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

Pineda-Knauseder, Alfons Jose

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

Description

Title

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

Author(s)

Pineda-Knauseder, Alfons Jose

Issue Date

2025-10-03

Director of Research (if dissertation) or Advisor (if thesis)

Guironnet, Damien S.

Doctoral Committee Chair(s)

Guironnet, Damien S.

Committee Member(s)

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

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

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

Abstract

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.

Graduation Semester

2025-12

Type of Resource

Thesis

Handle URL

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

Copyright and License Information

Copyright 2025 Alfons Pineda-Knauseder

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