Reversible addition fragmentation chain transfer (raft) and hetero-diels–alder chemistry as a convenient conjugation tool for access to complex macromolecular designs

Inglis, Andrew J.; Sinnwell, Sebastian; Davis, Thomas P.; Barner-Kowollik, Christopher; Stenzel, Martina H.

doi:10.1021/ma8002328

Cited by 172Advanced Polymer Synthesis and Characterizationbiodegradable polymer synthesis and propertiesPolymer Synthesis and Characterization

Reversible addition fragmentation chain transfer (raft) and hetero-diels–alder chemistry as a convenient conjugation tool for access to complex macromolecular designs

Inglis, Andrew J., Sinnwell, Sebastian, Davis, Thomas P., Barner-Kowollik, Christopher, Stenzel, Martina H.·2008·Macromolecules

DOI 10.1021/ma8002328

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Abstract

The combination of RAFT chemistry and the hetero-Diels−Alder (HDA) cycloaddition was successfully utilized in the synthesis of poly(styrene) (PS) star polymers with up to 4 arms. This variant of the “coupling onto” method of star polymer synthesis was investigated for two different RAFT end groups (diethoxyphosphoryldithioformate and pyridin-2-yldithioformate) and coupling agents bearing 2, 3, or 4 diene functional groups. When a diethoxyphosphoryldithioformate terminated polymer was reacted with the 2-, 3-, and 4-fold functionalized coupling agents, the yields of 2-arm star, 3-arm star, and 4-arm star polymers were 81%, 77%, and 65%, respectively, and when a pyridin-2-yldithioformate terminated polymer was reacted with the same coupling agents, the yields of 2-arm star, 3-arm star and 4-arm star polymers were 91%, 86% and 82% respectively. The HDA coupling reaction was monitored via UV/vis spectroscopy from the perspective of the RAFT end group as well as by 1 H NMR spectroscopy from the perspective of the diene functionality. The results of these investigations indicated that the phosphoryldiethoxydithioformate terminated polymer achieves 92% conversion within a 24 h time frame and the pyridin-2-yldithioformate terminated polymer achieves 96% conversion in 10 h. The 4-arm star polymers were also subjected to high-temperature environments, and GPC measurements indicated that complete cleavage of all 4 arms from the core was achieved in 24 h at 160 °C.

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Barner-Kowollik and Stenzel et al. first synthesized a series of star polymers by combination of RAFT chemistry and hetero Diels-Alder reaction, in which the reaction occurs between thiocarbonyl group and a diene in a [4 + 2] cycloaddition process.
“Barner-Kowollik and Stenzel et al. first synthesized a series of star polymers by a combination of RAFT chemistry and hetero Diels-Alder reaction [60], in which the reaction occurs between thiocarbonyl group and a diene in a [4 + 2] cycloaddition process (Scheme 6).”
From Block Copolymers: Synthesis, Self-Assembly, and Applications (2017) · cites this paper as [60]

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Authors: Inglis, A. J., Sinnwell, S., Davis, T. P., Barner-Kowollik, C., & Stenzel, M. H.
Affiliations: UNSW Sydney (AU)
Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia
Corresponding author: Stenzel, Martina H.
ORCID: Inglis, Andrew J.
Davis, Thomas P.
Stenzel, Martina H.
Venue: Macromolecules
Publisher: American Chemical Society (ACS)
Published: 2008-05-20
Volume: 41
Issue: 12
Pages: 4120-4126
ISSN: 0024-9297 (ISSN-L)
1520-5835
DOI: 10.1021/ma8002328
OpenAlex: W1982483962
Cited by: 172
References: 41
Citations by year: 2024: 3 · 2023: 2 · 2022: 6 · 2021: 10 · 2020: 2 · 2019: 4 · 2018: 5 · 2017: 6 · 2016: 6 · 2015: 9 · 2014: 8 · 2013: 9 · 2012: 16
FWCI: 14.25
Type: journal article
Language: en
Open access: closed
Locations: Macromolecules (publishedVersion)
QUT ePrints (Queensland University of Technology) (submittedVersion)
Topics: Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
Physical Sciences › Materials Science › Polymers and Plastics › Polymer Synthesis and Characterization
Keywords: RAFT polymerization, hetero-Diels-Alder reaction, star polymers, polystyrene

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Reversible addition fragmentation chain transfer (raft) and hetero-diels–alder chemistry as a convenient conjugation tool for access to complex macromolecular designs

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