Higher Polymerization Rate Research Articles

A highly efficient oxygen tolerant visible-light mediated RAFT polymerization

Recently, oxygen-tolerant reversible addition-fragmentation chain transfer (RAFT) polymerization has attracted increasing attention in polymer chemistry. Inspired by the monomers containing glycol ethers group have high polymerization rates and even achieved a desirable oxygen tolerance. Herein, we proposed a simple, effective, low-cost, and eco-friendly strategy to accomplish the oxygen-tolerant visible-light activated RAFT polymerization of acrylates and acrylamides in a mixed solution of glycol ether and water at ambient temperature. This photo-mediated RAFT polymerization does not require additives, prior deoxygenation, or inert gas protection. The acrylates and acrylamides with high conversion under irradiation for 2 h, and the resulting polymers were narrow unimodal and narrow molecular weight distributions (PDI<1.3). In addition, the “living” and well-controlled behaviors of this oxygen-tolerant photo-mediated RAFT polymerization were demonstrated through water content in solvents, headspace, initial concentration of monomers, various monomers, chain lengths, light ON/OFF experiment, and high-end group fidelity of block copolymers. This RAFT polymerization also opens up a wide avenue for the industrial production of functional polymeric materials via an in situ chain extension strategy. These results indicate that the mixed solution of glycol ethers and water are effective green media for promoting photo-mediated RAFT polymerization without additives or tedious degassing processes.

Mechanosensitive bonds induced complex cell motility patterns

The one-dimensional crawling movement of a cell is considered in this theoretical study. Our active gel model shows that a moving cell with weakly mechanosensitive adhesion complexes tends to move at constant velocity. As the mechanosensitivity of the adhesion complexes increases, a cell with sufficiently strong myosin contractile or high actin polymerization rate can exhibit stick-slip motion. Finally, a cell with highly mechanosensitive adhesion complexes exhibits periodic back-and-forth migration. A simplified model that assumes that the cell crawling dynamics are controlled by the evolution of the myosin density dipole and the asymmetry of adhesion complex distribution captures the motility behaviors of crawling cells qualitatively. It suggests that complex cell crawling behaviors could result from the interplay between the distribution of contractile force and mechanosensitive bonds. Published by the American Physical Society 2024

Theoretical formulation of the distribution function of critical nuclei under precipitation polymerization conditions

Precipitation Polymerization (Pre-Poly) can be considered a nucleation and growth process in which complex and high molecular weight branched polymers are involved. From an experimental point of view, it is well-known that under Pre-Poly conditions the phase transition (nucleation) occurs in the first minutes of polymerization, and then a long growth stage is observed in which the critical nuclei simultaneously grow until reaching a highly monodisperse distribution of microspheres (characteristic mechanism of binodal decomposition). The high rate at which nucleation and growth processes usually take place when radical polymerization (extremely high polymerization rate) under Pre-Poly conditions is used, makes it very difficult to study experimentally some aspects of these processes, such as the size and concentration of critical nuclei, among others. Based on the thermodynamic principles of Pre-Poly, this analytical paper covers for the first time, to the best of our knowledge, the theoretical formulation of the distribution function of critical nuclei under Pre-Poly conditions. In addition, a simple empirical method to calculate the concentration of critical nuclei was also developed using only three global, physical experimental parameters, and good agreement was found between empirical and theoretical calculations.

Expanding the toolbox for microfluidic-based in situ membrane characterization via microscopy

Polyamide thin film composite membranes are the commercial standard for aqueous nanofiltration and reverse osmosis. Establishing their synthesis-structure-performance relationships (SSPs), needed for rational membrane design, is hampered by the small scale and high reaction rate of interfacial polymerization (IP). Microfluidic devices, compatible with microscopic real-time visualization of IP and performance testing of the formed film, are interesting within this respect. In this study, a new microfluidic design and operational protocol for in situ characterization of IP is developed. Difficulties encountered with microfluidics and coping strategies are highlighted. The outcome of the optimization study proves that a parylene-coated PDMS-glass chip comprising a channel lay-out with 4 inlets, 2 outlets, a channel height of 20 μm, and a reaction channel length ≤50 μm is most compatible with IP and performance testing. Varying synthesis conditions show changing film morphology and water flux in line with trends for dip-coated membranes. Addition of NaHCO3 and ethyl acetate induce morphological features and increase water flux. Increasing TMC concentrations decrease water flux until an excess is generated. By combining the developed protocol and microfluidic device with an online measurement technique to probe film formation dynamics, such as fluorescence microscopy, SSPs can be derived in the future.

