Polymers constructed from copolymerizations of carbohydrates with C1 feedstocks are promising targets that provide transformation of sustainably sourced building blocks into next-generation, environmentally degradable plastic materials. In this work, the initial intention was to expand beyond polycarbonates prepared by the copolymerization of oxetanes derived from d-xylose with CO₂ and incorporate sulfur atoms through the establishment of monothiocarbonates that would provide the ability to modulate the backbone compositions and result in unique effects upon the chemical, physical, and mechanical properties. Therefore, the syntheses of poly(1,2-O-isopropylidene-α-d-xylofuranose monothiocarbonate)s were investigated by ring-opening copolymerizations of 3,5-anhydro-1,2-O-isopropylidene-α-d-xylofuranose with carbonyl sulfide (COS) facilitated by (salen)CrCl/cocatalyst systems. Unexpectedly, when copolymerization temperatures exceeded 40 °C, oxygen/sulfur exchange reactions occurred, causing in situ dynamic backbone restructuring through a series of inter-related and complex mechanistic pathways that transformed monothiocarbonate monomeric repeating units into carbonate and thioether dimeric repeating units. These backbone structural compositional transformations were investigated through a combination of Fourier transform infrared and nuclear magnetic resonance spectroscopic techniques and were demonstrated to be easily tuned via temperature and catalyst/cocatalyst stoichiometries. Furthermore, the regiochemistries of these d-xylose-based sulfur-containing polymers revealed that monothiocarbonate monomeric repeating units had a head-to-tail connectivity, while the carbonate and thioether dimeric repeating units had dual head-to-head and tail-to-tail connectivities. These sulfur-containing polymers exhibited enhanced thermal stabilities compared to their oxygen-containing polycarbonate analogues and revealed variations in the effects upon glass transition temperatures, demonstrating the effect of sulfur incorporation in the polymer backbone. These findings contribute to the advancement of sustainable polymer production by using feedstocks of natural origin coupled with COS.

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