Synthesis of Uniquely Branched Polyethylene by Anilinonaphthoquinone Ligated Nickel Complex Activated with Tris(pentafluorophenyl)borane

Okada, Mitsuhiro; Nakayama, Yuushou; Ikeda, Tomiki; Shiono, Takeshi

doi:10.1002/marc.200600335

Cited by 32 publications

(30 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, cationic diimino-nickel complexes have been found to be active as procatalysts in ethylene polymerization and oligomerization [7]. Extensive investigations for new procatalysts of various late-transition metal complexes have been conducted [8], and nickel complexes bearing bidentate [9][10][11][12][13][14][15][16][17][18][19] or tridentate ligands [20][21][22][23][24] have been the focus of much research. Beyond our efforts for iron procatalysts in ethylene reactivity [25,26], some nickel procatalysts were also investigated and possessed good activities [27][28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and ethylene oligomerization behavior of 2-(chloro-substituted-1H-benzoimidazol-2-yl)-6-(1-aryliminoethyl)pyridylnickel dihalides

Chen

Zhang

et al. 2011

Inorganica Chimica Acta

View full text Add to dashboard Cite

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and ethylene oligomerization behavior of 2-(chloro-substituted-1H-benzoimidazol-2-yl)-6-(1-aryliminoethyl)pyridylnickel dihalides

Chen

Zhang

et al. 2011

Inorganica Chimica Acta

View full text Add to dashboard Cite

“…77 %). Effect of B(C 6 F 5 ) 3 for anilinotropone complex (7c) is also attributed to the zwitterionic catalyst [118,119].…”

Section: Catalyst Having Tropone-imide Type Ligandsmentioning

confidence: 96%

“…Shiono reported that Ni complex with an aminonaphthoquinone ligand (7c) catalyzes ethylene polymerization, producing methyl branched polyethylene [118,119]. Addition of B(C 6 F 5 ) 3 leads to increase of the catalytic activity and Benzyl Ni complex with a-iminocarboxamide ligand (7d) is formed by the reaction of potassium salt of the carboxyamide with the Ni complex having a p-benzyl ligand [120].…”

Section: Catalyst Having Tropone-imide Type Ligandsmentioning

confidence: 98%

“…It is proposed that each complex catalyst forms one polyethylene particle. The catalysts are also active for ethylene/1-butene copolymerization [237] as well as homopolymerization of propylene, 1-butene, and 1-hexene [118] in water. Ni complexes with enolateimine ligands (6d, L = py) also promote ethylene polymerization in aqueous media [238] (Chart 4.13).…”

Section: Olefin Polymerization In Aqueous Mediamentioning

confidence: 98%

See 1 more Smart Citation

Olefin Polymerization with Non-metallocene Catalysts (Late Transition Metals)

Takeuchi

2014

Organometallic Reactions and Polymerization

View full text Add to dashboard Cite

Diimine Pd and Ni complexes catalyze the polymerization of ethylene, propylene, and a-olefins. The reaction involves isomerization of the growing terminal (chain walking) and, as its result, produces highly branched polyethylene and poy(a-olefin)s having a smaller number of the alkyl substituents than expected from the monomer structure. Ni complexes with salicylaldimine or iminocarboxamide ligands and Pd complexes with phosphinesulfonate ligands are used as single component catalysts for ethylene polymerization. Especially, the latter catalysts show tolerance towards polar functional groups and promote copolymerization of ethylene with wide varieties of polar monomers. The Pd and Ni complexes are able to catalyze ethylene polymerization in aqueous media to yield polyethylene particles. Fe and Co complexes with bis(imino)pyridine ligands show high catalytic activity for ethylene polymerization to yield linear polyethylene. Complexes of the metals such as Rh, Ir, Ru, and Ag were revealed to become catalytically active by proper design of the ligand. Not only monometallic complexes but also bimetallic or multimetallic complexes are used for ethylene polymerization. Late transition metal complexes catalyze selective cyclopolymerization of non-conjugated dienes and trienes to afford the polymers with cycloalkane groups with controlled stereochemistry.

