Vat 3D Printing of Bioderivable Photoresins – Toward Sustainable and Robust Thermoplastic Parts

Vat photopolymerization 3D printing (3DP) of thermoplastic materials is exceedingly difficult due to the typical reliance on cross-linking to form well-defined, solid objects on timescales relevant to 3DP. Additionally, photoresin build materials overwhelmingly rely upon nonrenewable feedstocks. To address these challenges, we report the vat 3DP of bioderivable photoresins that produced thermoplastic parts with highly tunable thermal and mechanical properties. The photoresins were formulated from two monomers that are easily obtainable from lignin deconstruction: 4-propylguaiacyl acrylate (4-pGA) and syringyl methacrylate (SMA). These bioderivable materials generated printed parts that ranged from soft elastomers to rigid plastics. For example, for 4-pGA-based materials, the breaking stresses varied from 0.20 to 20 MPa and breaking strains could be tuned from 4.7% up to 1700%, whereas 3D-printed SMA-based materials resulted in higher breaking stresses (∼30 MPa) and Tgs (∼132 °C). Notably, parts printed from these bioderivable formulations exhibited thermoplastic behavior and were largely soluble in common organic solvents─expanding the application and repurposing of the 3D-printed parts. We highlight this feature by reusing a 3DP part via solvent casting. Overall, the tunable properties and thermoplastic behavior of the lignin-derivable photoresins showcase renewable lignin resources as promising biofeedstocks for sustainable 3DP.

Mechanoactivation of Color and Autonomous Shape Change in 3D-Printed Ionic Polymer Networks

Stimuli-responsive materials can enhance the field of three-dimensional (3D) printing by generating objects that change shape in response to external cues. While temperature and pH are common inputs for initiating a response in a 3D-printed object, there are few examples of using a mechanical input to afford a response. Herein, we report a suite of mechanochromic ionic liquid gel inks that can be used to fabricate 3D-printed objects that use a single mechanoactivation event to elicit both a mechanochromic response and an autonomous shape change. Direct-ink write 3D printing was used to deposit ionic liquid gel inks to create multimaterial objects that underwent a predetermined mechanoactivated shape change (mechanomorphic) when the sample was pulled and then released. When spiropyran was incorporated into the inks, the onset of spiropyran isomerization into its purple merocyanine form occurred at strains dependent upon the particular ion gel ink formulation. We suggest that the color onset could be used as a simple indicator for when the strain required to achieve a predetermined change in shape has been reached, potentially serving as real-time visual cue for the user. Such morphing 3D-printed structures with integrated instructions have potential application to areas including stowable structures as well as multiresponsive autonomous components and sensors.

A highly efficient metal-free protocol for the synthesis of linear polydicyclopentadiene.

We have achieved breakthroughs for the efficient synthesis of linear polydicyclopentadiene (pDCPD) via photoredox mediated metal-free ring-opening metathesis polymerization (MF-ROMP). Molecular weight control from 1 to 16 kDa can be targeted in a straightforward manner. Assisted by this method, the Tg–Mn dependence of linear pDCPD is investigated and reported for the first time.

Mechanochemical Release of N‐heterocyclic Carbenes from Flex‐Activated Mechanophores.

We have discovered a new flex-activated mechanophore that releases an N-heterocyclic carbene (NHC) under mechanical load. The mechanophore design is based upon NHC-carbodiimide (NHC-CDI) adducts and demonstrates an important first step toward flex-activated designs capable of further downstream reactivities. Since the flex-activation is non-destructive to the main polymer chains, the material can be subjected to multiple compression cycles to achieve iterative increases in the activation percentage of mechanophores. Two different NHC structures were demonstrated, signifying the potential modularity of the mechanophore design.

An Ion‐Pairing Approach to Stereoselective Metal‐Free Ring‐Opening Metathesis Polymerization.

Stereochemistry can have profound impact on polymer and materials properties. Unfortunately, straightforward methods for realizing high levels of stereocontrolled polymerizations are often challenging to achieve. In a departure from traditional metal-mediated ring-opening metathesis polymerization (ROMP), we discovered a remarkably simple method for controlling alkene stereochemistry in photoredox mediated metal-free ROMP. Ion-pairing, initiator sterics, and solvation effects each had profound impact on the stereochemistry of polynorbornene (PNB). Simple modifications to the reaction conditions produced PNB with trans alkene content of 25 to >98%. High cis content was obtained from relatively larger counterions, toluene as solvent, low temperatures (-78 °C), and initiators with low Charton values. Conversely, smaller counterions, dichloromethane as solvent, and enol ethers with higher Charton values enabled production of PNB with high trans content. Data from a combined experimental and computational investigation are consistent with the stereocontrolling step of the radical cationic mechanism proceeding under thermodynamic control.

Advances in Polymerizations Modulated by External Stimuli

Synthetic polymer chemistry endeavors to imitate the spatial and temporal control exhibited within biological systems to obtain well-defined polymeric materials with unique structures, properties, and applications. This is often approached through the development of dynamic catalyst (or initiator) systems that use external stimuli to elicit discrete, site-specific transformations that impact the polymerization. Herein we highlight developments in polymerizations that are modulated by external stimuli, with particular focus on those systems that enable notable changes in kinetics, monomer selectivity, polymer architecture, or tacticity. Examples of external stimuli include chemical oxidants or reductants, light, applied voltage, and mechanical force.