Free-radical photoring-opening polymerization of cyclic allylic sulfide: From photocleavable photoinitiators to three components photoredox systems

Photopolymers form a family of materials that have been developed to meet specific demands in fields such as coatings, varnishes, semiconductors, optical fibers, printing plates, holographic recording, etc. However, the multifunctional acrylate monomers currently used present an important volume contraction. A drawback for applications where little shrinkage during polymerization is mandatory to keep shapes and properties of the material. To overcome this problem, monomers reacting by ring opening polymerization can be used. Among possible monomers, cyclic allylic sulfides are very interesting candidates: they are highly reactive and their polymerization mechanism is almost not affected by the presence of oxygen. In this work the effects of the photoinitiating systems on the free radical ring opening photopolymerization kinetics of an eight-member cyclic allylic sulfide is studied. It is shown that cleavable type I, bimolecular type II and three components redox photoinitiating systems allow the formation of linear photopolymers with high polymerization rates and final conversions. The photopolymerization kinetics obtained show that the photopolymerization is not sensitive to oxygen which leads to reduced exposure time and higher sensitivity. This remarkable property should also extend the usage of such monomers in the coating applications where oxygen inhibition is a drawback. Finally, the benefit of ring opening polymerization process is demonstrated trough the volume contraction measurement which was found to be lower than 1.5%.

Microwave Irradiation-Assisted Reversible Addition-Fragmentation Chain Transfer Polymerization-Induced Self-Assembly of pH-Responsive Diblock Copolymer Nanoparticles.

Herein, we present a versatile platform for the synthesis of pH-responsive poly([N-(2-hydroxypropyl)]methacrylamide)-b-poly[2-(diisopropylamino)ethyl methacrylate] diblock copolymer (PHPMA-b-PDPA) nanoparticles (NPs) obtained via microwave-assisted reversible addition-fragmentation chain transfer polymerization-induced self-assembly (MWI-PISA). The N-(2-hydroxypropyl) methacrylamide (HPMA) monomer was first polymerized to obtain a macrochain transfer agent with polymerization degrees (DPs) of 23 and 51. Subsequently, using mCTA and 2-(diisopropylamino)ethyl methacrylate (DPA) as monomers, we successfully conducted MWI-PISA emulsion polymerization in aqueous solution with a solid content of 10 wt %. The NPs were obtained with high monomer conversion and polymerization rates. The resulting diblock copolymer NPs were analyzed by dynamic light scattering (DLS) and cryogenic-transmission electron microscopy (cryo-TEM). cryo-TEM studies reveal the presence of only NPs with spherical morphology such as micelles and polymer vesicles known as polymersomes. Under the selected conditions, we were able to fine-tune the morphology from micelles to polymersomes, which may attract considerable attention in the drug-delivery field. The capability for drug encapsulation using the obtained in situ pH-responsive NPs, the polymersomes based on PHPMA23-b-PDPA100, and the micelles based on PHPMA51-b-PDPA100 was demonstrated using the hydrophobic agent and fluorescent dye as Nile red (NR). In addition, the NP disassembly in slightly acidic environments enables fast NR release.

Elucidating the Sectioning Fragmentation Mechanism in Silica‐Supported Olefin Polymerization Catalysts with Laboratory‐Based X‐Ray and Electron Microscopy

AbstractStrict morphological control over growing polymer particles is an indispensable requirement in many catalytic olefin polymerization processes. In catalysts with mechanically stronger supports, e. g., polymerization‐grade silicas, the emergence of extensive cracks via the sectioning fragmentation mechanism requires severe stress build‐up in the polymerizing catalyst particle. Here, we report on three factors that influence the degree of sectioning in silica‐supported olefin polymerization catalysts. Laboratory‐based X‐ray nano‐computed tomography (nanoCT) and focused ion beam‐scanning electron microscopy (FIB‐SEM) were employed to study catalyst particle morphology and crack propagation in two showcase catalyst systems, i.e., a zirconocene‐based catalyst (i.e., Zr/MAO/SiO2, with Zr=2,2’‐biphenylene‐bis‐2‐indenyl zirconium dichloride and MAO=methylaluminoxane) and a Ziegler‐Natta catalyst (i.e., TiCl4/MgCl2/SiO2), during slurry‐phase ethylene polymerization. The absence of extensive macropores in some of the catalysts’ larger constituent silica granulates, a sufficient accessibility of the catalyst particle interior at reaction onset, and a high initial polymerization rate were found to favor the occurrence of the sectioning pathway at different length scales. While sectioning is beneficial for reducing diffusion limitations, its appearance in mechanically stronger catalyst supports can indicate a suboptimal support structure or unfavourable reaction conditions.

