Synthesis of a Liquid Lignin-Based Methacrylate Resin and Its Application in 3D Printing without Any Reactive Diluents.

3D printing of bio-based and renewable polymers such as lignin has gained research attention during the last few decades. We report on the synthesis and characterization of a liquid lignin-based photopolymer and its application in additive manufacturing (AM). Wheat straw soda lignin is liquified in an oxyalkylation reaction with propylene oxide under alkaline conditions and modified with methacryloyl chloride to obtain a lignin-based methacrylate resin. Ninety percent of the functional hydroxyl groups are grafted during the synthesis. The photopolymerization efficiency was evaluated by real-time-NIR-photorheology experiments with two different photoinitiators, leading to double bond conversions (DBC) of ≥80%. 3D-printing experiments of the methacrylated lignin were performed with the hot lithography technology. For the first time, a light-curable lignin derivative with a lignin content of over 30% was successfully 3D printed via vat photopolymerization without any reactive diluents, which is a significant improvement over current state-of-the-art solutions. This outstanding result is a motivating proof of concept and a promising starting point for the in-depth evaluation of bio-based precursors as an alternative to nonrenewable derivatives for 3D printing.

UV-Induced Cationic Ring-Opening Polymerization of 2-Oxazolines for Hot Lithography.

The cationic ring-opening polymerization (CROP) of 2-oxazolines gives polymers with unique characteristics arising from its polyamide backbones and structural versatility. Up to now, poly(2-oxazoline)s were obtained by classical thermal polymerization methods not aiming for application in bulk curing of structural polymers. We introduce the cationic photopolymerization of 2-oxazolines at elevated temperatures for the direct UV-induced curing of materials with exclusive chemical and structural particularities. After efficient photoinitiation via onium salt photoacid generators (PAGs), the immanent low-rate propagation is crucially promoted by thermal energy input to the ring-opening reaction. In simultaneous thermal analysis (STA), photo-DSC, and (thermo)mechanical analyses we investigated the UV-induced CROP of 2-oxazolines in a temperature range of 100-140 °C and show the exceptional potential of the introduced photopolymers. Furthermore, we applied the photopolymerizable system in Hot Lithography, a stereolithography-based 3D printing technology at elevated temperatures.

Vinyl Sulfonate Esters: Efficient Chain Transfer Agents for the 3D Printing of Tough Photopolymers without Retardation.

The formation of networks through light-initiated radical polymerization allows little freedom for tailored network design. The resulting inhomogeneous network architectures and brittle material behavior of such glassy-type networks limit the commercial application of photopolymers in 3D printing, biomedicine, and microelectronics. An ester-activated vinyl sulfonate ester (EVS) is presented for the rapid formation of tailored methacrylate-based networks. The chain transfer step induced by EVS reduces the kinetic chain length of the photopolymer, thus shifting the gel point to higher conversion, which results in reduced shrinkage stress and higher overall conversion. The resulting, more homogeneous network is responsible for the high toughness of the material. The unique property of EVS to promote nearly retardation-free polymerization can be attributed to the fact that after the transfer step no polymerizable double bond is formed, as is usually seen in classical chain transfer agents. Laser flash photolysis, theoretical calculations, and photoreactor studies were used to elucidate the fast chain transfer reaction and exceptional regulating ability of EVS. Final photopolymer networks exhibit improved mechanical performance making EVS an outstanding candidate for the 3D printing of tough photopolymers.

In situ investigation of the kinetics and microstructure during photopolymerization by positron annihilation technique and NIR-photorheology.

The microstructural free volume evolution during a photopolymerization process was studied on a commercial photopolymer (SPOT LV) in situ by positron annihilation lifetime spectroscopy (PALS) and concomitant NIR-photorheology. Analysis of the positron lifetime spectra revealed a high sensitivity of the PALS technique to the different phases of photopolymerization associated with different reaction rates as well as to the evolution of microstructural free-volume shrinkage, which was described at the molecular level by the Kohlrausch-Williams-Watts equation. The in situ PALS study of microstructural changes in photopolymerization was related to the vitrification (gel point) accompanied by shrinkage stress registered via NIR-photorheology. The simultaneous NIR measurements yield information on the monomer conversion of SPOT LV, which can be correlated to the occurrence of the gel point and the evolution of the microstructural free volume. This combined study allows us to see deeper into the crosslinking process and its influence on the resulting material characteristics.

Silane-Acrylate Chemistry for Regulating Network Formation in Radical Photopolymerization.

Photoinitiated silane-ene chemistry has the potential to pave the way toward spatially resolved organosilicon compounds, which might find application in biomedicine, microelectronics, and other advanced fields. Moreover, this approach could serve as a viable alternative to the popular photoinitiated thiol-ene chemistry, which gives access to defined and functional photopolymer networks. A difunctional bis(trimethylsilyl)silane with abstractable hydrogens (DSiH) was successfully synthesized in a simple one-pot procedure. The radical reactivity of DSiH with various homopolymerizable monomers (i.e., (meth)acrylate, vinyl ester, acrylamide) was assessed via 1H NMR spectroscopic studies. DSiH shows good reactivity with acrylates and vinyl esters. The most promising silane-acrylate system was further investigated in cross-linking formulations toward its reactivity (e.g., heat of polymerization, curing time, occurrence of gelation, double-bond conversion) and compared to state-of-the-art thiol-acrylate resins. The storage stability of prepared resin formulations is greatly improved for silane-acrylate systems vs thiol-ene resins. Double-bond conversion at the gel point (DBCgel) and overall DBC were increased, and polymerization-induced shrinkage stress has been significantly reduced with the introduction of silane-acrylate chemistry. Resulting photopolymer networks exhibit a homogeneous network architecture (indicated by a narrow glass transition) that can be tuned by varying silane concentration, and this confirms the postulated regulation of radical network formation. Similar to thiol-acrylate networks, this leads to more flexible photopolymer networks with increased elongation at break and improved impact resistance. Additionally, swelling tests indicate a high gel fraction for silane-acrylate photopolymers.

