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Olefin Polymerization (olefin + polymerization)
Selected AbstractsPreparation of Diamidochloro(cyclopentadienyl)titanium Derivatives as Pre-Catalysts for Olefin Polymerization , X-ray Molecular Structure of [Ti(,5 -C5H5){1,2-C6H4(NCH2CH2CH3)2}Cl] and [Ti{,5 -C5H4(SiMe3)}{1,2-C6H4(NCH2CH2CH3)2}Cl]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2004Vanessa Tabernero Abstract The synthesis of N,N,-alkyl 1,2-phenylenediamines 1,2-C6H4(NHR)2 [R = CH2CH2CH3 (nPr), CH2tBu (Np)] was carried out in three steps by lithiation of the primary 1,2-phenylenediamine, reaction with the appropriate acyl chloride and reduction with LiAlH4. The addition of nBuLi to a stirred solution of N,N,-alkyl diamines in cold hexane resulted in the immediate deposition of the corresponding lithium salts, which react with [MCpR,Cl3] to give the diamidochloro(,5 -cyclopentadienyl)titanium and -zirconium complexes [MCpR,{1,2-C6H4(NR)2}Cl] (4,10) [M = Ti, Zr; CpR, = ,5 -C5H5, ,5 -C5(CH3)5, ,5 -C5H4(SiMe3); R = nPr, Np]. The compound [Ti(,5 -C5H5){1,2-C6H4(NnPr)2}Cl] (3) was obtained by treatment of [Ti(,5 -C5H5)Cl3] with 1,2-C6H4(NHnPr)2 in the presence of NEt3 in toluene. All the reported compounds were characterized by the usual analytical and NMR spectroscopic methods. The molecular structures of 3 and 7 were determined by single-crystal X-ray crystallography. The compounds described here were further investigated as potential olefin polymerization catalysts. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] FI Catalysts: A Molecular Zeolite for Olefin PolymerizationADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010Haruyuki Makio Abstract A bis(phenoxyimine) group 4 transition metal catalyst (now known as FI catalysts) can discern ethylene from a mixture of ethylene and propylene at more than 99% selectivity. Denisty function theory (DFT) calculations revealed a spatially confined reaction site in the transition states of the migratory insertion which is just the right size for an ethylene molecule but too small for a propylene one. The substituents adjacent to the phenoxy-oxygens are of crucial importance in developing the size/shape-selectivity. [source] New Approach in Modeling of Metallocene-Catalyzed Olefin Polymerization Using Artificial Neural NetworksMACROMOLECULAR THEORY AND SIMULATIONS, Issue 3 2009Mostafa Ahmadi Abstract A new approach for the estimation of kinetic rate constants in olefin polymerization using metallocene catalysts is presented. The polymerization rate has been modeled using the method of moments. An ANN has been used and trained to behave like the mathematical model developed before, so that it gets polymerization rate at different reaction times and predicts reaction rate constants. The network was trained using modeling results in desired operational window. The polymerization rates were normalized to make the network work independent of operational conditions. The model has also been applied to real polymerization rate data and the predictions were satisfactory. This model is specially useful in comparing different new metallocene catalysts. [source] Synthesis and Structure of Trialkyltantalum Complexes Stabilized by Aminopyridinato LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2006Awal Noor Abstract (4-Methylpyridin-2-yl)(trimethylsilyl)amine (1), (6-methylpyridin-2-yl)(trimethylsilyl)amine (2), and (2,6-diisopropylphenyl)(pyridin-2-yl)amine (3) were deprotonated and used as ligands to synthesize trialkyltantalum complexes. The reaction of 2 equiv. of 1 or 2 with pentabenzyltantalum afforded tribenzyltantalum(V) complexes by toluene elimination. Analogous reaction using 3 failed. Lithiation of 3 followed by the reaction with tribenzyltantalum dichloride gave rise to the corresponding tribenzyl complex. Other alkyltantalum complexes stabilized by this ligand environment can be prepared by treating tantalum pentachloride with 2 equiv. oflithiated 3 to form a bis(aminopyridinato)tantalum trichloride. The reaction of this trichloride with 3 equiv. of alkyllithium compounds like methyllithium affords the corresponding trialkyltantalum complexes. X-ray diffraction studies of four of the synthesized complexes were carried out. They adopt two different coordination environments, either slightly distorted capped octahedrons (sterically less demanding aminopyridinato ligands) or pentagonal bipyramids (bulkier aminopyridinato ligands). The alkyl species were surprisingly stable at elevated temperatures and no formation of mixed alkyl/alkylidene complexes was observed. Alkyl cation formation and the behaviour of a selection of these compounds in olefin polymerization were explored. