when the level of 6 mol-% was reached. Although the hafnocene catalyst was more reactive towards 1-octadecene, the molecular weights were higher than in the copolymers obtained with the zirconocene catalyst.The total activity of the zirconocene was 10 times higher than with the hafnocene catalyst. With the zirconocene catalyst the activity towards ethylene was constantly increasing by increasing the comonomer concentration but stayed nearly constant with the hafnocene catalyst. It seemed that there is no rate enhancement effect upon comonomer addition with the hafnocene catalyst.     

Polymerization of ethylene using zirconocenes supported on swellable cation-exchanged fluorotetrasilicic mica

Supported catalysts consisting of Cp₂ZrCl₂ and cation-exchanged fluorotetrasilicic mica (Mⁿ⁺-mica, Mⁿ⁺ = Na⁺, Mg²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺) were prepared and employed in the ethylene polymerization or ethylene/1-hexene copolymerization in the presence of R₃Al. The catalysts consisting of swellable Mg²⁺-mica and Zn²⁺-mica (both calcined at 200 °C) and Cp₂ZrCl₂ displayed high activity for the polymerization reaction. By contrast, when Mg²⁺-mica and Zn²⁺-mica were calcined above 250 °C, the swellability was lost, and the activities of Cp₂ZrCl₂ supported on these non-swellable micas were significantly reduced. The relationship between the activity and swellability of mica was clearly observed both in ethylene polymerizations employing (n-BuCp)₂ZrCl₂ in place of Cp₂ZrCl₂ and in ethylene/1-hexene copolymerizations using Cp₂ZrCl₂. The role of Mⁿ⁺-mica for the activation of the metallocene complex was investigated by surface observation using a scanning electron microscope and by XRD measurements of the catalysts after polymerization of ethylene for a short time. The results of the surface observations indicated that polyethylene was produced on the edges of Mⁿ⁺-mica lamellas at the initial stage of the polymerization. The XRD measurements show that the regularity of the stacked lamellas was immediately lost at this stage. The catalyst prepared by removing free Cp₂ZrCl₂ (i.e., unsupported Cp₂ZrCl₂, Cp₂ZrCl₂ dissolved into the catalyst slurry) showed extremely low activity, suggesting that the most of the active sites were formed through the reactions of Mⁿ⁺-mica and free Cp₂ZrCl₂. These results indicate that the lamellas of Mⁿ⁺-mica are peeled off at the initial stage of the polymerization and that exposed metal cations react with free-Cp₂ZrCl₂ to form additional active species. The swellability of Mⁿ⁺-mica strongly affects the formation of additional active sites, and therefore the supported catalysts based on non-swellable Mⁿ⁺-mica displayed only low activities.     

POLYMERIZATION KINETICS AND MODELING OF SLURRY ETHYLENE POLYMERIZATION PROCESS WITH METALLOCENE/MAO CATALYSTS

Polymerization methods of ethylene include the slurry, solution, and gas-phase processes. This study investigates polymerization conditions and kinetics under slurry process. Typical metallocene catalyst/cocatalyst Cp₂ZrCl₂/MAO system was used for ethylene polymerization. Two kinds of polymerization kinetics were compared in this study, multiple active-site model and transfer-effect model. The kinetic studies used metallocene-type polymerization kinetics, including catalyst activation, initiation, chain propagation, chain transfer, and termination steps. In addition, kinetic constants of polymerization reaction model were calculated. Calculation results of catalyst activity and molecular weight were compared with experimental results, indicating their good correlation. Moreover, the conventional polymerization was modified to accurately predict the molecular weight behaviors under various reaction conditions with the proposed transfer-effect model. Exactly, how reaction time, pressure, catalyst concentration, and cocatalyst ratio affect catalyst activity and molecular weight of the polymer were also discussed.     

Polymerization of ethylene using metallocene and aluminoxane systems

This paper describes ethylene polymerization using a number of metallocene and aluminoxane catalyst systems, Cp₂MR₂ and methylaluminoxane [M=Zr, W, Nb; R=Cl, CH₃]. Two types of methylaluminoxane, MAO (1) and MAO (2), were used as cocatalysts. The polymerization activities of the complexes Cp₂WCl₂ and Cp₂NbCl₂ were compared with that of Cp₂ZrCl₂. The Nb and W complexes were found to be less active than the Zr complex. Polyethylene characterization was also carried out by the following methods: gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). ©1997 SCI     

Characterization of polyethylene/kaolin composites by polymerization filling with Cp2ZrCl2/MAO catalyst system

