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

Abstract

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)-γhydroxymethyl-γ-butyrolactone methacrylate (2H-HBO-m) from (S)-γ-hydroxymethyl-γbutyrolactone (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.

Sustainable Synthesis and Polycondensation of Levoglucosenone‐Cyrene‐Based Bicyclic Diol Monomer: Access to Renewable Polyesters

“…Apart from a few studies on, for example, the reduction of the ketone moiety of Cyrene TM and its subsequent acrylation proposed by Saito and co‐workers to form the corresponding acrylate and polyacrylate, the use of LGO and Cyrene TM in material science appears limited. Recently, we reported the synthesis of renewable acrylate monomers with ( S )‐γ‐hydroxymethyl‐α,β‐butenolide (HBO), a bio‐based molecule derived from LGO, to produce high‐ T g bio‐based polymers with post‐polymerization possibilities (Scheme ) . Over the last decades, several processes that involve either chemical or chemoenzymatic conditions have been proposed to synthesize HBO from LGO by Baeyer–Villiger oxidations.…”

RDRP (Meth)acrylic Homo and Block Polymers from Lignocellulosic Sugar Derivatives

“…First, LGO was transformed into HBO via lipase mediated oxidation [ 100 ] or alternatively through a solvent/catalyst‐free H 2 O 2 ‐mediated process. [ 101 ] Next, the produced hydroxyl‐functional derivative was functionalized with a methacrylate moiety through a chemo‐enzymatic transesterification of methyl methacrylate using Candida antarctica type B lipase. The hydrogenated version of HBO, named ( S )‐ γ ‐hydroxymethyl‐ γ ‐butyrolactone (2H‐HBO), was also transformed into the corresponding methacrylate monomer (2H‐HBOMA).…”

Stereoregular functionalized polysaccharidesviacationic ring-opening polymerization of biomass-derived levoglucosan

“…[20][21][22][23][24] In addition, stereoselective cROP of levoglucosan to obtain polysaccharides with 1,6-a-glycosidic linkages is attractive from a sustainability standpoint since these linkages have demonstrated susceptibility to enzymatic and acidic hydrolysis. [25][26][27] Despite these advantages, levoglucosan has received considerably less attention in the sustainable polymers eld as compared to levoglucosenone, [28][29][30][31][32][33][34][35][36][37] another anhydrosugar than can be obtained in small quantities from cellulose pyrolysis. 13 The cROP of protected levoglucosan derivatives was rst reported more than 50 years ago, however the synthetic routes employed had some major drawbacks.…”