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Iminohydroxamato Early and Late Transition Metal Halide Complexes , New Precatalysts for Aluminoxane-Cocatalyzed Olefin Insertion PolymerizationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2004Alexander Krajete Abstract We report on new families of non-metallocene metal precatalysts for olefin polymerization with titanium, zirconium, vanadium and nickel as the active metal sites. The novel ligand design concept is based on iminohydroxamic acids and their derivatives as the principal chelating units. Various anionic and neutral [N,O] and [N,N] ligand systems are easily accessible by a modular synthetic sequence of imidoyl chlorides with substituted hydroxylamines or hydrazines, respectively. Steric protection of the metal coordination site, a necessary requirement for suppression of chain termination pathways of non-metallocene catalysts, is brought about by bulky aryl substituents on the imino nitrogen atoms. Crystal structures of some of the hydroxamato ligands reveal interesting intermolecular hydrogen-bridged structures, whereas in the solid-state structure of one titanium precatalyst a five-membered chelate was observed, in line with the design principle of these systems. Preliminary ethylene polymerization studies with methylaluminoxane-activated metal complexes (M = Ti, Zr, V, Ni) show that the most active systems are [N,O]NiBr2 catalysts containing neutral O -alkyl iminohydroxamate ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] The Extraordinary Cocatalytic Action of Polymethylaluminoxane (MAO) in the Polymerization of Terminal Olefins by Metallocenes: Chemical Change in the Group 4 Metallocene Dimethyl Derivatives Induced by MAO,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2005John J. Eisch Abstract In the polymerization of olefins with Group 4 metallocene dichlorides or dimethyl derivatives as procatalysts the use of polymethylaluminoxane (MAO) as the cocatalyst, especially in extreme excess (102,103 times the metallocene equivalent), has been shown to have an extraordinary accelerating effect on the rate of olefin polymerization, when compared with the cocatalytic action of alkylaluminum halides. In attempts at explaining the greatly superior catalytic activity of MAO in olefin polymerization (the MAO conundrum), hypotheses have generally paralleled the steps involved in the cocatalytic action of RnAlCl3,n, namely the alkylation of Cp2MtCl2, ionization of Cp2Mt(R)Cl into the metallocenium cation, [Cp2Mt,R]+, and anion, [Rn,1AlCl4,n], and subsequent ion-pair separation. In order to understand any differences in catalytic action between such cocatalysts, we have studied the individual action of MAO (100 equiv.) and of MeAlCl2 (1,2 equiv.) on each of the Group 4 metallocene derivatives, Cp2TiCl2, Cp2ZrCl2, Cp2Ti(CH3)2 and Cp2Zr(CH3)2. With MeAlCl2 each of the metallocene derivatives appeared to form the cation, [Cp2Mt,CH3]+, with greater (Ti) or lesser (Zr) ease, because an alkyne such as diphenylacetylene was then found to insert into the Mt,CH3 bond stereoselectively. In striking contrast, treatment of each metallocene with MAO gave two reactions very different from MeAlCl2, namely a steady evolution of methane gas upon mixing and a finding upon hydrolytic workup that the diphenylacetylene present had undergone no insertion into the Mt,CH3 bond but instead had been reductively dimerized completely to (E,E)-1,2,3,4-tetraphenyl-1,3-butadiene. To account for this astonishing difference in chemical behavior between MAO and MeAlCl2 in their cocatalytic activation of Group 4 metallocenes to olefin polymerization, it is necessary to postulate a novel, unique sequence of reaction steps occurring between MAO and the metallocene. If one starts with the metallocene dichloride, then the free TMA present in the MAO would generate the Cp2Mt(CH3)2. This metallocene dimethyl derivative, complexed with an oligomeric MAO unit, would undergo a transfer-epimetallation with added olefin or acetylene to form a metallacyclopropane or metallacyclopropene, respectively. With added diphenylacetylene the resulting 2,3-diphenylmetallacyclopropene would be expected rapidly to insert a second alkyne to form the 2,3,4,5-tetraphenyl-1-metallacyclopentadiene. Simple hydrolysis of the latter intermediate would generate (E,E)-1,2,3,4-tetraphenyl-1,3-butadiene while alternative workup with D2O would give the 1,4-dideuterio derivative of this butadiene. Both such expectations were confirmed by experiment. In the case of added olefin, similar metallacyclopropane and metallacyclopentane intermediates should be produced until ring opening of the latter five-membered ring leads to an open-chain zwitterion, a process having ample precedent in the research of Gerhard Erker. The solution to the MAO conundrum then, namely the extraordinary cocatalytic activity of MAO in olefin polymerization by metallocenes, lies in the unique catalytic activation of the Group 4 metallocene dimethyl derivative, which occurs by transfer-epimetallation of the olefin monomer by the Cp2Mt(CH3)2,MAO complex. The most advantageous Lewis acidic sites in the MAO,oligomeric mixture for such metallocene,MAO complexation are suggested to be terminal Me2Al,O,AlMe, segments of an open-chain oligomer. