Correction to “Correlating the Morphological Evolution of Individual Catalyst Particles to the Kinetic Behavior of Metallocene-Based Ethylene Polymerization Catalysts”
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PROVIDER: S-EPMC10466322 | biostudies-literature | 2023 Jul
REPOSITORIES: biostudies-literature
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Project description:Kinetics-based differences in the early stage fragmentation of two structurally analogous silica-supported hafnocene- and zirconocene-based catalysts were observed during gas-phase ethylene polymerization at low pressures. A combination of focused ion beam-scanning electron microscopy (FIB-SEM) and nanoscale infrared photoinduced force microscopy (IR PiFM) revealed notable differences in the distribution of the support, polymer, and composite phases between the two catalyst materials. By means of time-resolved probe molecule infrared spectroscopy, correlations between this divergence in morphology and the kinetic behavior of the catalysts' active sites were established. The rate of polymer formation, a property that is inherently related to a catalyst's kinetics and the applied reaction conditions, ultimately governs mass transfer and thus the degree of homogeneity achieved during support fragmentation. In the absence of strong mass transfer limitations, a layer-by-layer mechanism dominates at the level of the individual catalyst support domains under the given experimental conditions.
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Project description:Samples of random poly(butene-ran-ethylene) copolymers produced with metallocene catalysts were studied in order to elucidate the different behaviors of this particular class of materials as a function of increasing ethylene (C2) content. The samples cooled down from the melt are semi-crystalline or amorphous and crystallize in different crystal modifications, depending on the amount of C2. Thermal analysis, X-ray diffraction, and microscopic techniques were used to follow the changes of the materials with aging time and to understand the structural and morphological behavior with the aim of highlighting possible peculiar properties, which may be of great interest in the application of such materials in the field of Hot Melt adhesives.
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Project description:Ziegler-type catalysts are the grand old workhorse of the polyolefin industry, yet their hierarchically complex nature complicates polymerization activity-catalyst structure relationships. In this work, the degree of catalyst framework fragmentation of a high-density polyethylene (HDPE) Ziegler-type catalyst was studied using ptychography X-ray-computed nanotomography (PXCT) in the early stages of ethylene polymerization under mild reaction conditions. An ensemble consisting of 434 fully reconstructed ethylene prepolymerized Ziegler catalyst particles prepared at a polymer yield of 3.4 g HDPE/g catalyst was imaged. This enabled a statistical route to study the heterogeneity in the degree of particle fragmentation and therefore local polymerization activity at an achieved 3-D spatial resolution of 74 nm without requiring invasive imaging tools. To study the degree of catalyst fragmentation within the ensemble, a fragmentation parameter was constructed based on a k-means clustering algorithm that relates the quantity of polyethylene formed to the average size of the spatially resolved catalyst fragments. With this classification method, we have identified particles that exhibit weak, moderate, and strong degrees of catalyst fragmentation, showing that there is a strong heterogeneity in the overall catalyst particle fragmentation and thus polymerization activity within the entire ensemble. This hints toward local mass transfer limitations or other deactivation phenomena. The methodology used here can be applied to all polyolefin catalysts, including metallocene and the Phillips catalysts to gain statistically relevant fundamental insights in the fragmentation behavior of an ensemble of catalyst particles.
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Project description:Bis(1-methylethenyl-cyclopentadienyl)zirconium dichloride (7a) was prepared by a fulvene route. Photolysis at 0 degrees C with Pyrex-filtered UV light resulted in a rapid and complete intramolecular [2+2]cycloaddition reaction to yield the corresponding cyclobutylene-bridged ansa-zirconocene dichloride isomer (8a). This is one of the rare examples of an organic functional group chemistry that leads to carbon-carbon coupling at the framework of an intact sensitive group 4 bent metallocene complex. More sterically hindered open metallocenes that bear bulky isopropyl or tert-butyl substituents at their Cp rings in addition to the active 1-methylethenyl functional group undergo the photochemical ansa-metallocene ring closure reaction equally facile. The metallocene systems used and obtained in this study have served as transition metal components for the generation of active metallocene propene polymerization catalysts.
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Project description:Heterogeneous derivatives of catalysts discovered by Ziegler and Natta are important for the industrial production of polyolefin plastics. However, the interaction between precatalysts, alkylaluminum activators, and oxide supports to form catalytically active materials is poorly understood. This is in contrast to homogeneous or model heterogeneous catalysts that contain resolved molecular structures that relate to activity and selectivity in polymerization reactions. This study describes the reactivity of triisobutylaluminum with high surface area aluminum oxide and a zirconocene precatalyst. Triisobutylaluminum reacts with the zirconocene precatalyst to form hydrides and passivates -OH sites on the alumina surface. The combination of passivated alumina and zirconium hydrides formed in this mixture generates ion pairs that polymerize ethylene.
