Living/controlled hex-1-ene polymerization initiated by nickel diimine complexes activated by non-MAO cocatalysts: Kinetic and UV–vis study

Peleška, Jan; Hošťálek, Z.; Hasalíková, Darja; Merna, Jan

doi:10.1016/j.polymer.2010.11.029

Cited by 30 publications

(40 citation statements)

References 30 publications

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“…As to the other four solvents, polymerization in fully nonpolar n ‐heptane exhibited the lowest activity, and polymerization in polar dichloromethane (DCM) and 1,2,4‐trichlorobenzene (TCB) displayed higher activities than in toluene. This phenomenon is basically consistent with other coordination polymerization and α‐diimine Ni(II) complex catalyzed ethylene polymerization . Broadly speaking, there are three types of active sites in olefin polymerization with metallocene and typical late‐transition metal catalysts: loosely associated ion pairs, contact ion pairs and ion pairs with medium cation‐anion distance.…”

Section: Resultssupporting

confidence: 87%

Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et₂AlCl

Song

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Four nonconjugated diene comonomers 1,9‐decadiene (19DD), 6‐ethylundeca‐1,10‐diene (EUD), 1,5‐cyclooctadiene (COD) and cinene (1‐methyl‐4‐(prop‐1‐en‐2‐yl) cyclohex‐1‐ene) (CE) were used in copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex ([2,6‐(iPr)2C6H3N = C(CH3)−(CH3)C = N2,6‐(iPr)2C6H3)]NiBr2 (1)) activated by Et2AlCl. These dienes showed quite distinct copolymerization behaviors. Ethylene‐19DD copolymerization formed highly branched polyethylene with cyclic units and pendent vinyls, and a large part of crosslinked polymer when the 19DD concentration was relatively high. Using EUD as comonomer lead to evidently reduced gel formation and increased content of pendent vinyl. COD can be incorporated in the copolymer with evidently lower catalyst efficiency than the ethylene homopolymerization, and CE behaves like an inert compound as it was not incorporated in the copolymer. Homopolymerization of 19DD with the same catalyst produced polymer containing both cyclic units and pendent vinyls. The cyclic units were formed by cyclopolymerization of the inserted 19DD after several steps of chain walking. Crosslinking through the pendent vinyl took place when the initial 19DD concentration was relatively high, forming large amount of gel in the product. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1900–1909

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Section: Resultssupporting

confidence: 87%

Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et₂AlCl

Song

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…It is known that ligand electronics have a dramatic effect on catalytic activity and polymer molecular weight . The properties of resulting polyethylenes showed halide and polymerization temperature effects in that the polyethylenes produced with the chloride pre‐catalyst rac ‐ 3c (runs 13–16 in Table ) had slightly higher molecular weights than those produced with the methyl pre‐catalyst rac ‐ 3b (runs 9–12 in Table ).…”

Section: Resultsmentioning

confidence: 99%

“…The key feature of these complexes lies in the bulky α ‐diimine ligand that has steric hindrance in the axial direction of the metal coordination plane to suppress the associative chain transfer . Since the earlier studies, investigations have increasingly focused on improvement of the catalytic properties through modification of the structures of catalysts, especially on changes of the backbone substituents on the carbon atoms of imine groups and replacement of the aniline moiety as well as the resultant influence on ethylene polymerization. For instance, Rhinehart et al .…”

Section: Introductionmentioning

confidence: 99%

New nickel(II) diimine complexes bearing phenyl and sec‐phenethyl groups: synthesis, characterization and ethylene polymerization behaviour

