LAUSR

Cinnamic monomers, which are useful chemicals derived from biomass, contain α,β-unsaturated carbonyl groups with an aromatic ring at the β-position. Homopolymers synthesized by addition polymerization of these compounds are expected to be innovative bio-based polymer materials, as they have both polystyrene and polyacrylate structures. However, polymerization of these compounds by many methods is challenging, including by radical methods, owing to steric hindrance of the substituents and delocalization of electrons throughout the molecule via unsaturated π-bonding. Herein we report that homopolymers of these compounds with molecular weights (Mn) of ~18,100 g mol−1 and controlled polymer backbones can be synthesized by the group-transfer polymerization technique using organic acid catalysts. Additionally, these homopolymers are shown to have high heat resistance comparable to that of engineering plastics. Overall, these findings may open up possibilities for the convenient homopolymerization of cinnamic monomers to produce high-performance polymer materials.Cinnamic acid and related monomers are challenging to polymerise but offer interesting features combining structural elements of both acrylates and styrenes. Here homopolymers of cinnamic monomers are obtained by group transfer polymerisation under mild conditions.