Catalysis
Tatiana B. Mikenas; A. V. Sholma; Vladimir A. Zakharov; Mikhail Matsko
Abstract
The paper presents data on the effect exerted by magnesium dichloride in Ziegler-Natta catalysts on the activity and molecular weight of polyethylene (PE) produced by ethylene polymerization in the absence or presence of hydrogen. It was found that ethylene polymerization in the absence of hydrogen over ...
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The paper presents data on the effect exerted by magnesium dichloride in Ziegler-Natta catalysts on the activity and molecular weight of polyethylene (PE) produced by ethylene polymerization in the absence or presence of hydrogen. It was found that ethylene polymerization in the absence of hydrogen over titanium-magnesium catalysts (TMCs) with different ratio of titanium chloride and magnesium dichloride (Ti/Mg = 0.5 and 0.07), oxidation state of titanium (TiCl3 or TiCl4) and structural characteristics of the catalysts leads to the formation of PE with a close molecular weight. At the same time, PE obtained over a δ-TiCl3 catalyst has a much (threefold) higher molecular weight. The introduction of hydrogen during polymerization for decreasing the molecular weight of PE is accompanied by a sharp drop in activity of the δ-TiCl3 catalyst, in distinction to the highly active supported TMC containing 3 wt. % Ti. Data about the effect of hydrogen content during polymerization on the molecular weight of PE were used to calculate the ratio of rate constants for polymer chain transfer with hydrogen (KtrH) and polymer chain propagation reaction (Кр). This value was close for TMCs of different composition containing magnesium dichloride. In the case of δ-TiCl3, the KtrH/Кр value was approximately two times lower compared to TMCs.
Olefin polymerization and copolymerization
Hiren Bhajiwala; Virendrakumar Gupta
Abstract
Ultra-high molecular weight polyethylene (UHMWPE) was synthesized using Bi-supported SiO2/MgCl2/TiCl4 (Si-Mg-Ti) Ziegler-Natta catalyst in conjugation with triethyl aluminum (TEA). The impact of temperature and the presence of a chain-terminating agent were examined in the context of ethylene polymerization. ...
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Ultra-high molecular weight polyethylene (UHMWPE) was synthesized using Bi-supported SiO2/MgCl2/TiCl4 (Si-Mg-Ti) Ziegler-Natta catalyst in conjugation with triethyl aluminum (TEA). The impact of temperature and the presence of a chain-terminating agent were examined in the context of ethylene polymerization. The findings showed that as temperature decreases, the activity of the polymerization decreases, and the molecular weight of the polymer increases. Conversely, in the presence of a chain-terminating agent, the molecular weight of the polymer decreases. The introduction of Triethyl borate (TEB) and Tetraethoxy silane (TEOS) as an external donor has a pronounced effect on the catalyst activity, causing a significant decrease, while simultaneously leading to a substantial increase in the viscosity average molecular weight (Mv). Additionally, when a chain-terminating agent is added along with Triethyl borate (TEB) in the system, it results in a significant decrease in molecular weight, albeit with a slight increase in activity compared to a system without a donor. The crystallinity, particle size and bulk density of the polymer synthesized with and without external donor also investigated.
Catalysis
Kefeng Xie; Wei Hao; Shengyuan Xu; Jie Wang; Xiong Wang; Zhengang Han
Abstract
The substituents on cyclopentadienyl (Cp) can regulate the electronic effect and hindrance of the active center in the metallocene catalyst. This modification can greatly change the catalytic activity of the catalyst and affect some features of the polymer. In order to study the effect of alkyl substituents ...
