Photopolymerization Process Research Articles

Sculpting Mechanical Properties of Hydrogels by Patterning Seamlessly Interlocked Stiff Skeleton

AbstractFunctional soft materials, especially hydrogels have been widely developed to achieve various soft structures and machines. However, synthetic hydrogels commonly show formula‐dependent mechanical properties to fulfill the requirements of mechanical elasticity, stiffness, toughness, and tearing‐resistance for adapting to complex application scenario. Inspired by heterostructures and materials found in nature such as leaves and insect wings, a sequential photopolymerization process combined with site‐selective patterning exposure is reported to prepare programmable hydrogels with locally heterogeneous reinforcement skeletons, i.e., interpenetrating double networks. The heterogeneous interface between soft matrices and stiff skeletons is seamlessly interlocked through strong multiple hydrogen bonds induced by phase transition. By harnessing the size, shape, and distribution of the patterned stiff skeletons, a wide range of mechanical properties of hydrogels including modulus (0.32–5.92 MPa), toughness (0.15–18 kJ m−2), dissipated energy (1–100 kJ m−3), impact resistance, and mechanical anisotropy can be readily sculpted within one material system without needing design and optimization of the complex and elusive material formulation on demand. It is believed that this simple yet powerful method relying on heterogenous patterning would guide the development of functional hydrogel materials with programmable mechanical properties toward potential engineering applications, such as damping and flexible circuits.

The Effects of Intensity, Exposure Time, and Distance of Polymerization Light on Vickers Microhardness and Temperature Rise of Conventional Resin-Based Composite.

(1) Background: This study investigates the effects of curing light intensity, exposure time, and distance on the Vickers microhardness (VMH), hardness bottom-to-top ratio (HR), and temperature rise (TR) of conventional dental resin-based composite (RBC). (2) Materials and Methods: Specimens of one conventional RBC (Tetric EvoCeram, Ivoclar Vivadent) were cured with 12 different curing protocols (CPs), created with three different light intensities (Quartz Tungsten Halogen 300 mW/cm2, LED 650 mW/cm2, LED 1100 mW/cm2), two exposure times (20 and 40 s), and two distances of curing tip (0 and 8 mm). The VMH of top (VMH-T) and bottom (VMH-B) surfaces was measured. The hardness bottom-to-top ratio (HR) was calculated from VMH-B and VMH-T. The HR below 80% was rated as inadequate polymerization. The TR at the depth of 2 mm within the RBC was measured using a K-type thermocouple. Data were analyzed using Levene's test and the multivariate analysis of variance (MANOVA). The level of significance was set at p < 0.05. (3) Results: Exposure time and distance significantly influenced VMH-B and HR. Increased distance significantly reduced VMH-B, HR, and TR. CPs 300 mW/cm2/8 mm/20 s and 650 mW/cm2/8 mm/20 s produced inadequate polymerization (HR < 80%). Prolonged exposure time produced higher values of VMH-B and HR. The TR was significantly influenced by light intensity and distance. (4) Conclusions: Suboptimal light intensity (<800 mW/cm2) can produce inadequate polymerization at the lower side of the composite layer when used from a distance. Prolonged irradiation can improve the polymerization to a certain extent. Clinicians are advised to monitor the intensity of the LCUs in order to optimize the photopolymerization process. Caution is required when polymerizing with high-intensity curing light in direct contact with the RBC with longer exposure times than recommended.

Naturally Inspired Tree-Ring Structured Dressing Provides Sustained Wound Tightening and Accelerates Closure.

Mechanically regulated wound dressings require a rational combination of contraction and adhesion functions as well as balancing exudate-induced swelling issues. However, many of the reported dressings face the dilemma of impaired function and impeded wound self-contraction due to fluid-absorbing swelling. In this study, inspired by the tree ring, a core-ring structured hydrogel dressing capable of mechanical modulation is designed, and prepare it using a simple two-step photopolymerization process. The core covers the center of the wound, contracts spontaneously at body temperature to generate a contractile force of 3.4kPa, and resists swelling. Meanwhile, the ring adheres to the normal epidermis around the wound and transfers the contraction stress to the wound edge. The integration of a functionally independent core and ring ultimately achieves effective wound traction and avoids dressing swelling. In murine and porcine skin wound-healing models, this hydrogel with a closely connected core and ring promotes healing by accelerating epidermal closure (50% closure in mouse skin on day 2, 85% closure in pig skin on day 8), collagen deposition, vascular maturation, and extracellular matrix remodeling. These results can guide further research on mechanical force modulation in wound healing, with the potential for clinical translation.

