Ring-opening polymerization of six-membered cyclic hybrid dimers composed of an oxoester and thioester

Abstract

Three cyclic oxoester-thioester hybrid monomers, 1 (3-methyl-1,4-oxathiane-2,5-dione), 2 (6-methyl-1,4-oxathiane-2,5-dione), and 3 (3,6-dimethyl-1,4-oxathiane-2,5-dione), were studied for anionic and cationic ring-opening polymerizations. These monomers are six-membered cyclic cross-dimers corresponding to combinations of glycolic and lactic acids with their thiol analogs. Anionic polymerizations using thiol as the initiator and 2,6-lutidine as the base catalyst were successful for the chemoselective cleavage of the thioester with the thiol propagating end. The polymerizability increased in the order of 3 < 1 < 2, which was in good agreement with the increasing ring strain order evaluated by Density Functional Theory calculations. The living character, to some extent, was suggested by the postpolymerization reactions, which involved a two-stage feed of the monomers and a thiol-ene terminal coupling reaction to form a block copolymer with PEG. Additionally, it was found that the polymerization took place in 2,6-lutidine without a thiol initiator and produced macrocyclic polymers. The cationic polymerizations took place with the aid of CF3SO3H and benzyl alcohol but involved side reactions with low chemoselective ring cleavage. The thioester unit caused the polymers to exhibit a lower Tg with greater thermal and photo degradability. Three cyclic oxoester-thioester hybrid monomers were studied for anionic and cationic ring-opening polymerizations. Anionic polymerizations using thiol with 2,6-lutidine were successful for the chemoselective cleavage of the thioester with the thiol propagating end, exhibiting the living character to some extent. The polymerization in 2,6-lutidine without an initiator produced macrocyclic polymers. The cationic polymerizations occurred with the aid of CF3SO3H and benzyl alcohol but involved side reactions with low chemoselective ring cleavage. The thioester unit caused the polymers to exhibit a lower Tg with greater thermal and photo degradability.