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Supramolecular assemblies with chirality inversion were developed using a co-assembly system comprising solvent monomers and a pyridine-cholesterol gelator. The polarity-dependent chiralities were captured in situ through photopolymerization, enabling the formation of multi-color circularly polarized luminescence films. [ABSTRACT FROM AUTHOR]

Vanillyl alcohol has emerged as a widely used building block for the development of biobased monomers. More specifically, the cationic (photo‐)polymerization of the respective diglycidyl ether (DGEVA) is known to produce materials of outstanding thermomechanical performance. Generally, chain transfer agents (CTAs) are of interest in cationic resins not only because they lead to more homogeneous polymer networks but also because they strikingly improve the polymerization speed. Herein, the aim is to compare the cationic chain‐growth photopolymerization with the thermally initiated anionic step‐growth polymerization, with and without the addition of CTAs. Indeed, CTAs lead to faster polymerization reactions as well as the formation of more homogeneous networks, especially in the case of the thermal anionic step‐growth polymerization. Resulting from curing above the TG of the respective anionic step‐growth polymer, materials with outstanding tensile toughness (>5 MJ cm−3) are obtained that result in the manufacture of potential shape‐memory polymers. [ABSTRACT FROM AUTHOR]

Incorporation of polymer chain entanglements within a single network can synergistically improve stiffness and toughness, yet attaining such dense entanglements through vat photopolymerization additive manufacturing [e.g., digital light processing (DLP)] remains elusive. We report a facile strategy that combines light and dark polymerization to allow constituent polymer chains to densely entangle as they form within printed structures. This generalizable approach reaches high monomer conversion at room temperature without the need for additional stimuli, such as light or heat after printing, and enables additive manufacturing of highly entangled hydrogels and elastomers that exhibit fourfold- to sevenfold-higher extension energies in comparison to that of traditional DLP. We used this method to print high-resolution and multimaterial structures with features such as spatially programmed adhesion to wet tissues. [ABSTRACT FROM AUTHOR]

Here, methacrylated gelatin (GelMA) is obtained at different methacrylate anhydride concentrations (5.8% and 10% v/v), different reaction times (1 and 3 h), and under pH control. A ninhydrin test and nuclear magnetic resonance are used to determine the degree of functionalization (DoF) of the samples showing that pH controlling produces better functionalization degrees than an increase in methacrylate anhydride concentration or longer reaction times. The photopolymerization process of GelMA samples is studied by time‐resolved photoluminescence at different photoinitiator (PI) concentrations: 0.5%, 1%, and 2% w/v. An increase in PI concentration and DoF produces changes in the cross‐link. The 2% w/v concentration produces a higher reaction speed in the first 10 min and requires longer times to end the reaction. No significant differences are found in the use of smaller concentrations. [ABSTRACT FROM AUTHOR]

An approach of 'polymerization of monomers in its aggregated form' is unprecedentedly introduced to (i) tailor the water wettability of fibrous and porous substrates from hydrophobicity to superhydrophobicity, and (ii) associate patterned wettability. A solution of selected monomers—i.e., alkyl acrylate in a good solvent (indicating high solubility; ethanol) was transferred into a bad solvent (refers to poor solubility; water) to achieve a stable dispersion of monomer aggregates of size <1 μm for deposition on fibrous and porous substrates. Its photopolymerization provided a durable coating with the ability to tailor the water wettability from 134° to 153°. Furthermore, a spatially selective photopolymerization process yielded a patterned interface of superhydrophilicity and superhydrophobicity. Such a facile chemical approach with the ability to provide a durable coating embedded with tailored and patterned wettability would be useful for various potential applications. [ABSTRACT FROM AUTHOR]

Polymer systems induced by the reaction between monomers and photo-initiators play a crucial role in the formation of volume-phase gratings. In this paper, we fabricated a dual-photo-initiator photopolymer by doping EY (Eosin Yellow) molecules into a TI (Titanocene, Irgacure 784@BASF) dispersed PMMA (poly-[methyl methacrylate]) substrate system, with the aim of promoting the diffusion and polymerization processes in volume holographic storage. The two-wave interference system is adopted to record a permanent grating structure in our materials. The temporal diffraction variations of photopolymerization (during the interference exposure) and dark diffusion (after the interference exposure) processes have been investigated and analyzed. Aiming to analyze the influence of EY doping ratios on holographic performances, some key parameters were examined in the experiment. We first measured the temporal evolution of diffraction efficiency, then an exponential fitting was adopted to obtain the response time. Finally, the angular selectivity was evaluated by the Bragg condition after holographic recording. Also, the temporal evolution of each component is described by the nonlocal polymerization-driven diffusion model with a dual-photo-initiator composition, theoretically. Furthermore, we experimentally achieved the holographic grating enhancement in both the dark diffusion and photopolymerization processes by doping appropriate EY concentrations, respectively. This work provides a foundation for the acceptability of TI&EY/PMMA polymers in further holographic storage research. [ABSTRACT FROM AUTHOR]

Novel method of obtaining functional acrylic resins (FARs) containing carboxyl- and benzophenone groups (in-chain functionalization) and terminal Br atoms was verified. Acrylic oligomers were prepared by a solution-free, UV-initiated telomerization process of basic monomer (n-butyl acrylate) and functional monomers (acrylic acid and 4-acrylooxybenzophenone) in the presence of radical photoinitiator and different amount of tetrabromomethane (CBr4) as telogen. The effect of telogen content on UV-telomerization kinetics as well as physicochemical and thermal (Tg) properties of FARs was investigated. A telogen content higher than 5 wt. parts does not affect the UV-telomerization rate (photo-DSC), the molecular weights of telomers (GPC), or their glass transition temperature (DSC), but it significantly increases the conversion of monomers (up to 88%) and lowers the viscosity of FARs (approx. 6 Pa·s). NMR studies confirmed the inclusion of CBr4 in the structure of functional acrylic telomers. [ABSTRACT FROM AUTHOR]

