Recyclable Vitrimers from Biogenic Poly(itaconate) Elastomers

Abstract

We report a biobased vitrimer prepolymer that is synthesized from renewable itaconic acid and platform chemicals. The polyitaconate vinyl prepolymers are transferred into transesterification-based vitrimer materials after a curing step with two different cross-linkers. Bifunctional lactone cross-linkers enable faster curing kinetics compared to linear diesters at the same catalyst loading and reaction temperature. The rheological properties of the obtained vitrimer materials are easily controlled by the amount and nature of the cross-linker, as well as by the loading of the guanidine organocatalyst for transesterification. An increase in catalyst content leads to shorter relaxation times and lower apparent activation energies of the transesterification reactions. The materials show elastomeric properties and can easily be recycled. Up to this point, sustainable vitrimers have been largely limited to epoxy-based networks. Herein, we describe a multifunctional and sustainable vinyl monomer-based prepolymer system that can be integrated into polymers using facile free radical polymerization, whose vitrimer network properties can be conveniently adjusted.

Biobased Transesterification Vitrimers

“…[ 102 ] Kolsch et al synthesized vitrimers using itaconic acid vinyl monomer, diethyl succinate, and (4,4′‐bioxepane)‐7,7′‐dion in the presence of TBD as a transesterification catalyst. [ 67 ] The vitrimer showed faster relaxation times at higher amounts of the catalyst, owing to the faster transesterification exchange process. Vitrimers could be reprocessed in 1 h at 140–180 °C and 5–7 bar due to thermally activated transesterification reactions.…”

Synthesis of Renewable, Recyclable, Degradable Thermosets Endowed with Highly Branched Polymeric Structures and Reinforced with Carbon Fibers

“…Bio-based thermosets that consist of biogenic carbons can be a solution because their use can reduce fossil fuel consumption and the carbon footprint . In particular, with the help of dynamic covalent chemistry, they are reprocessable and chemically recyclable; thus, they constitute bio-based covalent adaptable networks. , A variety of biomasses have been exploited for this purpose: vegetable oils − (including vanillin, − eugenol, , and cardanol , ), natural acids, − flavonoids, , and biopolymers, for example, polysaccharides, natural resins, and lignins. − Most of them contain β-hydroxy ester bonds that are commonly derived from epoxide, promoting transesterification due to the presence of free hydroxyl groups adjacent to the esters . Moreover, dynamic covalent bonds such as imine, disulfide, hindered urea, , acetal, boronic ester, and carbamate have been applied to build renewable dynamic networks.…”

Comprehensive itaconic acid-based vitrimers via one-pot inverse vulcanization

“…15 The low-cost raw material IA is usually obtained by the fermentation of Aspergillus terreus from agricultural byproducts such as corn cobs, wheat bran, straw and wood wastes. [16][17][18] IA has been utilized to design vitrimers with considerable performance, [19][20][21][22] but attempts to obtain IAderived polysulfides have not been reported. In our design, the double bond of IA offered reactive sites with sulfur via efficient and solvent-free inverse vulcanization (Fig.…”