Search for: All records

Thermoset networks are chemically cross-linked materials that exhibit high heat resistance and mechanical strength; however, the permanently cross-linked system makes end-of-life degradation difficult. Thermosets that are inherently degradable and made from renewably derived starting materials are an underexplored area in sustainable polymer chemistry. Here, we report the synthesis of novel sugar- and terpene-based monomers as the enes in thiol–ene network formation. The resulting networks showed varied mechanical properties depending on the thiol used during cross-linking, ranging from strain-at-breaks of 12 to 200%. Networks with carveol or an isosorbide-based thiol incorporated showed plastic deformation under tensile stress testing, while geraniol-containing networks demonstrated linear stress–strain behavior. The storage modulus at the rubbery plateau was highly dependent on the thiol cross-linker, showing an order of magnitude difference between commercial PETMP, DTT, and synthesized Iso2MC. Thermal degradation temperatures were low for the networks, primarily below 200 °C, and the Tg values ranged from −17 to 31 °C. Networks were rapidly degraded under basic conditions, showing complete degradation after 2 days for nearly all synthesized thermosets. This library demonstrates the range of thermal and mechanical properties that can be targeted using monomers from sugars and terpenes and expands the field of renewably derived and degradable thermoset network materials. 

Additive manufacturing, otherwise known as three-dimensional (3D) printing, is a rapidly growing technique that is increasingly used for the production of polymer products, resulting in an associated increase in plastic waste generation. Waste from a particular class of 3D-printing, known as vat photopolymerization, is of particular concern, as these materials are typically thermosets that cannot be recycled or reused. Here, we report a mechanical recycling process that uses cryomilling to generate a thermoset powder from photocured parts that can be recycled back into the neat liquid monomer resin. Mechanical recycling with three different materials is demonstrated: two commercial resins with characteristic brittle and elastic mechanical properties and a third model material formulated in-house. Studies using photocured films showed that up to 30 wt% of the model material could be recycled producing a toughness of 2.01 ± 0.55 MJ/m3, within error of neat analogues (1.65 ± 0.27 MJ/m3). Using dynamic mechanical analysis and atomic force microscopy-based infrared spectroscopy, it was determined that monomers diffuse into the recycled powder particles, creating interpenetrating networks upon ultraviolet (UV) exposure. This process mechanically adheres the particles to the matrix, preventing them from acting as failure sites under a tensile load. Finally, 3D-printing of the commercial brittle material with 10 wt% recycle content produced high quality parts that were visually similar. The maximum stress (46.7 ± 6.2 MPa) and strain at break (11.6 ± 2.3%) of 3D-printed parts with recycle content were within error the same as neat analogues (52.0 ± 1.7 MPa; 13.4 ± 1.8%). Overall, this work demonstrates mechanical recycling of photopolymerized thermosets and shows promise for the reuse of photopolymerized 3D-printing waste. 

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.