Search Results (31)

This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), and 4,4′-methylenebis(N,N-diallylaniline) (ACA4). This unique combination enables the simultaneous activation of four polymerization mechanisms: radical photopolymerization, thiol-ene coupling, thiol-Michael addition, and anionic ring-opening, within a single resin matrix. A key innovation lies in the exothermic nature of DADS photopolymerization, which initiates and sustains ETES curing at room temperature, enabling 3D printing without thermal assistance. This represents a significant advancement over conventional systems that require elevated temperatures or post-curing steps. The resulting hybrid poly(acrylate–co-ether–co-thioether) network exhibits enhanced mechanical integrity, shape memory behavior, and intrinsic self-healing capabilities. Dynamic Mechanical Analysis revealed a shape fixity and recovery of 93%, while self-healing tests demonstrated a 94% recovery of viscoelastic properties, as evidenced by near-overlapping storage modulus curves compared to a reference sample. This integrated approach broadens the design space for multifunctional photopolymers and establishes a versatile platform for advanced applications in soft robotics, biomedical devices, and sustainable manufacturing. Full article

The photopolymerization process in 3D printing is considered greener once it involves a fast reaction and low energy consumption. Various reactions for photopolymerization can be used nowadays, but a special one is the thiol-ene “click” reaction that occurs in equimolar concentrations of thiol and alkene groups. In this sense, solvent-free photopolymerizable formulations were prepared to contain non-modified castor oil, Trimethylolpropane tris(3-mercapto propionate), and cellulosic fillers from hemp, tagua, and walnut. All formulations presented conversions higher than 70% and fast polymerization rates. Moreover, the filled formulations presented excellent curing depths in fewer seconds of light exposition, an important factor for their applicability in 3D printing. Furthermore, the hemp filler formulation presented the highest crosslinking density as determined by the DMTA, and was selected for printing two complex structures (pyramid and honeycomb shape). The rheology analysis showed that the formulations had adequate viscosities for the printer. Lastly, all polymers presented at least 97% bio-based contents, with gel contents superior to 96%. Full article

Three novel bio-based monomers were synthesized through an amidation reaction involving allylated derivatives of coumaric, ferulic and phloretic acid and a diamine obtained from a thiol-ene coupling reaction between limonene and cysteamine. The monomers containing the enone bond of the cinnamic moiety underwent photoisomerization and photocycloaddition reactions upon UV light irradiation. All three monomers were photocured via thiol-ene photopolymerization using a glycerol-derived trifunctional thiol, resulting in fully bio-based poly(amide–thioether)s. The polymers derived from monomers that contain the enone bond exhibited glass transition (T_g) temperatures of 85 °C when a stoichiometric ratio of the thiol was used, whereas polymers in which an excess of thiol was used exhibited T_g temperatures of 61 and 74 °C. The higher T_g of the synthesized polymers, compared with other reported polymers produced from thiol-ene photopolymerizations, was attributed to the combination of the aromatic rings of the cinnamic moiety and the cycloaliphatic ring of limonene, as well as the presence of the amide groups in the polymer, which can induce hydrogen bonding. The development of high T_g polymers from bio-based monomers through thiol-ene photopolymerization represents a significant advancement in the polymer synthesis sector, offering an improved performance and sustainability. Full article

Bioinks play a fundamental role in skin bioprinting, dictating the printing fidelity, cell response, and function of bioprinted 3D constructs. However, the range of bioinks that support skin cells’ function and aid in the bioprinting of 3D skin equivalents with tailorable properties and customized shapes is still limited. In this study, we describe a bioinspired design strategy for bioengineering double crosslinked pectin-based bioinks that recapitulate the mechanical properties and the presentation of cell-adhesive ligands and protease-sensitive domains of the dermal extracellular matrix, supporting the bioprinting of bilayer 3D skin models. Methacrylate-modified pectin was used as a base biomaterial enabling hydrogel formation via either chain-growth or step-growth photopolymerization and providing independent control over bioink rheology, as well as the mechanical and biochemical cues of cell environment. By tuning the concentrations of crosslinker and polymer in bioink formulation, dermal constructs were bioprinted with a physiologically relevant range of stiffnesses that resulted in strikingly site-specific differences in the morphology and spreading of dermal fibroblasts. We also demonstrated that the developed thiol-ene photo-clickable bioinks allow for the bioprinting of skin models of varying shapes that support dermis and epidermis reconstruction. Overall, the engineered bioinks expand the range of printable biomaterials for the extrusion bioprinting of 3D cell-laden hydrogels and provide a versatile platform to study the impact of material cues on cell fate, offering potential for in vitro skin modeling. Full article

