H. Kricheldorf, Dirk-Olaf Damrau
Nov 1, 1998
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Influential Citations
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Journal
Macromolecular Chemistry and Physics
Abstract
1,3-Dioxane-2-thione (trimethylene thiocarbonate (1)) was prepared by the reaction of 1,3-propanediol with thiophosgene and a tertiary amine. This new monomer crystallizes easily from ligroin, but it is difficult to purify because it is unstable at temperatures ≥25 °C due to spontaneous oligomerization. Its cationic polymerization in chloroform was studied using methyl triflate, BF 3 OEt 2 , SnCl 4 , BuSnCl 3 and Bu 2 SnCl 2 as initiators. Only two polymerizations yielded a relatively high molecular weight poly(trimethylene thiocarbonate). IR,'H NMR and 13 C NMR spectroscopy proved that the oligomers of the spontaneous polymerization and the polymers resulting from the cationic polymerizations possess the structure of a poly(mercaptopropanol carbonate), poly (MPOC). All attempts to prepare a polythiocarbonate of isomeric structure by anionic polymerizations failed. In contrast to the amorphous poly(trimethylene carbonate), the poly(MPOC) proved to be a rapidly crystallizing polymer.