Novel alkoxo-titanium(IV) complexes with fluorinated 2-hydroxymethylphenol derivatives as catalysts for the formation of ultra-high molecular weight polyethylene nascent reactor powders

Titanium(IV) coordination compounds are effectively used as precatalysts for ethylene polymerization and copolymerization with other olefins. New titanium(IV) complexes 3b-d with ligands containing two diphenylcarbinol fragments linked by the perfluorinated hydrocarbon units-CF 2or-C 2 F 4were synthesized. The structures of complexes 3b and 3d were determined by X-ray diffraction. Titanium atoms in 3b have a distorted trigonal-bipyramidal coordination environment while spiro-complex 3d is characterized by tetrahedral molecular geometry. The catalytic behavior of complexes activated by mixtures of Bu 2 Mg and alkylaluminium chlorides from among Me 2 AlCl, Et 2 AlCl, EtAlCl 2 , and Et 3 Al 2 Cl 3 were studied. The resulting catalytic systems catalyze ethylene polymerization to afford ultra-high molecular weight polyethylene, suitable for modern processing methods, and the solvent-free solid state formation of super high-strength (1.37-2.75 GPa) and high-modulus (up to 138 GPa) oriented film tapes. The same catalytic systems catalyze ethylene copolymerization with 1-hexene to afford high molecular weight semicrystalline elastomeric polymers containing up to 20% of comonomer units.

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“…Recrystallization of the crude product from hexane/toluene gave 3.24 g (78%) of a colorless solid. Calculated (%) for C 27…”

Section: 2-difluoro-1133-tetraphenylpropane-13-diol (2b)mentioning

confidence: 99%

Olefin polymerization behavior of titanium(IV) alkoxo complexes with fluorinated diolate ligands: The impact of the chelate ring size and the nature of organoaluminum compounds

Тuskaev

Гагиева

Kurmaev

et al. 2020

Applied Organom Chemis

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“…(A similar pattern was observed by us earlier. [16] ) All polyethylene samples obtained in this work are characterized by ultrahigh molecular weight (1.6Á10 6 to 6.4Á10 6 Da), high melting points, and high degree of crystallinity (Figures S8-S14 illustrate a representative GPC curve of UHMWPE samples).…”

Section: Catalytic Properties Of Ti(iv) Complexmentioning

confidence: 91%

“…Viscosity-average molecular weight of synthesized UHMWPE samples was calculated with the Mark-Houwink equation. [21] The method for preparing oriented films from UHMWPE powder, as well as determining their mechanical characteristics, is given in Tuskaev et al [16] Gel permeation chromatographic (GPC) analysis of copolymers was carried out at 135 C with a Waters GPCV-2000 chromatograph equipped with two columns (PLgel, 5 μ and Mixed-C, 3007.5 mm) and a refractometer. 1,2,4-Trichlorobenzene was used as a solvent; the elution rate was 1 ml min À1 .…”

Section: Polymer Evaluation Methodsmentioning

confidence: 99%

“…Mononuclear analogue complex 6 [16] serves as a control. In the crystalline state, this compound exists as a dimer, stabilized exclusively by coordination bonds, but in the process of activation, the dimer structure is obviously destroyed which allows us to consider it as a mononuclear complex.…”

Section: Catalytic Properties Of Ti(iv) Complexmentioning

confidence: 99%

“…Moreover, the values of tensile strength and average tensile modulus recorded at complex 4 are the highest in the entire series of titanium complexes stabilized by 2-hydroxymethylphenol derivatives. [16,[28][29][30][31] It is possible that the lower catalytic activity of binuclear complex 4 facilitates the formation of disentangled UHMWPE.…”

Section: Catalytic Properties Of Ti(iv) Complexmentioning

confidence: 99%

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Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Тuskaev

Гагиева

Bogdanov

et al. 2021

Applied Organom Chemis

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The coordination chemistry of a new compartmental ligand 2,6‐(bis‐CF3‐carbinol)‐4‐tert‐butylphenol with Ti(IV) and Zr(IV) has been studied. The structures of Al, Ti, and Zr complexes with the participation of this ligand were established by X‐ray diffraction. Upon activation with Et2AlCl or Et3Al2Cl3 and Bu2Mg, Ti(IV) complex exhibited moderate catalytic activity for ethylene polymerization. The obtained UHMWPE samples were processed into high‐strength (up to 2.7 GPa) and high‐modulus (up to 162 GPa) films through solid‐phase molding and orientation drawing. The mononuclear and binuclear Ti(IV) complexes catalyzed the ternary copolymerization of ethylene, propylene, and 5‐ethylidene‐norbornene. Tercopolymers with a content of propylene units up to 36 mol% and 5‐EBN up to 8.6 mol% were synthesized with a high activity (2.8–6.3 tons of copolymer/mol Ti h); the mechanical characteristics of elastomeric materials have been studied.

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MAO‐free copolymerization of ethylene and 1-hexene with Ti (IV) complexes supported by fluorinated 2-hydroxymethylphenol derivatives

et al. 2020

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Novel alkoxo-titanium(IV) complexes with fluorinated 2-hydroxymethylphenol derivatives as catalysts for the formation of ultra-high molecular weight polyethylene nascent reactor powders

Cited by 18 publications

References 38 publications

Olefin polymerization behavior of titanium(IV) alkoxo complexes with fluorinated diolate ligands: The impact of the chelate ring size and the nature of organoaluminum compounds

Olefin polymerization behavior of titanium(IV) alkoxo complexes with fluorinated diolate ligands: The impact of the chelate ring size and the nature of organoaluminum compounds

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

MAO‐free copolymerization of ethylene and 1-hexene with Ti (IV) complexes supported by fluorinated 2-hydroxymethylphenol derivatives

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Novel alkoxo-titanium(IV) complexes with fluorinated 2-hydroxymethylphenol derivatives as catalysts for the formation of ultra-high molecular weight polyethylene nascent reactor powders

Cited by 18 publications

References 38 publications

Olefin polymerization behavior of titanium(IV) alkoxo complexes with fluorinated diolate ligands: The impact of the chelate ring size and the nature of organoaluminum compounds

Olefin polymerization behavior of titanium(IV) alkoxo complexes with fluorinated diolate ligands: The impact of the chelate ring size and the nature of organoaluminum compounds

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF3‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

MAO‐free copolymerization of ethylene and 1-hexene with Ti (IV) complexes supported by fluorinated 2-hydroxymethylphenol derivatives

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Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene