Cited by 29Synthetic Organic Chemistry MethodsAdvanced Polymer Synthesis and CharacterizationOrganometallic Complex Synthesis and Catalysis

Efficient Synthesis of α,ω‐Divinyl‐Functionalized Polyolefins

Patil, Vishal B., Saliu, Kuburat O., Jenkins, Roxanne M., Carnahan, Edmund M., Kramer, Edward J., Fredrickson, Glenn H., Bazan, Guillermo C.·2014·Macromolecular Chemistry and Physics

Abstract

A facile one‐step olefin metathesis‐mediated ethenolysis reaction on polyolefins containing 1,4‐inserted butadiene units yields α,ω‐divinyl telechelic polymers. These reactions can be successfully performed with well‐defined thermally stable ruthenium catalysts to yield essentially complete metathesis of internal double bonds. The reaction progress is monitored by 1 H NMR spectroscopy over time, by tracking the disappearance of the signal due to internal unsaturation of 1,4‐butadiene at ca. 5.5 ppm in toluene‐d8 solvent. The reaction conditions are optimized for ethylene pressure, temperature, catalyst loading, and reaction time. Catalyst loading of 45:1 1,4‐butadiene unsaturation to catalyst at 90 °C with 25 psi ethylene pressure is successful in removing internal unsaturation with no detectable isomerization side reactions. High‐temperature gel‐permeation chromatography (GPC) analysis of the depolymerized product correlates to the calculated molecular weight based on the number of internal double bonds observed in the 1 H NMR analysis of the starting polyolefin. This method offers a single step, rapid, and clean route toward divinyl‐terminated telechelic polymers based on commodity materials in high yields. image

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Crossref · 10.1002/macp.201400139

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Authors
Patil, V. B., Saliu, K. O., Jenkins, R. M., Carnahan, E. M., Kramer, E. J., Fredrickson, G. H., & Bazan, G. C.
Affiliations
  • University of California, Santa Barbara (US)
  • Dow Chemical (United States) (US)
  • Materials Research Laboratory, Department of Materials University of California Santa Barbara CA 93106 USA
Corresponding author
Bazan, Guillermo C.
Venue
Macromolecular Chemistry and Physics
Publisher
Wiley
Published
2014-04-22
Volume
215
Issue
11
Pages
1140-1145
ISSN
  • 1022-1352 (ISSN-L)
  • 1521-3935
OpenAlex
W2138793178
Cited by
29
References
43
Citations by year
2025: 3 · 2024: 5 · 2023: 3 · 2022: 2 · 2021: 3 · 2020: 1 · 2018: 3 · 2017: 1 · 2016: 4 · 2015: 4
FWCI
1.32
Type
journal article
Language
en
Open access
closed
Locations
Macromolecular Chemistry and Physics (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Synthetic Organic Chemistry Methods
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
Keywords
telechelic polymers, olefin metathesis, ethenolysis, ruthenium catalysts, ethylene pressure, depolymerization

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