Towards polyethylene-based materials with non-alternatively incorporated carbon monoxide monomer

The synthesis of ethylene/carbon monoxide copolymers (polyketones) was pursued via insertion polymerization methods through palladium(II) and nickel(II) catalysis. Specifically, phosphine sulfonate palladium(II) precatalysts derived from the in situ complexation of palladium(II) acetate and phosphine sulfonate, were found to facilitate the copolymerization of ethylene and carbon monoxide, typically yielding polyketones with a CO composition ranging from 40 – 50 mol%. Well-defined (phosphine sulfonate)Pd(II)Me precatalysts, on the other hand, typically resulted in nearly alternating (~ 50 mol% CO) polyketones. Alternatives synthetic routes toward polyketones via the ring-opening metathesis copolymerization (ROMP) of 3-cyclopentanone with 1,5-cyclooctadiene followed by olefin hydrogenation were also pursued. Five new κ2-[phosphine-(di)phenolate]Ni(II)Me complexes with either mono- or trinuclear structures were also synthesized, characterized, and utilized in the catalytic (co)polymerization of ethylene. These complexes were accessed from the complexation of (TMEDA)NiMe2 (N,N,N′,N′-tetramethylethylenediamine nickel(II) dimethyl) with either a BINOL (1,1′-bi-2-naphthol)-based phosphine diphenol (P,O) ligand or an analogous ligand which features an ethyl ether in place of the nonortho phenol. All complexes were active for ethylene homopolymerization (featuring activity up to 81.3 × 105 g polymer × mol Ni–1 × hr–1 and Mn up to 4.2 kg/mol) and ethylene/methyl acrylate (MA) copolymerization (MAmol % up to 8.3%). Moreover, three of the five complexes were shown to be active for ethylene/carbon monoxide copolymerization, yielding up to 4.8 mol% CO copolymers.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois Urbana-Champaign

Year dc:date

2025

Author dc:creator

• Pineda-Knauseder, Alfons Jose

Contributors dc:contributor

• Guironnet, Damien S.
• Mirica, Liviu M.
• Olshansky, Lisa
• Snyder, Benjamin E.R.

• organometallics
• catalysis
• polyketone
• nickel
• palladium
• coordination polymerization
• polymerization
• copolymerization
• ethylene/carbon monoxide copolymer

Statement dc:rights

• Copyright 2025 Alfons Pineda-Knauseder

Language dc:language

en

Handle dc:identifier

https://hdl.handle.net/2142/132467

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/132467