Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular Weight Long-Chain Branched Polyethylenes

Dongxu Shu; Aidan R. Mouat; Casey J. Stephenson; Anna M. Invergo; Massimiliano Delferro; Tobin J. Marks

doi:10.1021/acsmacrolett.5b00781

Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular Weight Long-Chain Branched Polyethylenes

Dongxu Shu, Aidan R. Mouat, Casey J. Stephenson, Anna M. Invergo, Massimiliano Delferro^*, Tobin J. Marks

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

An unsymmetrical bimetallic catalyst, (CF₃/SO₂)FI²-Ni₂, having a CF₃-functionalized phenoxyiminato Ni(II) center, which produces linear high-M_w polyolefin (CF₃/Ni) joined to an adjacent SO₂-functionalized phenoxyiminato Ni(II) center, which produces highly branched low-M_w polyolefin (SO₂/Ni), was synthesized and fully characterized. In ethylene homopolymerizations, (CF₃/SO₂)FI²-Ni₂ affords monomodal (D = 1.7), highly, long-chain branched (69 branches/1000 C) polyethylenes with M_w = 24 kg/mol. In contrast, bimetallic (CF₃)FI²-Ni₂ and (SO₂)FI²-Ni₂ produce high-M_w (25 kg/mol) exclusively methyl-branched (40 branches/1000 C) and low-M_w (4.5 kg/mol) highly branched (105 branches/1000 C) polyethylenes, respectively, while tandem monometallic (CF₃)FI-Ni + (SO₂)FI-Ni catalyst mixtures yield a bimodal polyolefin mixture (D = 6.4).

Original language	English (US)
Pages (from-to)	1297-1301
Number of pages	5
Journal	ACS Macro Letters
Volume	4
Issue number	11
DOIs	https://doi.org/10.1021/acsmacrolett.5b00781
State	Published - Nov 6 2015

ASJC Scopus subject areas

Materials Chemistry
Polymers and Plastics
Inorganic Chemistry
Organic Chemistry

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10.1021/acsmacrolett.5b00781

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title = "Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular Weight Long-Chain Branched Polyethylenes",

abstract = "An unsymmetrical bimetallic catalyst, (CF3/SO2)FI2-Ni2, having a CF3-functionalized phenoxyiminato Ni(II) center, which produces linear high-Mw polyolefin (CF3/Ni) joined to an adjacent SO2-functionalized phenoxyiminato Ni(II) center, which produces highly branched low-Mw polyolefin (SO2/Ni), was synthesized and fully characterized. In ethylene homopolymerizations, (CF3/SO2)FI2-Ni2 affords monomodal (D = 1.7), highly, long-chain branched (69 branches/1000 C) polyethylenes with Mw = 24 kg/mol. In contrast, bimetallic (CF3)FI2-Ni2 and (SO2)FI2-Ni2 produce high-Mw (25 kg/mol) exclusively methyl-branched (40 branches/1000 C) and low-Mw (4.5 kg/mol) highly branched (105 branches/1000 C) polyethylenes, respectively, while tandem monometallic (CF3)FI-Ni + (SO2)FI-Ni catalyst mixtures yield a bimodal polyolefin mixture (D = 6.4).",

author = "Dongxu Shu and Mouat, {Aidan R.} and Stephenson, {Casey J.} and Invergo, {Anna M.} and Massimiliano Delferro and Marks, {Tobin J.}",

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doi = "10.1021/acsmacrolett.5b00781",

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AU - Shu, Dongxu

AU - Mouat, Aidan R.

AU - Stephenson, Casey J.

AU - Invergo, Anna M.

AU - Delferro, Massimiliano

AU - Marks, Tobin J.

PY - 2015/11/6

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N2 - An unsymmetrical bimetallic catalyst, (CF3/SO2)FI2-Ni2, having a CF3-functionalized phenoxyiminato Ni(II) center, which produces linear high-Mw polyolefin (CF3/Ni) joined to an adjacent SO2-functionalized phenoxyiminato Ni(II) center, which produces highly branched low-Mw polyolefin (SO2/Ni), was synthesized and fully characterized. In ethylene homopolymerizations, (CF3/SO2)FI2-Ni2 affords monomodal (D = 1.7), highly, long-chain branched (69 branches/1000 C) polyethylenes with Mw = 24 kg/mol. In contrast, bimetallic (CF3)FI2-Ni2 and (SO2)FI2-Ni2 produce high-Mw (25 kg/mol) exclusively methyl-branched (40 branches/1000 C) and low-Mw (4.5 kg/mol) highly branched (105 branches/1000 C) polyethylenes, respectively, while tandem monometallic (CF3)FI-Ni + (SO2)FI-Ni catalyst mixtures yield a bimodal polyolefin mixture (D = 6.4).

AB - An unsymmetrical bimetallic catalyst, (CF3/SO2)FI2-Ni2, having a CF3-functionalized phenoxyiminato Ni(II) center, which produces linear high-Mw polyolefin (CF3/Ni) joined to an adjacent SO2-functionalized phenoxyiminato Ni(II) center, which produces highly branched low-Mw polyolefin (SO2/Ni), was synthesized and fully characterized. In ethylene homopolymerizations, (CF3/SO2)FI2-Ni2 affords monomodal (D = 1.7), highly, long-chain branched (69 branches/1000 C) polyethylenes with Mw = 24 kg/mol. In contrast, bimetallic (CF3)FI2-Ni2 and (SO2)FI2-Ni2 produce high-Mw (25 kg/mol) exclusively methyl-branched (40 branches/1000 C) and low-Mw (4.5 kg/mol) highly branched (105 branches/1000 C) polyethylenes, respectively, while tandem monometallic (CF3)FI-Ni + (SO2)FI-Ni catalyst mixtures yield a bimodal polyolefin mixture (D = 6.4).

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Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular Weight Long-Chain Branched Polyethylenes

Abstract

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CCDC 1443070: Experimental Crystal Structure Determination

CCDC 1443072: Experimental Crystal Structure Determination

CCDC 1443068: Experimental Crystal Structure Determination

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Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular Weight Long-Chain Branched Polyethylenes

Abstract

ASJC Scopus subject areas

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Datasets

CCDC 1443070: Experimental Crystal Structure Determination

CCDC 1443072: Experimental Crystal Structure Determination

CCDC 1443068: Experimental Crystal Structure Determination

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