An Investigation of the Pathways for Oxygen/Sulfur Scramblings during the Copolymerization of Carbon Disulfide and Oxetane
writer：Ming Luo, Xing-Hong Zhang,*, and Donald J. Darensbourg*,
keywords：Carbon Disulfide, Oxetane, Oxygen/Sulfur Scramblings
source：期刊
specific source：Macromolecules 2015, 48, 5526-5532.
Issue time：2015年
The catalytic coupling of oxetane, the symmetric isomer of propylene oxide, with carbon disulfide has been investigated utilizing (salen)CrCl in the presence of various onium salts. Oxygen and sulfur atom exchange was observed in both the polymeric and cyclic carbonate products. The coupling of oxetane and CS2 was selective for copolymer formation over a wide range of reaction conditions. Five different polymer linkages and two cyclic products were determined by 1H and 13C NMR spectroscopy, and these results were consistent with in situ infrared spectroscopic monitoring of the process. The major cyclic product produced in the coupling process was trimethylene trithiocarbonate, which was isolated and characterized by single crystal X-ray crystallography. Upon increasing the CS2/oxetane feed ratio, a decrease in the O/S scrambling occurred. The reaction temperature had the most significant effect on the O/S exchange process, increasing exchange with increasing temperature. The presence of the onium salt initiator both accelerated the coupling process and promoted O/S scrambling. COS (observed), and CO2 intermediates are proposed in the reactions leading to various polymeric linkages.