Wang

Yuan

Liu

et al. 2014

Applied Organom Chemis

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A series of nickel(II) catalysts containing phenyl and chiral sec-phenethyl groups, {[(4-R 1 -2-R 2 C 6 H 2 N¼C) 2 Nap]NiBr 2 } (Nap: 1,8naphthdiyl, R 1 = Me, R 2 = Ph (3a); R 1 = Me, R 2 = sec-phenethyl (3b); R 1 = Cl, R 2 = sec-phenethyl (3c); R 1 = Me, R 2 = Me (3d) were synthesized and characterized. All organic compounds were fully characterized by FT-IR and NMR spectroscopy and elemental analysis. The single crystal for X-ray crystallography was isolated from 3a in CH 2 Cl 2 /n-hexane under air; the crystal structure showed a binuclear complex 3a′, in which each nickel atom was six-coordinate. The two nickel atoms together with two bromine atoms form a planar four-membered ring, with a bromine and H 2 O axial ligands. These complexes, activated by diethylaluminum chloride and chiral nickel pre-catalysts rac-3c, exhibited good activities (up to 2.85 × 10 6 g PE (mol Ni h bar) À1 ) for ethylene polymerization, and produced polyethylene products with a high degree of branching (up to 117 branched per 1000 carbons) at high temperature. The type and amount of branches of the polyethylenes obtained were determined by 1 H and 13 C NMR spectroscopy. . a, 1b, 1c, 2d and 3d are known compounds and characterization data can be seen in the supporting information.New nickel(II) diimine complexes for ethylene polymerization

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“…This ratio was chosen based on previous experiments which showed that for similar nickel diimine complexes activated by MAO a plateau of activity appears at MAO/Ni higher than 50 . Ortho‐aryl substituents of all studied complexes were fixed to be isopropyl groups as in a benchmark complex 3 , which is one of the first and the most common nickel α‐diimine complex used for living/controlled olefin polymerization and which also showed high degree of control in our previous works . The solubility of complexes in chlorobenzene, used as a polymerization media, decreases in the order 3 > 4 ∼ 2 > 1 .…”

Section: Resultsmentioning

confidence: 99%

Effect of ligand backbone substituents of nickel α‐diimine complexes on livingness/controllability of olefin polymerization: Competition between monomer isomerization and propagation

Sokolohorskyj

Mundil

Lederer

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Four a-diimine nickel complexes [(ArAN@C(R)A C(R)@NAAr)NiBr 2 ; R@H, CH 3 , cyclohexane-1,2-diyl, naphthalene-1,8-diyl, Ar@2,6-i-Pr 2 -C 6 H 3 -) were investigated in propene and hex-1-ene polymerization to identify the limits of backbone substituent R size needed to provide living/controlled a-olefins polymerization by the sufficient suppression of b-H elimination transfer. Propagation kinetics measurements, molar mass on monomer conversion dependencies and reinitiation tests were used to evaluate the livingness of hex-1-ene polymerization. Interestingly, living/controlled hex-1-ene polymerization was observed in the case of all diimine derivatives including the one bearing only hydrogen atom in backbone positions.Unexpectedly, in the case of catalysts bearing H and CH 3 backbone substituents, we observed the unusual isomerization of hex-1-ene into internal hexenes in parallel with its polymerization. Nevertheless, by subtracting the amount of monomer consumed in isomerization side reaction, polymerization still keeps the features of living/controlled process. V C 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3193-3202

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Living/controlled hex-1-ene polymerization initiated by nickel diimine complexes activated by non-MAO cocatalysts: Kinetic and UV–vis study

Cited by 30 publications

References 30 publications

Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et₂AlCl

Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et₂AlCl

New nickel(II) diimine complexes bearing phenyl and sec‐phenethyl groups: synthesis, characterization and ethylene polymerization behaviour

Effect of ligand backbone substituents of nickel α‐diimine complexes on livingness/controllability of olefin polymerization: Competition between monomer isomerization and propagation

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Living/controlled hex-1-ene polymerization initiated by nickel diimine complexes activated by non-MAO cocatalysts: Kinetic and UV–vis study

Cited by 30 publications

References 30 publications

Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et2AlCl

Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et2AlCl

New nickel(II) diimine complexes bearing phenyl and sec‐phenethyl groups: synthesis, characterization and ethylene polymerization behaviour

Effect of ligand backbone substituents of nickel α‐diimine complexes on livingness/controllability of olefin polymerization: Competition between monomer isomerization and propagation

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Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et₂AlCl

Nonconjugated diene homopolymerization and copolymerization with ethylene catalyzed by α‐diimine Ni(II) complex/Et₂AlCl