Fully Bio‐based Poly(ketal‐ester)s by Ring‐opening Polymerization of a Bicylcic Lactone from Glycerol and Levulinic Acid

A fully renewable bio-based bicyclic lactone (TOD) was prepared and its TBD-ROP afforded high molar mass amorphous PTOD that could be selectively degraded under acidic or basic conditions. In addition, under acidic conditions, the copolymers of TOD and L–LA degraded much faster than PLA via the selective cleavage of the cyclic ketal linkages in the copolymer backbone.

Abstract

A fully renewable bio-based bicyclic lactone containing a five-membered cyclic ketal moiety, 7-methyl-3,8,10-trioxabicyclo[5.2.1]decan-4-one (TOD), was synthesized through a two-step acid-catalyzed process from glycerol and levulinic acid. The ring-opening polymerization (ROP) of TOD at 30°C with benzyl alcohol (BnOH) as the initiator and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst can afford high molar mass PTOD with a cis-2.4-disubstitued 2-methyl 1,3-dioxolane moiety in its repeating unit. PTOD is an amorphous polymer with a glass transition temperature (T _g) of 13°C. It can be hydrolyzed into structurally defined small molecules under acidic or basic conditions by the selective cleavage of either the cyclic ketal or the ester linkage respectively. The TBD-catalyzed copolymerization of L-lactide (L–LA) and TOD at −20°C was investigated. It was confirmed that L–LA polymerized quickly with racemization to form PLA, followed by a slow incorporation of TOD into the formed PLA chains via transesterification. By varying the feed ratios of L–LA to TOD, a series of random copolymers (PLA-co-PTOD) with different TOD incorporation ratios and tunable T _gs were obtained. Under acidic conditions, PLA-co-PTOD degrades much faster than PLA via the selective cleavage of the cyclic ketal linkages. This work provides insights for the development of more sustainable and acid-accelerated degradable alternatives to aliphatic polyesters.

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