Cited by 50Organometallic Complex Synthesis and CatalysisAdvanced Polymer Synthesis and Characterizationbiodegradable polymer synthesis and properties

Heterogenized “Ligand-Free” Lanthanide Catalysts for the Homo- and Copolymerization of Ethylene and 1,3-Butadiene

Woodman, Timothy J., Sarazin, Yann, Fink, Gerhard, Hauschild, Klaus, Bochmann, Manfred·2005·Macromolecules

Abstract

Silica-supported lanthanide catalysts have been prepared from the reaction of dehydroxylated silica and tris(bistrimethylsilyl)amido lanthanides Ln[N(SiMe 3 ) 2 ] 3 (Ln = Sc, Y, La, Nd, Sm, Gd, Dy). On activation with Al i Bu 3 (TIBA), the compounds catalyze the polymerization of ethylene, with the scandium catalyst showing the highest activity. There is an inverse relationship between ionic radius of the lanthanide metal and the activity of the resulting catalyst. The polymer produced was highly linear and of high molecular weight. Activation with magnesium alkyls was less effective but gave polyethylene of slightly higher molecular weight. The supported lanthanides, when activated with TIBA, were also active for the polymerization of 1,3-butadiene, with very high molecular weight polymers being produced. In all cases the polymer was found to be predominately 1,4-cis (typically 85−90% by diad analysis), with only scandium producing a much higher level of 1,4-trans units. The system was also shown to copolymerize ethylene and butadiene, with large differences in the polymeric products depending on the both the choice of the lanthanide and the feed ratio of the monomer. With both neodymium and dysprosium multiblock polymers consisting of 1,4-cis, 1,4-trans, and ethylene blocks were obtained. With scandium two distinct modes of polymerization were detected, with both multiblock 1,4-cis and a somewhat alternating ethylene/1,4-trans block structure observed in the 13 C NMR spectra.

Integrity signals

Registry

Crossref · 10.1021/ma047454r

Cites

48 of 48 references verified0 citation errors · 0 not checkable

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

This paper’s full text isn’t openly available, so its claims and self-check weren’t run. The registry and citation checks still apply.

Cites

Flagged first, then by citations

Cited by

Sorted by citations

Authors
Woodman, T. J., Sarazin, Y., Fink, G., Hauschild, K., & Bochmann, M.
Affiliations
University of East Anglia (GB)
Corresponding author
Bochmann, Manfred
Venue
Macromolecules
Published
2005-03-18
Volume
38
Issue
8
Pages
3060-3067
ISSN
  • 0024-9297 (ISSN-L)
  • 1520-5835
OpenAlex
W1989271464
Cited by
50
References
48
Citations by year
2026: 1 · 2025: 1 · 2024: 4 · 2023: 2 · 2022: 1 · 2021: 1 · 2020: 3 · 2019: 3 · 2018: 1 · 2017: 9 · 2016: 5 · 2015: 1 · 2014: 2 · 2013: 1
FWCI
1.79
Type
journal article
Language
en
Open access
closed
Locations
  • Macromolecules (publishedVersion)
  • HAL (submittedVersion)
  • Max Planck Institute for Plasma Physics (submittedVersion)
  • MPG.PuRe (Max Planck Society) (submittedVersion)
  • UEA Digital Repository (University of East Anglia) (submittedVersion)
Funders
Thermal and Electric Energy Technology Foundation
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
Keywords
lanthanide catalysts, ligand-free catalyst, silica-supported catalysts, ethylene polymerization, 1,3-butadiene polymerization, multiblock copolymers, scandium catalyst, neodymium catalyst, ionic radius effect, catalytic activity, polymer molecular weight

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review