Herein we report the discovery of the intrinsic mechanochemical reactivity of vinyl‐addition polynorbornene (VA‐PNB), which has strained bicyclic ring repeat units along the polymer backbone. VA‐PNBs with three different side chains were found to undergo ring‐opening olefination upon sonication in dilute solutions. The sonicated polymers exhibited spectroscopic signatures consistent with conversion of the bicyclic norbornane repeat units into the ring‐open isomer typical of polynorbornene made by ring‐opening metathesis polymerization (ROMP‐PNB). Thermal analysis and evaluation of chain‐scission kinetics suggest that sonication of VA‐PNB results in chain segments containing a statistical mixture of vinyl‐added and ROMP‐type repeat units.
Herein we report the discovery of the intrinsic mechanochemical reactivity of vinyl‐addition polynorbornene (VA‐PNB), which has strained bicyclic ring repeat units along the polymer backbone. VA‐PNBs with three different side chains were found to undergo ring‐opening olefination upon sonication in dilute solutions. The sonicated polymers exhibited spectroscopic signatures consistent with conversion of the bicyclic norbornane repeat units into the ring‐open isomer typical of polynorbornene made by ring‐opening metathesis polymerization (ROMP‐PNB). Thermal analysis and evaluation of chain‐scission kinetics suggest that sonication of VA‐PNB results in chain segments containing a statistical mixture of vinyl‐added and ROMP‐type repeat units.
more » « less- PAR ID:
- 10088981
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 131
- Issue:
- 17
- ISSN:
- 0044-8249
- Page Range / eLocation ID:
- p. 5695-5698
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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trans alkene content of 25 to >98 %. Highcis content was obtained from relatively larger counterions, toluene as solvent, low temperatures (−78 °C), and initiators with low Charton values. Conversely, smaller counterions, dichloromethane as solvent, and enol ethers with higher Charton values enabled production of PNB with hightrans content. Data from a combined experimental and computational investigation are consistent with the stereocontrolling step of the radical cationic mechanism proceeding under thermodynamic control. -
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