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     

Influence of the method of mixing on homogeneity and crystallization kinetics of blends of linear and branched polyethylene

The influence of mixing method—solution and melt mixing—on the homogeneity and crystallization kinetics of a series of blends of single‐site materials of linear polyethylene and ethyl‐branched polyethylene was studied by differential scanning calorimetry. Data obtained for heats of melting and crystallization, melting and crystallization peak temperatures, and melting and crystallization temperature profiles were essentially the same for the samples obtained by the two mixing methods. The results obtained can be interpreted as indicating that melt mixing is capable of producing homogeneous melts of these relatively low molar mass polymers, given that solution mixing is considered to give perfectly homogeneous blends. The heat associated with the high temperature melting peak after crystallization at 125°C of the blend samples, obtained by the two preparation methods, was higher than that of the linear polyethylene included in the blends, suggesting that a part of the branched polyethylene crystallized at 125°C. The unblended branched polyethylene showed no crystallization at 125°C. Samples obtained by powder mixing showed independent crystallization and melting of the linear and branched polyethylene components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1730–1736, 2004     

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     

Homogeneous polymerization of ethylene using an iron‐based metal catalyst system

An iron‐based catalyst of 2,6‐bis‐[1‐(2‐methylphenylimino)ethyl]pyridine iron dichloride was prepared. The ligand was prepared using 2,6‐diacetylpyridine as the starting chemical under controlled conditions. The preparation procedure was followed using ¹³C‐NMR, ¹H‐NMR, FT‐IR, MS (mass spectroscopy), and elemental analysis methods. The homogeneous polymerization of ethylene was carried out using the prepared catalyst in toluene media. Methyl aluminoxane (MAO) was used as a cocatalyst. The effect of the [Al] : [Fe] molar ratio, polymerization temperature, and monomer pressure of 202,000 to 454,500 Pa on the polymerization behavior were studied. The highest activity of the catalyst was obtained at 30°C, the activity decreased with increasing temperature, while increasing pressure linearly increased its activity. The molecular weight distribution of the polyethylene obtained was 1.25 to 1.72. A weight average molecular weight of 7.1 × 10⁴ and 1.5 × 10³ were obtained. The crystallinity of the polymer was about 19% and its melting point was about 65°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1517–1522, 2007     

Ethylene Polymerization using Combined Ni and Ti Catalysts Supported in situ on MAO‐Modified Silica

Summary: Branched polyethylene/linear polyethylene blends (BPE/LPE) were prepared using the combined Ni(α‐diimine)Cl₂ ( 1 ) (α‐diimine = 1,4‐bis(2,6‐diisopropylphenyl)acenaphthenediimine) and {Tp^Ms*}TiCl₃ ( 2 ) (Tp^Ms* = hydridobis(3‐mesitylpyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl)) catalysts supported in situ on methylaluminoxane (MAO)‐modified silica (4.0 wt.‐% Al/SiO₂). The polymerization reactions were performed in toluene at two different polymerization temperatures (0 and 30 °C) and several nickel molar fractions (x_Ni), using MAO as external cocatalyst. At all temperatures, the activities show an approximate linear correlation with x_Ni, indicating a non‐synergistic effect between the nickel and the titanium species. Higher activities were found at 0 °C. The melting temperatures for the polyethylene blends produced at 0 °C decrease as x_Ni increases in the medium, indicating good compatibility between the polyethylene phases made by both catalysts. The melting temperature (T_m) of the polyethylene blends was shown to depend on the order in which the catalysts were immobilized on the MAO‐modified silica support. The initial immobilization of 1 on the support ( 2 / 1 /SMAO‐4) affords polymers with a lower T_m than those produced with 1 / 2 /SMAO‐4. In addition, scanning electron microscopy (SEM) studies revealed that the spherical morphology of the supported catalyst is replicated in the polyethylene particles.

Influence of polymerization temperature on the activity of 1 / 2 /SMAO‐4 with varying x_Ni.     

