Covalent Adaptable Polymethacrylate Networks by Hydrazide Crosslinking Via Isosorbide Levulinate Side Groups.

Reversible crosslinking offers an attractive strategy to modify and improve the properties of polymer materials while concurrently enabling a pathway for chemical recycling. This can, for example, be achieved by incorporating a ketone functionality into the polymer structure to enable post-polymerization crosslinking with dihydrazides. The resulting covalent adaptable network contains acylhydrazone bonds cleavable under acidic conditions, thereby providing reversibility. In the present work, we regioselectively prepare a novel isosorbide monomethacrylate with a pendant levulinoyl group via a two-step biocatalytic synthesis. Subsequently, a series of copolymers with different contents of the levulinic isosorbide monomer and methyl methacrylate are prepared by radical polymerization. Using dihydrazides, these linear copolymers are then crosslinked via reaction with the ketone groups in the levulinic side chains. Compared to the linear prepolymers, the crosslinked networks exhibit enhanced glass transition temperatures and thermal stability, up to 170 and 286 °C, respectively. Moreover, the dynamic covalent acylhydrazone bonds are efficiently and selectively cleaved under acidic conditions to retrieve the linear polymethacrylates. We next show that recovered polymers can again be crosslinked with adipic dihydrazide, thus demonstrating the circularity of the materials. Consequently, we envision that these novel levulinic isosorbide-based dynamic polymethacrylate networks have great potential in the field of recyclable and reusable biobased thermoset polymers.

Poly(alkanoyl isosorbide methacrylate)s: From Amorphous to Semicrystalline and Liquid Crystalline Biobased Materials.

We have prepared a series of 12 d-isosorbide-2-alkanoate-5-methacrylate monomers as single regioisomers with different pendant linear C2-C20 alkanoyl chains using biocatalytic and chemical acylations. By conventional radical polymerization, these monomers provided high-molecular-weight biobased poly(alkanoyl isosorbide methacrylate)s (PAIMAs). Samples with C2-C12 alkanoyl chains were amorphous with glass transition temperatures from 107 to 54 °C, while C14-C20 chains provided semicrystalline materials with melting points up to 59 °C. Moreover, PAIMAs with C13-C20 chains formed liquid crystalline mesophases with transition temperatures up to 93 °C. The mesophases were studied using polarized optical microscopy, and rheology showed stepwise changes of the viscosity at the transition temperature. Unexpectedly, a PAIMA prepared from a regioisomeric monomer (C18) showed semicrystallinity but not liquid crystallinity. Consequently, the properties of the PAIMAs were readily tunable by controlling the phase structure and transitions through the alkanoyl chain length and the regiochemistry to form fully amorphous, semicrystalline, or semi/liquid crystalline materials.

Hydroformylation of Olefinic Derivatives of Isosorbide and Isomannide.

The first time application of hydroformylation on olefinic derivatives of isosorbide and isomannide is shown by which a new carbon-carbon bond is formed. Depending on the ligand and reaction conditions used, the C6 regioisomer a can be obtained in 4:1 ratio and excellent yield, whereas C5 isomer b is achieved in almost complete regioselectivity (46:1) and good yield. In the majority of cases only the exo orientation is observed for the obtained aldehydes, and the method is easily applicable also on a 1 g scale.