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|Title:||Balancing high thermal stability with high activity in diaryliminoacenaphthene-nickel(II) catalysts for ethylene polymerization|
Solan, Gregory A.
|Citation:||Journal of Polymer Science, Part A: Polymer Chemistry, 2017|
|Abstract:||The N,N-diaryliminoacenaphthenes, 1,2-[2,4-((4-FC6H4)2CH)2-6-MeC6H4N]2-C2C10H6 (L1) and 1-[2,4-((4-FC6H4)2CH)2-6-MeC6H4N]-2-(ArN)C2C10H6 (Ar=2,6-Me2C6H3 L2, 2,6-Et2C6H3 L3, 2,6-i-Pr2C6H3 L4, 2,4,6-Me3C6H2 L5, 2,6-Et2-4-MeC6H2 L6), incorporating at least one N-2,4-bis(difluoro benzhydryl)-6-methylphenyl group, have been synthesized and fully characterized. Interaction of L1-L6 with (DME)NiBr2 (DME=1,2-dimethoxyethane) generates the corresponding nickel(II) bromide N,N-chelates, LNiBr2 (1-6), in high yield. The molecular structures of 3 and 6 reveal distorted tetrahedral geometries at nickel with the ortho-substituted difluorobenzhydryl group providing enhanced steric protection to only one side of the metal center. On activation with various aluminum alkyl co-catalysts, such as methylaluminoxane (MAO) or Et2AlCl, 1-6 displayed outstanding activity toward ethylene polymerization (up to 1.02 × 107 g of PE (mol of Ni)-1 h-1). Notably 1, bearing equivalent fluorobenzhydryl-substituted N-aryl groups, was able in the presence of Et2AlCl to couple high activity with exceptional thermal stability generating high molecular weight branched polyethylenes at temperatures as high as 100 °C.|
|Embargo on file until:||13-Mar-2018|
|Rights:||Copyright © 2017, Wiley. Deposited with reference to the publisher’s open access archiving policy.|
|Description:||The file associated with this record is under embargo until 12 months after publication, in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above.|
|Appears in Collections:||Published Articles, Dept. of Chemistry|
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|revised manuscript_GAS.doc||Post-review (final submitted author manuscript)||5.7 MB||Microsoft Word||View/Open|
|revised manuscript_GAS.pdf||Post-review (final submitted author manuscript)||1.88 MB||Adobe PDF||View/Open|
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