This publication describes the influence of residue monomers in synthesized pressure-sensitive adhesives based on acrylics on their main properties—tack, peel adhesion, shear strength and shrinkage—in the form of transfer tapes used for joining wooden elements in the furniture industry. The discussed carrier-free adhesive tapes are synthesized via photo-crosslinking and photopolymerization with UV radiation of the photoreactive prepolymers sandwiched between two adhesive siliconized polyester films. The simultaneous crosslinking and polymerization processes carried out under UV lamps placed simultaneously above and below the crosslinked photoreactive polymer layer lead to the production of a carrier-free adhesive film. The preliminary target of these studies was to investigate how the intensity of UV radiation and the time of its exposure affect the viscosity of the photoreactive compositions and the content of unreacted monomers in them. Next, the influence of the crosslinking agent concentration and UV irradiation time on the content of unreacted monomers after the crosslinking process was tested. The last step of the studies was the investigation of the influence of the residue monomer concentration on the application properties of the obtained pressure-sensitive adhesive layers. The typical PSA application properties were tested on the wood samples: tack, peel adhesion, shear strength (cohesion) and shrinkage. [ABSTRACT FROM AUTHOR]

Polyelectrolyte complexes (PECs), assemblies of oppositely charged polymers with powerful properties and wide‐ranging applications, are currently not melt‐processable via any conventional means and have been limited commercially to applications only as coatings. Herein, a unique strategy of pairing a polycation with an oppositely charged photopolymerizable monomer is employed. Vat photopolymerization of this mixture yields 3D spatial control over PECs for the first time. The properties of these 3D‐printed PECs are evaluated and are found to be similar to conventionally studied PEC materials. The water sensitivity of the PEC parts is adjustable through the incorporation of a small amount of a hydrophilic covalent crosslinker, highlighting potential future applications of these materials in 4D printing. Finally, the upcyclability of the additively manufactured PECs is demonstrated through the dissolution of a printed part and its incorporation into virgin resin to yield a part composed of partially recycled material. This chemistry has the potential to dramatically expand the application space of PEC materials and is a step towards a more circular economy for the field of additive manufacturing. [ABSTRACT FROM AUTHOR]

In this paper, epoxy-acrylate structural adhesives tapes (SATs) were obtained from Bisphenol A-based liquid epoxy resin and epoxy acrylic resins (EARs). A new method of EARs preparation, i.e., the free radical bulk photopolymerization process (FRBP), was studied in detail. The influence of methacrylic monomers (methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, (2-acetoacetoxy)ethyl methacrylate) and vinyl monomers (N-vinylpyrrolidone and styrene) on the FRBP process of base monomers (i.e., butyl acrylate, glycidyl methacrylate and 2-hydroxyethyl acrylate) was investigated. The kinetics of photopolymerization process was monitored by photo-differential scanning calorimetry method. The properties of the obtained EARs (viscosity and average molecular weights), as well as monomers conversion using 1H NMR, were determined. It was revealed that styrene significantly decreases the photopolymerization rate and increases the final monomers conversion (+27%). However, the resulting tetrapolymers BA-co-GMA-co-HEA-co-STY have low molecular weights and low polydispersity (2.2). Methacrylate monomers with shorter aliphatic chains (

Photochemical techniques have recently been revitalized as they can readily be adapted to different polymerization modes to yield a wide range of complex macromolecular structures. However, the implementation of the photoinduced cationic methods in the polymerization of cyclic siloxane monomers has scarcely been investigated. Octamethylcyclotetrasiloxane (D4) is an important monomer for the synthesis of polydimethylsiloxane (PDMS) and its copolymers. In this study, the cationic ring-opening polymerization (ROP) of D4, initiated by diphenyl iodonium hexafluorophosphate (DPI), has been studied. Both direct and indirect initiating systems acting at broad wavelength using benzophenone and pyrene were investigated. In both systems, photochemically generated protonic acids and silylium cations are responsible for the polymerization. The kinetics of the polymerization are followed by viscosimetry and GPC analyses. The reported approach may overcome the problems associated with conventional methods and therefore represents industrial importance for the fabrication of polysiloxanes. [ABSTRACT FROM AUTHOR]

3D ceramic parts are of great interest for various applications including aerospace, defense, electronics, photonics, and biomedical. Yet, additive manufacturing of ceramics is challenging due to their poor machinability. Herein, two approaches based on the chemical modification of silicon resins to obtain UV‐curable preceramic precursors of SiOC are described. The dual functionality of the synthesized resins acting both as preceramic precursor and as photopolymerizable entity under UV light is exploited. A set of characterization techniques has allowed the investigation of the mechanisms involved in the synthesis of the inorganic SiOC precursors according to the following approaches: (1) blend of the silicon resin with photoactive monomers and (2) synthesis of a single source UV‐curable preceramic silicon resin. A correlation between the nature of the precursor and the properties of the derived SiOC is analyzed. From a technological point of view, the materials can be fabricated as dense or crack‐free porous customized objects with low mass loss and optimal surface quality. [ABSTRACT FROM AUTHOR]

This study reports the utility of solid camphor as a novel diluent in photocurable hexanediol diacrylate (HDDA) monomer to manufacture 4 mol% yttria partially stabilized zirconia (4Y-PSZ) components for dental applications by digital light processing (DLP). The use of a 65 wt% HDDA–35 wt% camphor solution allowed 4Y-PSZ suspensions to have reasonably low viscosities (1399 ± 55.8 mPa·s at a shear rate of 75 s−1), measured by a cone/plate viscometer, at a high solid loading of 48 vol%, where 4Y-PSZ particles prepared by calcination of as-received 4Y-PSZ granules, followed by a ball-milling process, were used with assistance of a dispersant. These 4Y-PSZ suspensions could be successfully applied to our custom-made DLP machine for manufacturing 4Y-PSZ components. To this end, several processing parameters, including layer thickness of 4Y-PSZ suspension, UV illumination time for layer-by-layer photocuring process, and initial dimensions of 4Y-PSZ objects, were tightly controlled. As sintering temperature increased from 1300 °C to 1500 °C, relative density and grain size of 4Y-PSZ objects increased, and cubic phase content also increased. Thus, after sintering at the highest temperature of 1500 °C for 3 h, high mechanical properties (biaxial flexural strength = 911 ± 40.7 MPa, hardness = 1371 ± 14.4 Hv) and reasonably high optical transmittance (translucency parameter = 7.77 ± 0.32, contrast ratio = 0.809 ± 0.007), evaluated by a spectrophotometer, were obtained due to a high relative density (97.2 ± 1.38%), which would be useful for dental applications. [ABSTRACT FROM AUTHOR]

