Olefin polymerization behavior of metallocene immobilized inside pore of metal-organic frameworks

Manianglung, Clinton; Lee, Jeong Suk; Ko, Young Soo

doi:10.1016/j.cattod.2022.08.035

Cited by 4 publications

(4 citation statements)

References 27 publications

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“…A similar protocol was adopted to synthesize ZnAl-DDS, MgFe-DDS, NiAl-DDS, and MgAl-DDS Catalyst Immobilization: Metallocene catalysts were supported on different LDH supports using a procedure similar to those reported in the literature. [36,[46][47] The synthesis of the supported catalyst complex comprised two major steps: 1) activation of the support (LDH) with modified MAO and 2) immobilization of homogeneous metallocene catalysts on an activated support.…”

Section: Methodsmentioning

confidence: 99%

Enhancing Metallocene Catalyst Activity: Utilizing Layered Double Hydroxide for Ethylene–Propylene Copolymerization

Mazhar,

Shehzad,

Hong

et al. 2023

Macro Materials & Eng

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This study reports the heterogenization of metallocene catalysts on sodium dodecyl sulfate (DDS)‐modified layered double hydroxides (LDHs) for efficient ethylene–propylene (EP) slurry‐phase copolymerization. The LDH support offers considerable compositional tunability. NiFe LDHs with different anions () and metallic compositions are applied as support for the metallocene catalysts; these significantly influence the catalytic properties of the heterogenized catalyst system. The supported‐catalyst intercalating DDS− anion in the galleries of NiFe and ZnAl LDHs demonstrates a high catalytic activity. They produce EP copolymers with high molecular weights (Mw) and wide polydispersity, compared with the homogeneous Zr catalyst. Further, the supported catalyst complex containing anion produces EP with a tenfold high Mw and demonstrate subdued catalytic activity. The higher basicity of the support is associated with the enhanced activity and the wider polydispersity of the EP pertaining to the different interactions of the catalyst molecule with the support. Overall, Ni‐containing LDH favors a higher activity, whereas Fe‐containing LDH favors a higher Mw. Therefore, NiFe‐based LDH results in both higher activity and molecular weight. 13C and 27Al magnetic angle spinning solid‐state nuclear magnetic resonance confirm the formation of the supported catalyst complex.

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Section: Methodsmentioning

confidence: 99%

Enhancing Metallocene Catalyst Activity: Utilizing Layered Double Hydroxide for Ethylene–Propylene Copolymerization

Mazhar,

Shehzad,

Hong

et al. 2023

Macro Materials & Eng

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“…The control and tuneability afforded by single-site catalysts is brought into the realms of industrial-scale applicability through heterogenization . The immobilization of single-site catalysts on suitable carriers facilitates their use in slurry-phase or fluidized bed reactors previously used for Ziegler–Natta reactions with minimal modifications as well as ensuring the formation of polymer particles with dispersed morphologies and desirable bulk densities. , Many inert inorganic supports such as silica, , alumina, zirconia, metal−organic frameworks, and layered double hydroxides , have been developed, but these need pretreating to enable metallocene immobilization . Solid polymethylaluminoxane (sMAO) has been introduced as a dual-function activator and catalyst support.…”

Section: Introductionmentioning

confidence: 99%

Trends in Structure and Ethylene Polymerization Reactivity of Transition-Metal Permethylindenyl-phenoxy (PHENI*) Complexes