In this work, the preparation and characterization of metallocene‐catalyzed polyethylene (PE)/kaolin composites were presented. The composites was prepared by the so‐called polymerization‐filling method in which the PE matrix was formed directly on the kaolin surface by ethylene polymerization with the prefixed Cp₂ZrCl₂/methylaluminoxane (MAO) catalyst system on the kaolin surface. SEM, FTIR, and DMA were carried out to characterize the composites. The experimental results showed the new composites had homogeneous distribution of kaolin particles in the PE matrix and strong interfacial interaction between the PE matrix and kaolin particles. At the molecular level, the interfacial interaction caused the decrease of the mobility of PE molecular chains. In addition rheological testing showed that the introduction of kaolin by polymerization filling could improve the rheological behavior of prepared composites. The relationship between the rheological behaviors and the interfacial conditions were discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2913–2921, 2002     

Copolymerization of ethylene and 1-octene by homogeneous and different supported metallocenic catalysts

In this work, the performance of the homogeneous catalyst system based on Et(Flu)₂ZrCl₂/MAO was evaluated on the copolymerization of ethylene and 1-octene. Characteristics of some of the produced polymers were also investigated. A study was performed to compare this system with that of Cp₂ZrCl₂/MAO. The influence of different support materials for the Cp₂ZrCl₂ was also evaluated, using silica, MgCl₂, and the zeolite sodic mordenite NaM. An increase in activity was observed in relation to the comonomer addition for the two homogeneous catalysts. The copolymers produced by the Et(Flu)₂ZrCl₂/MAO system showed higher molecular weight and narrower molecular weight distribution. We verified that the catalyst supported on SiO₂ was the most active one, although the copolymers produced with the catalyst supported on NaM showed higher molecular weight and lower molecular weight distribution. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 724–730, 2001     

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.     

Polymerization of allylbenzene with metallocene catalysts

Summary Homopolymerization of allylbenzene was carried out with various metallocene/methylaluminoxane (MAO) catalysts. Different polymerization behavior was observed depending upon the catalysts empolyed. rac-Et(Ind)₂ZrCl₂ and rac-Me₂Si(Ind)₂ZrCl₂ gave semicrystalline polyallylbenzenes while i-Pr(CpFlu)ZrCl₂ and CpTiCl₃ did not give any polymeric product. The Cp₂ZrCl₂ gave amorphous polyallylbenzene with low molecular weight. The effect of temperature on the polymerization was investigated with a constant Al/Zr ratio. The temperature showing maximum catalyst activity is higher for the ansa metallocene catalysts than Cp₂ZrCl₂ catalyst. The IR and NMR spectra indicated that the polyallylbenzene consisted of allylbenzene repeating unit and no isomerization occurred. Received: 7 December 1998/Revised version: 29 January 1999/Accepted: 9 February 1999     

Methylaluminoxane: synthesis,characterization and catalysis of ethylene polymerization

Summary Three types of methylaluminoxanes (MAO-1, 2 and 3) were synthesized with different average molecular weights. In each MAO synthesis, two types of MAOs were isolated (Fractions A and B). Fractions A and B differ by the presence of different methyl/aluminum molar ratio and mol% trimethylaluminum. Kinetics of ethylene polymerization were studied using both fractions A and B of MAOs 1,2 and 3 as cocatalysts and Cp₂ZrCl₂ as catalyst at atmospheric pressure of ethylene. The poly(ethylene)s were analyzed for their molecular weight.     

Suppression of metallocene catalyst leaching by the removal of free trimethylaluminum from methylaluminoxane

The leaching of the catalyst zirconocene dichloride (Cp₂ZrCl₂) from an SBA‐15 silica support during ethylene polymerization was studied; severe leaching was observed when commercial methylaluminoxane (MAO) was used as the cocatalyst. However, the removal of free trimethylaluminum (TMA) from an MAO solution with a sterically hindered phenol reduced the catalyst leaching by 97–100%. The results obtained from the leaching experiments with TMA‐free MAO suggested that the major reason for catalyst leaching was the free TMA in the commercial MAO solution, not the pure MAO itself. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4632–4635, 2006     

Ethylene polymerization over (nBuCp)2ZrCl2/MAO catalytic system supported on aluminosilicate SBA‐15 mesostructured materials

