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Polymeryl exchange between ansa-zirconocene catalysts for norbornene-ethene copolymerization and aluminum or zinc alkyls

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2005

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Bhriain, Nollaig Ní
Ruchatz, Dieter
Fink, Gerhard

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http://nbn-resolving.de/urn:nbn:de:bsz:352-237210
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https://doi.org/10.1021/ma0401166
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Macromolecules. 2005, 38(6), pp. 2056-2063. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma0401166

Zusammenfassung

Addition of aluminum or zinc alkyls (AlR3 or ZnR2, R = Me or Et) lowers the molar masses of norbornene−ethene (N/E) copolymers obtained with the catalyst systems Me2C(Ind)(Cp)ZrCl2/MAO or rac-C2H4(2-tBuMe2SiO-Ind)2ZrCl2/MAO to different degrees. These chain-shortening effects and changes in relative end-group abundance indicate the degree to which E/N copolymers growing at a Zr catalyst center are transferred to Al or Zn centers by alkyl−polymeryl exchange. Increased molar masses of copolymers obtained in the presence of added Al(iBu)3 indicate that this reagent suppresses polymer chain exchange between Zr catalyst centers and methylaluminum species contained in the MAO activator. These observations are interpreted in terms of reversible adduct formation between Al or Zn alkyls and cationic zirconocene alkyl species.

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540 Chemie

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ISO 690BHRIAIN, Nollaig Ní, Hans-Herbert BRINTZINGER, Dieter RUCHATZ, Gerhard FINK, 2005. Polymeryl exchange between ansa-zirconocene catalysts for norbornene-ethene copolymerization and aluminum or zinc alkyls. In: Macromolecules. 2005, 38(6), pp. 2056-2063. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma0401166
BibTex
@article{Bhriain2005Polym-23721,
  year={2005},
  doi={10.1021/ma0401166},
  title={Polymeryl exchange between ansa-zirconocene catalysts for norbornene-ethene copolymerization and aluminum or zinc alkyls},
  number={6},
  volume={38},
  issn={0024-9297},
  journal={Macromolecules},
  pages={2056--2063},
  author={Bhriain, Nollaig Ní and Brintzinger, Hans-Herbert and Ruchatz, Dieter and Fink, Gerhard}
}
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    <dcterms:abstract xml:lang="eng">Addition of aluminum or zinc alkyls (AlR&lt;sub&gt;3&lt;/sub&gt; or ZnR&lt;sub&gt;2&lt;/sub&gt;, R = Me or Et) lowers the molar masses of norbornene−ethene (N/E) copolymers obtained with the catalyst systems Me&lt;sub&gt;2&lt;/sub&gt;C(Ind)(Cp)ZrCl&lt;sub&gt;2&lt;/sub&gt;/MAO or rac-C&lt;sub&gt;2&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;(2-&lt;sup&gt;t&lt;/sup&gt;BuMe&lt;sub&gt;2&lt;/sub&gt;SiO-Ind)&lt;sub&gt;2&lt;/sub&gt;ZrCl&lt;sub&gt;2&lt;/sub&gt;/MAO to different degrees. These chain-shortening effects and changes in relative end-group abundance indicate the degree to which E/N copolymers growing at a Zr catalyst center are transferred to Al or Zn centers by alkyl−polymeryl exchange. Increased molar masses of copolymers obtained in the presence of added Al(&lt;sup&gt;i&lt;/sup&gt;Bu)&lt;sub&gt;3&lt;/sub&gt; indicate that this reagent suppresses polymer chain exchange between Zr catalyst centers and methylaluminum species contained in the MAO activator. These observations are interpreted in terms of reversible adduct formation between Al or Zn alkyls and cationic zirconocene alkyl species.</dcterms:abstract>
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