Novel Copper Complexes as Visible Light Photoinitiators for the Synthesis of Interpenetrating Polymer Networks (IPNs).

This work is devoted to the study of two copper complexes (Cu) bearing pyridine ligands, which were synthesized, evaluated and tested as new visible light photoinitiators for the free radical photopolymerization (FRP) of acrylates functional groups in thick and thin samples upon light-emitting diodes (LED) at 405 and 455 nm irradiation. These latter wavelengths are considered to be safe to produce polymer materials. The photoinitiation abilities of these organometallic compounds were evaluated in combination with an iodonium (Iod) salt and/or amine (e.g., N-phenylglycine—NPG). Interestingly, high final conversions and high polymerization rates were obtained for both compounds using two and three-component photoinitiating systems (Cu1 (or Cu2)/Iodonium salt (Iod) (0.1%/1% w/w) and Cu1 (or Cu2)/Iod/amine (0.1%/1%/1% w/w/w)). The new proposed copper complexes were also used for direct laser write experiments involving a laser diode at 405 nm, and for the photocomposite synthesis with glass fibers using a UV-conveyor at 395 nm. To explain the obtained polymerization results, different methods and characterization techniques were used: steady-state photolysis, real-time Fourier transform infrared spectroscopy (RT-FTIR), emission spectroscopy and cyclic voltammetry.

Simultaneous Synthesis and Self-Assembly of Bottlebrush Block Copolymers at Room Temperature via Photoinitiated RAFT Dispersion Polymerization.

Bottlebrush polymers exhibiting unique properties have attracted considerable attention for applications in many research areas. Herein, the first simultaneous synthesis and self-assembly of bottlebrush block copolymers at room temperature via photoinitiated polymerization-induced self-assembly (photo-PISA) using multifunctional macromolecular chain transfer agents (macro-CTAs) is reported. Comparing with linear block copolymers, the bottlebrush block copolymers can promote the formation of higher-order morphologies (e.g., vesicles) when targeting similar degrees of polymerization (DPs). Moreover, a higher polymerization rate is observed in the case of bottlebrush block copolymers. Gel permeation chromatography (GPC) analysis shows that good polymerization control is maintained when synthesizing bottlebrush block copolymers by photo-PISA. Finally, the obtained bottlebrush block copolymer vesicles are used as seeds for further chain extension and multicompartment nanoparticles with a sponge internal structure are formed. It is expected that this study will not only expand polymer architectures employed in PISA, but also provide a new strategy to synthesize polymer nanoparticles with unique structures.

An aqueous photo-controlled polymerization under NIR wavelengths: synthesis of polymeric nanoparticles through thick barriers.

We report an aqueous and near-infrared (NIR) light mediated photoinduced reversible addition-fragmentation chain transfer (photo-RAFT) polymerization system using tetrasulfonated zinc phthalocyanine (ZnPcS4 -) as a photocatalyst. Owing to the high catalytic efficiency and excellent oxygen tolerance of this system, well-controlled polyacrylamides, polyacrylates, and polymethacrylates were synthesized at fast rates without requiring deoxygenation. Notably, NIR wavelengths possess enhanced light penetration through non-transparent barriers compared to UV and visible light, allowing high polymerization rates through barriers. Using 6.0 mm pig skin as a barrier, the polymerization rate was only reduced from 0.36 to 0.21 h-1, indicating potential for biomedical applications. Furthermore, longer wavelengths (higher λ) can be considered an ideal light source for dispersion photopolymerization, especially for the synthesis of large diameter (d) nanoparticles, as light scattering is proportional to d 6/λ 4. Therefore, this aqueous photo-RAFT system was applied to photoinduced polymerization-induced self-assembly (photo-PISA), enabling the synthesis of polymeric nanoparticles with various morphologies, including spheres, worms, and vesicles. Taking advantage of high penetration and reduced light scattering of NIR wavelengths, we demonstrate the first syntheses of polymeric nanoparticles with consistent morphologies through thick barriers.

