Amine-Functionalized Polybutadiene Synthesis by Tunable Postpolymerization Hydroaminoalkylation.
In: Journal of the American Chemical Society, Jg. 145 (2023-10-25), Heft 42, S. 22871-22877
academicJournal
Zugriff:
Early transition metal-catalyzed hydroaminoalkylation is a powerful single-step method to selectively add amines to polybutadienes, offering an efficient strategy to access amine-functionalized polyolefins. Aryl and alkyl secondary amines were used with a tantalum catalyst to functionalize both 28 wt% ( PBD13 ) and 70 wt% ( PBD50 ) 1,2-polybutadiene polymers. The degree of amination was controlled by modifying amine and catalyst loading in both small- and multigram-scale reactions. The vinyl groups of 1,2-polybutadiene were aminated with ease, and unexpectedly the hydroaminoalkylation of challenging internal alkenes of the 1,4-polybutadiene unit was observed. This unanticipated reactivity was proposed to be due to a directing group effect. This hypothesis was supported with small-molecule model substrates, which also showed directed internal alkene amination. Increasing degrees of amination resulted in materials with dramatically higher and tunable glass transition temperature ( T g ) values, due to the dynamic cross-linking accessible to hydrogen-bonding, amine-containing materials. Primary amine-functionalized polybutadiene was also prepared, demonstrating that a broad new class of amine-containing polyolefins can be accessed by postpolymerization hydroaminoalkylation.
Titel: |
Amine-Functionalized Polybutadiene Synthesis by Tunable Postpolymerization Hydroaminoalkylation.
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Autor/in / Beteiligte Person: | Scott, SS ; Kaur, B ; Zheng, CHM ; Brant, P ; Gilmour, DJ ; Schafer, LL |
Zeitschrift: | Journal of the American Chemical Society, Jg. 145 (2023-10-25), Heft 42, S. 22871-22877 |
Veröffentlichung: | Washington, DC : American Chemical Society ; <i>Original Publication</i>: Easton, Pa. [etc.], 2023 |
Medientyp: | academicJournal |
ISSN: | 1520-5126 (electronic) |
DOI: | 10.1021/jacs.3c07564 |
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