Polyester Adhesives via One-Pot, One-Step Copolymerization of Cyclic Anhydride, Epoxide, and Lactide

Polyesters (PEs) are sustainable alternatives for conventional polymers owing to their potential degradability, recyclability, and the wide availability of bio-based monomers for their synthesis. Herein, we used a one-pot, one-step self-switchable polymerization linking the ring-opening alternating copolymerization (ROAC) of epoxides/cyclic anhydrides with the ring-opening polymerization (ROP) of L-lactide (LLA) to synthesize PE-based hot-melt adhesives with a high bio-based content. In the cesium pivalate-catalyzed self-switchable polymerization of glutaric anhydride (GA), butylene oxide (BO), and LLA using a diol initiator, the ROAC of GA and BO proceeded whereas the ROP of LLA simultaneously proceeded very slowly, resulting in a copolyester consisting of poly(GA-<i>alt</i>-BO) and poly(L-lactide) (PLLA) segments with tapered regions, that is, PLLA-<i>tapered block</i>-poly(GA-<i>alt</i>-BO)-<i>tapered block</i>-PLLA (PLLA-<i>tb</i>-poly(GA-<i>alt</i>-BO)-<i>tb</i>-PLLA). Additionally, a series of tapered-block or real-block copolyesters consisting of poly(anhydride-<i>alt</i>-epoxide) (A segment) and PLLA (B segment) with AB-, BAB-, (AB)₃-, and (AB)₄-type architectures of different compositions and molecular weights were synthesized by varying the monomer combinations, alcohol initiators, and initial feed ratios. The lap shear tests of these copolyesters revealed an excellent relationship between the adhesive strength and polymer structural parameters. The (AB)₄-type star-block copolyester (poly(GA-<i>alt</i>-BO)-<i>tb</i>-PLLA)₄ exhibited the best adhesive strength (6.74 ± 0.64 MPa), comparable to that of commercial products, such as PE-based and poly(vinyl acetate)-based hot-melt adhesives.