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The substituents on cyclopentadienyl (Cp) can regulate the electronic effect and hindrance of the active center in the metallocene catalyst. This modification can greatly change the catalytic activity of the catalyst and affect some features of the polymer. In order to study the effect of alkyl substituents on Cp in the performance of a typical metallocene catalyst Cp2TiCl2 for ethylene polymerization, two types of catalyst active centers were designed, including non-bridge Cp2(R)TiCH3]+ and bridge [NCP2 (R)TiCH3]+ (R = H, Me, iPr). The effects of alkyl substituent steric hindrance were explored by density functional theory on the complex of catalyst active center with ethylene and the formation of transition state. The results showed that the increase of substituent steric hindrance was unfavorable to complex between ethylene monomer with catalyst active center. Moreover, the bigger alkyl substituent, the greater the activation energy of ethylene insertion into catalyst active center and the more difficult is ethylene polymerization. Therefore, the performance of metallocene catalysts could be regulated by the substituent on Cp.
Catalysis
Odilia Pérez-Camacho; Eduardo Cardozo-Villalba
Abstract
In this work, the interaction between a polystearylmethacrylate (Mn = 8,900 g mol-1, Xn = 26, Ð = 1.1) and modified methylaluminoxane 12 (MMAO-12) co-catalyst is studied using different spectroscopic methods. The effect of this oxygen-donor additive was measured by the changes in the bulk ...
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In this work, the interaction between a polystearylmethacrylate (Mn = 8,900 g mol-1, Xn = 26, Ð = 1.1) and modified methylaluminoxane 12 (MMAO-12) co-catalyst is studied using different spectroscopic methods. The effect of this oxygen-donor additive was measured by the changes in the bulk density of the raw polyethylene, which resulted increased respect to those obtained in blank reactions. A decrease in the activity was also observed as a penalty for the improvement of the bulk density, enhancing the possibility of reducing fouling. The coordination of the carbonyl oxygen groups of polystearylmethacrylate to aluminum (III) centers is confirmed by 1H-NMR and FTIR studies, and by a simple semi-empirical computational calculation. A method for obtaining a tri-component co-catalyst mixture is described using the methyl-bridging capacity of trimethylaluminum and its Lewis acidity to get the polystearylmethacrylate and MMAO-12 linked together. This robust adduct introduces a hierarchy over the PE chain growing, leading to higher bulk densities for PE beads (0.43 g cm-3) concerning blank reactions (0.26 g cm-3).
Catalysis
Nina V. Semikolenova; Valentina N. Panchenko; Mikhail A. Matsko; Vladimir A. Zakharov
Abstract
For preparation of highly active supported catalyst with bis(imino)pyridyl Fe(II) complexes (Fe1, Fe2) and N,N-α-diimine complex of Ni (Ni3), silica modified with alumina (SiO2 (Al)) was used as a support. Data on the possibility to regulate molecular weight (MW) and molecular weight distribution ...
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For preparation of highly active supported catalyst with bis(imino)pyridyl Fe(II) complexes (Fe1, Fe2) and N,N-α-diimine complex of Ni (Ni3), silica modified with alumina (SiO2 (Al)) was used as a support. Data on the possibility to regulate molecular weight (MW) and molecular weight distribution (MWD) of polyethylene (PE), produced over the supported catalyst Fe1/SiO2 (Al)+TIBA by variation of polymerization temperature and the addition of hydrogen and hexene-1, are obtained. The prepared PE samples were characterized by Mw values varied from 80 to 350 kg/mol and various MMD (Mw/Mn=4.6-11.7).By grafting on SiO2(Al) of two different iron bis(imino)pyridyl complexes, producing PE with diverse MW, bi-component catalyst was prepared. This catalyst generates linear PE with broad and bimodal MWD (Mw/Mn=33). Fixation on SiO2(Al) of α-diimine Ni(II) pre-catalyst (Ni3), yielding high molecular weight branched PE at the ethylene homopolymerization, and bis(imino)pyridyl Fe(II) complex (Fe2) that forms lower molecular weight linear PE, affords formation of a new bi-component catalyst. The catalyst produces PE with broad MWD and high content of branches concentrated in high molecular weight PE fraction.