Polymerization of propylene using MgCl2 (ethoxide type)/TiCl4/diether heterogeneous Ziegler–Natta catalyst

Heterogeneous Ziegler–Natta catalyst of MgCl₂ (ethoxide type)/TiCl₄/diether was prepared. 2,2‐Diisobutyl‐1,3‐dimethoxy propane (DiBDMP), diether, was used as internal donor. Slurry polymerization of propylene was carried out using the catalyst in dry heptane while triethylaluminium (TEA) was used as co‐catalyst. The co‐catalyst effects, such as catalyst molar ratio, polymerization temperature, H₂ pressure, external donor, triisobutylaluminium (TiBA) and monomer pressure, on the activity of the catalyst and isotacticity index (II) of the polymers obtained were studied. Rate of polymerization versus polymerization time is of a decay type with no acceleration period. There are an optimum Al/Ti molar ratio and temperature to obtain the highest activity of the catalyst. The maximum activity was obtained at 60 °C. Increasing the monomer pressure to 1 010 000 Pa linearly increased the activity of the catalyst. Addition of hydrogen to 151 500 Pa pressure increased activity of the catalyst from 2.25 to 5.45 kg polypropylene (PP) (g cat)^?1 h^?1 using 505 000 Pa pressure of monomer. The II decreased with increasing Al/Ti ratio, monomer pressure, hydrogen pressure and increased with increasing temperature to 60 °C, following with decrease as the temperature increases. Productivity of 11.55 kg (PP) (g cat)^?1 h^?1 was obtained at 1 010 000 Pa pressure of monomer and temperature of 60 °C. Addition of methyl p‐toluate (MPT) and dimethoxymethyl cyclohexyl silane (DMMCHS) as external donors decreased the activity of the catalyst sharply, while the II slightly increased. Some studies of the catalyst structure and morphology of the polymer were carried out using FTIR, X‐ray fluorescence, scanning electron microscopy and Brunauer–Emmett–Teller techniques. Copyright © 2005 Society of Chemical Industry     

Preparation of ethylene/1‐octene copolymers from ethylene stock with tandem catalytic system

Tandem catalysis offers a novel synthetic route to the production of linear low‐density polyethylene. This article reports the use of homogeneous tandem catalytic systems for the synthesis of ethylene/1‐octene copolymers from ethylene stock as the sole monomer. The reported catalytic systems involving a highly selective, bis(diphenylphosphino)cyclohexylamine/Cr(acac)₃/methylaluminoxane (MAO) catalytic systems for the synthesis of 1‐hexene and 1‐octene, and a copolymerization metallocene catalyst, rac‐Et(Ind)₂ZrCl₂/MAO for the synthesis of ethylene/1‐octene copolymer. Analysis by means of DSC, GPC, and ¹³C‐NMR suggests that copolymers of 1‐hexene and ethylene and copolymers of 1‐octene and ethylene are produced with significant selectivity towards 1‐hexene and 1‐octene as comonomers incorporated into the polymer backbone respectively. We have demonstrated that, by the simple manipulation of the catalyst molar ratio and polymerization conditions, a series of branched polyethylenes with melting temperatures of 101.1–134.1°C and density of 0.922–0.950 g cm^?3 can be efficiently produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of branching on the thermal and crystallization behavior of bimodal polyethylenes synthesized with binary late‐transition‐metal catalyst combinations

Two reactor blends of linear and branched polyethylene resins with bimodal molecular weight distributions were synthesized in a one‐reactor polymerization process through the combination of 2,6‐bis[1‐(2,6‐dimethyphenylimino)pyridyl]cobalt dichloride ( 1 ) and 2,3‐bis(2,6‐diisopropylphenyl)butanediimine nickel dibromide ( 2 ) or 1,2‐bis(2,6‐diisopropylphenyl)cyclohexene diimine nickel dibromide ( 3 ) in the presence of modified methylaluminoxane. The linear correlation between the catalyst activity and concentration of the nickel compounds suggested that the catalysts performed independently of one another. The molecular weights, molecular weight distributions, and crystalline and phase structures of the blends were investigated with a combination of high‐temperature gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, and small‐angle X‐ray scattering techniques. The branching degree of the polyethylene produced with 3 was much higher than the branching degree of the sample produced with 2 , although their molecular weights were relatively close. In addition, the crystallization rate, melting temperature, degree of crystallinity, and crystallization temperature of more highly branched blends produced with 1 / 3 were lower. The long periods and thickness of the crystalline region were greatly influenced by the addition of highly branched polyethylene. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of branched polyethylene by ethylene homopolymerization with a novel (α‐diimine)nickel complex in the presence of methylaluminoxane