In this work, new partially substituted derivatives of octa(3-thiopropyl)silsesquioxane (SSQ-8SH) were synthesized. The article compares the thiol-ene reaction using two methods: radical mechanism, thermally initiated (AIBN), and in the presence of a photoinitiator (DMPA). Both the crystalline and the oil forms of SSQ-8SH were functionalized. Olefins with nonpolar alkyl groups (hexene, octene, and octadecene) and vinyltrimethoxysilane, allyl glycidyl ether, allyl 2,2,3,3,4,4,5,5-octafluoropentylether, allyl methacrylate, and styrene were used in the reactions, allowing to obtain seven new derivatives. All compounds were characterized using spectroscopic (¹H NMR and ²⁹Si NMR) and spectrometric (MALDI-TOF-MS) methods. The influence of functional groups on the water contact angle value was determined. The functionalization of the compound led to a contact angle value above 95° (SSQ-4SH-4OD). Density measurements and thermogravimetric analysis (TGA) were carried out for all compounds. The highest onset temperature (357.4 °C) and temperature at the maximum mass loss rate (377.3 °C) were observed for SSQ-SH-4OD. The addition of alkyl groups significantly decreased the density of compounds with increasing chain length (1.198 g/cm³; 1.162 g/cm³; 1.095 g/cm³ for hexene, octene, and octadecene, respectively). Silsesquioxanes have potential applications in various materials, such as UV-curable resins, allowing to modify, for example, their surface properties. Modification of a commercial photocurable resin with selected derivatives was carried out to determine the impact on physicochemical properties (TGA, WCA). Full article

An eco-friendly epoxy/thiol-ene photopolymerization (ETEP) process was employed to prepare epoxy bio-composites using a commercial biobased epoxy resin and a woven jute fabric as reinforcement. In this process the components of the thiol-ene system, an allyl-functionalized ditertiary amine curing agent, a multifunctional thiol and a radical photoinitiator, were added to the epoxy resin to produce a polyether–polythioether crosslinked co-network. Moreover, the jute fibers were functionalized with thiol groups using the 3-mercaptopropyl (trimethoxysilane) with the purpose of creating a chemically bonded polymeric matrix/fiber system. The obtained bio-composites prepared with the thiol-functionalized cellulose fibers exhibited an increase up to 52% and 40% in flexural modulus and strength with respect to the non-functionalized counterparts. Under the three-point bending loadings, the composites displayed higher deformation at break and toughness due to the presence of polythioethers in the co-network. The prepared bio-composites developed in this work are excellent candidates to extend the use of cellulose fibers for structural applications. Full article

This study is focused on the structural influence of 1,2,4-triazolium ionic liquid (IL), that is, the effect of the length of the substituent and the type of substitution (1-methyl-4-alkyl or 1-alkyl-4-methyl) used in the mixture with propylene carbonate (PC) on the properties of thiol–ene polymer ionogels and on the preparation of an ionogel with satisfactory mechanical and conductive properties. PC allows for higher conductivity but also causes electrolyte leakage from the gel. When using triazolium IL (instead of the imidazolium one), because of the stronger interactions between components of the system, the ionogels do not leak. In this study, 1,4-dialkyl-1,2,4-triazolium ILs were successfully synthesized by the alkylation of 1,2,4-triazole. Subsequently, gel polymer electrolytes were obtained by one-pot thiol–ene photopolymerization reactions of tetrafunctional thiols with different chemical structures: pentaerythritol tetra(3-mercaptopropionate) (PETMP) or pentaerythritol tetra(3-mercaptobutyrate) (PETMB) and trifunctional ene (TATT) in the presence of a mixture of 1,4-dialkyl-1,2,4-triazolium IL with PC. Measurements made by electrochemical impedance spectroscopy showed that all ionogels with TATT+PETMB as a polymer matrix presented smaller relative ionic conductivity compared to ionogels containing TATT+PETMP. The puncture resistance and elongation at puncture, measured by the puncture resistance method, were higher for ionogels with poly(TATT+PETMB) than for those with poly(TATT+PETMP). Moreover, ILs containing a methyl group in position N1 of the 1,2,4-triazole ring presented lower puncture resistance than ionogels with ILs containing a methyl group in position N4, especially for shorter alkyl chains. Additionally, the photo-differential scanning calorimetry method was employed to characterize the course of photopolymerization. The compositions and their constituents were characterized by UV and IR spectroscopy. Full article