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Borane chain transfer reaction in olefin polymerization using trialkylboranes as chain transfer agentsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2010Wentian Lin Abstract This article discusses a new borane chain transfer reaction in olefin polymerization that uses trialkylboranes as a chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. Commercially available triethylborane (TEB) and synthesized methyl-B-9-borabicyclononane (Me-B-9-BBN) were engaged in metallocene/MAO [depleted of trimethylaluminum (TMA)]-catalyzed ethylene (Cp2ZrCl2 and rac -Me2Si(2-Me-4-Ph)2ZrCl2 as a catalyst) and styrene (Cp*Ti(OMe)3 as catalyst) polymerizations. The two trialkylboranes were found,in most cases,able to initiate an effective chain transfer reaction, which resulted in hydroxyl (OH)-terminated PE and s -PS polymers after an oxidative workup process, suggesting the formation of the B-polymer bond at the polymer chain end. However, chain transfer efficiencies were influenced substantially by the steric hindrances of both the substituent on the trialkylborane and that on the catalyst ligand. TEB was more effective than TMA in ethylene polymerization with Cp2ZrCl2/MAO, whereas it became less effective when the catalyst changed to rac -Me2Si(2-Me-4-Ph)2ZrCl2. Both TEB and Me-B-9-BBN caused an efficient chain transfer in the Cp2ZrCl2/MAO-catalyzed ethylene polymerization; nevertheless, Me-B-9-BBN failed in vain with rac -Me2Si(2-Me-4-Ph)2ZrCl2/MAO. In the case of styrene polymerization with Cp*Ti(OMe)3/MAO, thanks to the large steric openness of the catalyst, TEB exhibited a high efficiency of chain transfer. Overall, trialkylboranes as chain transfer agents perform as well as BH-bearing borane derivatives, and are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane-terminated polyolefins. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3534,3541, 2010 [source] Bis(,-enaminoketonato) vanadium (III or IV) complexes as catalysts for olefin polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2010Ji-Qian Wu Abstract Bis(,-enaminoketonato) vanadium(III) complexes (2a,c) [O(R1)CC(H)xC(R2)NC6H5]2VCl(THF) and the corresponding vanadium(IV) complexes (3a,c) [O(R1)CC(H)xC(R2) NC6H5]2VO (R1 = (CH2)4, R2 = H, x = 0, a; R1 = C6H5, R2 = H, x = 1, b; R1 = C6H5, R2 = C6H5, x = 1, c) have been synthesized from VCl3(THF)3 and VOCl2(THF)2, respectively, by treating with 2.0 equivalent ,-enaminoketonato ligands in tetrahydrofuran. Structures of 2b and 3a,c were further confirmed by X-ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et2AlCl. Complexes 2a,c and 3a,c exhibited high catalytic activities (up to 23.76 kg of PE/mmolV h bar), and afforded polymers with unimodal molecular weight distributions at 70 °C indicating the good thermal stability. The catalytic behaviors were influenced not only by the oxidation state of the catalyst precursors but also by the ligand structures. Complexes 2a,c and 3a,c were also effective catalyst precursors for ethylene/1-hexene copolymerization. The influence of polymerization parameters such as reaction temperature, Al/V molar ratio and hexene feed concentration on the ethylene/hexene copolymerization behaviors have bee also investigated in detail. In addition, the agents such as AlMe3, AliBu3, MeMgBr, MgCl2, and ZnEt2 were applied to control the molecular weight and molecular weight distribution modal. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3062,3072, 2010 [source] Preparation and characterization of SBA-15 supported iron(II)-bisimine pyridine catalyst for ethylene polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2004Chao Guo Abstract 2,6-Diacetylpyridinebis (2,6-diisopropylani) iron dichloride, a late-transition metal catalyst for olefin polymerization, was supported on SBA-15 successfully and the property of the supported catalyst was carefully studied. Ethylene polymerization was systematically investigated in the presence of MAO under various conditions employing this type of catalyst system. In general, after support, a decrease in the catalytic activity was observed and higher molecular weight and fibrous morphology of polyethylene were obtained. The "extrusion polymerization" phenomenon was