Branched polyethylene (PE) was prepared with a novel (α‐diimine)nickel(II) complex of 2,3‐bis(2,6‐dimethylphenyl)‐butanediimine nickel dichloride {[2,6‐(CH₃)₂C₆H₃? N?C(CH₃)C(CH₃)?N? 2,6‐(CH₃)₂C₆H₃]NiCl₂} activated by methylaluminoxane in the presence of a single ethylene monomer. The influences of various polymerization conditions, including the temperature, Al/Ni molar ratio, Ni catalyst concentration, and time, on the catalytic activity, molecular weight, degree of branching, and branch length of PE were investigated. According to gel permeation chromatography, the weight‐average molecular weights of the polymers obtained ranged from 1.7 × 10⁵ to 6.0 × 10⁵, with narrow molecular weight distributions of 2.0–3.5. The degree of branching in the polymers rapidly increased with the polymerization temperature increasing; this led to highly crystalline to totally amorphous polymers, but it was independent of the Al/Ni molar ratio and catalyst concentration. At polymerization temperatures greater than 20°C, the resultant PE was confirmed by ¹³C‐NMR to contain significant amounts of not only methyl but also ethyl, propyl, butyl, amyl, and long branches (longer than six carbons). The formation of the branches could be illustrated by the chain walking mechanism, which controlled their specific spacing and conformational arrangements with one another. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1123–1132, 2002; DOI 10.1002/app.10398     

Crystallinity in chemically crosslinked low density polyethylenes: 3. Morphology of the XLPE-2 system

Studies of the morphology of low density branched polyethylene crosslinked using 2% dicumyl peroxide have been carried out using transmission electron microscopy of replicas of surfaces etched with permanganic reagent. Under optimal etching conditions detailed information regarding the morphologies of bulk crystallized samples of low crystallinity can be obtained. The morphology of crosslinked polyethylene is compared with that of the original branched polyethylene as a function of crystallization temperature. Branched polyethylene crystallizes in the form of banded spherulites from 88°C to 103°C with a temperature dependent band periodicity. Introduction of a small amount of crosslinking produces profound effects with banded sheaf or bundle-like morphologies resulting. The absence of lamellar banding in the sheaves of the gel fraction of the crosslinked polyethylene is attributed to pre-existent tie-molecules which are an inherent feature of network junctions in a crosslinked system. In the case of a typical unextracted crosslinked polyethylene, the morphology is found to vary with crystallization temperature. D.s.c. studies reveal that the thermal behaviour of XLPE-2 is not too different from that of OPE. The cause of multiple melting behaviour in this class of material is discussed and it is suggested that in addition to other processes of reorganization, hindrance to solid state thickening may be important. A method of monitoring different stages of lamellar melting for semicrystalline polymers was developed involving annealing at elevated temperatures in the presence of chlorosulphonic acid.     

Ethylene polymerization with iron‐based diimine catalyst supported on MCM‐41

A mesoporous molecular sieve MCM‐41 supported iron‐based diimine catalyst ( MC ) was prepared for the first time. The kinetic behavior of ethylene polymerization with MC was studied. The effects of Al/Fe molar ratio and various cocatalysts on the catalytic activity and properties of the polyethylene obtained were investigated. The results showed that good catalytic activities can be reached with cocatalyst methylaluminoxane (MAO) and triethylaluminium (TEA). Ethylene polymerization with MC gave polymers with higher molecular weight, melting temperature and onset temperatures of decomposition (T_onset) and better morphology than those obtained with the corresponding homogeneous catalyst. Copyright © 2004 Society of Chemical Industry     

Preparation of branched polyethene using a soluble zirconocene catalyst

[Me₂C(Cp) (Ind)]ZrCl₂ metallocene catalyst has been prepared and employed in a study of ethene polymerization in the presence of the cocatalyst methylaluminoxane. C₁ and C₂ signals are detected in the ¹³C NMR spectra of the resultant polymers; this reveals that the resultant polymer is a branched polyethene (polyethylene). The influence of polymerization temperature, catalyst concentration and [Al]/[Zr] ratio on catalytic activities and polymerization kinetics is investigated. A plausible mechanism for forming branched polyethene is suggested. © 2000 Society of Chemical Industry     

Thermal and crystallization behaviors of polyethylene blends synthesized by binary late transition metal catalysts combinations

A series of reactor blends of linear and branched polyethylenes have been prepared, in the presence of modified methylaluminoxane, using a combination of 2,6‐bis[1‐(2,6‐dimethyphenylimino) pyridyl]‐cobalt(II) dichloride ( 1 ), known as an active catalyst for producing linear polyethylene, and [1,4‐bis(2,6‐diidopropylphenyl)] acenaphthene diimine nickel(II) dibromide ( 2 ), which is active for the production of branched polyethylene. The polymerizations were performed at various levels of catalyst feed ratio at 10 bar. The linear correlation between catalyst activity and concentration of catalyst 2 suggested that the catalysts performed independently from each other. The weight‐average molecular weights , crystalline structures, and phase structures of the blends were investigated, using a combination of gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, and small angle X‐ray scattering techniques. It was found that the polymerization activities and MWs and crystallization rate of the polymers took decreasing tendency with the increase of the catalyst 2 ratios, while melting temperatures (T_m), crystalline temperatures (T_c), and crystalline degrees took decreasing tendency. Long period was distinctly influenced by the amorphous component concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4188–4198, 2007     

