High polymerization of methyl methacrylate with organonickel/MMAO systems

Ihara, Eiji; Fujimura, Takenori; Yasuda, Hajime; Maruo, Tatsuya; Kanehisa, Nobuko

doi:10.1002/1099-0518(200012)38:1+<4764::aid-pola150>3.3.co;2-2

Cited by 8 publications

(9 citation statements)

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“…Recently, we reported1 that Ziegler–Natta‐type catalytic systems on the basis of the sterically hindered bis(salicylaldiminate)nickel(II) complex ( I ) (Chart ) and methylaluminoxane (MAO) are able to homopolymerize methyl methacrylate (MMA) affording high‐molecular‐weight poly(methyl methacrylate)s (PMMAs) with a relevant productivity (up to 70,000 g of polymer/mol Ni × h), much better than that previously obtained with other nickel catalysts, particularly bis(acetylacetonate)nickel/MAO systems 2–7…”

Section: Introductionmentioning

confidence: 93%

Homopolymerization of methyl methacrylate by novel salicylaldiminate‐nickel/methylaluminoxane catalysts obtained by oxidative addition of the chelate ligand to a nickel(0) precursor

Carlini

Martinelli

Galletti

et al. 2003

J. Polym. Sci. A Polym. Chem.

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Salicylaldimine ligands, such as 5-nitro-N(2,6-diisopropylphenyl)salicylaldimine, 3,5-dinitro-N(2,6-diisopropylphenyl)salicylaldimine, and 3-phenyl-N(2,6-diisopropylphenyl) salicylaldimine were checked in the oxidative addition to bis(1,5-cyclooctadiene)nickel(0) to prepare, after activation by methylaluminoxane (MAO), novel nickel-based catalytic systems active in the polymerization of methyl methacrylate. The catalytic behavior of the aforementioned systems, in terms of activity, molecular weight, and polydispersity of the resulting poly(methyl methacrylate) as well as its stereoregularity degree, was investigated as a function of the Al/Ni molar ratio, reaction temperature, and nature of the salicylaldimine ligand. The effect of ethylene atmosphere present during the preparation of the catalyst precursors was also investigated. The results are discussed and compared with those previously obtained by bis(salicylaldiminate)nickel(II)MAO catalytic systems. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1716-1724, 2003

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Section: Introductionmentioning

confidence: 93%

Homopolymerization of methyl methacrylate by novel salicylaldiminate‐nickel/methylaluminoxane catalysts obtained by oxidative addition of the chelate ligand to a nickel(0) precursor

Carlini

Martinelli

Galletti

et al. 2003

J. Polym. Sci. A Polym. Chem.

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“…A series of nickel(II) complexes bearing N,O-chelate ligand activation with MAO for MMA polymerization yield PMMA with rich syndiotacticity microstructure . Yasuda reported that a series of organo-nickel complexes activated with MMAO exhibited high catalytic activity for the polymerization of MMA . The Ni(acac) 2 /MAO catalyst system was found to be an effective catalyst for the polymerization of MMA. , Kim et al reported that late transition metal complexes such as (α-diimine)nickel, (pyridyl bisimine)iron(II), and (pyridyl bisimine)cobalt(II) complexes activated with MAO can polymerize MMA and obtained syndiotactic-rich PMMA.…”

Section: Introductionmentioning

confidence: 99%

Binuclear Nickel and Copper Complexes with Bridging 2,5-Diamino-1,4-benzoquinonediimines: Synthesis, Structures, and Catalytic Olefin Polymerization

