Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity Ratios
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Jana Herzberger
- Daniel Leibig
- Johannes C Liermann
- Holger Frey
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000388161100004&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1021/acsmacrolett.6b00701
- Externe Identifier
- Clarivate Analytics Document Solution ID: EC5GJ
- PubMed Identifier: 35614746
- ISSN
- 2161-1653
- Ausgabe der Veröffentlichung
- 11
- Zeitschrift
- ACS MACRO LETTERS
- Paginierung
- 1206 - 1211
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Titel
- Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity Ratios
- Sub types
- Article
- Ausgabe der Zeitschrift
- 5
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Autoren
- Jana Herzberger
- Daniel Leibig
- Johannes C Liermann
- Holger Frey
- DOI
- 10.1021/acsmacrolett.6b00701
- eISSN
- 2161-1653
- ISSN
- 2161-1653
- Ausgabe der Veröffentlichung
- 11
- Zeitschrift
- ACS Macro Letters
- Sprache
- en
- Online publication date
- 2016
- Paginierung
- 1206 - 1211
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Herausgeber
- American Chemical Society (ACS)
- Herausgeber URL
- http://dx.doi.org/10.1021/acsmacrolett.6b00701
- Datum der Datenerfassung
- 2023
- Titel
- Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity Ratios
- Ausgabe der Zeitschrift
- 5
Datenquelle: Crossref
- Abstract
- Detailed understanding of the monomer distribution in copolymers is essential to tailor their properties. For the first time, we have been able to utilize in situ <sup>1</sup>H NMR spectroscopy to monitor the monomer-activated anionic ring opening copolymerization (AROP) of ethylene oxide (EO) with a glycidyl ether comonomer, namely, ethoxy ethyl glycidyl ether (EEGE). We determine reactivity ratios and draw a direct comparison to conventional oxyanionic ROP. Surprisingly, the respective monomer reactivities differ strongly between the different types of AROP. Under conventional oxyanionic conditions similar monomer reactivities of EO and EEGE are observed, leading to random structures (<i>r</i><sub>EO</sub> = 1.05 ± 0.02, <i>r</i><sub>EEGE</sub> = 0.94 ± 0.02). Addition of a cation complexing agent (18-crown-6) showed no influence on the relative reactivity of EO and EEGE (<i>r</i><sub>EO</sub> = <i>r</i><sub>EEGE</sub> = 1.00 ± 0.02). In striking contrast, monomer-activated AROP produces very different monomer reactivities, affording strongly tapered copolymer structures (<i>r</i><sub>EO</sub> = 8.00 ± 0.16, <i>r</i><sub>EEGE</sub> = 0.125 ± 0.003). These results highlight the importance of understanding reactivity ratios of comonomer pairs under certain polymerization conditions, at the same time demonstrating the ability to generate both random and strongly tapered P(EO-<i>co</i>-EEGE) polyethers by simple one-pot statistical anionic copolymerization. These observations may be generally valid for the copolymerization of EO and glycidyl ethers.
- Addresses
- Institute of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, D-55128 Mainz, Germany.
- Autoren
- Jana Herzberger
- Daniel Leibig
- Johannes C Liermann
- Holger Frey
- DOI
- 10.1021/acsmacrolett.6b00701
- eISSN
- 2161-1653
- Externe Identifier
- PubMed Identifier: 35614746
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: GSC 266
- Open access
- false
- ISSN
- 2161-1653
- Ausgabe der Veröffentlichung
- 11
- Zeitschrift
- ACS macro letters
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2016
- Paginierung
- 1206 - 1211
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Datum der Datenerfassung
- 2022
- Titel
- Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity Ratios.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 5
Datenquelle: Europe PubMed Central
- Abstract
- Detailed understanding of the monomer distribution in copolymers is essential to tailor their properties. For the first time, we have been able to utilize in situ 1H NMR spectroscopy to monitor the monomer-activated anionic ring opening copolymerization (AROP) of ethylene oxide (EO) with a glycidyl ether comonomer, namely, ethoxy ethyl glycidyl ether (EEGE). We determine reactivity ratios and draw a direct comparison to conventional oxyanionic ROP. Surprisingly, the respective monomer reactivities differ strongly between the different types of AROP. Under conventional oxyanionic conditions similar monomer reactivities of EO and EEGE are observed, leading to random structures (rEO = 1.05 ± 0.02, rEEGE = 0.94 ± 0.02). Addition of a cation complexing agent (18-crown-6) showed no influence on the relative reactivity of EO and EEGE (rEO = rEEGE = 1.00 ± 0.02). In striking contrast, monomer-activated AROP produces very different monomer reactivities, affording strongly tapered copolymer structures (rEO = 8.00 ± 0.16, rEEGE = 0.125 ± 0.003). These results highlight the importance of understanding reactivity ratios of comonomer pairs under certain polymerization conditions, at the same time demonstrating the ability to generate both random and strongly tapered P(EO-co-EEGE) polyethers by simple one-pot statistical anionic copolymerization. These observations may be generally valid for the copolymerization of EO and glycidyl ethers.
- Autoren
- Jana Herzberger
- Daniel Leibig
- Johannes C Liermann
- Holger Frey
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/35614746
- DOI
- 10.1021/acsmacrolett.6b00701
- eISSN
- 2161-1653
- Ausgabe der Veröffentlichung
- 11
- Zeitschrift
- ACS Macro Lett
- Sprache
- eng
- Country
- United States
- Paginierung
- 1206 - 1211
- Datum der Veröffentlichung
- 2016
- Status
- Published
- Titel
- Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity Ratios.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 5
Datenquelle: PubMed
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