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We report a new class of degradable fluorinated polymers through the copolymerization of tetrafluorophthalic anhydride and propylene oxide or trifluoropropylene oxide which show up to 20 times quicker degradation than the non-fluorinated equivalents and allow for fluoride recovery. [ABSTRACT FROM AUTHOR]

Although sulfurated polymers promise unique properties, their controlled synthesis, particularly when it comes to complex and functional architectures, remains challenging. Here, we show that the copolymerization of oxetane and phenyl isothiocyanate selectively yields polythioimidocarbonates as a new class of sulfur containing polymers, with narrow molecular weight distributions (Mn=5–80 kg/mol with Đ≤1.2; Mn,max=124 kg/mol) and high melting points of up to 181 °C. The method tolerates different substituent patterns on both the oxetane and the isothiocyanate. Self‐nucleation experiments reveal that π‐stacking of phenyl substituents, the presence of unsubstituted polymer backbones, and the kinetically controlled linkage selectivity are key factors in maximising melting points. The increased tolerance to macro‐chain transfer agents and the controlled propagation allows the synthesis of double crystalline and amphiphilic diblock copolymers, which can be assembled into micellar‐ and worm‐like structures with amorphous cores in water. In contrast, crystallization driven self‐assembly in ethanol gives cylindrical micelles or platelets. [ABSTRACT FROM AUTHOR]

CS2 promises easy access to degradable sulfur-rich polymers and insights into how main-group derivatisation affects polymer formation and properties, though its ring-opening copolymerisation is plagued by low linkage selectivity and small-molecule by-products. We demonstrate that a cooperative Cr(III)/K catalyst selectively delivers poly(dithiocarbonates) from CS2 and oxetanes while state-of-the-art strategies produce linkage scrambled polymers and heterocyclic by-products. The formal introduction of sulfur centres into the parent polycarbonates results in a net shift of the polymerisation equilibrium towards, and therefore facilitating, depolymerisation. During copolymerisation however, the catalyst enables near quantitative generation of the metastable polymers in high sequence selectivity by limiting the lifetime of alkoxide intermediates. Furthermore, linkage selectivity is key to obtain semi-crystalline materials that can be moulded into self-standing objects as well as to enable chemoselective depolymerisation into cyclic dithiocarbonates which can themselves serve as monomers in ring-opening polymerisation. Our report demonstrates the potential of cooperative catalysis to produce previously inaccessible main-group rich materials with beneficial chemical and physical properties. CS2 promises easy access to degradable sulfur-rich polymers, but ring-opening copolymerisation using CS2 is challenging due to low linkage selectivity and small-molecule by-products. Here, the authors report a cooperative Cr(III)/K catalyst which selectively delivers poly(dithiocarbonates) from CS2 and oxetanes. [ABSTRACT FROM AUTHOR]

A recent research article in Angewandte Chemie by Alex J. Plajer et al. discusses the easy synthesis of sulfur-containing polymers with high melting points. The authors demonstrate that these polymers can be obtained through the copolymerization of phenylisothiocyanate and oxetane. Additionally, the resulting polythioimidocarbonate can be used as a core-forming block in the self-assembly of a diblock copolymer. This research provides valuable insights into the synthesis and potential applications of sulfurated copolymers. [Extracted from the article]