A renewably sourced, circular photopolymer resin for additive manufacturing.

The additive manufacturing of photopolymer resins by means of vat photopolymerization enables the rapid fabrication of bespoke 3D-printed parts. Advances in methodology have continually improved resolution and manufacturing speed, yet both the process design and resin technology have remained largely consistent since its inception in the 1980s1. Liquid resin formulations, which are composed of reactive monomers and/or oligomers containing (meth)acrylates and epoxides, rapidly photopolymerize to create crosslinked polymer networks on exposure to a light stimulus in the presence of a photoinitiator2. These resin components are mostly obtained from petroleum feedstocks, although recent progress has been made through the derivatization of renewable biomass3-6 and the introduction of hydrolytically degradable bonds7-9. However, the resulting materials are still akin to conventional crosslinked rubbers and thermosets, thus limiting the recyclability of printed parts. At present, no existing photopolymer resin can be depolymerized and directly re-used in a circular, closed-loop pathway. Here we describe a photopolymer resin platform derived entirely from renewable lipoates that can be 3D-printed into high-resolution parts, efficiently deconstructed and subsequently reprinted in a circular manner. Previous inefficiencies with methods using internal dynamic covalent bonds10-17 to recycle and reprint 3D-printed photopolymers are resolved by exchanging conventional (meth)acrylates for dynamic cyclic disulfide species in lipoates. The lipoate resin platform is highly modular, whereby the composition and network architecture can be tuned to access printed materials with varied thermal and mechanical properties that are comparable to several commercial acrylic resins.

Click Nucleophilic Conjugate Additions to Activated Alkynes: Exploring Thiol-yne, Amino-yne, and Hydroxyl-yne Reactions from (Bio)Organic to Polymer Chemistry.

The 1,4-conjugate addition reaction between activated alkynes or acetylenic Michael acceptors and nucleophiles (i.e., the nucleophilic Michael reaction) is a historically useful organic transformation. Despite its general utility, the efficiency and outcomes can vary widely and are often closely dependent upon specific reaction conditions. Nevertheless, with improvements in reaction design, including catalyst development and an expansion of the substrate scope to feature more electrophilic alkynes, many examples now present with features that are congruent with Click chemistry. Although several nucleophilic species can participate in these conjugate additions, ubiquitous nucleophiles such as thiols, amines, and alcohols are commonly employed and, consequently, among the most well developed. For many years, these conjugate additions were largely relegated to organic chemistry, but in the last few decades their use has expanded into other spheres such as bioorganic chemistry and polymer chemistry. Within these fields, they have been particularly useful for bioconjugation reactions and step-growth polymerizations, respectively, due to their excellent efficiency, orthogonality, and ambient reactivity. The reaction is expected to feature in increasingly divergent application settings as it continues to emerge as a Click reaction.

Intrinsically Re-curable Photopolymers Containing Dynamic Thiol-Michael Bonds.

The development of photopolymers that can be depolymerized and subsequently re-cured using the same light stimulus presents a significant technical challenge. A bio-sourced terpenoid structure, l-carvone, inspired the creation of a re-curable photopolymer in which the orthogonal reactivity of an irreversible thioether and a dynamic thiol-Michael bond enables both photopolymerization and thermally driven depolymerization of mechanically robust polymer networks. The di-alkene containing l-carvone was partially reacted with a multi-arm thiol to generate a non-crosslinked telechelic photopolymer. Upon further UV exposure, the photopolymer crosslinked into a mechanically robust network featuring reversible Michael bonds at junction points that could be activated to revert, or depolymerize, the network into a viscous telechelic photopolymer. The regenerated photopolymer displayed intrinsic re-curability over two recycles while maintaining the desirable thermomechanical properties of a conventional network: insolubility, resistance to stress relaxation, and structural integrity up to 170 °C. Our findings present an on-demand, re-curable photopolymer platform based on a sustainable feedstock.

Sugar-Based Polymers with Stereochemistry-Dependent Degradability and Mechanical Properties.

Stereochemistry in polymers can be used as an effective tool to control the mechanical and physical properties of the resulting materials. Typically, though, in synthetic polymers, differences among polymer stereoisomers leads to incremental property variation, i.e., no changes to the baseline plastic or elastic behavior. Here we show that stereochemical differences in sugar-based monomers yield a family of nonsegmented, alternating polyurethanes that can be either strong amorphous thermoplastic elastomers with properties that exceed most cross-linked rubbers or robust, semicrystalline thermoplastics with properties comparable to commercial plastics. The stereochemical differences in the monomers direct distinct intra- and interchain supramolecular hydrogen-bonding interactions in the bulk materials to define their behavior. The chemical similarity among these isohexide-based polymers enables both statistical copolymerization and blending, which each afford independent control over degradability and mechanical properties. The modular molecular design of the polymers provides an opportunity to create a family of materials with divergent properties that possess inherently built degradability and outstanding mechanical performance.

Ultra-Tough Elastomers from Stereochemistry-Directed Hydrogen Bonding in Isosorbide-Based Polymers.

The remarkable elasticity and tensile strength found in natural elastomers are challenging to mimic. Synthetic elastomers typically feature covalently cross-linked networks (rubbers), but this hinders their reprocessability. Physical cross-linking via hydrogen bonding or ordered crystallite domains can afford reprocessable elastomers, but often at the cost of performance. Herein, we report the synthesis of ultra-tough, reprocessable elastomers based on linear alternating polymers. The incorporation of a rigid isohexide adjacent to urethane moieties affords elastomers with exceptional strain hardening, strain rate dependent behavior, and high optical clarity. Distinct differences were observed between isomannide and isosorbide-based elastomers where the latter displays superior tensile strength and strain recovery. These phenomena are attributed to the regiochemical irregularities in the polymers arising from their distinct stereochemistry and respective inter-chain hydrogen bonding.

Renewable and recyclable covalent adaptable networks based on bio-derived lipoic acid.

The modern materials economy is inefficient since most products are principally derived from non-renewable feedstocks and largely single-use in nature. Conventional thermoset materials are often inherently unreprocessable due to their irreversible covalent crosslinks and hence are challenging to recycle and/or reprocess. Covalent adaptable networks (CAN)s, which incorporate reversible or dynamic covalent bonding, have emerged as an efficient means to afford reprocessable crosslinked materials and increasing the feedstock sustainability of CANs is a developing aim. In this study, the biomass-derived lipoic acid, which possesses a dynamic cyclic disulfide moiety, was transformed into a series of bifunctional monomers via a one-step esterification or amidation reaction and reacted with a commercially available multi-valent thiol in the presence of an organobase catalyst to afford dynamically crosslinked networks. Large differences in material properties, such as storage modulus and glass transition temperature, were observed when the ratio of the lipoic acid-based monomer to thiol (from 1 : 1 to 16 : 1) and the composition of the monomer were changed to modify the network architecture. The thermomechanical properties of an optimised formulation were investigated more thoroughly to reveal a moderately strong rubber (ultimate tensile strength = 1.8 ± 0.4 MPa) possessing a large rubbery plateau (from 0 to 150 °C) which provides an adaptable material with a wide operational temperature range. Finally, the chemical recycling, or depolymerisation, of the optimised network was also demonstrated by simply solvating the material in the presence of an organobase catalyst.