Synthesis of methylene butyrolactone polymers from itaconic acid

Herein, we report the transformation of β‐monomethyl itaconate, an inexpensive and biorenewable alternative to petroleum feedstocks, to the high‐value monomer α‐methylene‐γ,γ‐dimethyl‐γ‐butyrolactone (Me 2 MBL) through a selective addition strategy. This strategy is also applied to the synthesis of α‐methylene‐γ‐butyrolactone (MBL, tulipalin A), a monomer that can be polymerized to give materials with desirable properties (high decomposition temperature, glass transition temperature, and refractive index). Subsequent polymerization of both Me 2 MBL and MBL through reversible addition‐fragmentation chain‐transfer polymerization generates well‐defined poly(Me 2 MBL) and poly(MBL) (PMBL). Physical characterization of poly(Me 2 MBL) shows good physical properties comparable with known PMBL materials.