This study describes the synthesis of a curing agent derived from limonene as well as its application to prepare biobased thermoset polymers via the epoxy/thiol-ene photopolymerization (ETE) method. A biobased commercial epoxy resin was used to synthesize a crosslinked polymeric matrix of polyether-polythioether type. The preparation of the curing agent required two steps. First, a diamine intermediate was prepared by means of a thiol-ene coupling reaction between limonene and cysteamine hydrochloride. Second, the primary amino groups of the intermediate compound were alkylated using allyl bromide. The obtained ditertiary amine-functionalized limonene compound was purified and characterized by FTIR and NMR spectroscopies along with GC-MS. The curing agent was formulated with a tetrafunctional thiol in stoichiometric ratio, and a photoinitiator at 1 mol % concentration, as the components of a thiol-ene system (TES). Two formulations were prepared in which molar concentrations of 30 and 40 mol % of the TES were added to the epoxy resin. The kinetics of the ETE photopolymerizations were determined by means of Real-Time FTIR spectroscopy, which demonstrated high reactivity by observing photopolymerization rates in the range of 1.50–2.25 s⁻¹ for the epoxy, double bonds and thiol groups. The obtained polymers were analyzed by thermal and thermo-mechanical techniques finding glass transition temperatures (Tg) of 60 °C and 52 °C for the polymers derived from the formulations with 30 mol % and 40 mol % of TES, respectively. Potential applications for these materials can be foreseen in the area of coatings. Full article

Hybrid nanomaterials possess the properties of both organic and inorganic components and find applications in various fields of research and technology. In this study, aerosol photopolymerization is used in combination with thiol-ene chemistry to produce silver poly(thio-ether) hybrid nanospheres. In aerosol photopolymerization, a spray solution of monomers is atomized, forming a droplet aerosol, which then polymerizes, producing spherical polymer nanoparticles. To produce silver poly(thio-ether) hybrids, silver nanoparticles were introduced to the spray solution. Diverse methods of stabilization were used to produce stable dispersions of silver nanoparticles to prevent their agglomeration before the photopolymerization process. Successfully stabilized silver nanoparticle dispersion in the spray solution subsequently formed nanocomposites with non-agglomerated silver nanoparticles inside the polymer matrix. Nanocomposite particles were analyzed via scanning and transmission electron microscopy to study the degree of agglomeration of silver nanoparticles and their location inside the polymer spheres. The nanoparticle hybrids were then introduced onto various biofunctionalization reactions. A two-step bioconjugation process was developed involving the hybrid nanoparticles: (1) conjugation of (biotin)-maleimide to thiol-groups on the polymer network of the hybrids, and (2) biotin-streptavidin binding. The biofunctionalization with gold-nanoparticle-conjugates was carried out to confirm the reactivity of -SH groups on each conjugation step. Fluorescence-labeled biomolecules were conjugated to the spherical nanoparticle hybrids (applying the two-step bioconjugation process) verified by Fluorescence Spectroscopy and Fluorescence Microscopy. The presented research offers an effective method of synthesis of smart systems that can further be used in biosensors and various other biomedical applications. Full article

Micro-sized segregated liquid crystals (MSLCs) surrounded by a polymer medium can be used for haze film applications. When incident light passes through the MSLC film, the microsized particles act as light scattering centers. In this study, the results of the addition of a multi-functional acrylate to a commercial thiol-ene prepolymer system, as well as the morphology of (LC) droplets, fractal dimension (D), and the optical haze performance of the micro-sized segregated LCs formed by UV-initiated photopolymerization, are reported. With increasing fraction of the multi-functional acrylate within the host polymer matrix, the small scattering centers (LC droplets) also increase, giving rise to a large optical haze in the prepared film. The optical haze can be characterized by the D of the associated LC droplet morphology in the films. The optical haze and D exhibit a strong correlation; thus, a qualitative prediction of the optical haze is possible via geometric fractal analysis. Full article

Spherical, individual polymer nanoparticles with functional –SH groups were synthesized via aerosol photopolymerization (APP) employing radically initiated thiol-ene chemistry. A series of various thiol and alkene monomer combinations were investigated based on di-, tri-, and tetrafunctional thiols with difunctional allyl and vinyl ethers, and di- and trifunctional acrylates. Only thiol and alkene monomer combinations able to build cross-linked poly(thio-ether) networks were compatible with APP, which requires fast polymerization of the generated droplet aerosol during the photoreactor passage within a residence time of half-minute. Higher monomer functionalities and equal overall stoichiometry of functional groups resulted in the best nanoparticles being spherical and individual, proven by scanning electron microscopy (SEM). The presence of reactive –SH groups in the synthesized nanoparticles as a basis for post-polymerization modifications was verified by Ellman’s test. Full article

