Vanadium(V) imido chlorides and n-propoxides — Towards a rational design of vanadium imido precatalysts for ethylene polymerization

Kayda, Anatoliy S.; Rumyantsev, Andrey V.; Zubkevich, Sergey V.; Zhizhko, Pavel A.; Takazova, R. U.; Тuskaev, Vladislav А.; Гагиева, С. Ч.; Бузин, М. И.; Shatokhin, Stanislav S.; Никифорова, Г. Г.; Васильев, В. Г.; Павлов, А. А.; Saracheno, Daniele; Melnikova, Elizaveta K.; Magomedov, Kasim F.; Kolosov, Nikolay A.; Булычев, Б. М.

doi:10.1016/j.jorganchem.2020.121665

Cited by 5 publications

(5 citation statements)

References 64 publications

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“…It has become popular to use metallocenes, e.g., complex compounds containing d-block metals and organic ligands (precatalyst) [20,21]. The combination of a precatalyst with an activator, i.e., an organoaluminum compound, e.g., methylaluminoxane (MAO) or a modified methylaluminoxane (MMAO-12, 7% aluminum in toluene) creates a Ziegler-Natta catalyst [24][25][26][27]. The sixth generation of Ziegler-Natta catalysts is the most widespread due to high catalytic activity and attempts to replace MMAO with another activator.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Allyl Alcohol Oligomers Using Dipicolinate Oxovanadium(IV) Coordination Compound

et al. 2022

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Currently, new precatalysts for olefin oligomerization are being sought in the group of vanadium(IV) complexes. Thus, the aim of our research was to examine the catalytic activity of the oxovanadium(IV) dipicolinate complex [VO(dipic)(H2O)2] 2 H2O (dipic = pyridine-2,6-dicarboxylate anion) in 2-propen-1-ol oligomerization as well as to characterize oligomerization products using matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry (MALDI-TOF-MS), infrared spectroscopy (IR) and nuclear magnetic resonance (NMR). The oligomerization process took place at room temperature, under atmospheric pressure and under nitrogen atmosphere to prevent oxidation of the activator MMAO-12—the modified methylaluminoxane (7 wt.%) aluminum in toluene. The last point was to determine the catalytic activity of the complex in the oligomerization reaction of 2-propen-1-ol. The aspect that enriches this work is the proposed mechanism of oligomerization of allyl alcohol based on the literature.

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Section: Introductionmentioning

confidence: 99%

Preparation of Allyl Alcohol Oligomers Using Dipicolinate Oxovanadium(IV) Coordination Compound

et al. 2022

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“…[4,5,6,7,8] Although, the activity of classical Ziegler-Natta vanadium catalysts is lower compared to catalysts based on group 4 transition metals, it should be noted that they show an advantage over other catalysts due to the unique quality of the polymers produced. [1,9] For example, VCl 4 -AlBr 3 -AlPh 3 yielded linear, high molecular weight polyethylene with an activity of 1000 kg/(mol V • h) and other vanadium catalytic systems afforded syndiotactic polypropylene and high molecular weight amorphous ethylene/propylene copolymers with uniform compositions. [1,10,11,12] This feature is also the explanation why vanadium compounds are necessary in the technological processes of the production of ethylenepropylene copolymers and ethylene-propylene-diene terpolymers.…”

Section: Introductionmentioning

confidence: 99%

“…[1,13] For many years, vanadium catalysts have been less intensively studied compared to catalysts based on group 4 transition metals, but further progress in the catalytic polymerization of olefins associated with the discovery of postmetallocene catalysts [4] has again focused attention on them. To date, diverse vanadium(III, IV, V) complexes have been synthesized and evaluated in olefin polymerization (for example [9,14] ) and achievements in catalytic polymerization with the latest generation of vanadium catalysts are summarized in detail in the reviews. [1,13,15,16] Some representative vanadium(IV) complexes for ethylene polymerization are shown in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

Dipicolinate Oxovanadium(IV) Complexes – Well‐Defined, Universal Precatalysts for Ethylene Polymerization and Polar Monomers Oligomerization

Drzeżdżon,

Białek,

Parnicka

et al. 2024

ChemistrySelect

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In the field of polymers and organometallic chemistry, a significant gap is apparent in the area of research on well‐defined metal complexes targeted for using in catalysis leading to olefinic oligomers and polymers. Here, we report on the use in these processes the dipicolinate oxovanadium(IV) complexes, without and with auxiliary ligands, i. e. 1,10‐phenanthroline and 2,2’‐bipyridine. The investigated complexes turned out to be versatile precatalysts. After reaction with appropriate activator, they exhibited 11 times higher a catalytic activity than reference vanadium(IV) complexes with salen ligands – so far, precatalysts from a group of vanadium(IV) complexes with the highest known catalytic activity for polymerization of ethylene. In the case of the oligomerization of polar monomers (2‐chloro‐2‐propen‐1‐ol and 3‐buten‐2‐ol) the complexes described in this report have a catalytic activity (very high) similar to vanadium(IV) complexes known in the literature.

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“…Vanadium complexes can exist in many oxidation states. Studies performed on the actual mechanisms of ethylene polymerization have shown that vanadium species in the +5 oxidation state are the most active and long‐living 11,15 . Ligands that can stabilize these high‐valent vanadium complexes are, therefore, highly desirable.…”

Section: Introductionmentioning

confidence: 99%

Achieving ultra‐high molecular weight polyethylenes by vanadium aroylhydrazine‐arylolates

Suo

Phillips

Sutradhar

et al. 2022

Journal of Polymer Science

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A series of vanadium(V) aroylhydrazine-arylolates is employed in ethylene polymerization to produce ultra-high molecular weight polyethylene (UHMWPE), surprisingly extending to such coupling reactions beyond their common usage in the oxidation of hexanes and alcohols. Activated by either MAO or DMAC, the complexes V1-V3 efficiently catalyze the polymerization of ethylene into UHMWPE, that is, with an activity up to 3.37 Â 10 6 g mol À1 h À1 (60 C) and the polyethylene obtained has a molecular weight around 3 million g mol À1 , being the highest molecular weight achieved by a vanadium catalyst so far. More importantly, the significant effects of different cocatalysts are well illustrated; the catalytic system with MAO generally shows lower activity with almost one order in the magnitude than that with DMAC (0.43 vs. 3.37 Â 10 6 g mol À1 h À1 ), but the polyethylenes with higher molecular weights are obtained by the system with MAO.

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Vanadium(V) imido chlorides and n-propoxides — Towards a rational design of vanadium imido precatalysts for ethylene polymerization

Cited by 5 publications

References 64 publications

Preparation of Allyl Alcohol Oligomers Using Dipicolinate Oxovanadium(IV) Coordination Compound

Preparation of Allyl Alcohol Oligomers Using Dipicolinate Oxovanadium(IV) Coordination Compound

Dipicolinate Oxovanadium(IV) Complexes – Well‐Defined, Universal Precatalysts for Ethylene Polymerization and Polar Monomers Oligomerization

Achieving ultra‐high molecular weight polyethylenes by vanadium aroylhydrazine‐arylolates

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