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Cited by 255Advanced Polymer Synthesis and Characterizationbiodegradable polymer synthesis and propertiesSynthetic Organic Chemistry Methods

Zwitterionic Ring-Opening Polymerization for the Synthesis of High Molecular Weight Cyclic Polymers

Brown, Hayley A., Waymouth, Robert M.·2013·Accounts of Chemical Research
DOI 10.1021/ar400072z
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Abstract

Cyclic polymers are an intriguing class of macromolecules. Because of the constraints of the cyclic topology and the absence of chain ends, the properties of these molecules differ from those of linear polymers in ways that remain poorly understood. Cyclic polymers present formidable synthetic challenges because the entropic penalty of coupling the chain ends grows exponentially with increasing molecular weight. In this Account, we describe recent progress in the application of zwitterionic ring-opening polymerization (ZROP) as a strategy for the synthesis of high molecular weight, cyclic polymers. Zwitterionic ring-opening polymerization involves the addition of neutral organic nucleophiles to strained heterocyclic monomers; under appropriate conditions, cyclization of the resultant macrozwitterions generates cyclic macromolecules. We discuss the mechanistic and kinetic features of these zwitterionic ring-opening reactions and the conditions that influence the efficiency of the initiation, propagation, and cyclization to generate high molecular weight cyclic polymers. N-Heterocyclic carbenes (NHC) are potent nucleophiles and relatively poor leaving groups, two features that are important for the generation of high molecular weight polymers. Investigations of the nature of the monomer and nucleophile have helped researchers understand the factors that govern the reactivity of these systems and their impact on the molecular weight and molecular weight distributions of the resulting cyclic polymers. We focus primarily on ZROP mediated by N-heterocyclic carbene nucleophiles but also discuss zwitterionic polymerizations with amidine, pyridine, and imidazole nucleophiles. The ZROP of N-carboxyanhydrides with N-hetereocyclic carbenes generates a family of functionalized cyclic polypeptoids. We can synthesize gradient lactone copolymers by exploiting differences in relative reactivity present in ZROP that differ from those of traditional metal-mediated polymerizations. These new synthetic methods have allowed us to investigate the influence of topology on the crystallization behavior, stereocomplexation, and solution properties of cyclic macromolecules.

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  • This has led to the development of zwitterionic ring-opening polymerization for the synthesis of high molecular weight polyesters and polycarbonates with cyclic topology.

    “This has led to the development of zwitterionic ring-opening polymerization for the synthesis of high molecular weight polyesters 327 and polycarbonates 284 with cyclic topology.”

    From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [327]

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Authors
Brown, H. A., & Waymouth, R. M.
Affiliations
Stanford University (US)
Corresponding author
Waymouth, Robert M.
ORCID
Venue
Accounts of Chemical Research
Publisher
American Chemical Society (ACS)
Published
2013-06-21
Volume
46
Issue
11
Pages
2585-2596
ISSN
  • 0001-4842 (ISSN-L)
  • 1520-4898
DOI
10.1021/ar400072z
OpenAlex
W2326895255
Cited by
255
References
61
Citations by year
2026: 9 · 2025: 8 · 2024: 13 · 2023: 9 · 2022: 26 · 2021: 10 · 2020: 29 · 2019: 16 · 2018: 31 · 2017: 35 · 2016: 21 · 2015: 27 · 2014: 14 · 2013: 7
FWCI
10.48
Type
journal article
Language
en
Open access
closed
Locations
  • Accounts of Chemical Research (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Synthetic Organic Chemistry Methods
Keywords
ring polymers, high molecular weight polymers, N-heterocyclic carbenes, N-carboxyanhydride, polypeptoids, polymerization kinetics, molecular weight distribution, topology effects, crystallization, stereocomplexation, solution properties

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