The influence of ene and thiol monomer structure on the mechanical and electrochemical properties of thiol–ene polymeric ionogels were investigated. Ionogels were obtained in situ by thiol–ene photopolymerization of 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATT), 2,4,6-triallyloxy-1,3,5-triazine (TAT), diallyl phthalate (DAP), and glyoxal bis(diallyl acetal) (GBDA) used as enes and trimethylolpropane tris(3-mercaptopropionate) (TMPTP), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), and pentaerythritol tetrakis(3-mercaptobutyrate) (PETMB) used as thiols in 70 wt.% of ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImNTf₂). The mechanical strength of ionogels was studied by puncture resistance and ionic conductivity by electrochemical impedance spectroscopy. The course of photopolymerization by photo-DSC method (differential scanning calorimetry) as well as characterization of compositions and its components (by IR and UV spectroscopy-Kamlet–Taft parameters) were also studied. The resulting ionogels were opaque, with phase separation, which resulted from the dispersion mechanism of polymerization. The mechanical and conductive properties of the obtained materials were found to be largely dependent on the monomer structure. Ionogels based on triazine monomers TAT and TATT were characterized by higher mechanical strength, while those based on aliphatic GBDA had the highest conductivity. These parameters are strongly related to the structure of the polymer matrix, which is in the form of connected spheres. The conductivity of ionogels was high, in the range of 3.5–5.1 mS∙cm⁻¹. Full article

A facile method for the preparation of hierarchically porous spherical particles using high internal phase water-in-oil-in-water (w/o/w) double emulsions via the photopolymerization of the water-in-oil high internal phase emulsion (w/o HIPE) was developed. Visible-light photopolymerization was used for the synthesis of microspherical particles. The HIP emulsion had an internal phase volume of 80% and an oil phase containing either thiol pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) or trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) and acrylate trimethylolpropane triacrylate (TMPTA). This enabled the preparation of microspheres with an open porous morphology, on both the surface and within the microsphere, with high yields in a batch manner. The effect of the thiol-to-acrylate ratio on the microsphere diameter, pore and window diameter, and degradation was investigated. It is shown that thiol has a minor effect on the microsphere and pore diameter, while the acrylate ratio affects the degradation speed, which decreases with increasing acrylate content. The possibility of free thiol group functionalization was demonstrated by a reaction with allylamine, while the microsphere adsorption capabilities were tested by the adsorption of methylene blue. Full article

The synergic features and enhancing strategies for various photopolymerization systems are reviewed by kinetic schemes and the associated measurements. The important topics include (i) photo crosslinking of corneas for the treatment of corneal diseases using UVA-light (365 nm) light and riboflavin as the photosensitizer; (ii) synergic effects by a dual-function enhancer in a three-initiator system; (iii) synergic effects by a three-initiator C/B/A system, with electron-transfer and oxygen-mediated energy-transfer pathways; (iv) copper-complex (G1) photoredox catalyst in G1/Iod/NVK systems for free radical (FRP) and cationic photopolymerization (CP); (v) radical-mediated thiol-ene (TE) photopolymerizations; (vi) superbase photogenerator based-catalyzed thiol−acrylate Michael (TM) addition reaction; and the combined system of TE and TM using dual wavelength; (vii) dual-wavelength (UV and blue) controlled photopolymerization confinement (PC); (viii) dual-wavelength (UV and red) selectively controlled 3D printing; and (ix) three-wavelength selectively controlled in 3D printing and additive manufacturing (AM). With minimum mathematics, we present (for the first time) the synergic features and enhancing strategies for various systems of multi-components, initiators, monomers, and under one-, two-, and three-wavelength light. Therefore, this review provides not only the bridging between modeling and measurements, but also guidance for further experimental studies and new applications in 3D printings and additive manufacturing (AM), based on the innovative concepts (kinetics/schemes). Full article

Two new photopolymerizable vinyl (2-(allyloxy) 1,4-naphthoquinone, HNQA) and epoxy (2-(oxiran-2yl methoxy) 1,4-naphthoquinone, HNQE) photoinitiators derived from lawsone were designed in this paper. These new photoinitiators can be used as one-component photoinitiating systems for the free-radical photopolymerization of acrylate bio-based monomer without the addition of any co-initiators. As highlighted by the electron paramagnetic resonance (EPR) spin-trapping results, the formation of carbon-centered radicals from an intermolecular H abstraction reaction was evidenced and can act as initiating species. Interestingly, the introduction of iodonium salt (Iod) used as a co-initiator has led to (1) the cationic photopolymerization of epoxy monomer with high final conversions and (2) an increase of the rates of free-radical polymerization of the acrylate bio-based monomer; we also demonstrated the concomitant thiol–ene reaction and cationic photopolymerizations of a limonene 1,2 epoxide/thiol blend mixture with the HNQA/Iod photoinitiating system. Full article