Fabrication of Microstructured Hydrogels via Dehydration for On-Demand Applications.

Microstructured hydrogels show promising applications in various engineering fields from micromolds to anisotropic wetting surfaces and microfluidics. Although methods like molding by, e.g., casting as well as 3D printing are developed to fabricate microstructured hydrogels, developing fabrication methods with high controllability and low-cost is an on-going challenge. Here, a method is presented for creating microstructures through the dehydration of double network hydrogels. This method utilizes common acrylate monomers and a mask-assisted photopolymerization process, requiring no complex equipment or laborious chemical synthesis process. The shape and profile of microstructures can be easily controlled by varying the exposure time and the mask used during photopolymerization. By altering the monomer and the mask used for fabricating the second network hydrogel, both convex and concave microstructures can be produced. To showcase the utility of this method, the patterned hydrogel is utilized as a mold to fabricate a polydimethylsiloxane microlens array via soft lithography for imaging application. In addition, a patterned hydrogel surface exhibiting obvious anisotropic wetting properties and open microfluidic devices which can achieve fast directional superspreading within milliseconds are also fabricated to demonstrate the versatility of the method for different engineering fields.

Vat Photopolymerization 3D Printing of Hydrogels Embedding Metal-Organic Frameworks for Photodynamic Antimicrobial Therapy.

Given the variability in wounds based on the underlying causes, personalized medicine and tailored care for patients with wounds are required to ensure optimal therapeutic outcomes. With the emergence of high-precision and high-efficiency photocuring 3D printing technology, there is the potential for its use in customizing precise shapes that can match complex wound sites, thereby providing better treatment for patients with wound infections. In this work, porphyrinic metal-organic framework (MOF) crystals, serving as the functional filler, were incorporated into gelatin methacrylate (GelMA) as a photocurable composite resin to investigate the capabilities of producing customizable wound dressings through vat photopolymerization 3D printing. The embedded MOF crystals allow for better control of the photopolymerization process due to photon competition with the photoinitiator, enabling the precise printing of complex structures. In addition, these crystals impart photothermal and photodynamic capabilities to the printed object. The antibacterial assay confirms the potent photothermal and photodynamic bactericidal properties of the printed GelMA/MOF hydrogels. The hydrogel with the highest MOF content exhibited over 99.99% antibacterial efficiency against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli after 30 min of light exposure (∼30 mW/cm2, λ ≥ 420 nm). Simultaneously, hemolysis and cytotoxicity evaluations validated their excellent biocompatibility. The findings presented here introduce a strategy for integrating photosensitive MOF and 3D printing to fabricate size-adjustable photothermal/photodynamic monoliths and patches, opening perspectives toward personalized treatment for wound management.

Photopolymerization of Chlorpromazine-Loaded Gelatin Methacryloyl Hydrogels: Characterization and Antimicrobial Applications.

This study investigates the synthesis, characterization, and antimicrobial properties of hydrogels synthesized through the UV-pulsed laser photopolymerization of a polymer-photoinitiator-chlorpromazine mixture. Chlorpromazine was used for its known enhanced antimicrobial properties when exposed to UV laser radiation. The hydrogel was formed from a mixture containing 0.05% Irgacure 2959, 10% gelatin methacryloyl, and various concentrations of chlorpromazine (1, 2, and 4 mg/mL). Laser-induced fluorescence spectroscopy was employed to monitor the photoinduced changes of chlorpromazine and Irgacure 2959 during hydrogel formation, providing insight into the photodegradation dynamics. FTIR spectroscopy confirmed the incorporation of irradiated chlorpromazine within the hydrogel matrix, while the release profiles of chlorpromazine showed sustained release only in hydrogels containing 1 mg/mL of CPZ. The hydrogel showed significant antimicrobial activity against MRSA bacteria when compared to that of penicillin. These findings highlight the potential of CPZ loaded during the photopolymerization process into hydrogels as effective antimicrobial agents with sustained release properties, making them suitable for combating resistant bacterial strains.

Octaphenyl-POSS nanoparticles dispersed thick polyvinyl alcohol/acrylamide photopolymer with low volumetric shrinkage and high diffraction efficiency.

