RSS-Feed abonnieren
DOI: 10.1055/s-0043-1763653
Evaluating Catalyst Performance in Synthesizing Hydroxyl-Terminated Polybutadiene by Ring-Opening-Metathesis Polymerization
The authors wish to acknowledge financial support from DEVCOM ARL through cooperative agreement W911NF-20-2-0052. This work was made possible by the use of Virginia Tech’s Nuclear Magnetic Resonance Facility, which is supported by the Department of Chemistry at Virginia Tech.
Abstract
Hydroxyl-terminated polybutadiene (HTPB) can be synthesized by ring-opening metathesis polymerization (ROMP) in a one-step process using cyclooctadiene in the presence of a hydroxyl-functionalized chain-transfer agent (CTA). However, previous studies have shown that the presence of primary alcohols can lead to the degradation of some ruthenium catalysts and that the hydroxyl end groups may be converted into aldehydes. Here we compare the performance of five ruthenium-based catalysts — Grubbs first-, second-, and third-generation catalysts (G1, G2, and G3, respectively), Hoveyda–Grubbs Z-selective catalyst (HGZ), and Hoveyda–Grubbs second-generation catalyst (HG2) — in ROMP with a CTA containing primary alcohols. We found that HTPB can be rapidly synthesized in a single step using G3 while avoiding end-group isomerization (2.2% aldehyde formation after full conversion is reached in 5 min). This result suggests that G3 may enable a more effective approach to synthesizing HTPB that avoids protecting groups but still maintains high end-group fidelity.
Key words
catalyst performance - hydroxyl-terminated polybutadiene - ring-opening metathesis - polymerizationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1763653.
- Supporting Information
Publikationsverlauf
Eingereicht: 02. Oktober 2023
Angenommen nach Revision: 13. November 2023
Artikel online veröffentlicht:
15. Dezember 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1 Li J, Ning Z, Yang W, Yang B, Zeng Y. ACS Omega 2022; 7: 10156
- 2 Quagliano Amado JC, Ross PG, Mattos Silva Murakami L, Narciso Dutra JC. Propellants, Explos. Pyrotech. 2022; 47: e202100283
- 3 Sikder BK, Jana T. ACS Omega 2018; 3: 3004
- 4 Sample CS, Kellstedt EA, Hillmyer MA. ACS Macro Lett. 2022; 11: 608
- 5 Hillmyer MA, Grubbs RH. Macromolecules 1993; 26: 872
- 6 Hillmyer MA, Nguyen ST, Grubbs RH. Macromolecules 1997; 30: 718
- 7 Pitet LM, Hillmyer MA. Macromolecules 2009; 42: 3674
- 8 Martinez H, Hillmyer MA. Macromolecules 2014; 47: 479
- 9 Martinez H, Ren N, Matta ME, Hillmyer MA. Polym. Chem. 2014; 5: 3507
- 10 Zhou Z, Palermo EF. Macromolecules 2018; 51: 6127
- 11 Mandal I, Kilbinger AF. M. J. Am. Chem. Soc. 2022; 2: 2800
- 12 Yan T, Guironnet D. Polym. Chem. 2021; 12: 5126
- 13 Bielawski CW, Scherman OA, Grubbs RH. Polymer 2001; 42: 4939
- 14 McGrath DV, Grubbs RH. Organometallics 1994; 13: 224
- 15 Forcina V, García-Domínguez A, Lloyd-Jones G. Faraday Discuss. 2019; 220: 179
- 16 Hong SH, Wenzel AG, Salguero TT, Day MW, Grubbs RH. J. Am. Chem. Soc. 2007; 129: 7961
- 17 Jawiczuk M, Marczyk A, Trzaskowski B. Catalysts 2020; 10: 887
- 18 McClennan WL, Rufh SA, Lummiss JA. M, Fogg DE. A. J. Am. Chem. Soc. 2016; 138: 14668
- 19 Arrington KJ, Waugh JB, Radzinski SC, Matson JB. Macromolecules 2017; 50: 4180
- 20 Keitz BK, Fedorov A, Grubbs RH. J. Am. Chem. Soc. 2012; 134: 2040
- 21 Love JA, Morgan JP, Trnka TM, Grubbs RH. Angew. Chem. Int. Ed. 2002; 41: 4035