Hyperbranched homo and thermoresponsive graft copolymers by using ATRP‐macromonomer initiators

Macromonomer initiators behave as macro cross‐linkers, macro initiators, and macromonomers to obtain branched and cross‐linked block/graft copolymers. A series of new macromonomer initiators for atom transfer radical polymerization (MIM‐ATRP) based on polyethylene glycol (M_n = 495D, 2203D, and 4203D) (PEG) were synthesized by the reaction of the hydroxyl end of mono‐methacryloyl polyethylene glycol with 2‐bromo propanoyl chloride, leading to methacryloyl polyethylene glycol 2‐bromo propanoyl ester. Poly (ethylene glycol) functionalized with methacrylate at one end was reacted with 2‐bromopropionyl chloride to form a macromonomeric initiator for ATRP. ATRP was found to be a more controllable polymerization method than conventional free radical polymerization in view of fewer cross‐linked polymers and highly branched polymers produced from macromonomer initiators as well. In another scenario, ATRP of N‐isopropylacrylamide (NIPAM) was initiated by MIM‐ATRP to obtain PEG‐b‐PNIPAM branched block/graft copolymers. Thermal analysis, FTIR, ¹H NMR, TEM, and SEM techniques were used in the characterization of the products. They had a thermo‐responsive character and exhibited volume phase transition at ～ 36°C. A plasticizer effect of PEG in graft copolymers was also observed, indicating a lower glass transition temperature than that of pure PNIPAM. Homo and copolymerization kinetics were also evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

(Ind)₂ZrCl₂ catalyst was synthesized and used for copolymerization of ethylene and propylene (EPR) and terpolymerization of ethylene propylene and 5‐ethyldiene‐2‐norbornene (ENB). Methylaluminoxane (MAO) was used as cocatalyst. The activity of the catalyst was higher in copolymerization of ethylene and propylene (EPR) rather than in terpolymerization of ethylene, propylene and diene monomers. The effects of [Al] : [Zr] molar ratio, polymerization temperature, pressure ratio of ethylene/propylene and the ENB concentration on the terpolymerization behavior were studied. The highest productivity of the catalyst was obtained at 60°C, [Al] : [Zr] molar ratios of 750 : 1 and 500 : 1 for copolymerization and terpolymerization, respectively. Increasing the molar ratio of [Al] : [Zr] up to 500 : 1 increased the ethylene and ENB contents of the terpolymers, while beyond this ratio the productivity of the catalyst dropped, leading to lower ethylene and ENB contents. Terpolymerization was carried out batchwise at temperatures from 40 to 70°C. Rate time profiles of the polymerization were a decay type for both copolymerization and terpolymerization. Glass transition temperatures (T_g) of the obtained terpolymers were between ?64 and ?52°C. Glass transition temperatures of both copolymers and terpolymers were decreased with increased ethylene content of the polymers. Dynamic mechanical and rheological properties of the obtained polymers were studied. A compounded EPDM showed good thermal stability with time. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and Characterization of UHMWPE/Graphene Nanocomposites Using Bi-Supported Ziegler-Natta Polymerization

Ultrahigh-molecular-weight polyethylene (UHMWPE)/graphene nanocomposites with molecular weights as high as 3 × 10⁶ g/mol were prepared via in situ polymerization using a bi-supported Ziegler-Natta catalytic system. Effects of [Al]/[Ti] molar ratio, temperature, monomer pressure, and polymerization time on productivity of the catalyst have been investigated. Increasing [Al]/[Ti] molar ratio from 128 to 320, increased productivity from 1667 g PE/mmol Ti.h to maximum value which was 2420 g PE/mmol Ti.h. Further [Al]/[Ti] ratio decreased the productivity. Reaction temperature effect investigation reveals that the optimal activity was obtained at 60°C. the polymerization productivity increases with monomer pressure and decreased with polymerization time. Morphological information was determined by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Obtained results show that graphene layers in these nanocomposites were completely exfoliated and dispersed uniformly in the polyethylene matrix while no nanoparticle cluster has been formed.     