Hydrolytically degradable poly(β‐thioether ester ketal) thermosets are synthesized via radical‐mediated thiol‐ene photopolymerization using three novel dialkene acyclic ketal monomers and a mercaptopropionate based tetrafunctional thiol. For all thermoset compositions investigated, degradation behavior is highly tunable based on the structure of the incorporated ketal and pH. Complete degradation of the thermosets is observed upon exposure to acidic and neutral pH, and under high humidity conditions. Polymer networks composed of cross‐link junctions based on acyclic dimethyl ketals degrade the quickest, whereas networks containing acyclic cyclohexyl ketals undergo hydrolytic degradation on a longer timescale. Thermomechanical analysis reveals low glass transition temperatures and moduli typical of thioether‐based thermosets. [ABSTRACT FROM AUTHOR]

The synthesis of novel phosphorus-containing telomers (P-telomers) was conducted via a solution-free UV-initiated telomerization process of butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and styrene, different phosphorus telogens (dimethyl phosphite (DMPh), dibutyl phosphite (DBPh), diphenyl phosphite (DPPh) or dibutyl phosphate (DBP)), and a radical photoinitiator-acylphosphine oxide (APO). The course of the UV-phototelomerization process was monitored by photo-DSC and the chemical structures of telomers were assessed by FTIR. Final UV-photocurable varnish compositions consisted of prepared P-telomer syrups, crosslinking monomer (pentaerythritol triacrylate; PETIA), and a radical UV-photoinitiator (α-hydroxyalkylphenone, HAP). The influence of P- telomers on the optical and mechanical features of coatings was investigated. Relatively the highest hardness and satisfactory scratch values, as well as water and solvent resistance, were observed for varnish based on DMPh-telomers. While the strongest adhesive bond to a glass substrate was reported for DPPh-telomers. It is worth pointing out that the P-telomers did not affect the gloss values of varnishes in comparison to the telomer-free reference sample. [ABSTRACT FROM AUTHOR]

In this perspective, we explore the historical evolution, photochemical processes, and distinct utility of photoiniferter polymerization. We aim to provide a practical guide encompassing the selection of iniferter and monomer, coupled with the optimization of light wavelengths to conduct efficient photoiniferter polymerizations. We delve into the impact of iniferter structure on photophysical properties and the resulting polymerization behavior. Furthermore, we highlight ongoing research efforts employing photoiniferter polymerization, emphasizing its potential applications in cutting-edge areas of research such as 3D printing and the synthesis of ultra-high molecular weight polymers (≥ 106 g mol-1). Through this perspective, we aim to clarify both the fundamental principles and the practical considerations of photoiniferter polymerization, ultimately advancing its utility and paving the way for innovative applications in polymer science. [Display omitted] [ABSTRACT FROM AUTHOR]

A bifunctional diethylene glycol difuran acrylate (DEFA) and a trifunctional trimethylolpropane trifuran acrylate (TMFA) monomer for solid-state photopolymerization were synthesized from a biomass material, furfural. High molar extinction coefficients in the order of 104 indicate the good UV absorption properties of both monomers. The photopolymerization kinetics studies show that DEFA achieves a maximum polymerization rate (Rp) in 54 s and TMFA in 35 s without photoinitiators, and the maximum double bond conversion (DBC) reached 88% for DEFA and 78% for TMFA, which proves that they have high photosensitivity. The addition of the 2,4-dinitroaniline sensitizer increases the maximum DBC, but increases the maximum Rp markedly. The high crystallinity of DEFA and TMFA is prone to photodimerization and forms an amorphous polymer. Both the linear polyester from DEFA and the crosslinked polyester from TMFA have good thermal oxidation stability. Therefore, we developed a strategy to produce highly sensitive monomers for the application of photosensitive materials that polymerize quickly without photoinitiators and solvents. [ABSTRACT FROM AUTHOR]

Photopolymerizations of monomer methyl methacrylate being nanocomposite have been widely carried out because it has the advantage that it can improve the properties of the materials used. The purpose of this research was to study the synthesized characteristics of PMMA+ITO and PMMA+ITO+PE-b-PEG using the UV Curing method. The nanocomposites were synthesized with a variation of ITO concentrations were 5% w/t, 10% w/t, and 15% w/t. The characterization group functions using FTIR spectroscopy showed the loss of absorption peaks at wave numbers 3100 cm-1 and 1670 cm-1 at PMMA. The results of XRD characterization showed that effect addition of PE-b-PEG, peaks appeared around the 2θ 19°-28° area which was a typical peak for PE-b-PEG. the nanocomposite is an amorphous phase still dominated. Value of conductivity of nanocomposite PMMA addition of ITO with a concentration of 15% resulted in a nanocomposite with the highest conductivity value of 6.4068 x 10-7 S/m. [ABSTRACT FROM AUTHOR]