Relatively high volumetric shrinkage induced by polymerization of photopolymer severely limits its applications in high-density holographic storage. In this paper, what we believe to be a novel organic-inorganic hybrid nanoparticles (NPs) of octaphenyl-polyhedral Oligomeric silsesquioxane (POSS) are employed into polyvinyl alcohol (PVA)/acrylamide photopolymer with 300µm thickness. By optimizing the concentration of octaphenyl-POSS, the volumetric shrinkage is successfully suppressed from 1.11% to 0.41%, and satisfies the requirements of commercial holographic data storage (HDS) material. Moreover, the introduction of POSS NPs does not sacrifice other holographic recording capacities. Contrarily, the diffraction efficiency of photopolymer after dispersing 2‰(w/v) POSS increases from 86% to 90%. The physical mechanism of enhanced capacities is discussed by using photopolymerization and NPs diffusion process. To our knowledge, this is the best results of PVA/acrylamide photopolymer with low volumetric shrinkage, high diffraction efficiency and angular selectivity. The POSS-dispersed photopolymer system is expected to have good application prospects in angular-multiplexing high-density 3-D holographic storage.

Rapid investment casting: a techno-economic analysis for evaluating VAT photopolymerisation processes

Adopting additive manufacturing in investment casting, known as rapid investment casting, can significantly reduce lead time and cost. Despite many publications on these technologies, no quantitative techno-economic analyses refer to rapid investment casting. The paper provides helpful insights and a decision-making approach for replacing conventional production technologies (i.e. wax injection) with additive manufacturing technologies. The study is based on a techno-economic analysis framework. It allows assessing key performance indicators (e.g. crossover points and payback periods) for stakeholders to decide the suitable VAT photopolymerisation processes (i.e. stereolithography, digital light processing, and material jetting) according to specific production scenarios (i.e. load factors). Analytical cost models were developed in the frame of this work to assess the time and cost of the overall manufacturing process of the resin model for investment casting, considering the post-processing stages for each of the technologies investigated. The cost models were used to assess the benefits introduced by additive manufacturing in rapid investment casting. A sensitivity analysis evaluated the impact of energy, material, and labour costs for both key performance indicators (crossover points and payback periods). The techno-economic analysis yielded the following results: (i) crossover points in terms of production costs vary, ranging from thousands of units for small components in the jewellery or fashion industries to a few dozen units for larger parts in the mechanical industry, and (ii) crossover points in terms of time are lower than those related to cost. Additionally, digital light processing is regarded as the most promising technology, offering the best crossover points and payback periods across various scenarios, mainly when 3D printers are used at a low utilisation rate.

Multifractal signatures of light-driven self-organization in acrylated epoxidized soybean oil polymers

Multifractal properties of acrylated epoxidized soybean oil with and without a photoinitiator have been investigated. Using multifractal detrended fluctuation analysis, the photopolymerization process is analyzed by varying illumination duration and intensity. The research is conducted in two stages: the results concerning temperature fluctuations of the entire photoirradiation process are initially presented followed by a sliding window procedure to monitor system complexity during light cycling. Various multifractal mea-sures including the generalized Hurst exponent h(q), the multifractal Rényi exponent τ(q), the generalized fractal dimensions D(q) with the left and right side curvature (ΔDL, ΔDR), the multifractal singularity exponents α, the multifractal spectrum f (α), and the multifractal heat capacity C(q) with its integrated characteristic Carea are examined for both initial and shuffled series. The empirical results demonstrate that the moments of switching on and switching off photoirradiation are characterized by an instantaneous increase in the degree of multifractality of the system. It is hypothesized that the observed increase in multi-fractality at the light-switching-on/off stages is indicative of a quasi-phase transition, which may be associated with the transformation of orientational defects in the polymer network.

Exploring the Adaptability of 4D Printed Shape Memory Polymer Featuring Dynamic Covalent Bonds.

4D printing (4DP) of high-performance shape memory polymers (SMPs), particularly using digital light processing (DLP), has garnered intense global attention due to its capability for rapid and high-precision fabrication of complex configurations, meeting diverse application requirements. However, the development of high-performance dynamic shape memory polymers (DSMPs) for DLP printing remains a significant challenge due to the inherent incompatibilities between the photopolymerization process and the curing/polymerization of high-strength polymers. Here, a mechanically robust DSMP compatible is developed with DLP printing, which incorporates dynamic covalent bonds of imine linking polyimide rigid segments, exhibiting remarkable mechanical performance (tensile strength ≈41.7MPa, modulus ≈1.63GPa) and thermal stability (Tg ∼ 113°C, Td ∼ 208°C). More importantly, benefiting from the solid-state plasticity conferred by dynamic covalent bonds, 4D printed structures demonstrate rapid network adaptiveness, enabling effortless realization of reconfiguration, self-healing, and recycling. Meanwhile, the extensive π-π conjugated structures bestow DSMP with an intrinsic photothermal effect, allowing controllable morphing of the 4D configuration through dual-mode triggering. This work not only greatly enriches the application scope of high-performance personalized configurations but also provides a reliable approach to addressing environmental pollution and energy crises.

