Divergent Catalytic Strategies for the Cis/Trans Stereoselective Ring-Opening Polymerization of a Dual Cyclic Carbonate/Olefin Monomer

Thomas M. McGuire, Cécile Pérale, Rémi Castaing, Gabriele Kociok-Köhn, Antoine Buchard

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Abstract

A dual seven-membered cyclic carbonate/olefin monomer was synthesized from CO2 and cis-1,4-butenediol and polymerized. The properties of the polymer were controlled using divergent catalytic strategies toward the stereochemistry of the olefin. Ring-opening polymerization of the cyclic carbonate using an organocatalytic approach retained the cis-stereoconfiguration of the olefin and yielded a hard semicrystalline polymer (Tm 115 °C). Ring-opening metathesis polymerization using Grubbs’ catalyst proceeded with high trans-stereoregularity (95%) and produced a soft amorphous polymer (Tg −22 °C). Cis to trans isomerization of the polymer was possible using Cu(I) salts under UV light. In all polymers, the C═C double bond remained available for postpolymerization modification and thermoset resins were formed by cross-linking. From this single monomer, cis-trans-cis triblock copolymers, with potential applications as thermoplastic elastomers, were synthesized by combining both strategies using cis-1,4-butenediol as a chain transfer agent.
Original languageEnglish
Pages (from-to)13301-13305
Number of pages5
JournalJournal of the American Chemical Society
Volume141
Issue number34
Early online date20 Aug 2019
DOIs
Publication statusPublished - 28 Aug 2019

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Divergent Catalytic Strategies for the Cis/Trans Stereoselective Ring-Opening Polymerization of a Dual Cyclic Carbonate/Olefin Monomer",
abstract = "A dual seven-membered cyclic carbonate/olefin monomer was synthesized from CO2 and cis-1,4-butenediol and polymerized. The properties of the polymer were controlled using divergent catalytic strategies toward the stereochemistry of the olefin. Ring-opening polymerization of the cyclic carbonate using an organocatalytic approach retained the cis-stereoconfiguration of the olefin and yielded a hard semicrystalline polymer (Tm 115 °C). Ring-opening metathesis polymerization using Grubbs’ catalyst proceeded with high trans-stereoregularity (95{\%}) and produced a soft amorphous polymer (Tg −22 °C). Cis to trans isomerization of the polymer was possible using Cu(I) salts under UV light. In all polymers, the C═C double bond remained available for postpolymerization modification and thermoset resins were formed by cross-linking. From this single monomer, cis-trans-cis triblock copolymers, with potential applications as thermoplastic elastomers, were synthesized by combining both strategies using cis-1,4-butenediol as a chain transfer agent.",
author = "McGuire, {Thomas M.} and C{\'e}cile P{\'e}rale and R{\'e}mi Castaing and Gabriele Kociok-K{\"o}hn and Antoine Buchard",
year = "2019",
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T1 - Divergent Catalytic Strategies for the Cis/Trans Stereoselective Ring-Opening Polymerization of a Dual Cyclic Carbonate/Olefin Monomer

AU - McGuire, Thomas M.

AU - Pérale, Cécile

AU - Castaing, Rémi

AU - Kociok-Köhn, Gabriele

AU - Buchard, Antoine

PY - 2019/8/28

Y1 - 2019/8/28

N2 - A dual seven-membered cyclic carbonate/olefin monomer was synthesized from CO2 and cis-1,4-butenediol and polymerized. The properties of the polymer were controlled using divergent catalytic strategies toward the stereochemistry of the olefin. Ring-opening polymerization of the cyclic carbonate using an organocatalytic approach retained the cis-stereoconfiguration of the olefin and yielded a hard semicrystalline polymer (Tm 115 °C). Ring-opening metathesis polymerization using Grubbs’ catalyst proceeded with high trans-stereoregularity (95%) and produced a soft amorphous polymer (Tg −22 °C). Cis to trans isomerization of the polymer was possible using Cu(I) salts under UV light. In all polymers, the C═C double bond remained available for postpolymerization modification and thermoset resins were formed by cross-linking. From this single monomer, cis-trans-cis triblock copolymers, with potential applications as thermoplastic elastomers, were synthesized by combining both strategies using cis-1,4-butenediol as a chain transfer agent.

AB - A dual seven-membered cyclic carbonate/olefin monomer was synthesized from CO2 and cis-1,4-butenediol and polymerized. The properties of the polymer were controlled using divergent catalytic strategies toward the stereochemistry of the olefin. Ring-opening polymerization of the cyclic carbonate using an organocatalytic approach retained the cis-stereoconfiguration of the olefin and yielded a hard semicrystalline polymer (Tm 115 °C). Ring-opening metathesis polymerization using Grubbs’ catalyst proceeded with high trans-stereoregularity (95%) and produced a soft amorphous polymer (Tg −22 °C). Cis to trans isomerization of the polymer was possible using Cu(I) salts under UV light. In all polymers, the C═C double bond remained available for postpolymerization modification and thermoset resins were formed by cross-linking. From this single monomer, cis-trans-cis triblock copolymers, with potential applications as thermoplastic elastomers, were synthesized by combining both strategies using cis-1,4-butenediol as a chain transfer agent.

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