This study reports an ultra‐facile, economical, and environmentally friendly hydrogel synthesis method using renewable raw materials. The synthesis and photopolymerization of oleyl methacrylate (OM) and the epoxidized derivative of OM monomers are evaluated. In the first step, oleyl alcohol is esterified with methacryloyl chloride and then epoxidized via the Prilezhaev reaction. These monomers are used for hydrogel synthesis. For this purpose, they are polymerized with N‐isopropyl acrylamide, N,N‐methylene bis(acrylamide), or ethylene glycol dimethacrylate (EDGMA) via the photopolymerization technique. Novel hydrogels are successfully fabricated using a green process. Epoxidized OM‐based hydrogel achieves an excellent yield of 87.1%. Moreover, low‐energy UV irradiation and short reaction times reduces energy consumption. The thermal properties of the gels are also considered by differential scanning calorimetry (DSC) and thermogravimetric analysis techniques. DSC results reveal that the epoxidized OM‐based hydrogel exhibits a melting peak at 84.5 °C. The highest 5% weight loss temperature is obtained for the OM‐EDGMA copolymer as an indicator of thermal stability. [ABSTRACT FROM AUTHOR]

• Micron-sized silver reduces slurry viscosity by 60% for nano-hydroxyapatite slurry. • Silver flakes increase sintering density of printed structures to 95%, versus 92% for pure hydroxyapatite (HA). • Adding over 5% silver reduces slurry's cured depth, leading to poor printability. • Potential for biomedical implants with improved strength and antibacterial properties. The present work deals with the processing of HA-silver photocurable slurry to make composites using the Vat-photopolymerization process. Slurries with increasing amount of silver addition in the HA-Ag (0, 5, 10, 15%) slurry have been prepared using monomers with photo-initiators and printed successfully. Silver powder used in this study is in the form of flakes and spheres. A shear thinning behaviour of all the compositions of the slurries has been observed which is essential to fabricate defect-free parts. With increase in silver addition to 15 wt%, the viscosity decreased by around 60 % however curing depth was compromised. From SEM micrographs it was observed that HA with silver flakes showed better sintering with sintering density of 95% compared to only HA and HA with spherical silver samples. [ABSTRACT FROM AUTHOR]

The photopolymerization process is a high-precision and efficient technology to obtain solid polymers starting from a photosensible liquid resin made of monomer units. This technology is widely used in Additive Manufacturing (AM) to produce objects whose size can fall within the range 10 − 5 − 10 0 m. The outstanding potentialities of this technology can be harnessed to tailor the structure of a polymeric material by controlling how the light-induced polymerization process is performed, typically by operating on subsequent layers forming the final object. The present research illustrates the chemical-physics phenomena involved in the photopolymerization and presents a multi-physics framework and the related governing equations. Its implementation within a computational framework is developed and several simulations demonstrating the influence of the AM printing setup on the final microstructure of the obtained polymer are presented. It is shown that photopolymerization-based AM technology allows us to finely tune the mechanical properties distribution within the material domain, enabling the material's architecture to be tailored to the application of interest. • Multi-physics model of layered photopolymerization. • Mechanics of polymers obtained through photopolymerization. • Numerical implementation of the photopolymerization process. • Numerical simulations. • Layer-interface characterization. [ABSTRACT FROM AUTHOR]

The microfluidic production of Janus/Hecate polymer microfibers with well-defined interfaces from miscible phases is reported. The process offers tunability of the width and composition of each part of the fibers by controlling the flow rate and nature of the monomers in a single step. The enhanced performances of the fibers are outlined for the simultaneous removal of dyes of opposite charges using amphoteric Janus fibers. [ABSTRACT FROM AUTHOR]

Hierarchical patterns are widely found on the biological skins in nature and can provide unique functions to surfaces such as wettability, optical, and adhesive properties. Herein, a facile and robust strategy to generate the self‐wrinkling pattern on the surface of the photo‐curing coating is proposed, which comprises a crosslinking monomer, photoinitiator, and fluorinated copolymer as additive. The fluorinated copolymer, which contains fluorocarbon chains possessing low surface‐energy, tertiary amine as coinitiator, and anthracene in the side chain, can self‐assemble to the top layer for constructing the gradient photo‐crosslinking system. Upon the irradiation of ultraviolet (UV) light, the mismatch of shrinkage caused by the gradient photo‐crosslinking leads to the formation of wrinkles, the morphology of which can be regulated by monomer proportion, the content of fluorinated copolymer, and the thickness of the film. Taking the spatiotemporal advantages of light, the hierarchical patterns of wrinkle are generated by programmed exposure with photomask, which has potential applications in anti‐counterfeiting and encapsulation of light‐emitting diode (LED) chip for displaying. This strategy provides a rapid and universal alternative method to fabricate a hierarchical pattern of the surface. [ABSTRACT FROM AUTHOR]

The aim of the present study was to investigate and compare the quantity of residual monomers leached from the bulk-fill composites with different compositions polymerized at varying layer thickness. Three bulk-fill (X-tra-fil, Beautifil Bulk Restorative, Fill-Up) and a nanohybrid composite (Filtek Z550) were used for the study. The composite resin samples were prepared with a stainless steel mold. For each composite, two groups were constructed. The samples in the first group were prepared using the 2 + 2 mm layering technique. In the second group, the composite samples were applied as a 4 mm-thick one layer and polymerized. Then, each composite samples were kept in a 75% ethanol solution and residual monomers released from composite resins were analyzed with an HPLC device after 24hour and 1 month. The data were analyzed using Kruskal-Wallis and Mann-Whitney U tests. Except the Fill-Up, all of residual monomer elution from the bulk-fill composites was significantly affected by the layer thickness (p < 0.05). The greatest monomer release was detected at 1 month after polymerization as a single 4 mm layer for Beautifil Bulk Restorative. Fill-Up composite showed similar residual monomer release in polymerization at different layer thicknesses compared to other composite resins. In the 2 + 2 mm layering technique, the least monomer elution was detected in the Filtek Z550 composite group. While Bis-GMA was the most released monomer in X-tra fil composite, UDMA was the most released monomer in all other composite resins. During polymerization of the bulk-fill composite, the layer thickness of the composite applied may affect the amount of residual monomers released from the composite resins. Conventional composites may release less monomer than bulk-fill composites when used with layering. [ABSTRACT FROM AUTHOR]