observed in ethylene polymerization by using the supported catalyst system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4830,4837, 2004 [source] Micron-granula polyolefin with self-immobilized nickel and iron diimine catalysts bearing one or two allyl groupsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2004Guoxin Jin Abstract Self-immobilized nickel and iron diimine catalysts bearing one or two allyl groups of [ArNC]2(C10H6)NiBr2 [Ar = 4-allyl-2,6-(i -Pr)2C6H2] (1), [ArNC(Me)][Ar,N C(Me)]C5H3NFeCl2 [Ar = Ar, = 4-allyl-2,6-(i -Pr)2C6H3, Ar = 2,6-(i -Pr)2C6H3, and Ar, = 4-allyl-2,6-(i -Pr)2C6H3] were synthesized and characterized. All three catalysts were investigated for olefin polymerization. As a result, these catalysts not only showed high activities as the catalyst free from the allyl group, such as [ArNC]2C10H6NiBr2 (Ar = 2,6-(i-Pr)2C6H2)], but also greatly improved the morphology of polymer particles to afford micron-granula polyolefin. The self-immobilization of catalysts, the formation mechanism of microspherical polymer, and the influence on the size of the particles are discussed. The molecular structure of self-immobilized nickel catalyst 1 was also characterized by crystallographic analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1018,1024, 2004 [source] Mathematical Modeling of Homopolymerization on Supported Metallocene CatalystsMACROMOLECULAR MATERIALS & ENGINEERING, Issue 5 2004Alessio Alexiadis Abstract Summary: In this paper, a mathematical model describing olefin polymerization with metallocene catalysts is presented. It is an improvement of a previous model, the "particle growth model" (PGM) proposed by, among others, one of the authors of the present work and derives from the so-called "multigrane model" (MGM). The main differences between this work and others is a more sophisticated approach to fragmentation with respect to the MGM. Additionally, there is a more specific modeling for the unfragmented core with respect to the PGM. The numerical results obtained by the model are compared with experimental data. The results of this work allow to extend the PGM to catalysts with lower activity. The importance of those catalysts depends on the fact that high activity catalysts could bring, in some cases, too poor polymer morphology. Geometrical representation of the micro- and macroparticle. [source] Heat Transfer in Gas Phase Olefin PolymerisationMACROMOLECULAR SYMPOSIA, Issue 1 2009Estevan Tioni Abstract A fixed bed microreactor has been used to study heat transfer during the initial transient state of gas phase olefin polymerization on a supported catalyst. It has been shown that heat transfer during this stage of the polymerisation is critical, and under conditions found commercially problems can arise with hot spots and polymer melting. It is proven how the thermal properties of the gas mixture flowing on the catalytic bed exert great influence on heat dissipation reducing the sudden increase in temperature by as much as a factor of 5. Flow rate and especially the process gas composition are the key factors in controlling the bed temperature. [source] Recent data on the number of active centers and propagation rate constants in olefin polymerization with supported ZN catalystsMACROMOLECULAR SYMPOSIA, Issue 1 2004V.A. Zakharov Abstract Data on the number of active centers (Cp) and propagation rate constants (Kp) have been obtained by means of polymerization quenching with 14CO of propylene and ethylene polymerization with supported titanium-magnesium catalysts (TMC) with different composition. In the case of propylene polymerization the Cp and Kp values have been measured separately for isospecific, aspecific and low stereospecific centers. Effects of MgCl2 support, internal and external donors are discussed on the basis of data obtained. Data on the strong effect of diffusion limitation at ethylene polymerization with number of TMC have been obtained and a set of methods have been used to exclude this effect. Data on Cp and Kp values at ethylene polymerization with low stereospecific and highly stereospecific catalysts are presented. [source] Heterogenization of metalorganic catalysts of olefin polymerization and evaluation of active site non-uniformityMACROMOLECULAR SYMPOSIA, Issue 1 2004Lyudmila Novokshonova Abstract Heterogenized activators - "support-H2O/AlR3" (where R=Me, iBu, support=montmorillonite, zeolite), synthesized directly on the support, form with metallocenes metal alkyl complexes highly active in olefin polymerization without the use of commercial methylaluminoxane (MAO). It was shown by the method of temperature programmed desorption with the application of mass-spectrometry (TPD-MS) that the aluminumorganic compound in