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

Abstract

The already‐reported, low‐yielding, and non‐sustainable Et3N‐mediated homocoupling of levoglucosenone (LGO) into the corresponding LGO‐CyreneTM diketone has been revisited and greened‐up. The use of methanol as both a renewable solvent and catalyst and K2CO3 as a safe inorganic base improved the reaction significantly with regards to yield, purification, and green aspects. LGO‐CyreneTM was then subjected to a one‐pot, H2O2‐mediated Baeyer–Villiger oxidation/rearrangement followed by an acidic hydrolysis to produce a new sterically hindered bicyclic monomer, 2H‐HBO‐HBO. This diol was further polymerized in bulk with diacyl chlorides to access new promising renewable polyesters that exhibit glass transition temperatures (Tg) from −1 to 81 °C and a good thermostability with a temperature at which 50 % of the mass is lost (Td50 %) of 349–406 °C.

Sustainable Hyperbranched Functional Materials via Green Polymerization of Readily Accessible Levoglucosenone‐Derived Monomers

“…All analytical data were in agreement with the ones reported in the literature. [23] Synthesis of DCI: In a 250 mL double-necked bottom round flask equipped with a Dena-Stark trap and condenser, 5 g of isosorbide (34.21 mmol) was reacted with 90 mL of dimethyl carbonate (1.07 mol) in presence of 0.95 g of K 2 CO 3 as a base (6.80 mmol), at 90°C for 6 h. After cooling, the reaction crude was filtered and concentrated in vacuo to achieve DCI in quantitative yield. A pure sample of DCI was obtained via column chromatography using DCM/MeOH (99/4).…”

“…Following our recent work on the preparation of polyesters via solvent-free polycondensation of 2H-HBO-HBO with diacyl chlorides, [23] we decided to investigate the synthesis of polycarbonates by reacting 2H-HBO-HBO with a dialkyl carbonate derivative of the biobased platform chemical isosorbide, [30] namely di(methylcarbonate) isosorbide (DCI).…”

Synthesis and Enzymatic Degradation of Sustainable Levoglucosenone-Derived Copolyesters with Renewable Citronellol Side Chains

“…Given our strong expertise in levoglucosenone (LGO), a wood-based functional molecule produced at the scale of several tons per year [ 28 , 29 , 30 ], we have recently become interested in developing not only renewable functional monomers and polymers from LGO [ 31 , 32 , 33 , 34 , 35 , 36 ] but also biodegradation protocols to evaluate the end-of-life of our in-house corresponding materials. In this context, we recently reported the first fully renewable citronellol-containing monomers from LGO [ 34 , 35 ].…”

Catalytic Strategies for Levoglucosenone Production by Pyrolysis of Cellulose and Lignocellulosic Biomass

“…A one-pot synthesis of HMF from cellulose via LGO is also possible, as discussed in a later section of this paper. , There have been studies on the production of functional polymers having unique structures of LGO or its derivative, ( S )-γ-hydroxymethyl-α,β-butenolide (HBO). A ring-opening metathesis polymerization of Diels–Alder adducts of LGO or HBO with cyclopentadiene produces polymers with a high thermal stability with a T d50% well-above 400 °C. − A high thermal stability is also found for polyesters produced from LGO-Cyrene diketone-derived bicyclic monomer, 2H-HBO-HBO, by polycondensation with diacyl chlorides …”

“…LGO-Cyrene diketone-derived bicyclic monomer, 2H-HBO-HBO, by polycondensation with diacyl chlorides. 32 In the course of thermal processing under catalysis, cellulose is moderately deoxygenated to form LGO. The lower oxygen/ carbon atomic ratio (O/C = 0.5) of LGO is attractive for use as a feedstock for commodity chemicals, having an O/C ratio at similar or lower values, because less hydrogen is required for the conversion, compared to glucose, 23 while the reactive and chiral structure allows for the addition of functionalities for synthesizing innovative fine chemicals.…”