Recyclable Vitrimers from Biogenic Poly(itaconate) Elastomers

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.