et al. 2007

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A series of binuclear, divalent nickel and copper acetylacetonato complexes of the type [M(acac)-{µ-C 6 H 2 (dNAr) 4 }M(acac)] (M ) Ni, Cu) have been synthesized by reaction of the corresponding M(acac) 2 precursor with various bulky steric hindrace π-acceptor N-substituted 2,5-diamino-1,4-benzoquinonediimines C 6 H 2 (NHAr) 2 ()NAr) 2 (1a, Ar ) 4-C 6 H 4 Me; 1b, Ar ) 2-C 6 H 4 Me; 1c, Ar ) 2,6-C 6 H 3 Me 2 ), which are metalated and become bridging ligands. The ligands and complexes were determined by IR and UV-visible spectra and element analysis. Cyclic voltammetric behavior of complexes 2c and 3c has been tested. The molecular structures of the ligand 1c and the complexes [Ni(acac){µ-C 6 H 2 (dN(4-methyl-Ph)) 4 }Ni(acac)]) (2a), [Ni(acac){µ-C 6 H 2 (dN(2,6-dimethyl-Ph)) 4 }Ni(acac)]) (2c), and [Cu(acac)-{µ-6 H 2 (dN(2,6-dimethyl-Ph)) 4 }Cu(acac)]) (3c) have been determined by X-ray diffraction. The coordination geometry around the metal ions of the Ni and Cu complexes is square-planar, and a complete electronic delocalization of the quinonoid π-system occurs between the metal centers over the two NdC-CdCdN halves of the ligand. In the presence of MAO as cocatalyst, all the Ni complexes exhibited high activities both for addition polymerization of norbornene and for methyl methacrylate (MMA) polymerization, which produce syndiotactic-rich poly(methyl methacrylate) (PMMA) with broad molecular weight distribution; however, the Cu complexes show moderate activities for norbornene polymerization and are inactive for MMA polymerization.

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“…Recently, we reported1 that catalytic systems obtained from a sterically hindered bis[ N (2,6‐diisopropylphenyl)salicylaldiminate]nickel(II) complex ( I ; Chart ) and methylaluminoxane (MAO) were active in the polymerization of methyl methacrylate (MMA), affording high molecular weight poly(methyl methacrylate) (PMMA) with a relevant productivity [up to 70,000 g of polymer/(mol of Ni × h)] much better than that previously achieved with other nickel catalysts, particularly the bis(acetylacetonate)nickel/MAO system 2–7. Moreover, contrary to what was observed for these last catalysts, which gave substantially atactic polymers in the absence of any ancillary ligands, I /MAO catalysts afforded at room temperature PMMAs with a prevalent syndiotacticity (up to 80% of rr triads) 1…”

Section: Introductionmentioning

confidence: 99%

Highly active methyl methacrylate polymerization catalysts obtained from bis(3,5‐dinitro‐salicylaldiminate)nickel(II) complexes and methylaluminoxane

Carlini

Martinelli

Galletti

et al. 2003

J. Polym. Sci. A Polym. Chem.

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The homopolymerization of methyl methacrylate was investigated with bis(salicylaldiminate)nickel(II) complexes, such as bis [3,5-dinitro-N(2,6-diisopropylphenyl)salicylaldiminate]nickel(II) (IIIa) and bis[3,5-dinitro-N(phenyl)salicylaldiminate]nickel(II) (IIIb), and with methylaluminoxane (MAO) as an activator. In particular, the effect of the Al/Ni molar ratio on the catalytic activity and on the properties of the resulting poly(methyl methacrylate) (PMMA) was checked. The maximum activity was ascertained when an Al/Ni molar ratio equal to about 100 was used. However, the productivity of the catalytic systems was rather low. When the IIIa/MAO catalytic system was prepared under an ethylene atmosphere, an extremely high activity was observed, a productivity value of up to around 150,000 g of PMMA/(mol of Ni ϫ h) being obtained, the highest ever found with nickel-based catalysts. No appreciable presence of ethylene counits in the polymeric products was also ascertained. When the IIIb/MAO system was used, similar results were found, and high molecular weight PMMAs were obtained, despite the absence of bulky isopropyl substituents in positions ortho and orthoЈ to the N-aryl moiety of the salicylaldiminate ligand.

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High polymerization of methyl methacrylate with organonickel/MMAO systems

Cited by 8 publications

References 0 publications

Homopolymerization of methyl methacrylate by novel salicylaldiminate‐nickel/methylaluminoxane catalysts obtained by oxidative addition of the chelate ligand to a nickel(0) precursor

Homopolymerization of methyl methacrylate by novel salicylaldiminate‐nickel/methylaluminoxane catalysts obtained by oxidative addition of the chelate ligand to a nickel(0) precursor

Binuclear Nickel and Copper Complexes with Bridging 2,5-Diamino-1,4-benzoquinonediimines: Synthesis, Structures, and Catalytic Olefin Polymerization

Highly active methyl methacrylate polymerization catalysts obtained from bis(3,5‐dinitro‐salicylaldiminate)nickel(II) complexes and methylaluminoxane

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