Collins Rice,

Hayden,

Hawkins

et al. 2024

Organometallics

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A family of ansa-permethylindenyl-phenoxy (PHENI*) transition-metal chloride complexes has been synthesized and characterized (1−7; {(η 5 -C 9 Me 6 )Me(R″)Si(2-R-4-R′-C 6 H 2 O)}MCl 2 ; R,R′ = Me, t Bu, Cumyl (CMe 2 Ph); R″ = Me, n Pr, Ph; M = Ti, Zr, Hf). The ancillary chloride ligands could readily be exchanged with halides, alkyls, alkoxides, aryloxides, or amides to form PHENI* complexes [L]TiX 2 (8−17; X = Br, I, Me, CH 2 SiMe 3 , CH 2 Ph, NMe 2 , OEt, ODipp). The solid-state crystal structures of these PHENI* complexes indicate that one of two conformations may be preferred, parametrized by a characteristic torsion angle (TA′), in which the η 5 system is either disposed away from the metal center or toward it. Compared to indenyl PHENICS complexes, the permethylindenyl (I*) ligand appears to favor a conformation in which the metal center is more accessible. When heterogenized on solid polymethylaluminoxane (sMAO), titanium PHENI* complexes exhibit exceptional catalytic activity toward the polymerization of ethylene. Substantially greater activities are reported than for comparable PHENICS catalysts, along with the formation of ultrahigh-molecular-weight polyethylenes (UHMWPE). Catalyst−cocatalyst ion pairing effects are observed in cationization experiments and found to be significant in homogeneous catalytic regimes; these effects are also related to the influence of the ancillary ligand leaving groups in slurry-phase polymerizations. Catalytic efficiency and polyethylene molecular weight are found to increase with pressure, and PHENI* catalysts can be categorized as being among the most active for the controlled synthesis of UHMWPE.

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“…This results in virtually limitless potential regarding composition, functionality, and porosity. , So far, MOFs have been utilized as materials for carbon capturing and storage (CCS), as well as in other applications, such as chemical sensing, gas adsorption, and separation. − In the past decade, there has also been research on the use of MOFs for olefin polymerization catalysis. Numerous studies have already encompassed the effects of properties, such as porosity, active site, crystallite size, and organic linker on ethylene polymerization activity, and also produced polyethylene materials. − However, comprehensive studies are still relatively rare for MOFs as support materials for metallocene complexes for catalytic olefin polymerization.…”

Section: Introductionmentioning

confidence: 99%

Ethylene Polymerization over Metal–Organic Framework-Supported Zirconocene Complexes

Wu,

Dorresteijn,

Weckhuysen

2024

ACS Catal.

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Metallocene immobilization onto a solid support helps to overcome the drawbacks of homogeneous metallocene complexes in the catalytic olefin polymerization. In this study, valuable insights have been obtained into the effects of pore size, linker composition, and surface groups of metal−organic frameworks (MOFs) on their role as support materials for metallocenebased ethylene polymerization catalysis. Three distinct Zn-based metal−organic frameworks (MOFs), namely, MOF-5, IRMOF-3, and ZIF-8, with different linkers have been activated with methylaluminoxane (MAO) and zirconocene complexes, followed by materials characterization and testing for ethylene polymerization. Characterization has been performed by multiple analytical tools, including X-ray diffraction (XRD), scanning electron microscopy (SEM), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and CO Fourier transform infrared (FT-IR) spectroscopy. It was found that the interactions between MOFs, MAO, and the zirconocene complex not only lead to both catalyst activation and deactivation but also result in the creation of multiple active sites. By alteration of the MOF support, it is possible to obtain polyethylene with different properties. Notably, ultrahigh molecular weight polyethylene (UHMWPE, M W = 5.34 × 10 6 ) was obtained using IRMOF-3 as support. This study reveals the potential of MOF materials as tunable porous supports for metallocene catalysts active in ethylene polymerization.

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Olefin polymerization behavior of metallocene immobilized inside pore of metal-organic frameworks

Cited by 4 publications

References 27 publications

Enhancing Metallocene Catalyst Activity: Utilizing Layered Double Hydroxide for Ethylene–Propylene Copolymerization

Enhancing Metallocene Catalyst Activity: Utilizing Layered Double Hydroxide for Ethylene–Propylene Copolymerization

Trends in Structure and Ethylene Polymerization Reactivity of Transition-Metal Permethylindenyl-phenoxy (PHENI*) Complexes

Ethylene Polymerization over Metal–Organic Framework-Supported Zirconocene Complexes

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