Chemo-Enzymatic Synthesis and Free Radical Polymerization of Renewable Acrylate Monomers from Cellulose-Based Lactones

A chemo-enzymatic pathway involving a Candida antarctica type B lipase was developed to produce (S)-γ-hydroxymethyl-α,β-butenolide methacrylate (HBO-m) and (S)-γ-hydroxymethyl-γ-butyrolactone methacrylate (2H-HBO-m) from (S)-γ-hydroxymethyl-γ-butyrolactone (HBO), a biobased molecule obtained from cellulose-derived levoglucosenone. The acrylated monomer was then copolymerized through a free radical process with methacrylamide and methylene-γ-valerolactone, a green intermediate. Finally, methylene-tetrahydropyranyl (S)-γ-hydroxymethyl-γ-butyrolactone (M-THP-2H-HBO), synthesized via α-methylenation of 2H-HBO, was copolymerized with methyl methacrylate to access copolyacrylates exhibiting high glass transition temperatures