Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene

Caitlin S. Sample, Elizabeth A. Kellstedt, Marc A. Hillmyer

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Hydroxy-telechelic polyalkenamers have long been synthesized using ring-opening metathesis polymerization (ROMP) in the presence of an acyclic olefin chain-transfer agent (CTA); however, this route typically requires protected diols in the CTA due to the challenge of alcohol-mediated degradation of ruthenium metathesis catalysts that can not only deactivate the catalysts, but also compromise the CTA. We demonstrate the synthesis and implementation of a new hydroxyl-containing CTA in which extended methylene spacers isolate the olefin and alcohol moieties to mitigate decomposition pathways. This CTA enabled the direct ROMP synthesis of hydroxy-telechelic polycyclooctene with controlled chain lengths dictated by the initial ratio of monomer to CTA. The elimination of protection/deprotection steps resulted in improved atom economy. Subsequent hydrogenation of the backbone olefins was performed by a one-pot, catalytic approach employing the ruthenium complex used for the initial ROMP. The resultant approach is a streamlined, atom-economic, and low-waste route to hydroxy-telechelic linear polyethylene that uses a green solvent, succeeds with miniscule quantities of catalyst (0.005 mol %), and requires no additional purification steps.

Original languageEnglish (US)
Pages (from-to)608-614
Number of pages7
JournalACS Macro Letters
Volume11
Issue number5
DOIs
StateAccepted/In press - 2022

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation (Award No. DMR-2003454). NMR experiments were performed on instruments supported by the Office of the Vice President of Research, College of Science and Engineering, the Department of Chemistry at the University of Minnesota, and the Office of the Director, National Institutes of Health (Award No. S10OD011952). The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. The authors would like to acknowledge Dr. Letitia Yao, Dr. David Giles, Keun-Young Park, and Stephanie Liffland for their assistance with characterization, as well as Emily Wilborn for preliminary studies on cis-4-octene-1,8-diol and supplying a portion of the C16D CTA used in this study. We would also like to thank Claire Dingwell and Emily Wilborn for their helpful discussions.

Publisher Copyright:
©

Keywords

  • Alkenes
  • Hydrogenation
  • Polyethylene
  • Polymerization
  • Ruthenium

PubMed: MeSH publication types

  • Journal Article
  • Research Support, Non-U.S. Gov't

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