Mechanism of ring-opening and elimination cooligomerization of cyclic carbonates and ε-caprolactone: Formation of cyclic cooligomers

S. Kéki, János Török, G. Deák, M. Zsuga

Research output: Article

4 Citations (Scopus)

Abstract

The cooligomerization reactions of the comonomers ethylene carbonate-propylene carbonate, ethylene carbonate-ε-caprolactone and propylene carbonate-ε-caprolactone initiated by the p-tert-butylphenol/ KHCO3 system were investigated by means of electrospray ionization mass spectrometry combined with liquid chromatography. Three major cooligomer series were found in each case which were identified such as cooligomers with tert-butylphenol and hydroxyl headgroups. The presence of cyclic cooligomers was also unambigously observed. In addition, cooligomers carrying carbonate linkages were also identified, however, their fraction was very small compared to the cooligomer series without carbonate linkages. Besides the cooligomerization reaction, homooligomerization of ethylene and propylene carbonate was observed, as well as no linear homooligomers of ε-caprolactone were detected. Based on the LC-ESI MS results a mechanism is proposed for the formation of cyclic co-oligomers and the chain degradation of cooligomers containing carbonate linkages.

Original languageEnglish
Pages (from-to)1478-1483
Number of pages6
JournalEuropean Polymer Journal
Volume41
Issue number7
DOIs
Publication statusPublished - júl. 2005

Fingerprint

Carbonates
elimination
carbonates
rings
Electrospray ionization
propylene
Liquid chromatography
linkages
Propylene
Oligomers
Hydroxyl Radical
Ethylene
ethylene
Mass spectrometry
Degradation
propylene carbonate
ethylene carbonate
caprolactone
liquid chromatography
oligomers

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics

Cite this

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title = "Mechanism of ring-opening and elimination cooligomerization of cyclic carbonates and ε-caprolactone: Formation of cyclic cooligomers",
abstract = "The cooligomerization reactions of the comonomers ethylene carbonate-propylene carbonate, ethylene carbonate-ε-caprolactone and propylene carbonate-ε-caprolactone initiated by the p-tert-butylphenol/ KHCO3 system were investigated by means of electrospray ionization mass spectrometry combined with liquid chromatography. Three major cooligomer series were found in each case which were identified such as cooligomers with tert-butylphenol and hydroxyl headgroups. The presence of cyclic cooligomers was also unambigously observed. In addition, cooligomers carrying carbonate linkages were also identified, however, their fraction was very small compared to the cooligomer series without carbonate linkages. Besides the cooligomerization reaction, homooligomerization of ethylene and propylene carbonate was observed, as well as no linear homooligomers of ε-caprolactone were detected. Based on the LC-ESI MS results a mechanism is proposed for the formation of cyclic co-oligomers and the chain degradation of cooligomers containing carbonate linkages.",
keywords = "ε-caprolactone, Chromatography/mass spectrometry, Copolymerization, Ethylene carbonate, Macrocyclics, Propylene carbonate",
author = "S. K{\'e}ki and J{\'a}nos T{\"o}r{\"o}k and G. De{\'a}k and M. Zsuga",
year = "2005",
month = "7",
doi = "10.1016/j.eurpolymj.2005.02.010",
language = "English",
volume = "41",
pages = "1478--1483",
journal = "European Polymer Journal",
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TY - JOUR

T1 - Mechanism of ring-opening and elimination cooligomerization of cyclic carbonates and ε-caprolactone

T2 - Formation of cyclic cooligomers

AU - Kéki, S.

AU - Török, János

AU - Deák, G.

AU - Zsuga, M.

PY - 2005/7

Y1 - 2005/7

N2 - The cooligomerization reactions of the comonomers ethylene carbonate-propylene carbonate, ethylene carbonate-ε-caprolactone and propylene carbonate-ε-caprolactone initiated by the p-tert-butylphenol/ KHCO3 system were investigated by means of electrospray ionization mass spectrometry combined with liquid chromatography. Three major cooligomer series were found in each case which were identified such as cooligomers with tert-butylphenol and hydroxyl headgroups. The presence of cyclic cooligomers was also unambigously observed. In addition, cooligomers carrying carbonate linkages were also identified, however, their fraction was very small compared to the cooligomer series without carbonate linkages. Besides the cooligomerization reaction, homooligomerization of ethylene and propylene carbonate was observed, as well as no linear homooligomers of ε-caprolactone were detected. Based on the LC-ESI MS results a mechanism is proposed for the formation of cyclic co-oligomers and the chain degradation of cooligomers containing carbonate linkages.

AB - The cooligomerization reactions of the comonomers ethylene carbonate-propylene carbonate, ethylene carbonate-ε-caprolactone and propylene carbonate-ε-caprolactone initiated by the p-tert-butylphenol/ KHCO3 system were investigated by means of electrospray ionization mass spectrometry combined with liquid chromatography. Three major cooligomer series were found in each case which were identified such as cooligomers with tert-butylphenol and hydroxyl headgroups. The presence of cyclic cooligomers was also unambigously observed. In addition, cooligomers carrying carbonate linkages were also identified, however, their fraction was very small compared to the cooligomer series without carbonate linkages. Besides the cooligomerization reaction, homooligomerization of ethylene and propylene carbonate was observed, as well as no linear homooligomers of ε-caprolactone were detected. Based on the LC-ESI MS results a mechanism is proposed for the formation of cyclic co-oligomers and the chain degradation of cooligomers containing carbonate linkages.

KW - ε-caprolactone

KW - Chromatography/mass spectrometry

KW - Copolymerization

KW - Ethylene carbonate

KW - Macrocyclics

KW - Propylene carbonate

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