Heterogeneous metallocene catalysts were prepared by incipient wetness impregnation of AlSBA‐15 (Si/Al = 4.8, 15, 30, 60, and ∞) mesostructured materials with (nBuCp)₂ZrCl₂/MAO. For comparative purposes commercial silica and silica–alumina (Si/Al = 4.8) supports were also impregnated with the MAO/metallocene catalytic system. A combination of X‐ray powder diffraction, nitrogen adsorption–desorption isotherms at 77 K, transmission electron microscopy, ICP‐atomic emission spectroscopy, and UV–vis spectroscopic data, were used to characterize the supports and the heterogeneous catalysts. Ethylene polymerizations were carried out in a schlenk tube at 70 °C and 1.2 bar of ethylene pressure. The polyethylene obtained was characterized by GPC, DSC, and SEM. Catalysts prepared with mesostructured SBA‐15 supports exhibited better catalytic performance than those supported on amorphous silica and silica–alumina. In general, higher ethylene polymerization activity was achieved if (nBuCp)₂ ZrCl₂/MAO catalytic system was heterogenized using supports with lower pore size in the range of the mesopores and lower Si/Al ratio. All catalysts produced high‐density polyethylene, with high crystallinity values and fibrous morphology when SBA‐15 mesostructured materials were used as supports. POLYM. ENG SCI., 2008. © 2008 Society of Plastics Engineers     

Concentration effects of methylalumoxane,zirconocene dichloride and trimethylaluminum in ethylene polymerization

A quantitative study was carried out on the homogeneous zirconocene dichloride/methylalumoxane/trimethylaluminum (Cp₂ZrCl₂/MAO/TMA) catalyst system in ethylene polymerization. The effects of variation of the Al_MAO/Zr ratio, absolute Zr concentration, and addition of TMA on ethylene polymerization activity and polymer properties were investigated. The polymerization profiles for small Al_MAO/Zr ratios and the changes with the Zr concentration are explained with a complexation equilibrium for the active homogeneous complex and with the change to a heterogeneous catalyst upon polymer precipitation. Good polymer productivities can be achieved at Al_MAO/Zr < 1000 when working at Zr concentrations between 10^?4 and 10^?5 mol/l with addition of TMA (Al_MAO/Al_TMA≈ 1.4).     

Polymerization of ethylene: Some aspects of metallocene catalyst stabilization under homogeneous and heterogeneous reaction conditions

The development of metallocene‐based catalysts is an important advance on the study of polyolefinic materials. However, due to the rather different conditions that are established in actual applications, only around 3% of these polymers are obtained from metallocene technology. In view of this, novel strategies must be developed to produce metallocene‐based catalysts that are more thermally stable, which is a fundamental requirement to establish metallocene technologies. Homogeneous and heterogeneous polymerizations of ethylene were compared, using the Ph₂C(Cp)(Flu)ZrCl₂/MAO system. Homogeneous polymerizations were more active than the corresponding supported reactions. At low ethylene pressure, the addition of 1‐hexene increases the activity under homogeneous conditions. Nevertheless, this is not observed on the respective supported systems. At higher pressure conditions, all polymerizations attained higher yields. However, when the reaction temperature increases the activity significantly decreases under homogeneous conditions. Furthermore, when the polymerization was performed under heterogeneous conditions the deactivation was lower. The homogeneous and supported catalytic systems show different characteristics and, in all attempted reactions, immobilization of the molecular catalyst reduces the activity. However, the deactivation ratio was lower when the polymerization was performed under heterogeneous conditions. This means that immobilization of Ph₂C(Cp)(Flu)ZrCl₂ on silica can improve the thermal stability of the catalytic species. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modification of a Ziegler-Natta catalyst with a metallocene catalyst and its olefin polymerization behavior

A Ziegler-Natta catalyst was modified with a metallocene catalyst and its polymerization behavior was examined. In the modification of the TiCl₄ catalyst supported on MgCl₂ (MgCl₂-Ti) with a rac-ethylenebis(indenyl)zirconium dichloride (rac-Et(Ind)₂ZrCl₂, EIZ) catalyst, the obtained catalyst showed relatively low activity but produced high isotactic polypropylene. These results suggest that the EIZ catalyst might block a non-isospecific site and modify a Ti-active site to form highly isospecific sites. To combine two catalysts in olefin polymerization by catalyst transitioning methods, the sequential addition of catalysts and a co-catalyst was tried. It was found that an alkylaluminum like triethylaluminum (TEA) can act as a deactivation agent for a metallocene catalyst. In ethylene polymerization, catalyst transitioning was accomplished with the sequential addition of bis(cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂)/methylaluminoxane (MAO), TEA, and a titanium tetrachloride/vanadium oxytrichloride (TiCl₄/VOCl₃, Ti-V) catalyst. Using this method, it was possible to control the molecular weight distribution (MWD) of polyethylene in a bimodal pattern. In the presence of hydrogen, polyethylene with a very broad MWD was obtained due to a different hydrogen effect on the Cp₂ZrCl₂ and Ti-V catalyst. The obtained polyethylene with a broader MWD exhibited more apparent shear thinning.