Oxidized Dihydrocarvone as a Renewable Multifunctional Monomer for the Synthesis of Shape Memory Polyesters

Abstract

The natural product dihydrocarvone, found in caraway oil, was oxidized to an epoxylactone on a multigram scale. The resulting epoxylactone was used as a multifunctional monomer and cross-linker in ring-opening polymerizations. Homopolymerization using diethylzinc and tin(II) 2-ethylhexanoate gave only low molecular weight oligomers (apparent M(n) less than 2.5 kg/mol). Copolymerizations of ε-caprolactone and 0.3 to 50% of the epoxylactone gave flexible cross-linked materials on a multigram scale in a one-step synthesis. The gel fraction of these copolymers was determined. These copolymers showed near perfect shape memory properties even after repeated bending.

Recent Progress in Sustainable Polymers Obtained from Cyclic Terpenes: Synthesis, Properties, and Application Potential

“…The epoxide moiety wasu tilized as ac ross-linkingf unction,a nd the amount of cross-linking within these copolymers was estimated by gel swelling experiments. [87] In another study,c ompound 7 was transformed through Baeyer-Villiger oxidation into the two polymerizablel actones carvomenthidea nd dihydrocarvide. The latter of these contains an extracyclic double bond.…”

“…[85] Scheme8.A) Synthesis of 7-based lactones and copolymerization with caprolactone. [87] B) Polymerization of 7-based lactones to polydihydrocarvide (PD) and polycarvomenthide (PCM). [88] mCPBA = m-chloroperbenzoic acid.…”

Application of a thermostable Baeyer–Villiger monooxygenase for the synthesis of branched polyester precursors

“…BVMOs display a broad substrate scope,4, 5 which include cyclic ketones with a heteroatom,6, 7 macrocyclic ketones,8, 9, 10, 11 and substituted derivatives of various ring size (for example, terpene‐based substrates12, 13). 14, 15 BVMOs are also especially interesting in the synthesis of branched lactones, from which branched aliphatic polyesters with low glass transition temperatures can be made 16, 17, 18, 19, 20, 21, 22, 23, 24, 25…”

Monomers and Resulting Polymers from Biomass

“…With a supply of more than 10 5 ton per year and a growing number of synthetic routes to higher molecular polymers, growing applications for terpene-based polymers can be expected. With the ability to incorporate biodegradable ester linkages through polycondensation reactions or ring-opening polymerizations, these polymers become good candidates for biomedical applications [140].…”