The demand to produce materials from non-fossil based sources, i.e. bio-based raw materials, is increasing due to environmental concerns and limited resources. Bio-based building blocks result in new materials with sometimes unprecedented properties rendering them an interesting subject to study.<br/>Two of these building blocks are the itaconic acid-derived α-methylene-γ-butyrolactone and the structurally similar α-methylene-γ-valerolactone which can be synthesized from the bio-based levulinic acid. Itaconic acid is a promising platform chemical that is produced by the fermentation of carbohydrates and it was listed by the U.S. Department of Energy as one of the top-value added chemicals from biomass. In this study, we report the free-radical polymerization of these two lactones into homopolymers or together with fossil-based (meth)acrylate monomers, methyl acrylate and methyl methacrylate in different ratios. 2,2′-Azobisisobutyronitrile or lauroyl peroxide were used as initiators to investigate their effect on the polymerization behaviors. Polymerizations were monitored by monomer conversion, and the final polymers were characterized with respect to molecular weight, composition, glass transition temperature and thermal degradation. The incorporation of the monomers in the copolymers was significantly affected by the differences in reactivity ratios, sometimes to such an extent that the polymers exhibited a substantial compositional drift as corroborated by assessed thermal properties.<br/>Increased thermal stability and tailored T<sub>g</sub>’s were achieved by copolymerizing the lactones and the (meth)acrylates in different ratios, making the lactones interesting building blocks for synthesis of bio-based or partially bio-based materials.

Free-radical polymerization of bio-based monomers

ACS Fall 2021

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