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Project description:We report the synthesis of two novel binuclear Pd⁻diimine catalysts and their unique behaviors in initiating "living" polymerization of ethylene and 1-hexene. These two binuclear catalysts, [(N^N)Pd(CH₂)₃C(O)O(CH₂)mO(O)C(CH₂)₃Pd(N^N)](SbF₆)₂ (3a: m = 4, 3b: m = 6) (N^N≡ArN=C(Me)⁻(Me)C=NAr, Ar≡2,6⁻(iPr)₂C₆H₃), were synthesized by simply reacting [(N^N)Pd(CH₃)(N≡CMe)]SbF₆ (1) with diacrylates, 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate, respectively. Their unique binuclear structure with two identical Pd⁻diimine acrylate chelates covalently linked together through an ester linkage was confirmed by NMR and single crystal XRD measurements. Ethylene "living" polymerizations were carried out at 5 °C and under ethylene pressure of 400 and 100 psi, respectively, with the binuclear catalysts, along with a mononuclear chelate catalyst, [(N^N)Pd(CH₂)₃C(O)OMe]SbF₆ (2), for comparison. All the polyethylenes produced with both binuclear catalysts show bimodal molecular weight distribution with the number-average molecular weight of the higher molecular weight portion being approximately twice that of the lower molecular weight portion. The results demonstrate the presence of monofunctional chain growing species resembling catalyst 2, in addition to the expected bifunctional species leading to bifunctional "living" polymerization, in the polymerization systems. Both types of chain growing species exhibit "living" characteristics under the studied conditions, leading to the simultaneous linear increase of molecular weight in both portions. However, when applied for the "living" polymerization of 1-hexene, the binuclear catalyst 3a leads to polymers with only monomodal molecular weight distribution, indicating the sole presence of monofunctional chain growing species. These two binuclear catalysts are the first Pd⁻diimine catalysts capable of initiating bifunctional ethylene "living" polymerization.
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Project description:A series of cobalt complexes with bis(imino)pyridine derivatives featuring unsymmetrical substitution with bulky groups has been synthesized and characterized. The molecular structures of two representatives have been determined by the single-crystal X-ray diffraction study, revealing distorted tetrahedral geometry with different degrees of steric hindrance imparted by the two inequivalent aryl groups attached to the imine nitrogen atoms. On activation with either MAO or MMAO, these complexes display high activity toward ethylene polymerization, reaching 8.71 × 106 g of PE (mol of Co)-1 h-1 at 60 °C and produce polyethylene of high molecular weight (M w = 5.27 × 105 g mol-1) and low dispersity. The presence of the methoxy-substituent noticeably enhances the activity of the cobalt catalyst and increases the molecular weight of the resultant polyethylene.
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Project description:Catalysts that employ late transition-metals, namely Ni and Pd, have been extensively studied for olefin polymerizations, co-polymerizations, and for the synthesis of advanced polymeric structures, such as block co-polymers. Unfortunately, many of these catalysts often exhibit poor thermal stability and/or non-living polymerization behavior that limits their ability to access tailored polymer structures. Due to this, the development of catalysts that display controlled/living behavior at elevated temperatures is vital. In this manuscript, we describe a Ni α-diimine complex that is capable of polymerizing ethylene in a living manner at temperatures as high as 75 °C, which is one of the highest temperatures reported for the living polymerization of ethylene by a late transition metal-based catalyst. Furthermore, we will demonstrate that this catalyst's living behavior is not dependent on the presence of monomer, and that it can be exploited to access polyethylene-based block co-polymers.
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Project description:The catalytic emulsion polymerization of ethylene has been a long-lasting technical challenge as current techniques still suffer some limitations. Here we report an alternative strategy for the production of semi-crystalline polyethylene latex. Our methodology consists of encapsulating a catalyst precursor within micelles composed of an amphiphilic block copolymer. These micelles act as nanoreactors for the polymerization of ethylene in water. Phosphinosulfonate palladium complexes were used to demonstrate the success of our approach as they were found to be active for hours when encapsulated in micelles. Despite this long stability, the activity of the catalysts in micelles remains significantly lower than in organic solvent, suggesting some catalyst inhibition. The inhibition strength of the different chemicals present in the micelle were determined and compared. The combination of the small volume of the micelles, and the coordination of PEG appear to be the culprits for the low activity observed in micelles.
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Project description:Single-site polymerization catalysts enable exquisite control over alkene polymerization reactions to produce new materials with unique properties. Knowledge of catalyst speciation and fundamental kinetics are essential for full mechanistic understanding of zirconocene-catalyzed alkene polymerization. Currently the effect of activators on fundamental polymerization steps is not understood. Progress in understanding activator effects requires determination of fundamental kinetics for zirconocene catalysts with noncoordinating anions such as [B(C6F5)4]-. Kinetic NMR studies at low temperature demonstrate a very fast propagation rate for 1-hexene polymerization catalyzed by [(SBI)Zr(CH2SiMe3)][B(C6F5)4] [where SBI is rac-Me2Si(indenyl)2] with complete consumption of 1-hexene before the first NMR spectrum. Surprisingly, the first NMR spectrum reveals, aside from uninitiated catalyst, Zr-allyls as the sole catalyst-containing species. These Zr-allyls, which exist in two diastereomeric forms, have been characterized by physical and chemical methods. The mechanism of Zr-allyl formation was probed with a trapping experiment, leading us to favor a mechanism in which Zr-polymeryl undergoes beta-H transfer to metal without dissociation of coordinated alkene followed by sigma-bond metathesis to form H2 and Zr-allyl. Zr-allyl species undergo slow reactions with alkene but react rapidly with H2 to form hydrogenation products.
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