Facile synthesis of poly(trimethylene carbonate) by alkali metal carboxylate-catalyzed ring-opening polymerization

• Published in: Polymer journal Vol. 52; no. 1; pp. 103 - 110
• Main Authors: Takojima, Kaoru, Saito, Tatsuya, Vevert, Cedric, Ladelta, Viko, Bilalis, Panayiotis, Watanabe, Jun, Hatanaka, Shintaro, Konno, Takashi, Yamamoto, Takuya, Tajima, Kenji, Hadjichristidis, Nikos, Isono, Takuya, Satoh, Toshifumi
• Format: Journal Article
• Language: English
• Published: Tokyo Nature Publishing Group 01.01.2020
• Subjects: Alcohol; Alkali metals; Alkynes; Biodegradability; Block copolymers; Carboxylates; Chemical synthesis; Copolymerization; Elastomers; Food additives; Functional groups; Polylactic acid; Polymerization; Ring opening polymerization; Sodium; Sodium acetate; Sodium benzoate
• ISSN: 0032-3896; 1349-0540
• DOI: 10.1038/s41428-019-0264-6

Alkali metal carboxylates, including sodium acetate, sodium benzoate, and sodium sorbate, which are all readily available and widely used as food additives, were found to promote the ring-opening polymerization (ROP) of trimethylene carbonate (TMC) to produce poly(trimethylene carbonate) (PTMC). The sodium acetate-catalyzed ROP of TMC proceeded in the presence of an alcohol initiator under solvent-free conditions at 70 °C, even at very low catalyst loadings of 0.01–0.0001 mol%. The controlled nature of this ROP system enabled the synthesis of PTMCs with predicted molecular weights ranging from 2400 to 11 700 g mol−1 and narrow dispersities (~1.23). Importantly, ROP is initiated by an alcohol initiator, allowing PTMC production with desired functional groups, such as azido, alkyne, and methacrylate groups, at the α-chain end. Furthermore, the poly(l-lactic acid)-b-PTMC-b-poly(l-lactic acid) triblock copolymer, a biodegradable thermoplastic elastomer, was successfully synthesized in one pot via the sodium acetate-catalyzed ring-opening block copolymerization of TMC and l-lactide with a 1,3-propanediol initiator.