Analysis of Mechanical Properties and Parameter Dependency of Novel, Doubly Re-Entrant Auxetic Honeycomb Structures.

This study proposes a new, doubly re-entrant auxetic unit-cell design that is based on the widely used auxetic honeycomb structure. Our objective was to develop a structure that preserves and enhances the advantages of the auxetic honeycomb while eliminating all negative aspects. The doubly re-entrant geometry design aims to enhance the mechanical properties, while eliminating the buckling deformation characteristic of the re-entrant deformation mechanism. The effects of the geometric modification are described and evaluated using two parameters, offset and deg. A series of experiments were conducted on a wide range of parameters based on these two parameters. Specimens were printed via the vat photopolymerization process and were subjected to a compression test. Our aim was to investigate the mechanical properties (energy absorption and compressive force) and the deformation behaviour of these specimens in relation to the relevant parameters. The novel geometry achieved the intended properties, outperforming the original auxetic honeycomb structure. Increasing the offset and deg parameters results in increasing the energy absorption capability (up to 767%) and the maximum compressive force (up to 17 times). The right parameter choice eliminates buckling and results in continuous auxetic behaviour. Finally, the parameter dependency of the deformation behaviour was predicted by analytical approximation as well.

Antimicrobial Coatings Based on a Photoreactive (Meth)acrylate Syrup and Ferulic Acid-The Effectiveness against Staphylococcus epidermidis.

A novel photopolymerizable (meth)acrylate oligomer syrup modified with ferulic acid (FA) was verified as an antimicrobial coating binder against a biofilm of Staphylococcus epidermidis. A solution-free UV-LED-initiated photopolymerization process of aliphatic (meth)acrylates and styrene was performed to prepare the oligomer syrup. The influence of ferulic acid on the UV crosslinking process of the varnish coatings (kinetic studies using photo-DSC) as well as their chemical structure (FTIR) and mechanical (adhesion, hardness), optical (gloss, DOI parameter), and antibacterial properties against S. epidermidis were investigated. The photo-DSC results revealed that FA has a positive effect on reducing the early occurrence of slowing processes and has a favorable effect on the monomer conversion increment. It turned out, unexpectedly, that the more FA in the coating, the greater its adhesion to a glass substrate and hardness. The coating containing 0.9 wt. part of FA exhibited excellent antimicrobial properties against S. epidermidis, i.e., the bacterial number after 24 h was only 1.98 log CFU/mL. All the coatings showed relatively high hardness, gloss (>80 G.U.), and DOI parameter values (30-50 a.u.).

Response mechanisms for the photopolymerization profiles, microstructures, and properties in ceramics prepared by stereolithography

Insight into the response mechanisms among the photopolymerization process, profile curves, microstructure, and physicomechanical properties is essential for microstructural and performance control during ceramic stereolithographic manufacturing. This work establishes and validates the photopolymerization profile equation and investigates the response mechanisms of photopolymerization profiles on microstructures and lamellar defects and the response mechanisms of cured powder concentration gradient on dimensional shrinkage, porosity, and physicomechanical properties. The results illustrate that the profile control equations perfectly predict the photopolymerization experiment profile and the lamellar profile shape to control the volume of lamellar defects, and the surface microstructures are mainly affected by the z-direction lamellar profile. The optimal surface roughness values of the green bodies before and after sintering are 3.95 μm and 3.32 μm, respectively. Besides, the attenuation of the Gaussian-distributed laser intensity in the slurry results in a gradient change in double-bond conversion to create a gradient in the cured powder concentration. The z-direction shrinkage strongly correlated with the cured powder concentration is much greater than the x- and y-direction shrinkages. The variation range of the anisotropic shrinkage is from 1.54 % to 3.77 %. Furthermore, the cured powder concentration on the top area of the cured layer near the laser irradiation is greater than that on the bottom area away from the irradiation, influencing the physicomechanical properties. Finally, the best process parameters for multiobjective optimization are achieved by combining response surface experiments and principal components analysis. The response mechanisms of the lamellar profile and cured powder concentration are expected to provide new ideas for controlling the performance of vat photopolymerization.