The photopolymerization process has been widely studied due to its use in painting/coating, dentistry, creating photoresist materials and more recently in 3D printing. Therefore, new monomers have been synthesized to be used in this growing area. Here, a new Brazilian biomass derived, renewable monomer from macaw vegetable oil is presented. This monomer can self-polymerize without photoinitiation under UV light, reaching a monomer conversion of 75% and a conversion of 88% when ethyl 4-(dimethylamino)benzoate is present as a coinitiator. Furthermore, the final polymer has an orange color under visible light and exhibits fluorescence (a blue color) under UV radiation. Monomers and polymers formed from macaw (macaúba) vegetable oil are thermally stable up to 220 °C, as evidenced by thermogravimetry (TG). The polymers formed also exhibited a glass transition temperature of 2.6 °C, as observed in differential scanning calorimetry (DSC) curves and dynamic-mechanical analysis (DMA). This new monomer presents an alternative monomer to be used in 3D printing, in a similar manner to other vegetable oils such as soybean and linseed. [ABSTRACT FROM AUTHOR]

Fast and well-controlled photoinduced atom transfer radical polymerization (photoATRP) in the organized medium of a bilayer activated by visible light under environmentally friendly mild aqueous conditions leads to polymers with predetermined molecular weight and low dispersity. The decisive parameter for photoATRP of monomers in the organized medium was their mobility and orientation with respect to the bilayer and the photoredox catalyst localized in the interstitial layer. [ABSTRACT FROM AUTHOR]

The distinct features of UV induced polymerization of epoxy-acrylate blends leading to the formation of simultaneous interpenetrating polymer networks (IPNs) have been studied. Different ratios of components within a prevailing content of an epoxy one have been used for the synthesis. Such a content of epoxy monomer is required to create a barrier preventing oxygen diffusion into a curing sample. It allows retardation of the well-known oxygen-inhibition effect, which acrylate monomers are susceptible to. Hence, the conduction of their polymerization in open-air conditions is possible. The proceeding of the polymerization reactions of acrylate (TEGDM) via free radical mechanism and of epoxy (UP-650D) via cationic one have been monitored by FTIR-spectroscopy. Namely, the conversion degrees have been calculated for double bonds of TEGDM and for epoxy groups of UP-650D respectively. A mixture of triphenylsulfonium hexafluorophosphate salts, which is capable of generating both free radical and cationic reactive species, have been used as a single photoinitiator for the formulations being investigated. Almost complete conversion of acrylate double bonds was reached after 60 min of UV irradiation irrespective of epoxy content. On the contrary, conversion of epoxy groups of aliphatic epoxy, which is known to be rather unreactive towards cationic photopolymerization, when mixed may be either higher or lower compared to the neat epoxy network. Such results are attributed to dual influence of acrylate network on the formation of epoxy one. Firstly, cationic polymerization of epoxy component is sensitized by acrylate macroradicals in terms of free radical promoted cationic polymerization. On the other hand, the mobility of epoxy macrocations is restricted by the rapid build-up of acrylate network. At the weight ratio of UP-650D and TEGDM 70/30 the sensitizing effect of acrylate is revealed to be dominant, so the given composition may be considered as optimal. Regardless of low conversion of epoxy groups, the content of the estimated gel fraction is high, and the epoxy component is found not to be leached in the process of extraction in acetone. Furthermore, physicomechanical properties of obtained UV-cured IPNs have been investigated. The results of the measurements, namely, impact resistance by the Gardner test, crosshatch adhesion test to different substrates (including silicon), and accelerated weathering test in a climatic chamber, show that all the samples exhibit good operational properties essential for effective protecting coatings of outdoor exposure. [ABSTRACT FROM AUTHOR]

Conductive polymers find key applications ranging from optoelectronics and OLEDs to conductive composite materials. The synthesis of conductive polymers from monomers, such as thiophene derivatives, pyrroles and aniline, mainly relies on oxidative polymerization, and the processing of so‐formed (insoluble) polymers is a major issue that needs to be addressed. In the present work, oxidative photopolymerization of 3,4‐ethylenedioxythiophene (EDOT) by visible light employing the metal‐free semiconductor graphitic carbon nitride (g‐CN) is presented. Two main reaction pathways based on g‐CN content are described, and the formation of processable oligo‐EDOT is demonstrated. [ABSTRACT FROM AUTHOR]

Several difunctional oligomers were synthesized by functionalizing perfluoropolyalkylether (PFPAE) chains with different vinyl ethers and epoxides end-groups. Due to their innate synthetic challenges and demanding purification protocols, the PFPAE derivatives were obtained in low yield and with an average functionality lower than 2. However, the functionalized PFPAE oligomers were successful in being used in photo-induced cationic polymerization processes, obtaining transparent and soft films. The influences of the fluorinated chains, and various end-groups on the photopolymerization process were investigated, as well their chemical stability, thermal degradation, and surface properties. [ABSTRACT FROM AUTHOR]

The global market for 3D printing materials has grown exponentially in the last decade. Today, photopolymers claim almost half of the material sales worldwide. The lack of sustainable resins, applicable in vat photopolymerization that can compete with commercial materials, however, limits the widespread adoption of this technology. The development of "green" alternatives is of great importance in order to reduce the environmental impact of additive manufacturing. This paper reviews the recent evolutions in the field of sustainable photopolymers for 3D printing. It highlights the synthesis and application of biobased resin components, such as photocurable monomers and oligomers, as well as reinforcing agents derived from natural resources. In addition, the design of biologically degradable and recyclable thermoset products in vat photopolymerization is discussed. Together, those strategies will promote the accurate and waste‐free production of a new generation of 3D materials for a sustainable plastics economy in the near future. [ABSTRACT FROM AUTHOR]

