Highly active new α-diimine nickel catalyst for the polymerization of α-olefins

Liu, Huarong; Gomes, Pedro T.; Costa, Sandra I.; Duarte, M. Teresa; Branquinho, Rita; Fernandes, Anabela C.; Chien, James C. W.; Singh, Rojendra; Marques, M. Manuel B.

doi:10.1016/j.jorganchem.2004.11.046

Cited by 51 publications

(26 citation statements)

References 30 publications

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“…This oxophilicity renders metallocenes inactive toward most functionalized monomers and highly sensitive to polar solvents and impurities. The sensitivity of metallocenes to polar substituents is largely responsible for an increase in interest in late-transition-metal complexes as olefin polymerization catalysts over the past several years [34][35][36][37]. Late-metal catalysts complement early-metal catalysts in several ways.…”

Section: Introductionmentioning

confidence: 99%

“…(1) Polymers exhibiting quite different microstructures are frequently obtained [36,[38][39][40][41]. This arises from the ability of the metal to walk along the growing polymer chain via a series of -elimination and reinsertion reactions which can occur at rates competitive with or faster than olefin insertion.…”

Section: Introductionmentioning

confidence: 99%

“…This arises from the ability of the metal to walk along the growing polymer chain via a series of -elimination and reinsertion reactions which can occur at rates competitive with or faster than olefin insertion. This process results information of branched polymers from ethylene and "chain-straightened" polymers from -olefins [36,38]. (2) Certain monomers such as trans-2-butene, which cannot be polymerized by early-metal systems, can be successfully polymerized with late-metal systems [42].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Titanium (IV) and Nickel (II) Catalysts Based on Anilinotropone Ligands

Sandaroos¹,

Cuenca²,

Zohuri³

et al. 2012

Polymerization

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Titanium (IV) and Nickel (II) Catalysts Based on Anilinotropone Ligands

Sandaroos¹,

Cuenca²,

Zohuri³

et al. 2012

Polymerization

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“…To gain more insight into the factors controlling the activity of such catalysts and the effect of catalyst structure on polymer structure and properties, the steric effects of the ortho substituent of the 2,6-dialkylaryl imine group on the catalytic activity of a-diimine-Ni(II) complexes has been studied in detail by Brookhart [6]. However, the effects of para substituents of the 2,6-dialkylaryl imine group [24,25], especially of electron-withdrawing substituents, on the catalytic behavior of a-diimine-Ni(II) complexes and the properties of the resulting polymers has only been reported in limited cases [3].…”

Section: Introductionmentioning

confidence: 99%

An α-Diimine-Nickel(II) catalyst bearing an electron-withdrawing substituent for olefin polymerization

Yuan

Wang

Mei

et al. 2011

Transition Met Chem

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A Br-substituted a-diimine ligand, bis[N,N 0 -(4-bromo-2,6-dimethylphenyl)imino]-2,3-butadiene L1, and its corresponding Ni(II) complex, {bis[N,N 0 -(4-bromo-2,6-dimethylphenyl)imino]-2,3-butadiene} dibromonicke [NiBr 2 (L1)], have been synthesized and characterized. The crystal structure of the free ligand (L1) was determined by X-ray crystallography. Two a-diimine-Ni(II) catalysts, {bis[N,N 0 -(2,4,6-dimethylphenyl)imino]-2,3-butanedione} dibromonickel [NiBr 2 (L2)] and {bis[N,N 0 -(2,6-dimethylphenyl)imino]-2,3-butanedione} dibromonickel [NiBr 2 (L3)], were also synthesized and characterized for comparison. The complex [NiBr 2 (L1)], when activated by diethylaluminum chloride, produces the most active catalytic system for the polymerization of ethylene among the three complexes. NMR analysis shows that the degree of branching of polyethylene increases in the presence of electronwithdrawing groups under the same reaction conditions.

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“…Ni(II)a-diimine catalysts, when activated with methylaluminoxane (MAO), exhibit high activity towards the polymerization of ethylene, 1-hexene, and propylene as well as their block copolymerization. [5][6][7] Moreover, this kind of catalysts can be used as ATRP catalysts for the polymerization of styrene and methyl methacrylate (MMA) with poor to moderate control process. 8 Divalent nickel complex bearing acetylide ligand Ni(CBCPh) 2 (PBu 3 ) 2 has been a potential effective catalyst for the ATRP of MMA.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

Harrar-Ferfera

2007

J of Applied Polymer Sci

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Copolymerizations of methyl methacrylate (MMA) with 4-vinylpyridine (4VP) were performed from different monomer feed ratios in 1,4-dioxan at 308C under free radical initiation experimental conditions, using Ni(II)a-Benzoinoxime complex as initiator. The obtained copolymers (PMMA4VP) were examined by FTIR and 1 H NMR spectroscopies. The composition of these copolymers was calculated, using 1 H NMR spectra and elemental analysis. Monomer reactivity ratios were estimated from Fineman-Ross (FR, r m 5 0.550, r v 5 1.165) and Kelen-Tudos (KT, r m 5 0.559, r v 5 1.286) linearization methods, as well as nonlinear error in variables model (EVM) method using the RREVM computer program (RREVM, r m 5 0.559, r v 5 1.264). These values suggest that MMA-4VP pair copolymerizes randomly. 1 H NMR spectra provide information about the stereochemistry of the copolymers in terms of sequence distributions and configurations. These results showed that the age of the Ni complex has an impact not only on its activity towards polymerization reactions but also on the features of the corresponding copolymers, whereas the chemical composition was insensitive to this prominent factor. The mechanism of MMA-4VP copolymerization is consistent with a radical process as supported by microstructure and molecular weight distribution studies. Thermal behaviours of these copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis.

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Highly active new α-diimine nickel catalyst for the polymerization of α-olefins

Cited by 51 publications

References 30 publications

Titanium (IV) and Nickel (II) Catalysts Based on Anilinotropone Ligands

Titanium (IV) and Nickel (II) Catalysts Based on Anilinotropone Ligands

An α-Diimine-Nickel(II) catalyst bearing an electron-withdrawing substituent for olefin polymerization

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

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