support-H2O/AlR3 is in general similar to the structure of commercial MAO. The heterogenization of Zr-cenes on support-H2O/AlR3 is accompanied by the appearance of the energy non-uniformity of active sites. The activation energy of thermal destruction of active Zr-C bonds in the active sites of prepared catalysts changes in the range from 25 to 32 kcal/mol. [source] New Approach in Modeling of Metallocene-Catalyzed Olefin Polymerization Using Artificial Neural NetworksMACROMOLECULAR THEORY AND SIMULATIONS, Issue 3 2009Mostafa Ahmadi Abstract A new approach for the estimation of kinetic rate constants in olefin polymerization using metallocene catalysts is presented. The polymerization rate has been modeled using the method of moments. An ANN has been used and trained to behave like the mathematical model developed before, so that it gets polymerization rate at different reaction times and predicts reaction rate constants. The network was trained using modeling results in desired operational window. The polymerization rates were normalized to make the network work independent of operational conditions. The model has also been applied to real polymerization rate data and the predictions were satisfactory. This model is specially useful in comparing different new metallocene catalysts. [source] Effect of Reaction Conditions and Catalyst Design on the Rheological Properties of Polyolefins Produced in Gas-Phase Olefin Polymerization ReactorsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 9 2008P. Pladis Abstract A model is developed to predict the viscoelastic behavior of polyolefins produced in catalytic polymerization reactors. The approach is based on the solution of different sub-models (e.g., a kinetic model, a single particle model, a macroscopic reactor model and a rheological model). From the calculated rheological curve, the polymer melt index is determined. The ability of the proposed model to predict the viscoelastic behavior of linear polymer melts quantitatively is examined for the operation of a catalytic olefin polymerization cascade-loop reactor process. In addition, the transient rheological properties of polyolefins produced in a Ziegler-Natta gas-phase olefin polymerization fluidized-bed reactor are calculated. [source] Influence of supported vanadium catalyst on ethylene polymerization reactionsPOLYMER INTERNATIONAL, Issue 2 2008Sutapa Ghosh Abstract BACKGROUND: In the research area of homogeneous Ziegler,Natta olefin polymerization, classic vanadium catalyst systems have shown a number of favourable performances. These catalysts are useful for (i) the preparation of high molecular weight polymers with narrow molecular weight distributions, (ii) the preparation of ethylene/R -olefin copolymers with high R -olefin incorporation and (iii) the preparation of syndiotactic polypropylenes. In view of the above merits of vanadium-based catalysts for polymerization reactions, the development of well-defined single-site vanadium catalysts for polymerization reactions is presently an extremely important industrial goal. The main aim of this work was the synthesis and characterization of a heterogeneous low-coordinate non-metallocene (phenyl)imido vanadium catalyst, V(NAr)Cl3, and its utility for ethylene polymerization. RESULTS: Imido vanadium complex V(NAr)Cl3 was synthesized and immobilized onto a series of inorganic supports: SiO2, methylaluminoxane (MAO)-modified SiO2 (4.5 and 23 wt% Al/SiO2), SiO2 Al2O3, MgCl2, MCM-41 and MgO. Metal contents on the supported catalysts determined by X-ray fluorescence spectroscopy remained between 0.050 and 0.100 mmol V g,1 support. Thermal stability of the catalysts was determined by differential scanning calorimetry (DSC). Characterization of polyethylene was done by gel permeation chromatography and DSC. All catalyst systems were found to be active in ethylene polymerization in the presence of MAO or triisobutylaluminium/MAO mixture (Al/V = 1000). Catalyst activity was found to depend on the support nature, being between 7.5 and 80.0 kg PE (mol V),1 h,1. Finally, all catalyst systems were found to be reusable for up to three cycles. CONCLUSION: Best results were observed in the case of silica as support. Acid or basic supports afforded less active systems. In situ immobilization led to higher catalyst activity. The resulting polyethylenes in all experiments had ultrahigh molecular weight. Finally, this work explains the synthesis and characterization of reusable supported novel vanadium catalysts, which are useful in the synthesis of very high molecular weight ethylene polymers. Copyright © 2007 Society of Chemical Industry [source] A lab-scale reaction calorimeter for olefin polymerizationTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 