Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization

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2016
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Macromolecules. 2016, 49(4), pp. 1172-1179. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.5b02749
Zusammenfassung

We report the reactivities of a comprehensive range of polar vinyl comonomers and 1-olefins in the copolymerization with ethylene by [{(o-MeOC6H4)2PC6H4SO3}PdMe(L)] from pressure reactor studies (95 °C, 3–20 bar), as defined by rE = kethylene/kcomonomer from Markov statistics. 13C NMR chemical shifts of the monomers’ β vinyl carbon atom and Charton and Sterimol parameters were found to be appropriate descriptors for the monomers’ electronic nature and steric demand, respectively. A comprehensive picture of their impact on monomer reactivity and also regioselectivity of insertion arises. This shall also allow for predictions of the reactivity of other monomers.

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ISO 690SCHUSTER, Nicole, Thomas RÜNZI, Stefan MECKING, 2016. Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization. In: Macromolecules. 2016, 49(4), pp. 1172-1179. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.5b02749
BibTex
@article{Schuster2016-02-23React-33687,
  year={2016},
  doi={10.1021/acs.macromol.5b02749},
  title={Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization},
  number={4},
  volume={49},
  issn={0024-9297},
  journal={Macromolecules},
  pages={1172--1179},
  author={Schuster, Nicole and Rünzi, Thomas and Mecking, Stefan}
}
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    <dcterms:abstract xml:lang="eng">We report the reactivities of a comprehensive range of polar vinyl comonomers and 1-olefins in the copolymerization with ethylene by [{(o-MeOC&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;PC&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;SO&lt;sub&gt;3&lt;/sub&gt;}PdMe(L)] from pressure reactor studies (95 °C, 3–20 bar), as defined by r&lt;sub&gt;E&lt;/sub&gt; = kethylene/k&lt;sub&gt;comonomer&lt;/sub&gt; from Markov statistics. 13C NMR chemical shifts of the monomers’ β vinyl carbon atom and Charton and Sterimol parameters were found to be appropriate descriptors for the monomers’ electronic nature and steric demand, respectively. A comprehensive picture of their impact on monomer reactivity and also regioselectivity of insertion arises. This shall also allow for predictions of the reactivity of other monomers.</dcterms:abstract>
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