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Polymers of carbonic acid, 26. Synthesis and ionic polymerization of 1,3‐dioxane‐2‐thione
Author(s) -
Kricheldorf Hans R.,
Damrau DirkOlaf
Publication year - 1998
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19981101)199:11<2589::aid-macp2589>3.0.co;2-p
Subject(s) - cationic polymerization , trimethylene carbonate , polymer chemistry , polymerization , monomer , chemistry , polymer , trifluoromethanesulfonate , copolymer , ring opening polymerization , materials science , organic chemistry , catalysis
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, 1 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.