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Authors
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Gallizioli, C.; Sebastian, M.; Cornelsen, M.; Rossner, C.; Plajer, A. J.
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Title
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Sulfur-containing polyesters from thioanhydride/CS2/epoxide ring-opening terpolymerisation: Monomer scope and gold-nanoparticle functionalisation
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Date
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15.12.2025
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Number
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0
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Abstract
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Sulfur-containing polymers are receiving increasing attention due to their unique material and chemical properties, yet access to functional variants remains limited. To address this challenge, the ring-opening terpolymerisation (ROTERP) of phthalic thioanhydride (PTA), carbon disulfide (CS<sub>2</sub>), and a range of substituted epoxides was investigated. Polymerisation of linear, branched, aromatic, fluorinated, ether-functionalized, and multi-functional epoxides was achieved, thus providing access to a versatile range of sulfur-rich polymers bearing trithiocarbonate functionalities. Most systems exhibited moderate to high sequence selectivity for an alternating poly(ester-alt-ester-alt-trithiocarbonate) terpolymer structure, with some incorporation of polymer links from the competing ring-opening copolymerisation (ROCOP). The materials demonstrated moderate thermal stability under nitrogen (T<sub>d,5%</sub> up to 314 °C) and tunable glass transition temperatures (T<sub>g</sub> ranging from −20 to 163 °C). The trithiocarbonate groups incorporated along the main chain were employed for grafting the polymer chains to gold nanoparticle surfaces, yielding colloidally stable agglomerates. Furthermore, aldehyde-bearing polymers enabled attachment of organic moieties to the polymer grafted-to the nanoparticles via imine condensation, which could be selectively released under acidic conditions. Our study demonstrates the power of ROTERP as a synthetic platform to access a broad catalogue of functional sulfur-containing polymers and nanomaterials from readily available epoxides.
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Publisher
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Elsevier
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Wikidata
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Citation
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European Polymer Journal 241 (2025) 114373
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DOI
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https://doi.org/10.1016/j.eurpolymj.2025.114373
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