Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands

Vladislav A. Tuskaev; Kasim F. Magomedov; Svetlana Ch. Gagieva; Dmitry A. Kurmaev; Yulia V. Nelyubina; Evgenii K. Golubev; Maria D. Evseeva; Viktor G. Vasil’ev; Galina G. Nikiforova; Mikhail I. Buzin; Vyacheslav S. Bogdanov; Boris M. Bulychev

doi:10.1007/s10118-023-3032-1

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Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands

RESEARCH ARTICLE | Updated：2023-12-26

- Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands
- Chinese Journal of Polymer Science Vol. 42, Issue 1, Pages: 52-62(2024)
- Affiliations：
  
  a.Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119992, Russian Federation
  b.A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow 119991, Russian Federation
  c.Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences, Moscow 117393, Russian Federation
- Author bio：
  
  tuskaev@yandex.ru
- Funds：
- DOI：10.1007/s10118-023-3032-1
  CLC：
- Received：27 June 2023，
  
  Revised：2023-7-17，
  
  Accepted：21 July 2023，
  
  Online First：01 September 2023，
  
  Published：01 January 2024
- Accepted：
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Tuskaev, V. A.; Magomedov, K. F.; Gagieva, S. Ch.; Kurmaev, D. A.; Nelyubina, Y. V.; Golubev, E. K.; Evseeva, M. D.; Vasil’ev, V. G.; Nikiforova, G. G.; Buzin, M. I.; Bogdanov, V. S.; Bulychev, B. M. Olefin polymerization behavior of titanium(IV) complexes with fluorinated and non-fluorinated aliphatic phenoxyimine ligands. Chinese J. Polym. Sci. 2024, 42, 52–62

Vladislav A. Tuskaev, Kasim F. Magomedov, Svetlana Ch. Gagieva, et al. Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands[J]. Chinese Journal of Polymer Science, 2024, 42(1): 52-62.
Tuskaev, V. A.; Magomedov, K. F.; Gagieva, S. Ch.; Kurmaev, D. A.; Nelyubina, Y. V.; Golubev, E. K.; Evseeva, M. D.; Vasil’ev, V. G.; Nikiforova, G. G.; Buzin, M. I.; Bogdanov, V. S.; Bulychev, B. M. Olefin polymerization behavior of titanium(IV) complexes with fluorinated and non-fluorinated aliphatic phenoxyimine ligands. Chinese J. Polym. Sci. 2024, 42, 52–62 DOI： 10.1007/s10118-023-3032-1.

Vladislav A. Tuskaev, Kasim F. Magomedov, Svetlana Ch. Gagieva, et al. Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands[J]. Chinese Journal of Polymer Science, 2024, 42(1): 52-62. DOI： 10.1007/s10118-023-3032-1.

摘要

The synthesized Ti(IV) complexes with aliphatic phenoxyimine ligands in the presence of Al/Mg activators initiate the synthesis of disentangled UHMWPE with high productivity. The polymer is suitable for solventless processing into oriented high-strength films. In ethylene/octene-1 copolymerization

fluorine-containing systems provide greater activity and higher comonomer content.

Abstract

A series of Ti(IV) dichloride and dialkoxide complexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been synthesized. The molecular structures of complexes

and

were established by single-crystal X-ray diffraction studies. The complexes adopt a distorted octahedral coordination structure around the titanium atom and two oxygen atoms are situated in

trans

position while two nitrogen atoms and two outgoing ligands (Cl or

PrO) are situated in

cis

position. Effect of activators (MMAO-12 and combinations Et

AlCl

3−

+ Bu

Mg) and outgoing ligand (Cl or

PrO) nature on the catalytic activity and properties of the resulting polymers was studied. The Ti complexes

despite the nature of the outgoing ligands (Cl or

PrO) in the presence of Al/Mg activators

was found to display a high ethylene polymerization activity in the range 1600−3830 kg

polymer

·mol

−1

·h

−1

·atm

−1

with a viscosity average molecular weight (

) value in the range 1.1×10

−7.1×10

Dalton (Da). The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films. The rheological characteristics of a polymer melt have been studied. The absence of a cross-over point did not allow to compare the values of the molecular weight distribution of polymers obtained on fluorinated and non-fluorinated pre-catalysts

however

the estimation of the entanglement density is in good agreement with the mechanical characteristics of oriented films. Upon activation with methylalumoxane

the activity of the complexes decreased very significantly; however

a polymer with a molecular weight of about 12 million Da was obtained. In the process of ethylene/octene-1 copolymerization

fluorine-containing precatalysts showed a clear advantage over non-fluorinated analogues both in activity and in comonomer content.

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