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

Chemical Engineering and Materials Science

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

30 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

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© 2015 American Chemical Society.

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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.\}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

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doi = "10.1021/acsmacrolett.5b00781",

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T1 - Ligand-Unsymmetrical Phenoxyiminato Dinickel Catalyst for High Molecular Weight Long-Chain Branched Polyethylenes

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

Y1 - 2015/11/6

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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ER -

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

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