Nanocrystal Formation in Aqueous Insertion Polymerization

Lade...
Vorschaubild
Dateien
Godin_0-409000.pdf
Godin_0-409000.pdfGröße: 5.14 MBDownloads: 441
Datum
2016
Herausgeber:innen
Kontakt
ISSN der Zeitschrift
Electronic ISSN
ISBN
Bibliografische Daten
Verlag
Schriftenreihe
Auflagebezeichnung
ArXiv-ID
Internationale Patentnummer
Angaben zur Forschungsförderung
Projekt
Open Access-Veröffentlichung
Open Access Hybrid
Sammlungen
Core Facility der Universität Konstanz
Gesperrt bis
Titel in einer weiteren Sprache
Forschungsvorhaben
Organisationseinheiten
Zeitschriftenheft
Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published
Erschienen in
Macromolecules. 2016, 49(23), pp. 8825-8837. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.6b01974
Zusammenfassung

High molecular weight linear polyethylene, in the form of 7 nm thin single-lamella nanocrystals with a diameter of up to 200 nm, is generated via aqueous catalytic polymerization using the water-soluble catalyst precursor [κ2-N,O-{2,6-(3′,5′-(F3C)2C6H3)2C6H3-N═C(H)-(3,5-I2-2-O-C6H2)}NiCH3{P(3-C6H4SO3Na)3}] (1-TPPTS). Studies under true pressure reactor conditions using a 13C-labeled catalyst precursor 1-13C-TPPTS show that in the first 30 s, 21–28% of the catalyst precursor initiates polymer chains. Catalyst deactivation occurs preferentially by hydrolysis, resulting in the formation of fully saturated polyethylene chains. The catalyst lifetime can be extended for more than 10 h upon addition of weakly coordinating compounds like N,N-dimethylformamide. Alternatively, at strongly basic conditions (pH 12.5) nanoparticle dispersions consisting of polyethylene with molecular weight of up to Mn = 7 × 105 g mol–1 and Mw/Mn = 1.2 are accessible after 60 min polymerization time. “Living”-type polymerization also can be performed by substituting water with deuterium oxide as the reaction medium. Here, catalyst lifetimes of more than 24 h are observed, and dispersions with more than 20 wt % nanocrystals are accessible at turnover frequencies (TOF) of ∼4000 ethylene (catalyst precursor)−1 h–1. A pressurizable sampling chamber was used to draw samples at high pressure and enabled the in-depth analysis and monitoring of the polymerization reaction and the particle formation in a time range of 30 s–24 h. It was shown that under most reaction conditions studied each nickel center produces one single-chain polyethylene particle, and the diameter of the resulting nanoplatelet is determined by the molecular weight of the polyethylene chain.

Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
540 Chemie
Schlagwörter
Konferenz
Rezension
undefined / . - undefined, undefined
Zitieren
ISO 690GODIN, Alexandra, Inigo GÖTTKER-SCHNETMANN, Stefan MECKING, 2016. Nanocrystal Formation in Aqueous Insertion Polymerization. In: Macromolecules. 2016, 49(23), pp. 8825-8837. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.6b01974
BibTex
@article{Godin2016-12-13Nanoc-39104,
  year={2016},
  doi={10.1021/acs.macromol.6b01974},
  title={Nanocrystal Formation in Aqueous Insertion Polymerization},
  number={23},
  volume={49},
  issn={0024-9297},
  journal={Macromolecules},
  pages={8825--8837},
  author={Godin, Alexandra and Göttker-Schnetmann, Inigo and Mecking, Stefan}
}
RDF
<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/39104">
    <dc:contributor>Mecking, Stefan</dc:contributor>
    <dcterms:issued>2016-12-13</dcterms:issued>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/39104/1/Godin_0-409000.pdf"/>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/39104/1/Godin_0-409000.pdf"/>
    <dcterms:abstract xml:lang="eng">High molecular weight linear polyethylene, in the form of 7 nm thin single-lamella nanocrystals with a diameter of up to 200 nm, is generated via aqueous catalytic polymerization using the water-soluble catalyst precursor [κ2-N,O-{2,6-(3′,5′-(F3C)2C6H3)2C6H3-N═C(H)-(3,5-I2-2-O-C6H2)}NiCH3{P(3-C6H4SO3Na)3}] (1-TPPTS). Studies under true pressure reactor conditions using a 13C-labeled catalyst precursor 1-13C-TPPTS show that in the first 30 s, 21–28% of the catalyst precursor initiates polymer chains. Catalyst deactivation occurs preferentially by hydrolysis, resulting in the formation of fully saturated polyethylene chains. The catalyst lifetime can be extended for more than 10 h upon addition of weakly coordinating compounds like N,N-dimethylformamide. Alternatively, at strongly basic conditions (pH 12.5) nanoparticle dispersions consisting of polyethylene with molecular weight of up to Mn = 7 × 105 g mol–1 and Mw/Mn = 1.2 are accessible after 60 min polymerization time. “Living”-type polymerization also can be performed by substituting water with deuterium oxide as the reaction medium. Here, catalyst lifetimes of more than 24 h are observed, and dispersions with more than 20 wt % nanocrystals are accessible at turnover frequencies (TOF) of ∼4000 ethylene (catalyst precursor)−1 h–1. A pressurizable sampling chamber was used to draw samples at high pressure and enabled the in-depth analysis and monitoring of the polymerization reaction and the particle formation in a time range of 30 s–24 h. It was shown that under most reaction conditions studied each nickel center produces one single-chain polyethylene particle, and the diameter of the resulting nanoplatelet is determined by the molecular weight of the polyethylene chain.</dcterms:abstract>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2017-06-01T09:41:28Z</dc:date>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:creator>Göttker-Schnetmann, Inigo</dc:creator>
    <dc:rights>terms-of-use</dc:rights>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2017-06-01T09:41:28Z</dcterms:available>
    <dc:creator>Godin, Alexandra</dc:creator>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:language>eng</dc:language>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dcterms:title>Nanocrystal Formation in Aqueous Insertion Polymerization</dcterms:title>
    <dc:creator>Mecking, Stefan</dc:creator>
    <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/39104"/>
    <dc:contributor>Godin, Alexandra</dc:contributor>
    <dc:contributor>Göttker-Schnetmann, Inigo</dc:contributor>
  </rdf:Description>
</rdf:RDF>
Interner Vermerk
xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter
Kontakt
URL der Originalveröffentl.
Prüfdatum der URL
Prüfungsdatum der Dissertation
Finanzierungsart
Kommentar zur Publikation
Allianzlizenz
Corresponding Authors der Uni Konstanz vorhanden
Internationale Co-Autor:innen
Universitätsbibliographie
Ja
Begutachtet
Diese Publikation teilen