On-Demand Transformation of Carbon Dioxide into Polymers Enabled by a Comb-Shaped Metallic Oligomer Catalyst

In addition to harsh conditions, CO2 is an excess in most chemical transformations due to its sluggish reactivity. Herein, we realize the on-demand transformation of CO2 in the synthesis of poly(ether carbonate) polyols through a comb-shaped metallic oligomer catalyst, displaying quantitative reaction and product specificity. In contrast to conventional single-site catalysts that suffer from direct depolymerization long before quantitative CO2 conversion, the metallic oligomer catalyst anchoring multiple aluminum porphyrin complexes at the side chain maintains excellent polyol selectivity (>99%), exhibits high polymerization rate (turnover number of 50,000), and exquisitely places all CO2 monomers in the middle of the polyol backbone with oligoetherol end groups. The composition of polyol exactly corresponds to initial CO2 feed ratios of 0.07–0.39. Further studies on the kinetic rate law and activation parameters of key intermediates decipher the multimetallic synergistic catalysis. Hence, this work offers a fresh view of CO2 as an indeed countable monomer rather than ambiguous pressure as normally considered.

Recoverable Thermo-Responsive Polymeric Surfactants for the Synthesis of Bulk Plastics from Latexes

Free-radical emulsion polymerization (eFRP) is widely adopted in industries due to the great advantages that this technique offers in terms of a high polymerization rate, good heat management, and conduction in a non-toxic solvent like water. On the other hand, eFRP requires surfactants to stabilize the produced polymer nanoparticles (NPs). At the same time, the recovery of a bulk material from a NP suspension needs the addition of salts or alkali for the destabilization of the emulsion and the precipitation of the polymer. These can contaminate the final product and affect its properties. For this reason, alternative strategies able to coagulate the NP latex avoiding the addition of exogenous compounds are needed. In this work, we synthesized thermo-responsive polymeric surfactants that are able to promote the NP formation during the eFRP and to allow the recovery of the bulk polymer by simply increasing the environment temperature. Surfactants with a tunable hydrophilic–lipophilic balance were produced through reversible-addition fragmentation chain transfer (RAFT) emulsion polymerization by chain-extending a polyethylene glycol-based macromolecular chain transfer agent with butyl methacrylate, in order to obtain a series of block copolymers with high blocking efficiency, controlled molecular weight distribution, and well-defined thermo-responsive behavior. Then, the RAFT agent was removed to avoid the further extension of the block copolymers, and the surfactants were tested in the eFRP of different monomers (i.e., butyl methacrylate, methyl methacrylate, and styrene) to produce stable NP latexes. Finally, the possibility of triggering the NP aggregation and of guaranteeing the recovery of both surfactants and bulk material by simply changing the temperature of the system was assessed.

Efficient Visible-Light-Driven RAFT Polymerization Mediated by Deep Eutectic Solvents under an Open-to-Air Environment

In this work, we investigate the effects of deep eutectic solvents (DESs) on a facile reversible addition–fragmentation chain-transfer (RAFT) polymerization driven by visible light. A DES composed of tetrabutylammonium chloride (TBACl) and ethylene glycol served as a nonvolatile medium for a variety of monomers, including methyl methacrylate, methyl acrylate, dimethylacrylamide, and styrene. We first employed the polymerization-through pathway to overcome oxygen inhibition in an open-to-air environment using methyl methacrylate as the model compound. The photoiniferter polymerization using trithiocarbonates as the chain transfer agent (CTA) in DESs exhibited enhanced polymerization rates and achieved a narrow molecular weight distribution. Interestingly, even dithiobenzoate, the CTA with low efficiency for photoiniferter polymerization, exhibited a nearly 4.5-fold increase in the apparent polymerization rate constants when compared to the reaction in dimethyl sulfoxide. Moreover, the stability of the CTAs was increased in DESs for efficient control of molecular weight distribution and preservation of functional chain ends. We then surveyed photocatalysts for photoelectron/energy transfer (PET) RAFT polymerization and found that eosin Y was compatible with DESs. The PET-RAFT polymerization using dithiobenzoate in DESs showed even higher polymerization rates than the photoiniferter polymerization and enabled the polymerization under natural sunlight. Besides methyl methacrylate, other monomers also exhibited an increased polymerization rate in DESs, comparable to reactions in ionic liquids. These results suggest that DESs are effective and green media to facilitate photo-induced RAFT polymerization without additives or tedious degassing processes.

