Controlled cationic ring‐opening polymerization of cyclic thiocarbonates with ester groups

摘要: This work deals with the cationic ring-opening polymerization of cyclic thiocarbonates 5-benzoyloxymethyl-5-methyl-1,3-dioxane-2-thione (1), 5,5-dimethyl-1,3-dioxane-2-thione (2), and 4-benzoyloxymethyl-1,3-dioxane-2-thione (3). The was carried out 2 mol % trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, boron trifluoride etherate, or triethyloxonium tetrafluoroborate as initiator to afford polythiocarbonate a narrow molecular weight distribution accompanying isomerization thiocarbonate group. obtained polymer could be controlled by feed ratio monomer increased when second added mixture after quantitative consumption in first stage. block copolymerization 3 also achieved, this supported idea that these monomers proceeded via living process. order rate > 1. 1 involved neighboring group participation ester groups according orbital calculations ab initio method. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Chem 41: 185–195, 2003