• Three aromatic monofunctional methacrylates are evaluated as high refractive index diluents for the formulation of radiopaque bulk-fill composites. • Photopolymerization kinetics of these monomers are investigated by photo-DSC. • Bulk-fill composites based on the new diluent monomers exhibit improved mechanical properties, reduced shrinkage force and lower water sorption in comparison with a reference composite containing TEGDMA. To evaluate high refractive index methacrylates as diluents for the formulation of radiopaque esthetic bulk-fill composites. 2-(4-Cumylphenoxy)ethyl methacrylate 1 , 2-(2-phenylphenoxy)ethyl methacrylate 2 and 2-[2-(2-phenylphenoxy)ethoxy]ethyl methacrylate 3 were synthesized and characterized by 1H NMR spectroscopy. The reactivity of each monomer was studied using photo-DSC. Bulk-fill composites based on monomers 1–3 were formulated. Translucency (before and after light cure) was measured using a spectrophotometer. The depth of cure and the water sorption of these materials were determined according to ISO 4049. The flexural strength and modulus of elasticity were measured using a three-point bending setup, according to ISO 4049. The shrinkage force was assessed based on a method described by Watts et al. using a universal testing machine. Monomers 1–3 were easily synthesized in two steps. They exhibit a low viscosity and a high refractive index (1.553–1.573). Monofunctional methacrylates 1–3 were found to be more reactive than triethylene glycol dimethacrylate (TEGDMA). Bulk-fill composites based on these monomers were successfully prepared. They exhibit a high depth of cure and excellent esthetic properties (low transparency). These composites provide higher flexural modulus as well as lower water sorption than a corresponding material based on TEGDMA. Methacrylates 1 and 3 are particularly interesting as they led to composites showing lower shrinkage force. Methacrylates 1–3 are promising diluents for the formulation of highly esthetic radiopaque bulk-fill composites. [ABSTRACT FROM AUTHOR]

UV curing of photopolymerizable monomers, like (meth)acrylates, has been utilized for coatings for more than half a century and more recently in further developed areas such as tissue engineering. However, these monomers have major disadvantages, e.g., high irritancy and cytotoxicity, which leads to limited use in tissue engineering regarding health issues. Vinyl esters (VE) and vinyl carbonates (VC) can compete with (meth)acrylates in terms of material properties and have significantly lower toxicity, but lack in cost efficient synthesis methods. The purpose of this communication is to establish new pathways to overcome this drawback. It was shown that VEs can be synthesized either by vinyloxy trimethylsilane or by acetaldehyde in excellent yields. Moreover, a new method to synthesize vinyl chloroformate as precursor for VCs in lab scale was evolved by a catalyzed reaction of vinyloxy trimethylsilane with a phosgene solution. Finally, the cytotoxicity tests showed auspicious results. [ABSTRACT FROM AUTHOR]

In this study, we fabricated liquid crystal polymer networks (LCNs) containing a large amount of crosslinker by scanning wave photopolymerization, and examined the effect of crosslinker concentration on molecular alignment behavior. Samples with different crosslinker concentrations were photopolymerized by unidirectionally scanning ultraviolet light, resulting in LCN films with uniaxial molecular alignment. The LCN films obtained from the compositions of only monomer or monomer and crosslinker had mesogens aligned in parallel to the light scanning direction. Moreover, the LCN films with high crosslinker concentrations were able to maintain their initial molecular alignment after repeated heating cycles. [ABSTRACT FROM AUTHOR]

The fabrication of molecularly imprinted nanoparticles (MIP-NPs) specific for myoglobin by using thiol-ene photopolymerization in miniemulsion was described. Allyl derivatives of phenylalanine as a functional monomer was synthesized and copolymerized with acrylic monomers via miniemulsion polymerization to produce NIP-NPs with approximately 74 nm number average particle diameter. FTIR and 1H-NMR analysis confirmed the synthesis of functional monomer. MIP-NPs were prepared in the existence of myoglobin as a template protein. Morphological investigations exhibited that the particle size of the MIP-NPs, increased compared to the corresponding NIPs and the mean particle diameter by number was measured as 141 nm with narrow distribution. NIP-NPs that were polymerized without myoglobin were found to have less affinity to the target protein. In addition, the rebinding ability of MIP-NPs was much bigger than that of the corresponding NIPs. ELISA results showed that MIPs interact particularly with the myoglobin and show little affinity for BSA in competitive binding experiments. Allyl N,N-diallyl phenylalaninate was synthesized as a functional monomer. Imprinted nanoparticles were prepared by using thiol-ene photopolymerization in miniemulsion. The nanoparticles were 141 nm with narrow size distribution. The imprinted nanoparticles showed selectivity toward myoglobin. [ABSTRACT FROM AUTHOR]

Bisphenol A glycidyl methacrylate (BisGMA) is well established as photocurable resin in dental restoratives and 3D printing. At present there are raising concerns regarding the estrogen‐mimicking bisphenol A (BPA) contamination of health care and consumer products. It is an important challenge to substitute BPA‐based resins for bio‐based cycloaliphatic monomers while lowering resin viscosity without sacrificing high stiffness and glass temperature. Particularly high viscosity is critical for 3D printing by photopolymerization. Unlike BPA the cyclic monoterpene limonene, extracted from citrus fruit peels, is safe in human uses. Herein it is reported on limonene‐based dimethacrylate (LDMA) tailored for 3D printing application and derived from limonene oxide (LO) and methacrylic acid (MA). Residual MA is converted into glycerol dimethacrylate (GDMA) serving as an in situ reactive diluent. The influences of temperature, catalysts, MA/LO stoichiometry, and the addition of glycidyl methacrylate (GMA) and magnesium oxide on the LDMA‐based resin performance are elucidated. As compared to BisGMA (560 Pa s) LDMA‐based resins exhibit significantly lower viscosity (5–117 Pa s) governed by the MA/LDMA molar ratio and the GMA addition. At 30 wt% LDMA content photocured resin yields thermosets having high Young's Modulus (3.4–3.7 GPa), tensile strength (88–98 MPa), and glass transition temperature (119–135 °C), surpassing the performance of the corresponding BisGMA‐based resins. [ABSTRACT FROM AUTHOR]