show abstract

“…23,31 Methyl branch was a dominant branch, while ethyl, propyl, butyl, amyl, and long branch were minor branches. The order of branch was methyl ) long > ethyl > propyl $ butyl > amyl, which was similar to the previous result.…”

mentioning

confidence: 99%

Ethylene Polymerizations with Unsymmetrical (α-Diimine)nickel(II) Catalysts

Jeon

Kim

2008

Polym J

View full text Add to dashboard Cite

Four unsymmetrical (-diimine)nickel(II) catalysts were synthesized by sequential stepwise condensation of acenaphthenequinone with the corresponding aniline compounds and subjected to ethylene polymerizations with MAO. Interestingly, when the catalysts have the same composition of the ortho substituents, the catalyst with two ortho isopropyl substitients on one side and two ortho methyl substituents on the other side produced polyethylenes with higher branching densities and lower molecular weights than the catalyst with one ortho isopropyl and one ortho methyl substituent on each side. However, branch distribution was not changed by the position of the ortho substituents. The catalysts have unique characteristic, production of branched polyethylene only from ethylene monomers. A chain walking (-hydride elimination and readdition to the other carbon) followed by ethylene coordination and insertion produces a methyl branch. Repeated chain walkings followed by ethylene coordination and insertion make a longer branch.Control of ortho substituents on aromatic rings of (-diimine)nickel(II) catalysts is important to achieve a proper catalytic activity. 13 The ortho substituents have been reported to locate at axial site of the catalysts, and they retard chain transfer reactions, promote the chain walking, and accelerate the rate of migratory insertion. Therefore, as steric bulkiness of the ortho substituents increases, molecular weights of polyethylenes, branching densities of polyethylenes, and polymerization activities increased.14 Some researchers further modified the ortho substituents of the (-diimine)nickel(II) catalysts to get novel polymerization results. Brookhart et al. reported that electron withdrawing ortho substituents of the (-diimine)-nickel(II) catalyst increased turnover frequency of ethylene polymerization presumably because electron withdrawing ortho substituents made nickel more electrophilic.14 Rieger et al. reported chiral C 2 symmetric (-diimine)nickel(II) catalysts bearing ortho phenyl substituents produced high molecular weight polyethylenes with high activities.15 Guan et al. reported cyclophane-based (-diimine)nickel(II) catalyst which was highly active for ethylene polymerizations even at high temperature ($90 C). 16 Zhu et al. reported that molecular weights of the polyethylenes produced by rac-(-diimine)-nickel(II) catalyst were significantly higher than those produced by meso-(-diimine)nickel(II) catalyst. 17Another way to modify the ortho substituents of the (-diimine)nickel(II) catalysts is making the (-diimine)nickel(II) catalysts as unsymmetric. But there have been few reports on ethylene polymerizations with unsymmetrical (-diimine)-nickel(II) catalysts due to the lack of proper synthetic method for unsymmetrically substituted -diimine ligands. [18][19][20][21][22] In this study, new unsymmetrical (-diimine)nickel(II) catalysts were synthesized by stepwise acid catalyzed condensation reaction followed by condensation with TiCl 4 /DABCO. The catalysts were subjected to ethylene poly...

show abstract

Synthesis of Uniquely Branched Polyethylene by Anilinonaphthoquinone Ligated Nickel Complex Activated with Tris(pentafluorophenyl)borane

Cited by 32 publications

References 47 publications

Synthesis, characterization and ethylene oligomerization behavior of 2-(chloro-substituted-1H-benzoimidazol-2-yl)-6-(1-aryliminoethyl)pyridylnickel dihalides

Synthesis, characterization and ethylene oligomerization behavior of 2-(chloro-substituted-1H-benzoimidazol-2-yl)-6-(1-aryliminoethyl)pyridylnickel dihalides

Olefin Polymerization with Non-metallocene Catalysts (Late Transition Metals)

Ethylene Polymerizations with Unsymmetrical (α-Diimine)nickel(II) Catalysts

Contact Info

Product

Resources

About