Metallo-Supramolecular Gels that are Photocleavable with Visible and Near-Infrared Irradiation.

A photolabile ruthenium-based complex, [Ru(bpy)2 (4AMP)2 ](PF6 )2 , (4AMP=4-(aminomethyl)pyridine) is incorporated into polyurea organo- and hydrogels via the reactive amine moieties on the photocleavable 4AMP ligands. While showing long-term stability in the dark, cleavage of the pyridine-ruthenium bond upon irradiation with visible or near-infrared irradiation (in a two-photon process) leads to rapid de-gelation of the supramolecular gels, thus enabling spatiotemporal micropatterning by photomasking or pulsed NIR-laser irradiation.

Real Time-NIR/MIR-Photorheology: A Versatile Tool for the in Situ Characterization of Photopolymerization Reactions.

In photopolymerization reactions, mostly multifunctional monomers are employed, as they ensure fast reaction times and good final mechanical properties of the cured materials. Drawing conclusions about the influence of the components and curing conditions on the mechanical properties of the subsequently formed insoluble networks is challenging. Therefore, an in situ observation of chemical and mechanical characteristics during the photopolymerization reaction is desired. By coupling of an infrared spectrometer with a photorheometer, a broad spectrum of different photopolymerizable formulations can be analyzed during the curing reaction. The rheological information (i.e., time to gelation, final modulus, shrinkage force) can be derived from a parallel plate rheometer equipped with a UV- and IR-translucent window (glass for NIR and CaF2 window for MIR). Chemical information (i.e., conversion at the gel point and final conversion) is gained by monitoring the decrease of the corresponding IR-peak for the reactive monomer unit (e.g., C═C double bond peak for (meth)acrylates, H-S thiol and C═C double bond peak in thiol-ene systems, C-O epoxy peak for epoxy resins). Depending on the relative concentration of reactive functional groups in the sample volume and the intensity of the IR signal, the conversion can be monitored in the near-infrared region (e.g., acrylate double bonds, epoxy groups) or the MIR region (e.g., thiol signal). Moreover, an integrated Peltier element and external heating hood enable the characterization of photopolymerization reactions at elevated temperatures, which also widens the window of application to resins that are waxy or solid at ambient conditions. By switching from water to heavy water, the chemical conversion during photopolymerization of hydrogel precursor formulations can also be examined. Moreover, this device could also represent an analytical tool for a variety of thermally and redox initiated systems.

Tetraacylgermanes: Highly Efficient Photoinitiators for Visible-Light-Induced Free-Radical Polymerization.

In this contribution a convenient synthetic method to obtain tetraacylgermanes Ge[C(O)R]4 (R=mesityl (1 a), phenyl (1 b)), a previously unknown class of highly efficient Ge-based photoinitiators, is described. Tetraacylgermanes are easily accessible via a one-pot synthetic protocol in >85 % yield, as confirmed by NMR spectroscopy, mass spectrometry, and X-ray crystallography. The efficiency of 1 a,b as photoinitiators is demonstrated in photobleaching (UV/Vis), time-resolved EPR (CIDEP), and NMR/CIDNP investigations as well as by photo-DSC studies. Remarkably, the tetraacylgermanes exceed the performance of currently known long-wavelength visible-light photoinitiators for free-radical polymerization.

Exploring Network Formation of Tough and Biocompatible Thiol-yne Based Photopolymers.

This work deals with the in-depth investigation of thiol-yne based network formation and its effect on thermomechanical properties and impact strength. The results show that the bifunctional alkyne monomer di(but-1-yne-4-yl)carbonate (DBC) provides significantly lower cytotoxicity than the comparable acrylate, 1,4-butanediol diacrylate (BDA). Real-time near infrared photorheology measurements reveal that gel formation is shifted to higher conversions for DBC/thiol resins leading to lower shrinkage stress and higher overall monomer conversion than BDA. Glass transition temperature (Tg ), shrinkage stress, as well as network density determined by double quantum solid state NMR, increase proportionally with the thiol functionality. Most importantly, highly cross-linked DBC/dipentaerythritol hexa(3-mercaptopropionate) networks (Tg ≈ 61 °C) provide a 5.3 times higher impact strength than BDA, which is explained by the unique network homogeneity of thiol-yne photopolymers.

Frontal polymerization: polymerization induced destabilization of peracrylates.

Frontal photopolymerization has attracted much attention in the last decade as it allows the curing of thick films. Unfortunately, the use of peroxides, which feature appropriate storage stability, also requires inappropriately high initiation temperatures. Here, a new approach involving a copolymerisation-induced destabilization of (meth)acrylate-based peroxides that allows lower front temperatures is presented. The increasing degree of branching next to the carbonyl group lowers the decomposition temperature by at least 20 °C. In classical monomer formulations, sufficient storage stability is confirmed.