This study presents a novel strategy to construct ceramic structures comprised of microporous filaments using photocurable ceramic/monomer feedstocks containing terpene crystals as sublimable porogens for UV curing-assisted 3D plotting technique. The biphasic calcium phosphate (BCP) feedstock, composed of frozen terpene crystals surrounded by BCP/UDMA walls, could be favorably extruded through a fine nozzle and then effectively photopolymerized by UV light. Thus, green filaments with high shape retention could be obtained. In addition, a number of pores could be created in BCP filaments after removing terpene crystals via freeze-drying and the porosity could be tailored by adjusting terpene content in BCP feedstocks. This approach allowed for the construction of dual-scale porous structures comprising microporous filaments in a periodic pattern, with tailored overall porosities and compressive strengths. Several types of self-supporting structures were also successfully constructed using our approach. [ABSTRACT FROM AUTHOR]

Herein, we demonstrated the synthesis of multifunctional alkyne building blocks from commercially available acrylate monomers exploiting the carbon and oxa Michael addition reaction. These compounds were obtained in decent yields and show similar or even higher photoreactivity than the initial acrylates. Importantly, selected thiol‐yne formulations can be processed by stereolithography and significantly outperform the corresponding acrylate in terms of modulus and toughness. The high compatibility of such cured materials with osteosarcoma cells makes these photopolymers interesting for hard tissue engineering. [ABSTRACT FROM AUTHOR]

The cytotoxicity of methacrylate-based biopolymers crosslinked by in situ photopolymerization has been attributed mainly to residual methacrylate monomers released due to incomplete polymerization. The residual monomers, primarily triethyleneglycol dimethacrylate or 2-hydroxyethyl methacrylate, may irritate adjacent tissue, or be released into the bloodstream and reach practically all tissues. Increased production of reactive oxygen species, which may be connected to concomitant glutathione depletion, has been the most noticeable effect observed in vitro following the exposure of cells to methacrylates. Radical scavengers such as glutathione or N-acetylcysteine represent the most important cellular strategy against methacrylate-induced toxicity by direct adduct formation, resulting in monomer detoxification. Reactive oxygen species may participate in methacrylate-induced genotoxic or pro-apoptotic effects and cell-cycle arrest via induction of corresponding molecular pathways in cells. A deeper understanding of the biological mechanisms and effects of methacrylates widely used in various bioapplications may enable a better estimation of potential risks and thus, selection of a more appropriate composition of polymer material to eliminate potentially harmful substances such as triethyleneglycol dimethacrylate. [ABSTRACT FROM AUTHOR]

Current approaches to synthesize π‐conjugated polymers (CPs) are dominated by thermally driven, transition‐metal‐mediated reactions. Herein we show that electron‐deficient Grignard monomers readily polymerize under visible‐light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain‐growth process; correspondingly, chain extension produces all‐conjugated n‐type block copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor–acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n‐type CPs without the need for transition‐metal catalysis. [ABSTRACT FROM AUTHOR]

This contribution details an efficient and controlled photopolymerization regulated by far‐red (λ=680 nm) and NIR (λ=780 and 850 nm) light in the presence of aluminium phthalocyanine and aluminium naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerization of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q‐bands of these photocatalysts with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source, such as sunlight. [ABSTRACT FROM AUTHOR]

This contribution details an efficient and controlled photopolymerization regulated by far‐red (λ=680 nm) and NIR (λ=780 and 850 nm) light in the presence of aluminium phthalocyanine and aluminium naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerization of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q‐bands of these photocatalysts with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source, such as sunlight. [ABSTRACT FROM AUTHOR]

The single crystals of two structural isomers of bis‐olefinic molecules were shown to have contrasting properties in terms of their photoreactivity: one exhibits an excellent ability to form polymers, accompanied with bending of crystals upon irradiation, while the other is photostable. The photoreactive crystal is a first example in which [2+2] polymerization leads to bending of the crystals, with implications for the design of photoactuators. The hydrate formation ability of one of these molecular isomers promotes the solid‐state reactivity in its crystal, as the H2O molecules act as a template to bring the olefin molecules into the required arrangement for [2+2] polymerization. Further, the crystals of the polymer exhibited better flexibility and smoothed surfaces compared to those of the monomers. In addition, under UV‐light the diene emits bluish violet light while the polymer emits green light, indicating that the luminescence property can be tuned through photoirradiation. [ABSTRACT FROM AUTHOR]

Two-photon-induced photopolymerization (2PP) has gained increased interest due to the capability of manufacturing three-dimensional structures with very high feature resolution. To assess the suitability of photopolymer systems for 2PP, methods have to be developed that allow a screening of the efficiency of monomer-initiator combinations in the context of high throughput, large processing window and geometric quality of the final parts. In this paper, a method for evaluating 2PP structures is described. For this purpose, the double-bond conversion of fabricated 2PP structures was measured giving quantifiable results about the efficiency of the photoinitiator. The method is based on local measurement of the double-bond conversion of the photopolymer using a microscope in combination with infrared spectroscopy. The obtained double-bond conversion is a measure for the efficiency of the photopolymer system (initiator in combination with monomer), and thus allows to compare different photopolymers in a quantitative way. Beside this evaluation of 2PP structures, fabrication of complex 3D structures was done to determine the limits of the 2PP technology for miscellaneous components. [ABSTRACT FROM AUTHOR]

