Levoglucosenone to 3D-printed green materials: synthesizing sustainable and tunable monomers for eco-friendly photo-curing

Flourat, Amandine L.; Pezzana, Lorenzo; Belgacem, S.; Dosso, Abdouramane; Sangermano, Marco; Fadlallah, Sami; Allais, Florent

doi:10.1039/d3gc01833d

Cited by 9 publications

(11 citation statements)

References 43 publications

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“…The majority of the current photopolymerizable resins for additive manufacturing 3D printing techniques such as SLA or DIW are petroleum-derived. Previous reports of biobased polymers , have illustrated their systems to be amenable to 3D printing. The LGA pentenoyl monomer LGA-DP-4SH was examined to determine its suitability as a biobased 3D printing resin.…”

Section: Resultsmentioning

confidence: 99%

“…23 Recent reports involve using cellulose-derived levoglucosenone (LGO) as a green monomer for 3D printing, whereby bis-allylated compounds were synthesized and subsequently photocured with a trifunctional thiol. 10 Additionally, recent work by Porwal et al 24 presents methods to synthesize LGA-derived monomers for UV-cured thiol−ene thermosets. LGA was modified with allyl bromide to install three allyl groups amenable to polymerization based on a previous publication.…”

Section: ■ Introductionmentioning

confidence: 99%

“…This is due to their high shape stability, solvent resistance, and thermal stability. , Currently, it is standard to synthesize thermosetting materials from petroleum-derived compounds . As a result, biomass-derived materials present as a possible sustainable alternative for the production of thermoset materials. − Indeed, biomass-derived compounds are being increasingly incorporated into thermosetting systems across a wide range of applications, including coatings, adhesives, inks, electronics, and three-dimensional (3D) printing. − …”

Section: Introductionmentioning

confidence: 99%

“…These include substrates such as isosorbide, eugenol, and vanillin . Recent reports involve using cellulose-derived levoglucosenone (LGO) as a green monomer for 3D printing, whereby bis-allylated compounds were synthesized and subsequently photocured with a trifunctional thiol . Additionally, recent work by Porwal et al presents methods to synthesize LGA-derived monomers for UV-cured thiol–ene thermosets.…”

Section: Introductionmentioning

confidence: 99%

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Biobased Transparent Thiol–Ene Polymer Networks from Levoglucosan

Stanfield,

Kotlarewski,

Smith

et al. 2023

ACS Appl. Polym. Mater.

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Developing thermosets from renewable feedstocks for the production of sustainable polymer networks is of great significance as the world transitions from its heavy reliance on petroleum-derived polymeric materials. Levoglucosan is a renewable chemical, obtained from the pyrolysis of cellulosic biomass and was selected for this study due to its rich functionality. Allyl and pentenoyl levoglucosan monomers were synthesized with selective chemical functionality and were rapidly cured via ultraviolet (UV)-initiated thiol−ene click chemistry to obtain optically transparent, degradable networks. The mechanical properties (tensile strength and Young's modulus) and glass-transition temperature are tunable over the range of 1.08−3.40, 2.50−4.72 MPa, and 3.93−22.8 °C based on the monomer compositions. The resulting thermosets are able to be tailored for desired properties and applications, as demonstrated by stereolithography (SLA) three-dimensional (3D) printing and postcuring modification.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Biobased Transparent Thiol–Ene Polymer Networks from Levoglucosan

Stanfield,

Kotlarewski,

Smith

et al. 2023

ACS Appl. Polym. Mater.

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“…The successful large-scale production of LGO and Cyrene by Circa Group Ltd. has led to extensive investigations into their applications. LGO is an important optically pure starting material for the chemical synthesis of pharmaceuticals, , and Cyrene is an environmentally friendly solvent. ,− Recently, the use of LGO and Cyrene in the synthesis of polymeric materials has gained attention. − However, in most reported cases, the bicyclic acetal moiety is not used to construct the polymer main chain. Notably, Schlaad and co-workers reported the cROP of LGO-derived levoglucosenyl methyl ether, which could be transformed into (1→6)-polysaccharide derivatives via postpolymerization modification …”

mentioning

confidence: 99%

Chemically Recyclable Unnatural (1→6)-Polysaccharides from Cellulose-Derived Levoglucosenone and Dihydrolevoglucosenone

Mizukami,

Kakehi,

et al. 2024

ACS Macro Lett.

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Unnatural polysaccharide analogs and their biological activities and material properties have attracted considerable research interest. However, these efforts often encounter challenges, especially those related to synthetic complexity and scalability. Here, we report the chemical synthesis of unnatural (1→6)-polysaccharides using levoglucosenone (LGO) and dihydrolevoglucosenone (Cyrene), which are derived from cellulose. Using a versatile monomer synthesis from LGO and Cyrene and cationic ring-opening polymerization, (1→6)-polysaccharides with various tailored substituent patterns are obtained. Additionally, environmentally benign and easy-to-handle organic Brønsted acid catalysts are investigated. This study demonstrates well-controlled first-order polymerization kinetics for the reactive (1S,5R)-6,8-dioxabicyclo[3,2,1]octane (DBO) monomer. The synthesized (1→6)-polysaccharides exhibit high thermal stability and form amorphous solids under ambient conditions, which could be processed into highly transparent self-standing films. Additionally, these polymers exhibit excellent closed-loop chemical recyclability. This study provides an important approach to explore the chemical spaces of unnatural polysaccharides and contributes to the development of sustainable polymer materials from abundant biomass resources.

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Synthesis and Characterization of Thiol‐Ene Networks Derived from Levoglucosenone

Timilsina,

Stanfield,

Smith

et al. 2024

ChemPlusChem

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Levoglucosenone (LGO), a renewable compound obtained from cellulose biomass, has been utilized to prepare novel monomers bearing alkene functional groups. These monomer derivatives of LGO were subsequently cured via ultraviolet (UV)‐initiated radical thiol‐ene “click” chemistry with commercially available multifunctional thiols to obtain colourless, optically transparent cross‐linked thermosets. The monomers prepared in this work are unique due to utilising the internal double bond of the LGO ring during polymerization as part of the cross‐linked network. The thermal and mechanical properties along with the degradation of thermosets containing both ether and ester linkages within the LGO monomers were studied. These thermosets had tensile strengths of 1.3–3.3 MPa, glass transition temperatures between 23.2 and 27.2 °C, and good thermal stability of up to 300 °C.

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Levoglucosenone to 3D-printed green materials: synthesizing sustainable and tunable monomers for eco-friendly photo-curing

Abstract: 3D-printing technologies for polymeric formulations are experiencing a huge development due to the complex and specific geometries that can be covered employing additive manufacturing. However, to ensure sustainable growth, it...

Cited by 9 publications

References 43 publications

Biobased Transparent Thiol–Ene Polymer Networks from Levoglucosan

Biobased Transparent Thiol–Ene Polymer Networks from Levoglucosan

Chemically Recyclable Unnatural (1→6)-Polysaccharides from Cellulose-Derived Levoglucosenone and Dihydrolevoglucosenone

Synthesis and Characterization of Thiol‐Ene Networks Derived from Levoglucosenone

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