Ethylene polymerization with imine and phosphine nickel complexes containing isothiocyanate

Crossetti, Geraldo Lopes; Dias, Marcos L.; Queiroz, Bruno T.; Silva, Luciana P.; Ziglio, Cláudio M.; Bomfim, João A. S.; Filgueiras, Carlos A. L.

doi:10.1002/aoc.633

Cited by 17 publications

(12 citation statements)

References 23 publications

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“…The Ni (II) complex was synthesized as described elsewhere [25] and manipulated under nitrogen atmosphere with standard Schlenk techniques. Ethylene (99.8%) and nitrogen (99.5%) were purchased from AGA (Rio de Janeiro, Brazil).…”

Section: Experimental Partmentioning

confidence: 99%

“…The main objective of this work is to investigate the polymerization of ethylene, based on the previous remarks, with a nickel (α‐diimine) complex activated by ethylaluminum sesquichloride (EASC). The catalyst of interest has been synthesized by one of the authors and is described in detail elsewhere [25]. Figure 1 shows the catalyst structure, as presented in the original reference (see Fig.…”

Section: Introductionmentioning

confidence: 99%

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Polymerization of ethylene by (α‐Diimine) nickel catalyst and statistical analysis of the effects of reaction conditions

Ferreira

Melo

Crossetti

et al. 2010

Polymer Engineering & Sci

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This article regards the ethylene polymerization catalyzed by a nickel catalyst and activated by ethylaluminum sesquichloride (EASC). The effects of the reaction conditions [polymerization temperature, cocatalyst (EASC) concentration, and ethylene concentration] on the average molecular weights of the final polymers and reaction yields were evaluated with the help of empirical statistical models. It is shown that reaction temperature and cocatalyst (EASC) concentration exert the most important effects on average molecular weights and catalyst activity. The polydispersities of the obtained polyethylenes are larger than the polydispersities of polyethylenes obtained with typical Brookhart catalysts. The analysis of polymer branching frequencies shows new types of short branching and significant amounts of long branches, which may explain the relatively large polydispersities of the obtained polymer samples. POLYM. ENG. SCI., 50:1797–1808, 2010. © 2010 Society of Plastics Engineers

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Section: Experimental Partmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polymerization of ethylene by (α‐Diimine) nickel catalyst and statistical analysis of the effects of reaction conditions

Ferreira

Melo

Crossetti

et al. 2010

Polymer Engineering & Sci

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“…The maximum point endotherm (heating scan) were taken as the melting temperature ( T m ). Nickel complex Ni3 were prepared according to literature procedure. Dichloromethane, toluene, THF and hexanes were purified by solvent purification systems.…”

Section: Methodsmentioning

confidence: 99%

Bulky iminophosphine‐based nickel and palladium catalysts bearing 2,6‐dibenzhydryl groups for ethylene oligo‐/polymerization

Wang

et al. 2020

Applied Organom Chemis

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A series of 2,6‐dibenzhydryl substituted bulky Ni and Pd complexes containing P,N‐chelating ligands, {[2,6‐(Ph2CH)2‐4‐R‐C6H2‐N=CH‐C6H4‐2‐PPh2]MX2; MX2 =NiBr2; R = Me (Ni1); R = F (Ni2); MX2 =PdCl2, R = Me (Pd1)}, have been prepared and used as catalyst precursors for ethylene oligo‐/polymerization. Compared to the corresponding 2,6‐diisopropyl Ni catalyst, these bulky Ni precatalysts activated by Et2AlCl exhibited excellent catalytic performance toward ethylene polymerization with activity of up to 1.90 × 105 g PE (mol Ni)−1 h−1, and result in semicrystalline PEs with high molecular weight. The catalytic performance of these bulky P,N‐type complexes was significantly improved by introducing two ortho‐dibenzhydryl on the N‐aryl substituents. However, the formation of C10–C24 oligomers were generated using their palladium catalysts through ethylene oligomerization at high temperatures.

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“…Previous results11, 14 showed that the substitution of Br by NCS in the coordination sphere of a Brookhart system, affects the catalytic activity and the amount of branches, suggesting that the nature of the species is not the same. The difference in the catalytic species was explained by considering that the active site is an ionic pair formed by the metal cation and the counterion made up by methylaluminoxane (MAO) and the abstracted ligand [DADNi(alkyl) + (MAO‐X) − ].…”

Section: Introductionmentioning

confidence: 94%

“…During the past decade, olefin polymerization/oligomerization catalysts promoted by nickel have received increasing interest. The reduced oxophilicity of Ni catalysts, and hence, their enhanced functional group tolerance make them attractive for the incorporation of polar monomers into a linear or branched polyolefin backbone, yielding polymers with unusual microstructures 10, 11. However, Marques and coworkers12, 13 using α‐diimine Ni catalysts to copolymerized ethylene with ω‐alkenols found that even with Ni catalysts it is necessary to protect the polar monomers to avoid deactivation of the active center.…”

Section: Introductionmentioning

confidence: 99%

Ethylene polymerization and copolymerization with 10‐undecen‐1‐ol using the catalyst system DADNi(NCS)₂/MAO

Carone

Crossetti

Basso

et al. 2007

J. Polym. Sci. A Polym. Chem.

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The catalyst DADNi(NCS) 2 (DAD ¼ (ArN¼ ¼C(Me)À ÀC(Me)¼ ¼ArN); Ar ¼ 2,6-C 6 H 3 ), activated by methylaluminoxane, was tested in ethylene polymerization at temperatures above 25 8C and variable Al/Ni ratio. The system was shown to be active even at 80 8C and when supported on silica. However, catalyst activity decreased.The catalyst system was also tested in ethylene and 10-undecen-1-ol copolymerization at different ethylene pressures. The best activities were obtained at low polar monomer concentration (0.017 mol/L), using triisopropylaluminum (Al-i-Pr 3 ) to protect the polar monomer. The incorporation of the comonomer increased with the increase of polar monomer concentration. According to 13 C NMR analyses, all the resulting polyethylenes were highly branched and the polar monomer incorporation decreased as ethylene pressure increased. V V C 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5199-5208, 2007

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Ethylene polymerization with imine and phosphine nickel complexes containing isothiocyanate

Cited by 17 publications

References 23 publications

Polymerization of ethylene by (α‐Diimine) nickel catalyst and statistical analysis of the effects of reaction conditions

Polymerization of ethylene by (α‐Diimine) nickel catalyst and statistical analysis of the effects of reaction conditions

Bulky iminophosphine‐based nickel and palladium catalysts bearing 2,6‐dibenzhydryl groups for ethylene oligo‐/polymerization

Ethylene polymerization and copolymerization with 10‐undecen‐1‐ol using the catalyst system DADNi(NCS)₂/MAO

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Ethylene polymerization with imine and phosphine nickel complexes containing isothiocyanate

Cited by 17 publications

References 23 publications

Polymerization of ethylene by (α‐Diimine) nickel catalyst and statistical analysis of the effects of reaction conditions

Polymerization of ethylene by (α‐Diimine) nickel catalyst and statistical analysis of the effects of reaction conditions

Bulky iminophosphine‐based nickel and palladium catalysts bearing 2,6‐dibenzhydryl groups for ethylene oligo‐/polymerization

Ethylene polymerization and copolymerization with 10‐undecen‐1‐ol using the catalyst system DADNi(NCS)2/MAO

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Ethylene polymerization and copolymerization with 10‐undecen‐1‐ol using the catalyst system DADNi(NCS)₂/MAO