5 2010Virginie F. Tisse A reaction calorimeter was built to follow slurry-phase polymerizations of ethylene using different types of supported catalysts. It was shown that heat flow calorimetry, employing a high-gain observer for the evaluation of the initial conditions was an extremely useful tool for the measurement of on-line reaction rates, and a study of the influence of different parameters such as the stirring rate or solid content in real time. It was shown that if one uses solid contents under 30% (volume) then it is not necessary to account for the influence of this quantity on the overall heat transfer coefficient. Un calorimètre de réaction a été construit pour le suivi des polymérisations des phases de suspension de l'éthylène utilisant différents types de catalyseurs adaptés. Il a été démontré que la calorimétrie du flux thermique, utilisant un observateur à gain élevé pour l'évaluation des conditions initiales s'est avérée un outil extrêmement utile pour mesurer les taux de réaction en ligne, et pour l'étude en temps réel de l'influence de différents paramètres tels que la vitesse d'agitation ou le contenu en matière solide. Il a été démontré que si l'on utilise la matière solide en dessous de 30% (en termes de volume), alors il n'est pas nécessaire de prendre en compte l'influence de cette quantité sur le coefficient global de transfert thermique. Can. J. Chem. Eng. © 2010 Canadian Society for Chemical Engineering [source] FI Catalysts: new olefin polymerization catalysts for the creation of value-added polymersTHE CHEMICAL RECORD, Issue 3 2004Makoto Mitani Abstract This contribution reports the discovery and application of phenoxy,imine-based catalysts for olefin polymerization. Ligand-oriented catalyst design research has led to the discovery of remarkably active ethylene polymerization catalysts (FI Catalysts), which are based on electronically flexible phenoxy,imine chelate ligands combined with early transition metals. Upon activation with appropriate cocatalysts, FI Catalysts can exhibit unique polymerization catalysis (e.g., precise control of product molecular weights, highly isospecific and syndiospecific propylene polymerization, regio-irregular polymerization of higher ,-olefins, highly controlled living polymerization of both ethylene and propylene at elevated temperatures, and precise control over polymer morphology) and thus provide extraordinary opportunities for the syntheses of value-added polymers with distinctive architectural characteristics. Many of the polymers that are available via the use of FI Catalysts were previously inaccessible through other means of polymerization. For example, FI Catalysts can form vinyl-terminated low molecular weight polyethylenes, ultra-high molecular weight amorphous ethylene,propylene copolymers and atactic polypropylenes, highly isotactic and syndiotactic polypropylenes with exceptionally high peak melting temperatures, well-defined and controlled multimodal polyethylenes, and high molecular weight regio-irregular poly(higher ,-olefin)s. In addition, FI Catalysts combined with MgCl2 -based compounds can produce polymers that exhibit desirable morphological features (e.g., very high bulk density polyethylenes and highly controlled particle-size polyethylenes) that are difficult to obtain with conventionally supported catalysts. In addition, FI Catalysts are capable of creating a large variety of living-polymerization-based polymers, including terminally functionalized polymers and block copolymers from ethylene, propylene, and higher ,-olefins. Furthermore, some of the FI Catalysts can furnish living-polymerization-based polymers catalytically by combination with appropriate chain transfer agents. Therefore, the development of FI Catalysts has enabled some crucial advances in the fields of polymerization catalysis and polymer syntheses. © 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 4: 137,158; 2004: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20010 [source] UV,visible spectroscopy for zirconocene activation by MAO in olefin polymerization: activity versus wavenumberAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 6 2009Carlos Alonso-Moreno Abstract Activation of ansa -zirconocenes of the type Rac [Zr{1-Me2Si(3-R-(,5 -C9H5))(3-R,-(,5 -C9H5))}Cl2] [R = Et, R, = H (1); R = Pr, R, = H (2); and R = Et, R, = Pr (3), R, R, = Me (4) and R, R, = Bu (5)] by MAO has been studied by UV,visible spectroscopy. Compounds 1,3 have been tested in the polymerization of ethylene at different Al:Zr ratios. UV,vis spectroscopy was used to determine a correlation between the electronic structures of (1,5) and their polymerization activity. Copyright © 2009 John Wiley & Sons, Ltd. [source] | |||||||||||||