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Simultaneous ring-opening copolymerization is a powerful strategy for the synthesis of highly functional copolymers from different types of cyclic monomers. Although copolymers are essential to the plastics industry, environmental concerns associated with current fossil-fuel-based synthetic polymers have led to an increasing interest in the use of renewable feedstock for polymer synthesis. Herein, we report a scalable synthetic platform to afford unique polysaccharides with different pendant functional groups from biomass-derived levoglucosan and ε-caprolactone via cationic ring-opening copolymerization (cROCOP). Biocompatible and recyclable bismuth triflate was identified as the optimal catalyst for cROCOP of levoglucosan. Copolymers from tribenzyl levoglucosan and ε-caprolactone, as well as from tribenzyl and triallyl levoglucosan, were successfully synthesized. The tribenzyl levoglucosan monomer composition ranged from 16% to 64% in the copolymers with ε-caprolactone and 22% to 79% in the copolymers with triallyl levoglucosan. The allylic levoglucosan copolymer can be utilized as a renewably derived scaffold to modify copolymer properties and create other polymer architectures via postpolymerization modification. Monomer reactivity ratios were determined to investigate the copolymer microstructure, indicating that levoglucosan-based copolymers have a gradient architecture. Additionally, we demonstrated that the copolymer glass transition temperature (Tg, ranging from −44.3 to 33.8 °C), thermal stability, and crystallization behavior could be tuned based on the copolymer composition. Overall, this work underscores the utility of levoglucosan as a bioderived feedstock for the development of functional sugar-based copolymers with applications ranging from sustainable materials to biomaterials. 

Levoglucosan is a renewable chemical obtained in high yields from pyrolysis of cellulosic biomass, which offers rich functionality for synthetic modification and crosslinking. Here, we report the facile and scalable synthesis of a family of biobased networks from triallyl levoglucosan and multifunctional thiols via UV-initiated thiol–ene click chemistry. The multifunctional thiols utilized in this study can also be sourced from renewable feedstocks, leading to overall high bio-based content of the synthesized levoglucosan networks. The thermomechanical and hydrolytic degradation properties of the resultant networks are tailored based on the type and stoichiometric ratio of thiol crosslinker employed. The Young's modulus and glass transition temperature of levoglucosan-based networks are tunable over the wide ranges of 3.3 MPa to 14.5 MPa and −19.4 °C to 6.9 °C, respectively. The levoglucosan-based thermosets exhibit excellent thermal stability with Td,10% > 305 °C for all networks. The suitability of these resin formulations for extrusion-based 3D printing was illustrated using a UV-assisted direct ink write (DIW) system creating 3D printed parts with excellent fidelity. Hydrolytic degradation of these 3D printed parts via ester hydrolysis demonstrated that levoglucosan-based resins are excellent candidates for sustainable rapid prototyping and mass production applications. Overall, this work displays the utility of levoglucosan as a renewable platform chemical that enables access to tailored thermosets important in applications ranging from 3D printing to biomaterials. 

We report the facile synthesis and characterization of 1,6-α linked functional stereoregular polysaccharides from biomass-derived levoglucosan via cationic ring-opening polymerization (cROP). Levoglucosan is a bicyclic acetal with rich hydroxyl functionality, which can be synthetically modified to install a variety of pendant groups for tailored properties. We have employed biocompatible and recyclable metal triflate catalysts – scandium and bismuth triflate – for green cROP of levoglucosan derivatives, even at very low catalyst loadings of 0.5 mol%. Combined experimental and computational studies provided key kinetic, thermodynamic, and mechanistic insights into the cROP of these derivatives with metal triflates. Computational studies reveal that ring-opening of levoglucosan derivatives is preferred at the 1,6 anhydro linkage and cROP proceeds in a regio- and stereo-specific manner to form 1,6-α glycosidic linkages. DFT calculations also show that biocompatible metal triflates efficiently coordinate with levoglucosan derivatives as compared to the highly toxic PF 5 used previously. Post-polymerization modification of levoglucosan-based polysaccharides is readily performed via UV-initiated thiol–ene click reactions. The reported levoglucosan based polymers exhibit good thermal stability ( T d > 250 °C) and a wide glass transition temperature ( T g ) window (<−150 °C to 32 °C) that is accessible with thioglycerol and lauryl mercaptan pendant groups. This work demonstrates the utility of levoglucosan as a renewably-derived scaffold, enabling facile access to tailored polysaccharides that could be important in many applications ranging from sustainable materials to biologically active polymers. 

3D printing is an essential tool for rapid prototyping in a variety of sectors such as automotive and public health. The 3D printing market is booming, and it is projected that it will continue to thrive in the coming years. Unfortunately, this rapid growth has led to an alarming increase in the amount of 3D printed plastic waste. 3D printing processes such as stereolithography (SLA) and digital light projection (DLP) in particular generally produce petroleum-based thermosets that are further worsening the plastic pollution problem. To mitigate this 3D printed plastic waste, sustainable alternatives to current 3D printing materials must be developed. The present review provides a comprehensive overview of the sustainable advances in SLA/DLP 3D printing to date and offers a perspective on future directions to improve sustainability in this field. The entire life cycle of 3D printed parts has been assessed by considering the feedstock selection and the end-of-use of the material. The feedstock selection section details how renewable feedstocks (from lignocellulosic biomass, oils, and animal products) or waste feedstocks ( e.g. , waste cooking oil) have been used to develop SLA/DLP resins. The end-of-use section describes how materials can be reprocessed ( e.g. thermoplastic materials or covalent adaptable networks) or degraded (through enzymatic or acid/base hydrolysis of sensitive linkages) after end-of-use. In addition, studies that have employed green chemistry principles in their resin synthesis and/or have shown their sustainable 3D printed parts to have mechanical properties comparable to commercial materials have been highlighted. This review also investigates how aspects of sustainability such as recycling for feedstock/end-of-use or biodegradation of 3D printed parts in natural environments can be incorporated as future research directions in SLA/DLP.