Seyed Mehdi Ghafelebashi Zaranda; Ali Safinejad
Abstract
In this study, slurry polymerization kinetics of ethylene with TiCl4/Mg(OEt)2/AlR3 Ziegler-Natta catalysts in various conditions using the model of sum square error (SSE) (method I) and model of least square error (LSE) (Method II) was investigated. For this purpose the molecular weight distributions ...
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In this study, slurry polymerization kinetics of ethylene with TiCl4/Mg(OEt)2/AlR3 Ziegler-Natta catalysts in various conditions using the model of sum square error (SSE) (method I) and model of least square error (LSE) (Method II) was investigated. For this purpose the molecular weight distributions of the samples were deconvoluted to the minimum number of Flory type distributions where each represents a different active center type of Ziegler-Natta catalyst. The first method used to determine the leading apparent polymerization kinetic constants for each site in absence of hydrogen by simultaneously fitting the instantaneous polymerization rate, cumulative polymer yield, and molecular weight distribution measured for various samples with various conditions. Second method was used to determine all kinetics parameters such as initiation, propagation, termination and transfer to monomer reaction in absence and also in the presence of hydrogen. For the later, transfer to hydrogen also determined. The results showed that this simulation package is a powerful tool for design and scale up this kind of processes.
Catalysis
Qiaoqiao Sun; Ruihua Cheng; Zhen Liu; Xuelian He; Ning Zhao; Boping Liu
Abstract
Chromium-vanadium (Cr-V) bimetallic catalysts are prepared by the introduction of vanadium into the Phillips catalyst which is one of the most significant industrial ethylene polymerization catalysts for tuning the Phillips catalyst performances and improving polyethylene properties. In the present work, ...
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Chromium-vanadium (Cr-V) bimetallic catalysts are prepared by the introduction of vanadium into the Phillips catalyst which is one of the most significant industrial ethylene polymerization catalysts for tuning the Phillips catalyst performances and improving polyethylene properties. In the present work, titanium species were introduced into the fluorine-modified chromium-vanadium bimetallic catalysts (Cr-V-F) and the prepared catalysts were systematically explored. The element content results of multi-component catalysts showed that a competitive inhibition interaction existed between chromium and vanadium, whereas chromium was more preferable to attach to the Ti-SiO2 than vanadium. In addition, ethylene homopolymerization and ethylene/1-hexene copolymerization were carried out and examined with different catalysts. The introduction of titanium into fluorine-modified bimetallic catalysts enhanced the molecular weight (MW) and broadened the molecular weight distribution (MWD) of polyethylene. The MW of the titanium- and fluorine-modified bimetallic catalysts (Cr-V-F/Ti) firstly rose up and then dropped down with the increasing of the Al/Cr molar ratio. The Cr-V-F/Ti catalysts showed slightly depressed hydrogen response and incorporation of 1-hexene. The short-chain branch distribution (SCBD) results, which were characterized by TREF/SSA, showed that the introduction of the titanium species increased the SCB content in low MW fractions and decreased the SCB content in the high Mw fractions of ethylene/1-hexene copolymers obtained from (Cr-V-F/3Ti)600 in contrast to that from (Cr-V-F)600.
Catalysis
Ting Fu; Ruihua Cheng; Xuelian He; Zhen Liu; Zhou Tian; Boping Liu
Abstract
A novel imido-modified SiO2-supported Ti/Mg Ziegler-Natta catalyst for ethylene and ethylene/1-hexene polymerization is investigated. The catalyst is prepared by modification of (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts via supporting vanadium species followed by reaction with p-tolyl isocyanate ...
