Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene

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

doi:10.1021/acsmacrolett.2c00144

Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene

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

Research output: Contribution to journal › Article › peer-review

15 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 language	English (US)
Pages (from-to)	608-614
Number of pages	7
Journal	ACS Macro Letters
DOIs	https://doi.org/10.1021/acsmacrolett.2c00144
State	Accepted/In press - 2022
Externally published	Yes

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.

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title = "Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene",

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.",

author = "Sample, {Caitlin S.} and Kellstedt, {Elizabeth A.} and Hillmyer, {Marc A.}",

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: {\textcopyright} ",

year = "2022",

doi = "10.1021/acsmacrolett.2c00144",

language = "English (US)",

pages = "608--614",

journal = "ACS Macro Letters",

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T1 - Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene

AU - Sample, Caitlin S.

AU - Kellstedt, Elizabeth A.

AU - Hillmyer, Marc A.

N1 - 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: ©

PY - 2022

Y1 - 2022

N2 - 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.

AB - 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.

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JO - ACS Macro Letters

JF - ACS Macro Letters

ER -

Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene

Abstract

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