Naphthyl-Naphthalimides as High-Performance Visible Light Photoinitiators for 3D Printing and Photocomposites Synthesis

In this article, five new organic dyes based on the naphthalimide scaffold (Napht-1–Napht-5) were synthesized and tested as high-performance photoinitiators for both the Free Radical Photopolymerization (FRP) of acrylates and the Cationic Polymerization (CP) of epoxides using blue Light-Emitting Diodes (LEDs) as a safe irradiation source (LED @405 nm and 455). In fact, very good photopolymerization profiles (high final conversions and high polymerization rates) were obtained once these photoinitiators were combined with an Iodonium salt (Iod) or Iod/amine NPG and NVK). Remarkably, these dyes were able to generate interpenetrating polymer networks (IPN) by polymerization of a blend of monomers. These experiments were carried out to improve the polymerization profiles as well as the mechanical properties of the obtained materials. Due to their high photoinitiation abilities, these compounds were used in some applications such as photocomposite synthesis, direct laser write, and 3D printing experiments. To determine the chemical mechanisms, the photochemical/photophysical properties of these compounds were studied using different characterization techniques such as UV–visible absorption spectroscopy, steady-state photolysis, Fluorescence quenching, time-resolved fluorescence spectroscopy, FTIR spectroscopy, and cyclic voltammetry

2D Porphyrinic Metal-Organic Framework Nanosheets as Multidimensional Photocatalysts for Functional Materials.

Ultrathin porphyrinic 2D MOFs, ZnTCPP nanosheets (TCPP: 5,10,15,20-(tetra-4-carboxyphenyl) porphyrin) were employed as heterogeneous photocatalysts to activate PET-RAFT polymerization under various wavelengths ranging from violet to orange light. High polymerization rates, oxygen tolerance, and precise temporal control were achieved. The polymers showed narrow molecular weight distributions and good chain-end fidelity. The 2D ZnTCPP nanosheets were applied as photocatalysts in stereolithographic 3D printing in an open-air environment under blue light to yield well-defined 3D printed objects. Apart from providing an efficient catalytic system, 2D ZnTCPP nanosheets reinforced the mechanical properties of the 3D printed materials. The presence of ZnTCPP embedded in the materials conferred effective antimicrobial activity under visible light by production of singlet oxygen, affording 98 % and 93 % anti-bacterial efficiency against Gram-positive and Gram-negative bacteria, respectively.

2D Porphyrinic Metal–Organic Framework Nanosheets as Multidimensional Photocatalysts for Functional Materials

AbstractUltrathin porphyrinic 2D MOFs, ZnTCPP nanosheets (TCPP: 5,10,15,20‐(tetra‐4‐carboxyphenyl) porphyrin) were employed as heterogeneous photocatalysts to activate PET‐RAFT polymerization under various wavelengths ranging from violet to orange light. High polymerization rates, oxygen tolerance, and precise temporal control were achieved. The polymers showed narrow molecular weight distributions and good chain‐end fidelity. The 2D ZnTCPP nanosheets were applied as photocatalysts in stereolithographic 3D printing in an open‐air environment under blue light to yield well‐defined 3D printed objects. Apart from providing an efficient catalytic system, 2D ZnTCPP nanosheets reinforced the mechanical properties of the 3D printed materials. The presence of ZnTCPP embedded in the materials conferred effective antimicrobial activity under visible light by production of singlet oxygen, affording 98 % and 93 % anti‐bacterial efficiency against Gram‐positive and Gram‐negative bacteria, respectively.

Bismuthonium‐ and pyrylium‐based radical induced cationic frontal polymerization of epoxides

AbstractCationic polymerization is a powerful tool when it comes to adhesive, coating, composite, and bulk material production. A variety of monomers is suitable for this technique, however epoxy‐based systems are used in many applications, due to their high reactivity and versatility. With the introduction of the radical induced cationic frontal polymerization (RICFP), an even more efficient pathway to cure epoxides and with it a variety of new applications was obtained. The prevailing initiator class for RICFP applications is the iodonium salt. Decades of research and fine‐tuning of the formulations lead to a highly effective and versatile initiator system. With the introduction of bismuth‐ and oxygen‐based onium salts for frontal polymerization, the well‐known iodonium salt is challenged. Bismuthonium hexafluoroantimonates shows high rate of polymerization and conversions of 84% in an epoxy system. The advantage of bismuthonium‐based systems is the pot life of the formulations, which can be cured at the press of a button. In this study, iodonium salts last around 3 days before a significant viscosity increase is measured, while the bismuthonium initiator lasts over 10 times as long with no significant drop in reactivity or frontal velocity.