A photo-chemo-mechanical coupling constitutive model for photopolymerization-based 3D printing hydrogels

Photopolymerization-based 3D printing has emerged as a key technology in hydrogel manufacturing, broadening the attributes of hydrogels and extending their applications into diverse engineering fields. However, the mechanical properties of hydrogels dramatically impact the functionality and quality in practice. It is necessary to develop an appropriate theoretical model to predict the evolution of the mechanical properties of hydrogels during the photopolymerization process. In this work, systematical experiments were performed to investigate mechanical properties of PAAm hydrogel under different photopolymerization condition. The results reveal a noticeable increasement in both elastic and viscous behavior of hydrogel with the advancement of polymerization. To fully capture the experimental observations, we developed a coupled photo-chemo-mechanical theoretical framework that integrates reaction kinetics with a physically-based viscoelastic constitutive model. Within this model, the degree of conversion serves as an internal variable, which related to microscopic structures such as correlation length, and tube diameter. The developed model exhibits remarkable prediction ability for hydrogels with various degree of polymerization. The current work paves a potentially new avenue for understanding the evolution of mechanical properties in photopolymerized hydrogels, providing theoretical guidance for the manufacturing of hydrogels through photopolymerization-based 3D printing.

UV‐cured epoxy‐acrylate interpenetrating polymer networks with different contents of epoxidized soybean oil

AbstractThis work aims to study the effect of epoxidized soybean oil (ESO) concentration on the process of formation and characteristics of UV‐cured ternary epoxy‐acrylate interpenetrating polymer networks (IPNs). Whereas the amount of triethylene glycol dimethacrylate (TEGDMA) keeps constant, the one of ESO incorporated to substitute the respective quantity of diglycidyl ether of bisphenol A (DGEBA) is equal to 10, 20, and 30 parts by weight (pbw). A total of 30 pbw of ESO is found to be the most effective content for altering the conversion degree of epoxy groups and for enhancing the impact resistance of cured materials while providing their transparency. The addition of ESO induces the decrease in cross‐linking density and in the values of glass transition temperature. The samples exhibite good water and chemical resistance with some variations dependent on their composition. Thermooxidative stability of the specimens gradually reduces as the content of aromatic epoxy decreases. Overall, the introduction of ESO into epoxy‐acrylate IPNs not only lessens the fraction of synthetic epoxide but also facilitates the photopolymerization process of DGEBA and diminishes its brittleness. Considering fine atmospheric resistance testified by accelerated weathering test, given materials may be purposed as transparent films or protective coatings for both indoor and outdoor applications.

A few aspects of controlling the photopolymerisation process in additive manufacturing

A few aspects of controlling the photopolymerisation process in additive manufacturing

In vitro Comparison of the Efficiency of Celluloid and Metallic Matrices in Proximal Restorations with a Bulk Polymer-based Biomaterial

The purpose of the study was the comparison of the contact tightness of the restored proximal area of lateral teeth with celluloid and metallic matrices and a bulk polymer-based biomaterial using an original in vitro assessing method.In 300 plastic right upper molars, mesial and distal vertical boxes (4 mm width in all directions) were prepared. 150 teeth were restored using circumferential celluloid bands and the rest were restored with sectional metallic saddle bands with the same thickness. The mesial/distal contact tightness was measured, before preparations and after restorations using dental floss and an original system consisting in a dynamometer connected to the model fixed on a plate that could slide gravitationally on vertical metallic rails actioned by a mass of 850 g attached with a string. The passing through force was recorded. For the mesial surfaces, the force varied from 4.782 � 0.014 N (sound) to 5.086 � 0.011 N (restored) (p [ 0.05) for circumferential celluloid matrix while for the sectional metallic matrix, the values varied from 4.787 � 0.016 N (sound) to 5.596 � 0.01 N (restored) (p [ 0.05). For the distal surfaces, the force varied from 5.589 � 0.01 N (sound) to 4.777 � 0.011 N (restored) (p [ 0.05) for circumferential celluloid matrix while, for the sectional metallic matrix, the values varied from 5.586 � 0.012 N (sound) to 5.793 � 0.015 N (restored) (p [ 0.05). Comparing to the sound surfaces, the bulk polymer-based material with high consistency and the circumferential celluloid matrices generated poorer distal and slightly stronger mesial contact area tightness while the sectional metallic ones drove to stronger mesial and distal contacts. However, the celluloid bands are often preferred because they allow the photopolymerization process and permit a good visual control during most of the steps of the working protocol.