We investigate volume holographic recording in a ZrO2 nanoparticle-polymer composite film at a wavelength of 404 nm. Dependences of the polymerization kinetics on concentrations of an initiator and ZrO2 nanoparticles doped in acrylate monomer are examined by using a photodifferential scanning calorimeter. It is found that there exists the optimum concentration of ZrO2 nanoparticles to maximize the polymerization rate. The diffraction and scattering properties of transmission volume gratings are also investigated. It is found that the refractive index modulation and the material recording sensitivity are as high as 8×10-3 and 9000 cm/J, respectively, at the optimum ZrO2 nanoparticle concentration of 35 vol % and at a recording intensity of 5 mW/cm2. These material parameters are larger than typical minimum ones of 5×10-3 and 500 cm/J, respectively, for optimized performance in holographic data storage. [ABSTRACT FROM AUTHOR]

[Display omitted] Photopolymerization is an unavoidable polymerization technique used in plethora applications. If benzophenone or thioxanthone have been popular UV photoinitiators, these two structures are unsuitable for performing polymerization experiments in the visible region due to insufficient absorptions. With regards to thioxanthone and in order to redshift its absorption towards the visible range, numerous core-extended thioxanthones have been proposed, enabling to shift their absorptions at longer wavelengths and thus to elaborate visible light photoinitiators. In this field, thioxanthonation of dyes has been extensively studied but the major drawback of this approach was the access to polyaromatic structures exhibiting a low solubility in monomers, adversely affecting the monomer conversion. To address this issue, innovative strategies were envisioned to extend the π-conjugation of thioxanthone while providing an excellent solubility to photoinitiators both in common organic solvents and in monomers. In this review, the different strategies developed to access to these core-extended thioxanthones are detailed and the photopolymerization performance discussed. [ABSTRACT FROM AUTHOR]

Disulfide-containing coatings are gaining importance due to the peculiar properties and responsiveness of S S bonds, which make them suitable for several applications, first among them self-healable materials. Herein, a novel UV-curable diacrylated polyurethane monomer containing disulfide bonds (DSPDA) was synthesized through a one-step process without the need for further purification, as assessed by NMR and HPLC analyses. The photopolymerization kinetics of the monomer was studied through real-time FTIR, highlighting a fast and complete conversion even in the absence of a photoinitiator, thus demonstrating the self-initiating capabilities of the synthesized monomer based on the disulfide cleavage upon UV light exposure. Clear coatings having a T g = 72 °C were obtained. The self-healing ability of the films was assessed: thanks to the presence of disulfide bonds in the cured coating, a recovery of the damage was obtained in only 10 min by heating at 100 °C. • Synthesis of novel photocurable disulfide-containing diacrylate monomer • Self-initiating photopolymerization exploiting disulfide photocleavage • Production of clear and transparent coatings • Self-healing of the coating by thermally induced metathesis of disulfide bonds [ABSTRACT FROM AUTHOR]

A peculiar radical polymerization reaction is presented in which oxygen serves as a cocatalyst, alongside triethylamine, to provide activation with light in the far‐red (690 nm, 3 mW cm−2) of the PET‐RAFT process in the presence of zinc(II) (2,3,7,8,12,13,17,18‐octaethyl‐5,10,15,20‐tetraphenylporphyrin) as photocatalyst. Apart from the ability to exert temporal control by switching the light on or off, this system possesses the exciting capability of inducing temporal control by removal or reintroduction of oxygen. Furthermore, this multicomponent catalytic system was typified by controlled polymerizations of various acrylate and acrylamide monomers, which all resulted in well‐defined polymers with low dispersity (<1.2). The process displayed excellent living characteristics that were demonstrated through chain extensions and a range of degrees of polymerization (200–1600). [ABSTRACT FROM AUTHOR]

A peculiar radical polymerization reaction is presented in which oxygen serves as a cocatalyst, alongside triethylamine, to provide activation with light in the far‐red (690 nm, 3 mW cm−2) of the PET‐RAFT process in the presence of zinc(II) (2,3,7,8,12,13,17,18‐octaethyl‐5,10,15,20‐tetraphenylporphyrin) as photocatalyst. Apart from the ability to exert temporal control by switching the light on or off, this system possesses the exciting capability of inducing temporal control by removal or reintroduction of oxygen. Furthermore, this multicomponent catalytic system was typified by controlled polymerizations of various acrylate and acrylamide monomers, which all resulted in well‐defined polymers with low dispersity (<1.2). The process displayed excellent living characteristics that were demonstrated through chain extensions and a range of degrees of polymerization (200–1600). [ABSTRACT FROM AUTHOR]

Well defined homopolymers and block copolymers from renewable monomer α‐methylene‐γ‐butyrolactone (MBL) were prepared using photochemically induced atom transfer radical polymerization (photoATRP) in the presence of only 50–200 ppm of copper catalyst without the requirement of air removal from the polymerization mixture. The effect of solvent type and volume, ligand‐to‐copper ratio, catalyst concentration, ligand type, and the possible partial replacement of an expensive ligand with cheap simple amines, were investigated. The livingness of the oxygen‐tolerant photoATRP system was investigated by chain extension polymerization and the possibility to prepare block copolymers by chain extension of PMBL‐Br macroinitiator with methyl methacrylate (MMA) as well as by chain extension of PMMA‐Br macroinitiator with PMBL block was studied. It was shown that a concentration of catalyst as low as 50 ppm is sufficient to provide good control over the molecular characteristics and kinetics. [ABSTRACT FROM AUTHOR]

This study proposes a simple approach for the fabrication of microspherical catalysts with a hierarchical porous structure. The cross-linked porous microspheres with catalytic ability were prepared directly from small-molecular monomers via low-temperature phase-separation photopolymerization of water/oil suspension. The morphology, pore size, chemical structure, and thermal stability of the obtained porous microspheres were characterized by SEM, Mercury Intrusion Porosimetry, FTIR, and TGA. The porous microspheres directly served as an acid catalyst for the condensation reaction of benzaldehyde and ethylene glycol, which exhibited superior catalytic activity and recyclability. The results indicated that such porous microspheres have great potential in the application of acid catalysis. [ABSTRACT FROM AUTHOR]