Polyurethanes and Polyallophanates via Sequence-Selective Copolymerization of Epoxides and Isocyanates

Jurat, Mark, Pointer-Gleadhill, Benjamin, Ball, Liam , Chapman, Andy and Adriaenssens, Louis (2020) Polyurethanes and Polyallophanates via Sequence-Selective Copolymerization of Epoxides and Isocyanates. Journal of the American Chemical Society, 142 (18). pp. 8136-8141. ISSN 0002-7863

Full content URL: https://doi.org/10.1021/jacs.0c03520

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Item Type:Article
Item Status:Live Archive


Aryl isocyanates are introduced as comonomers for ring-opening copolymerization (ROCOP) with epoxides. Informed by studies of reaction kinetics, we show that divergent sequence selectivity for AB- and ABB-type copolymers can be achieved with a single dimagnesium catalyst. The resulting materials respectively constitute a new class of polyurethanes (PUs) and a new class of materials featuring an unprecedented backbone structure, the polyallophanates (PAs). The successful use of isocyanate comonomers in this way marks a new direction for the field of ROCOP while providing distinct opportunities for expansion of PU structural diversity. Specifically, the methodology reported herein delivers PUs featuring fully substituted (tertiary) carbamyl nitrogen atoms, a structural motif that is almost inaccessible via extant polymerization strategies. Thus, in one step from commercially available comonomers, our methodology expands the scope of ROCOP and gives access to diverse materials featuring both privileged (PU) and unexplored (PA) microstructures.

Subjects:F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Chemistry
ID Code:43201
Deposited On:22 Jan 2021 16:15

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