Photopolymerization Approach to Advanced Polymer Composites: Integration of Surface-Modified Nanofillers for Enhanced Properties.

The incorporation of functionalized nanofillers into polymers via photopolymerization approach has gained significant attention in recent years due to the unique properties of the resulting composite materials. Surface modification of nanofillers plays a crucial role in their compatibility and polymerization behavior within the polymer matrix during photopolymerization. This review focuses on the recent developments in surface modification of various nanofillers, enabling their integration into polymer systems through photopolymerization. The review discusses the key aspects of surface modification of nanofillers, including the selection of suitable surface modifiers, such as photoinitiators and polymerizable groups, as well as the optimization of modification conditions to achieve desired surface properties. The influence of surface modification on the interfacial interactions between nanofillers and the polymer matrix is also explored, as it directly impacts the final properties of the nanocomposites. Furthermore, the review highlights the applications of nanocomposites prepared by photopolymerization, such as sensors, gas separation membranes, purification systems, optical devices, and biomedical materials. By providing a comprehensive overview of the surface modification strategies and their impact on the photopolymerization process and the resulting nanocomposite properties, this review aims to inspire new research directions and innovative ideas in the development of high-performance polymer nanocomposites for diverse applications.

Aryl structural effect on the photoinitiation abilities of aryl glycine derivatives for polymerization upon exposure to blue light

AbstractThe design and development of photoinitiating systems applicable to visible light delivered from light‐emitting diodes (LEDs) have attracted increasing attention owing to the wide application of photopolymerization. In this study, four aryl glycine derivatives are designed and synthesized, and their applicability as visible light‐sensitive photoinitiators is thoroughly investigated. Specifically, the photoinitiation mechanism of these aryl glycine derivatives, when combined with iodonium salt, is investigated using steady‐state photolysis, fluorescence, and electron paramagnetic resonance spin trapping techniques. It is revealed that radicals can be generated from aryl glycine derivatives/iodonium salt combinations upon exposure to blue LEDs (410 and 445 nm) to induce free radical photopolymerization (FRP) of (meth)acrylates. Additionally, besides FRP, a photobase generator based on one of the investigated aryl glycine derivatives is synthesized and demonstrates the capability to initiate epoxy‐thiol polymerization under light irradiation. The remarkable photolatent characteristics demonstrate the significant potential in broadening the application of aryl glycine derivatives in controlled photopolymerization processes.

Quercetin allylation and thiol–ene click photopolymerization to produce biobased polymer thermosets with robust thermomechanical properties

AbstractThe development of biobased and functionalized monomers along with eco‐friendly photopolymerization processes represent promising methods for the development of renewable and more environmentally friendly thermosets. Thiol–ene ‘click’ photopolymerization is particularly advantageous in this regard; however, the materials derived from this method often exhibit low glass transition temperatures (Tg) and unsuitable thermomechanical properties for applications at room temperature. Herein, we report the synthesis of biobased allyl derivatives from quercetin, a renewable flavonoid compound widely available in fruits, vegetables and plants. We demonstrated the isolation of tetra‐ and penta‐allylated quercetin (Q1 and Q2, respectively) and their subsequent photoactivated thiol–ene polymerization. By introducing a biobased thiol curing agent (PTTMP) derived from glycerol and mercaptopropionic acid, we produced fully biobased crosslinked thermosets with high content of aromatic moieties provided by the framework of the monomers. Real‐time infrared spectroscopy showed the effective thiol–ene photopolymerization of Q1 and Q2 and PTTMP with conversions of 60% and 75%, respectively, after 15 min of UV irradiation. Due to the modulated crosslinking degree from the allyl group functionalization in the monomers, the biobased crosslinked networks showed storage moduli from 420 to 739 MPa, thermal stability from 220 to 257 °C and Tg values ranging from 75 to 90 °C. This work outlines straightforward strategies for creating biobased thermosets that overcome the limited thermomechanical properties of thiol–ene networks and offer potential antimicrobial and antioxidant properties. © 2024 Society of Chemical Industry.