Synthesis, Properties, and Biodegradability of Novel Sequence-Controlled Copolyesters Composed of Glycolic Acid, Dicarboxylic Acids, and C(3) or C(4) Diols

We have previously reported that sequence-controlled copolyesters such as poly((ethylene diglycolate) terephthalate) (poly(GEGT)) showed higher melting temperatures than those of the corresponding random copolymers and high biodegradability in seawater. In this study, to elucidate the effect of the diol component on their properties, a series of new sequence-controlled copolyesters composed of glycolic acid, 1,4-butanediol or 1,3-propanediol, and dicarboxylic acid units was studied. 1,4-Butylene diglycolate (GBG) and 1,3-trimethylene diglycolate (GPG) were prepared by the reactions of 1,4-dibromobutane or 1,3-dibromopropane with potassium glycolate, respectively. Polycondensation of GBG or GPG with various dicarboxylic acid chlorides produced a series of copolyesters. Terephthalic acid, 2,5-furandicarboxylic acid, and adipic acid were used as the dicarboxylic acid units. Among the copolyesters bearing terephthalate or 2,5-furandicarboxylate units, the melting temperatures (T(m)) of the copolyesters containing 1,4-butanediol or 1,2-ethanediol units were substantially higher than those of the copolyester containing the 1,3-propanediol unit. Poly((1,4-butylene diglycolate) 2,5-furandicarboxylate) (poly(GBGF)) showed a T(m) at 90 °C, while the corresponding random copolymer was reported to be amorphous. The glass-transition temperatures of the copolyesters decreased as the carbon number of the diol component increased. Poly(GBGF) was found to show higher biodegradability in seawater than that of poly(butylene 2,5-furandicarboxylate) (PBF). On the other hand, the hydrolysis of poly(GBGF) was suppressed in comparison with that of poly(glycolic acid). Thus, these sequence-controlled copolyesters have both improved biodegradability compared to PBF and lower hydrolyzability than PGA.