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A novel imido-modified SiO2-supported Ti/Mg Ziegler-Natta catalyst for ethylene and ethylene/1-hexene polymerization is investigated. The catalyst is prepared by modification of (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts via supporting vanadium species followed by reaction with p-tolyl isocyanate as imido agents, to get the merits from both the SiO2-supported imido vanadium catalyst and the (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalyst. The effects of cocatalyst amount, hydrogen and dosage of 1-hexene on polymerization behavior and the microstructures of their polymers are systematically investigated. Compared with (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts and vanadium-modified (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts, the imido-modified SiO2-supported Ti/Mg catalysts show lower but more stable activity including homopolymerization, polymerization with hydrogen and copolymerization owing to imido ligands, indicating that p-Tolyl isocyanate was unfavorable to improving catalytic activity but benefited the stability, and the products of all catalysts show lower 1-hexene incorporation but much higher molecular weight (MW) with medium molecular weight distribution (MWD). The most unique feature of the novel catalysts is the excellent hydrogen response without lowering the polymerization activity, showing great potential for industrial application.
Catalysis
Ebrahim Ahmadi; Zahra Mohamadnia; Sajjad Rahimi; Mohammad Hasan Armanmehr; Mohammad Hossein Heydari; Mahmood Razmjoo
Abstract
Ethylene polymerization was carried out using Phillips chromium catalyst based on silica supports such as silica aerogel, SiO2 (Grace 643), and titanium modified SiO2 (G 643), and the results were compared with other catalysts based on SiO2 (Aldrich), SBA-15(Hex), SBA-15(Sp) and MCM-41. A combination ...
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Ethylene polymerization was carried out using Phillips chromium catalyst based on silica supports such as silica aerogel, SiO2 (Grace 643), and titanium modified SiO2 (G 643), and the results were compared with other catalysts based on SiO2 (Aldrich), SBA-15(Hex), SBA-15(Sp) and MCM-41. A combination of TGA, DSC, XRD, nitrogen adsorption, SEM, ICP, FTIR and other analyses were used to characterize the materials. The results showed that the chromium was successfully introduced into silica supports. Shish-kebab polyethylene was prepared via in situ ethylene polymerization with the Cr/SiO2 (G 643) and Cr/Ti/SiO2 (G 643) catalytic systems. A comparison between different types of catalysts revealed that the polymerization activity of Cr/SiO2 (G 643) was significantly increased to 191 kg PE (g Cr)-1 h-1 due to the higher pore volume and pore diameter of Grace silica compared to the other supports. Also, the polymerization activity of the Cr/SiO2 (G 643) catalyst was significantly improved by Ti-modification.
Catalysis
G. Hossein Zohuri; Saman Damavandi; Saeid Ahmadjo; Reza sandaroos; Mohammad A. Shamekhi
Abstract
A FI Zr-based catalyst of bis[N-(3,5-dicumylsalicylidene)-2′,6′diisopropylanilinato]zirconium(IV) dichloride was prepared and used for polymerization of ethylene. The effects of reaction conditions on the polymerization were examined in detail. The increase in ethylene pressure and rise ...
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A FI Zr-based catalyst of bis[N-(3,5-dicumylsalicylidene)-2′,6′diisopropylanilinato]zirconium(IV) dichloride was prepared and used for polymerization of ethylene. The effects of reaction conditions on the polymerization were examined in detail. The increase in ethylene pressure and rise in polymerization temperature up to 35 oC were favorable for catalyst/MAO to raise the catalytic activity as well as the viscosity-average molecular weight (Mv) of polyethylene. The activity of the catalyst was linearly increased with increasing MAO concentration and no optimum activity was observed in the range studied. Although introduction of the bulky cumyl and 2′,6′-diisopropyl alkyl substitution groups on ortho positions to the phenoxy-oxygen and on phenyl ring on the N, respectively enhanced the viscosity average molecular weight (Mv) of the obtained polymer strongly, diminished the activity of the catalyst. Neither the activity of the catalyst nor the (Mv) of the obtained polymer were sensitive to hydrogen concentration. However, higher amount of hydrogen could slightly increase the activity of the catalyst. The (Mv) of polyethylene ranged from 2.14×106 to 2.77×106 at the monomer pressure of 3 and 5 bar respectively which are much higher than that of the reported FI Zr-based catalysts.
