Ring opening metathesis polymerization (ROMP) of five- to eight-membered cyclic olefins

Computational, thermodynamic, and experimental approach

Antsar R. Hlil, Janos Balogh, Salvador Moncho Escriva, Haw Lih Su, Robert Tuba, Edward Brothers, Mohammed Al-Hashimi, Hassan S. Bazzi

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Ring opening metathesis polymerization (ROMP) of a series of low-strain cyclic olefins and their hydroxyl derivatives using second generation Hoveyda–Grubbs catalyst has been investigated. Additionally, density functional theory (DFT) calculations were performed to evaluate the ring strain energies of the cyclic olefins and their hydroxyl derivatives, coupled with kinetic studies for the ROMP reactions. It was found that among different ring size monomers, Cy8 having a relatively moderate ring strain energy in comparison with the other cyclic olefins, exhibited the highest monomer conversion. The effect of temperature (0, 10, 15, and 25 °C) and monomer concentration (1 M; 2.5 M and 5 M for Cy5; and 1 M and 5 M for Cy7) for the cyclic olefins Cy5 and Cy7 were investigated. In general, the experimental results for the kinetic ROMP studies obtained using complex HG2 correlate really well with the DFT calculations determined for the ring strain energies of the cyclic olefins. For comparison, DFT calculations predicted the following trend for the ring strain energies Cy8 > Cy5 > Cy7 > Cy6, and the polymerizations carried out experimentally followed the same trend in terms of monomer conversion, with the exception of Cy5 and Cy7 at lower concentrations, which followed this trend Cy8 > Cy7 > Cy5 > Cy6.

Original languageEnglish
Pages (from-to)3137-3145
Number of pages9
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume55
Issue number18
DOIs
Publication statusPublished - 15 Sep 2017

Fingerprint

Cycloparaffins
Ring opening polymerization
Olefins
Strain energy
Thermodynamics
Monomers
Density functional theory
Hydroxyl Radical
Derivatives
Kinetics
Polymerization
cyanine dye 5
Catalysts

Keywords

  • catalysis
  • cyclic olefins
  • metathesis
  • ROMP
  • ruthenium catalyst

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

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title = "Ring opening metathesis polymerization (ROMP) of five- to eight-membered cyclic olefins: Computational, thermodynamic, and experimental approach",
abstract = "Ring opening metathesis polymerization (ROMP) of a series of low-strain cyclic olefins and their hydroxyl derivatives using second generation Hoveyda–Grubbs catalyst has been investigated. Additionally, density functional theory (DFT) calculations were performed to evaluate the ring strain energies of the cyclic olefins and their hydroxyl derivatives, coupled with kinetic studies for the ROMP reactions. It was found that among different ring size monomers, Cy8 having a relatively moderate ring strain energy in comparison with the other cyclic olefins, exhibited the highest monomer conversion. The effect of temperature (0, 10, 15, and 25 °C) and monomer concentration (1 M; 2.5 M and 5 M for Cy5; and 1 M and 5 M for Cy7) for the cyclic olefins Cy5 and Cy7 were investigated. In general, the experimental results for the kinetic ROMP studies obtained using complex HG2 correlate really well with the DFT calculations determined for the ring strain energies of the cyclic olefins. For comparison, DFT calculations predicted the following trend for the ring strain energies Cy8 > Cy5 > Cy7 > Cy6, and the polymerizations carried out experimentally followed the same trend in terms of monomer conversion, with the exception of Cy5 and Cy7 at lower concentrations, which followed this trend Cy8 > Cy7 > Cy5 > Cy6.",
keywords = "catalysis, cyclic olefins, metathesis, ROMP, ruthenium catalyst",
author = "Hlil, {Antsar R.} and Janos Balogh and {Moncho Escriva}, Salvador and Su, {Haw Lih} and Robert Tuba and Edward Brothers and Mohammed Al-Hashimi and Bazzi, {Hassan S.}",
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TY - JOUR

T1 - Ring opening metathesis polymerization (ROMP) of five- to eight-membered cyclic olefins

T2 - Computational, thermodynamic, and experimental approach

AU - Hlil, Antsar R.

AU - Balogh, Janos

AU - Moncho Escriva, Salvador

AU - Su, Haw Lih

AU - Tuba, Robert

AU - Brothers, Edward

AU - Al-Hashimi, Mohammed

AU - Bazzi, Hassan S.

PY - 2017/9/15

Y1 - 2017/9/15

N2 - Ring opening metathesis polymerization (ROMP) of a series of low-strain cyclic olefins and their hydroxyl derivatives using second generation Hoveyda–Grubbs catalyst has been investigated. Additionally, density functional theory (DFT) calculations were performed to evaluate the ring strain energies of the cyclic olefins and their hydroxyl derivatives, coupled with kinetic studies for the ROMP reactions. It was found that among different ring size monomers, Cy8 having a relatively moderate ring strain energy in comparison with the other cyclic olefins, exhibited the highest monomer conversion. The effect of temperature (0, 10, 15, and 25 °C) and monomer concentration (1 M; 2.5 M and 5 M for Cy5; and 1 M and 5 M for Cy7) for the cyclic olefins Cy5 and Cy7 were investigated. In general, the experimental results for the kinetic ROMP studies obtained using complex HG2 correlate really well with the DFT calculations determined for the ring strain energies of the cyclic olefins. For comparison, DFT calculations predicted the following trend for the ring strain energies Cy8 > Cy5 > Cy7 > Cy6, and the polymerizations carried out experimentally followed the same trend in terms of monomer conversion, with the exception of Cy5 and Cy7 at lower concentrations, which followed this trend Cy8 > Cy7 > Cy5 > Cy6.

AB - Ring opening metathesis polymerization (ROMP) of a series of low-strain cyclic olefins and their hydroxyl derivatives using second generation Hoveyda–Grubbs catalyst has been investigated. Additionally, density functional theory (DFT) calculations were performed to evaluate the ring strain energies of the cyclic olefins and their hydroxyl derivatives, coupled with kinetic studies for the ROMP reactions. It was found that among different ring size monomers, Cy8 having a relatively moderate ring strain energy in comparison with the other cyclic olefins, exhibited the highest monomer conversion. The effect of temperature (0, 10, 15, and 25 °C) and monomer concentration (1 M; 2.5 M and 5 M for Cy5; and 1 M and 5 M for Cy7) for the cyclic olefins Cy5 and Cy7 were investigated. In general, the experimental results for the kinetic ROMP studies obtained using complex HG2 correlate really well with the DFT calculations determined for the ring strain energies of the cyclic olefins. For comparison, DFT calculations predicted the following trend for the ring strain energies Cy8 > Cy5 > Cy7 > Cy6, and the polymerizations carried out experimentally followed the same trend in terms of monomer conversion, with the exception of Cy5 and Cy7 at lower concentrations, which followed this trend Cy8 > Cy7 > Cy5 > Cy6.

KW - catalysis

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