Nascent morphology of polyethylene polymerized on flat model catalysts

The morphology and the thermal behavior of nascent polyethylene (PE) polymerized on flat models for the Phillips CrO_x/SiO₂ catalyst were investigated using low‐voltage scanning electron microscopy (LVSEM) and differential scanning calorimetry (DSC). Ethylene polymerizations were performed at 25 °C and 70 °C in gas phase. For the applied polymerization conditions, microscopy observations reveal that the formation of the macromolecules at the active catalyst sites, and their subsequent crystallization on the catalyst, result in homogeneous polymer layers having a thickness of the order of micrometers. The surface morphology of the nascent samples consists of spherical entities having a diameter less than one micrometer. Pillar‐like objects form the internal structure of the PE films. Because these entities are only loosely connected, high porosity is observed within the entire film. Thermal analysis of the samples shows that melting temperature and crystallinity of the nascent PE samples polymerized at 25 °C are noticeably higher than after melting and recrystallization. Samples polymerized at 70 °C, however, do not show these features. Copyright © 2004 Society of Chemical Industry     

Star poly(2‐ethyl‐2‐oxazoline)s—synthesis and thermosensitivity

A series of star‐shaped poly(2‐ethyl‐2‐oxazoline)s was prepared by cationic polymerization. The polymerization was initiated by dipentaerythrityl hexakis(4‐nitrobenzene sulfonate) and a tosylated hyperbranched polymer of glycidol. The polymerization proceeded in a controlled manner. The star structure of the products was determined by nuclear magnetic resonance. The molar mass distributions that were measured by gel permeation chromatography with multiangle laser light scattering were narrow, and the experimental values of the molar masses were close to those predicted. The very compact structure of the polymers obtained (compared with the linear counterparts) confirmed the star formation. The star poly(2‐ethyl‐2‐oxazoline)s show a phase transition temperature in the range 62–75 °C. Comparison of this phase transition temperature with that of the linear poly(2‐ethyl‐2‐oxazoline)s with the same molar masses indicates the influence of molar mass and topological structure of the macromolecule on temperature behavior. The prepared copolymers are spherical, which might be useful for the controlled transport and release of active compounds. Copyright © 2011 Society of Chemical Industry     

Preparation of ultra‐high‐molecular‐weight polyethylene and its morphological study with a heterogeneous Ziegler–Natta catalyst

Ultra‐high‐molecular‐weight polyethylene (PE) with viscosity‐average molecular weight (M_v) of 3.1 × 10⁶ to 5.2 × 10⁶ was prepared with a heterogeneous Ziegler–Natta MgCl₂ (ethoxide type)/TiCl₄/triethylaluminum catalyst system under controlled conditions. The optimum activity of the catalyst was obtained at a [Al]/[Ti] molar ratio of 61 : 1 and a polymerization temperature of 60°C, whereas the activity of the catalyst increased with monomer pressure and decreased with hydrogen concentration. The titanium content of the catalyst was 2.4 wt %. The rate/time profile of the catalyst was a decay type with a short acceleration period. M_v of the PE obtained decreased with increasing hydrogen concentration and polymerization temperature. The effect of stirrer speeds from 100 to 400 rpm did not so much affect the catalyst activity; however, dramatic effects were observed on the morphology of the polymer particles obtained. A stirrer speed of 200 rpm produced PE with a uniform globulelike morphological growth on the polymer particles. The particle size distributions of the polymer samples were determined and were between 14 and 67 μm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Late Transition Metal Catalyst Based on Cobalt for Polymerization of Ethylene

The late transition metal catalyst of [2,6-diacethylpyridinebis(2,6-diisopropylphenylimine)]cobalt(II) dichloride was prepared under controlled conditions and used for polymerization of ethylene. Methylaluminoxane (MAO) and triisobuthylaluminum (TIBA) were used as a cocatalyst and a scavenger, respectively. The highest activity of the catalyst was obtained at about 30°C; the activity decreased with increasing temperature. At polymerization temperatures higher than 50°C not only was a sharp decrease in the activity observed but also low molecular weight polyethylene product that was oily in appearance was obtained. The polymerization activity increased with increasing both of the monomer pressure and [MAO]:[Co] ratio. However, fouling of the reactor was strongly increased with increasing both of the monomer pressure and the amount of MAO used for the homogeneous polymerization. Hydrogen was used as the chain transfer. The activity of the catalyst and the viscosity average molecular weight (M_v) of the polymer obtained were not sensitive to hydrogen concentration. However, the viscosity average molecular weight of the polymer decreased with the monomer pressure. The (M_v), the melting point, and the crystallinity of the resulting polymer at the monomer pressure of 1 bar and polymerization temperature of 20°C were 1.2 × 10⁵, 133°C, and 67%, respectively. Heterogeneous polymerization of ethylene using the catalyst and the MAO/SiO₂ improved morphology of the resulting polymer; however, the activity of the catalyst was also decreased. Fouling of the reactor was eliminated using the supported catalyst system.