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
The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel ...The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts(Ni1: Ar = Ph;Ni2: Ar = 2-(C_(6)H_(5))C_(6)H_(4);Ni3: Ar = 2-[2',6'-(Me O)_(2)-C_(6)H3]C_(6)H_(4)) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities(up to 7.24×10^(6) and 9.04×10^(6)g·mol Ni^(-1)·h^(-1), respectively), and produced high-molecular-weight polyethylene(Mw up to 545.7 k Da). Complex Ni3 exhibited high activities for ethylene polymerization at the level of 10^(6) g·mol Ni^(-1)·h^(-1) across a wide range from 30 ℃ to 120 ℃, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights(Mw up to 80.5 k Da) and high polar monomer incorporation(up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.展开更多
Nickel(Ⅱ)complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene.We have prepared ten new nickel(Ⅱ)dibromide complexes w...Nickel(Ⅱ)complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene.We have prepared ten new nickel(Ⅱ)dibromide complexes with various substituted bis(azolyl)methanes.They have been characterized using^(1)H NMR,IR,high resolution mass spectrometry and elemental analysis.The structures of three complexes have been unambiguously established using X-ray diffraction.It was found that these complexes in the presence of Et2AlCl or Et_(3)Al_(2)Cl_(3)are active both in ethylene oligomerization and Friedel-Crafts alkylation processes(activity up to 3720 kgoligomer·mol[Ni]^(−1)·h^(−1)).The use of Et_(3)Al_(2)Cl_(3)results in a higher share of alkylated products(up to 60%).Moreover,catalytic systems activated with Et_(3)Al_(2)Cl_(3)produced small amounts of odd carbon number olefins(up to 0.8%).The Friedel-Crafts alkylation was used as a trap for previously undetected short-chain odd carbon number olefins(C_(3)and C_(5)).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 National Natural Science Foundation of China (No. 52130307)。
文摘The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts(Ni1: Ar = Ph;Ni2: Ar = 2-(C_(6)H_(5))C_(6)H_(4);Ni3: Ar = 2-[2',6'-(Me O)_(2)-C_(6)H3]C_(6)H_(4)) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities(up to 7.24×10^(6) and 9.04×10^(6)g·mol Ni^(-1)·h^(-1), respectively), and produced high-molecular-weight polyethylene(Mw up to 545.7 k Da). Complex Ni3 exhibited high activities for ethylene polymerization at the level of 10^(6) g·mol Ni^(-1)·h^(-1) across a wide range from 30 ℃ to 120 ℃, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights(Mw up to 80.5 k Da) and high polar monomer incorporation(up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.
基金This work was financially supported by the Russian Science Foundation-Russia(Project No.22-23-00578)NMR measurement was performed according to the Development Program of the Interdisciplinary Scientific and Educational School of Lomonosov Moscow State University"The future of the planet and global environmental change"'X-Ray analysis was supported by the RUDN University Strategic Academic Leadership Program.Elemental and GC analyses were performed with the financial support from the Ministry of Science and Higher Education of the Russian Federation using the equipment of the Centre for molecularcomposition studies of INEOS RAS.
文摘Nickel(Ⅱ)complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of toluene.We have prepared ten new nickel(Ⅱ)dibromide complexes with various substituted bis(azolyl)methanes.They have been characterized using^(1)H NMR,IR,high resolution mass spectrometry and elemental analysis.The structures of three complexes have been unambiguously established using X-ray diffraction.It was found that these complexes in the presence of Et2AlCl or Et_(3)Al_(2)Cl_(3)are active both in ethylene oligomerization and Friedel-Crafts alkylation processes(activity up to 3720 kgoligomer·mol[Ni]^(−1)·h^(−1)).The use of Et_(3)Al_(2)Cl_(3)results in a higher share of alkylated products(up to 60%).Moreover,catalytic systems activated with Et_(3)Al_(2)Cl_(3)produced small amounts of odd carbon number olefins(up to 0.8%).The Friedel-Crafts alkylation was used as a trap for previously undetected short-chain odd carbon number olefins(C_(3)and C_(5)).
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.