Investigation of the composite materials photopolymerization efficiency in the hree-dimensional 3D printing objects formation

The development and investigation of photopolymerization composite (PhPC) materials with improved photochemical and physical-mechanical properties, providing the possibility of using them during image formation processes in 3D printing technologies, have been carried out. The effect of the nature and amount the polymerization composition constituents on the photocuring of urethane methacrylate and etheracrylate oligomers with the inclusion of organosilicon modifiers, as well as tertiary aminemethacrylates in the process of their irradiation with LED lamps of different wavelengths in the presence of photoinitiators, has been investigated. The effect of the nature and amount of photoinitiators on the optical and polymerization properties of materials and coatings was studied using a PLAZMON-71 spectrometer. According to the results of the calculated photopolymerization kinetic parameters (rate, induction period), it was found that the composition containing the photoinitiators Irgacure 819 (2%), Darocur 1173 (1%), as well as tertiary aminemethacrylate (5%) provides a high polymerization rate and a slight induction period among the investigated compositions. The surface plasmon resonance method allows to determine and control the rate of composite materials photocuring during forming images in 3D printing technology. The possibility of regulating the photochemical and operational characteristics of the constructed nanocomposite materials with the inclusion of organosilicon modifiers in the composition according to their purpose in technological processes of stereolithographic recording of 3D information during printing volumetric images is demonstrated.

3-Carboxylic Acid and Formyl-Derived Coumarins as Photoinitiators in Photo-Oxidation or Photo-Reduction Processes for Photopolymerization upon Visible Light: Photocomposite Synthesis and 3D Printing Applications.

In this paper, nine organic compounds based on the coumarin scaffold and different substituents were synthesized and used as high-performance photoinitiators for free radical photopolymerization (FRP) of meth(acrylate) functions under visible light irradiation using LED at 405 nm. In fact, these compounds showed a very high initiation capacity and very good polymerization profiles (both high rate of polymerization (Rp) and final conversion (FC)) using two and three-component photoinitiating systems based on coum/iodonium salt (0.1%/1% w/w) and coum/iodonium salt/amine (0.1%/1%/1% w/w/w), respectively. To demonstrate the efficiency of the initiation of photopolymerization, several techniques were used to study the photophysical and photochemical properties of coumarins, such as: UV-visible absorption spectroscopy, steady-state photolysis, real-time FTIR, and cyclic voltammetry. On the other hand, these compounds were also tested in direct laser write experiments (3D printing). The synthesis of photocomposites based on glass fiber or carbon fiber using an LED conveyor at 385 nm (0.7 W/cm2) was also examined.

Naphthalimide‐Based Dyes as Photoinitiators under Visible Light Irradiation and their Applications: Photocomposite Synthesis, 3D printing and Polymerization in Water

AbstractIn this work, six new fluorescent dyes derived from the naphthalimide scaffold (Napht1–Napht6) were synthesized and used as high‐performance photoinitiating systems (PISs) in two and three‐component systems (combined with iodonium salt (Iod) and/or an electron donor amine (such as N‐phenylglycine[NPG])) for the radical photopolymerization of acrylate and methacrylate monomers under visible light using a light‐emitting diode at 405 nm. Markedly, these dyes were never synthesized before. In fact, these PISs showed high initiation efficiency with both demonstrating high final reactive function conversions and high polymerization rates. A further interest of our study is to determine the effect of the different substituents (chromophoric group) on the naphthalimide function, concerning the efficiency of initiation of the free radical polymerization. In order to improve the mechanical properties of the obtained polymers, these derivatives were also tested for the photopolymerization of a blend of acrylate/epoxy monomers (TA/EPOX); these latter properties were characterized by traction tests. To demonstrate the initiation efficiency of these dyes, several methods and characterization techniques were used, including steady state photolysis, real‐time Fourier transform infrared spectroscopy, emission spectroscopy as well as cyclic voltammetry. In our study, these naphthalimides were used for the synthesis of photocomposites (one and multiple layers of glass fibres) using a UV@395 nm (4 W/cm2) conveyor, as well as in the preparation of 3D printed polymers. Markedly, one of the naphthalimide derivatives (Napht‐4) can be used as a new high‐performance water soluble photoinitiator for photopolymerization in water and hydrogel synthesis.