A series of Ti(Ⅳ) dichloride and dialkoxide com plexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been synthesized.The molecular structures of complexes 1 and 4...A series of Ti(Ⅳ) dichloride and dialkoxide com plexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been synthesized.The molecular structures of complexes 1 and 4 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 iPrO) are situated in cis position.Effect of activators(MMAO-12 and combinations Et_nAICl_(3-n)+Bu_(2)Mg) and outgoing ligand(Cl or iPrO) 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 iPrO) in the presence of Al/Mg activators,was found to display a high ethylene polymerization activity in the range 1600-3830 kg_(polymer)·mol_(Ti)^(-1)·h^(-1)·atm^(-1) with a viscosity average molecular weight(M_v) value in the range 1.1×10~6-7.1×10~6 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 film s.Upon activation with methylalumoxane,the activity of the com plexes 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.展开更多
Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]^(4–)-type ligand were active in ethylene polymerization in the presence of Et2 AlCl/Bu2 Mg binary co-catalyst, giving high molecular weig...Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]^(4–)-type ligand were active in ethylene polymerization in the presence of Et2 AlCl/Bu2 Mg binary co-catalyst, giving high molecular weight polyethylene. The binuclear complex showed significantly higher catalytic activity and thermal stability in comparison to mononuclear analogue. Ultra high molecular weight polyethylene(UHMWPE) samples were processed by a solid-state uniaxial deformation into high-strength(up to 2.5 GPa) and highmodulus(over 100 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.展开更多
基金supported by the Russian Science Foundation (No.22-23-00578)the financial support from the Ministry of Science and Higher Education of the Russian Federation using the equipment of Center for molecular composition studies of INEOS RAS (No.075-00697-22-00)the financial support of the Ministry of Science and Higher Education of the Russian Federation employing the equipment of Center for molecular composition studies of INEOS RAS。
文摘A series of Ti(Ⅳ) dichloride and dialkoxide com plexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been synthesized.The molecular structures of complexes 1 and 4 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 iPrO) are situated in cis position.Effect of activators(MMAO-12 and combinations Et_nAICl_(3-n)+Bu_(2)Mg) and outgoing ligand(Cl or iPrO) 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 iPrO) in the presence of Al/Mg activators,was found to display a high ethylene polymerization activity in the range 1600-3830 kg_(polymer)·mol_(Ti)^(-1)·h^(-1)·atm^(-1) with a viscosity average molecular weight(M_v) value in the range 1.1×10~6-7.1×10~6 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 film s.Upon activation with methylalumoxane,the activity of the com plexes 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.
基金financially supported by the Russian Science Foundation(No.16-13-10502)
文摘Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]^(4–)-type ligand were active in ethylene polymerization in the presence of Et2 AlCl/Bu2 Mg binary co-catalyst, giving high molecular weight polyethylene. The binuclear complex showed significantly higher catalytic activity and thermal stability in comparison to mononuclear analogue. Ultra high molecular weight polyethylene(UHMWPE) samples were processed by a solid-state uniaxial deformation into high-strength(up to 2.5 GPa) and highmodulus(over 100 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.