The role of polymer mechanochemistry in responsive materials and additive manufacturing.

The use of mechanical forces to chemically transform polymers dates back decades. In recent years, the use of mechanochemistry to direct constructive transformations in polymers has resulted in a range of engineered molecular responses that span optical, mechanical, electronic and thermal properties. The chemistry that has been developed is now well positioned for use in materials science, polymer physics, mechanics and additive manufacturing. Here, we review the historical backdrop of polymer mechanochemistry, give an overview of the existing toolbox of mechanophores and associated theoretical methods, and speculate as to emerging opportunities in materials science for which current capabilities are seemingly well suited. Non-linear mechanical responses and internal, amplifying stimulus–response feedback loops, including those enabled by, or coupled to, microstructured metamaterial architectures, are seen as particularly promising.

Metal-Free Ring-Opening Metathesis Polymerization: From Concept to Creation

Ring-opening metathesis polymerization (ROMP), which is derived from transition-metal-based olefin metathesis, has evolved into one of the most prevalent technologies for making functional polymeric materials in academia and in industry. The initial discovery of and advances in ROMP used ill-defined mixtures of metal salts to initiate polymerization. The initiators most commonly used today, developed with tremendous efforts, are well-defined metal−alkylidene complexes that have enabled a good mechanistic understanding of the polymerization as well as improvement of the initiators’ activity, stability, and functional group tolerance.

The evolution of ROMP has been decidedly metal-centric, with the path to accolades being paved primarily in ruthenium-, molybdenum-, and tungstenbased systems. Our departure from the ROMP trailhead was inspired in part by recent breakthroughs in radical-mediated polymerizations, whereby their mechanisms were leveraged to develop metal-free reaction conditions. Inventing a metal-free complement to traditional ROMP would essentially involve stepping away from decades of inorganic and organometallic developments, but with the promise of crossing new synthetic capabilities and curiosities. Driven by this motivation, as well as a community-inspired desire to develop “greener” controlled polymerizations, our team pioneered the search for, and discovery of, a wholly organic alternative to traditional metal-mediated ROMP. In this Account, we review our recent efforts to develop metal-free ring-opening metathesis polymerization (MF-ROMP), which is inspired by previous reports in electro- and photo-mediated organic transformations.

This work began with an exploration of the direct oxidation of enol ethers and the propensity of the ensuing radical cations to initiate ROMP. To overcome limitations of the electrochemical conditions, a photoredox-mediated method was investigated next, using photoexcited pyrylium salts to oxidize the enol ethers. With this system, we demonstrated the ability to produce ROMP products and temporally control the polymerization.

Further investigations into different aspects of the reaction included monomer scope, functional group tolerance, the impact of changing photocatalyst properties, and the ability to control molecular weight. The unique mechanism of MF-ROMP, along with the relative ease of synthesizing enol ether initiators, enabled the preparation of numerous polymeric materials that are hard to access through traditional metal-mediated pathways. At the end of this Account, we provide a perspective on future opportunities in this emerging area.

Mechanical characterization and constitutive modeling of visco-hyperelasticity of photocured polymers

In this work, we study the nonlinear behavior of soft photocured polymers typically used in 3D-printing. We perform experimental testing of 3D-printed samples cured at various controlled light intensities. The experimental data show the dependency of the material elasticity and rate-sensitivity on the curing light intensity. To elucidate these relations, we develop a physically-based visco-hyperelastic model in the continuum thermodynamics framework. In our model, the macroscopic viscoelastic behavior is bridged to the microscopic molecular chain scale. This approach allows us to express the material constants in terms of polymer chain physical parameters. We consider different physical mechanisms governing hyperelasticity and rate-dependent behaviors. The hyperelastic behavior is dictated by the crosslinked network; whereas, the viscous part originates in the free and dangling chains. Based on our experimental data, we illustrate the ability of the new constitutive model to accurately describe the influence of the light intensity on photocured polymer viscoelasticity.

Not all PLA filaments are created equal: an experimental investigation.

Additive manufacturing (AM) methods such as material extrusion (ME) are becoming widely used by engineers, designers and hobbyists alike for a wide variety of applications. Successfully manufacturing objects using ME three-dimensional printers can often require numerous iterations to attain predictable performance because the exact mechanical behavior of parts fabricated via additive processes are difficult to predict. One of that factors that contributes to this difficulty is the wide variety of ME feed stock materials currently available in the marketplace. These build materials are often sold based on their base polymer material such as acrylonitrile butadiene styrene or polylactic acid (PLA), but are produced by numerous different commercial suppliers in a wide variety of colors using typically undisclosed additive feed stocks and base polymer formulations. This paper aims to present the results from an experimental study concerned with quantifying how these sources of polymer variability can affect the mechanical behavior of three-dimensional printed objects. Specifically, the set of experiments conducted in this study focused on following: several different colors of PLA filament from a single commercial supplier to explore the effect of color additives and three filaments of the same color but produced by three different suppliers to account for potential variations in polymer formulation.