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 (CS2), 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 (Td,5 up to 314 °C) and tunable glass transition temperatures (Tg 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.
Gallizioli et al. (Wed,) studied this question.