Cited by 47Organometallic Complex Synthesis and Catalysisbiodegradable polymer synthesis and propertiesAdvanced Polymer Synthesis and Characterization

Butadiene Insertion and Constitutional Units in Ethene Copolymerizations by C2-Symmetric Metallocenes

Longo, Pasquale, Napoli, Mariagrazia, Pragliola, Stefania, Costabile, Chiara, Milano, Giuseppe, Guerra, Gaetano·2003·Macromolecules

Abstract

Copolymerizations of ethylene with 1,3-butadiene in the presence of catalytic systems based on some C 2 -symmetric zirconocenes ( rac -[CH 2 (3-R-1-indenyl) 2 ]ZrCl 2 where R = −C(CH 3 ) 3 ( 1 ), −CH(CH 3 ) 2 ( 2 ), −CH 2 CH 3 ( 3 ), −CH 3 ( 4 ), and −H ( 5 )) are compared. The chemical nature and the relative amount of constitutional comonomer units from butadiene are strongly affected by the bulkiness of the substituent in positions 3 and 3‘. DFT calculations indicate that the observed dependence of constitutional units from butadiene on the bulkiness of the alkyl ligand substituent can be easily rationalized by the occurrence of an unusual insertion mechanism for butadiene. This mechanism, involving butadiene η 2 primary coordination followed by its primary vinyl insertion, becomes largely predominant for catalytic systems based on the zirconocenes ( 1 − 4 ), which present R ≥ CH 3 . This kind of butadiene insertion mechanism is also able to account for the high stereoregularity which is observed for adjacent methylene-1,2-cyclopropane units.

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Crossref · 10.1021/ma034830j

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Authors
Longo, P., Napoli, M., Pragliola, S., Costabile, C., Milano, G., & Guerra, G.
Affiliations
University of Salerno (IT)
Corresponding author
Longo, Pasquale
Venue
Macromolecules
Published
2003-11-06
Volume
36
Issue
24
Pages
9067-9074
ISSN
  • 0024-9297 (ISSN-L)
  • 1520-5835
OpenAlex
W2065978985
Cited by
47
References
35
Citations by year
2026: 2 · 2025: 1 · 2024: 2 · 2023: 3 · 2022: 1 · 2021: 2 · 2019: 2 · 2018: 5 · 2017: 5 · 2015: 3 · 2014: 2 · 2013: 1 · 2012: 1
FWCI
1.88
Type
journal article
Language
en
Open access
closed
Locations
Macromolecules (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Keywords
zirconocene catalysts, tacticity, DFT calculations

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