Polymeric Iodonium Salts to Trigger Free Radical Photopolymerization.

In a significant breakthrough from classical molecular (i.e., nonpolymeric) iodonium salts in light-induced photochemistry, the synthesis and use of new safer polymeric iodonium salts are reported here. They are shown to be involved in charge transfer complexes (CTCs) while in interaction with a safe amino acid derivative (N-phenylglycine). Also, this study demonstrates i) the formation of CTCs between the iodonium (acceptor) and an aryl/alkyl amine (donor) through UV-vis measurements of the monomer, ii) the formation of radicals in electron spin resonance spin trapping experiments when the CTCs are irradiated by visible light (405 nm), and iii) their efficiency as a photoinitiator to polymerize three different acrylic monomers under LED irradiation at 405 nm under air and their application to 3D resolved laser writing of thick samples (3 mm). High reactivity for polymeric iodonium salts comparable with molecular ones is exhibited with the advantage of potential lower migration. To the best of the authors' knowledge, this is the first reported instance of polymeric iodonium salts acting as polymerization initiators.

Fillers as Heaters for Photothermal Polymerization upon NIR Light.

Photo-induced thermal polymerization upon near-infrared (NIR) light irradiation has been reported in the literature. In this approach, a component able to convert the NIR light into heat must be used in combination with a thermal initiator to initiate the free-radical polymerization of (meth)acrylates. In recent studies, some absorbers have been presented as very efficient heat generators (called heaters). In the present work, different fillers are investigated as heaters and compared to organic NIR absorbers. An alkoxyamine (e.g., BlocBuilder-MA) is used as thermal initiator and is dissociated by the heat generated by the NIR photoexcitation of the fillers. In the present work, several fillers are examined: graphene oxide, graphene nanoplatelets, multi-walled carbon nanotubes, and silicon carbide. Due to the energy of the photon delivered, NIR light curing is challenging but offers several advantages compared to visible light. The most interesting feature is the deeper penetration of the light inside the photocurable resin, enabling the polymerization of thick samples. Parallel to this, incorporation of fillers in resins allows unique access to composites through photothermal polymerization of (meth)acrylates. Three different wavelengths of irradiation have been studied: 785, 940, and 1064 nm.

Carbazole-based compounds as photoinitiators for free radical and cationic polymerization upon near visible light illumination.

Six new carbazole based compounds (Ca1-Ca6) are synthesized and proposed as high performance photoinitiators with iodonium salt (iod) and/or an amine (EDB) for both the free radical polymerization (FRP) of acrylates and the cationic polymerization (CP) of epoxides upon near UV and visible light exposure using light emitting diodes (LEDs) @385 nm and @405 nm. Excellent polymerization initiating abilities are found and high final reactive function conversions are acquired. A full picture of the involved photochemical mechanisms is given.

Multihydroxy-Anthraquinone Derivatives as Free Radical and Cationic Photoinitiators of Various Photopolymerizations under Green LED.

Multihydroxy-anthraquinone derivatives [i.e., 1,2,4-trihydroxyanthraquinone (124-THAQ), 1,2,7-trihydroxyanthraquinone (127-THAQ), and 1,2,5,8-tetrahydroxyanthraquinone (1258-THAQ)] can interact with various additives [e.g., iodonium salt, tertiary amine, N-vinylcarbazole, and 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine] under household green LED irradiation to generate active species (cations and radicals). The relevant photochemical mechanism is investigated using quantum chemistry, fluorescence, cyclic voltammetry, laser flash photolysis, steady state photolysis, and electron spin resonance spin-trapping techniques. Furthermore, the multihydroxy-anthraquinone derivative-based photoinitiating systems are capable of initiating cationic photopolymerization of epoxides or divinyl ethers under green LED, and the relevant photoinitiation ability is consistent with the photochemical reactivity (i.e., 124-THAQ-based photoinitiating system exhibits highest reactivity and photoinitiation ability). More interestingly, multihydroxy-anthraquinone derivative-based photoinitiating systems can initiate free radical crosslinking or controlled (i.e., reversible addition-fragmentation chain transfer) photopolymerization of methacrylates under green LED. It reveals that multihydroxy-anthraquinone derivatives can be used as versatile photoinitiators for various types of photopolymerization reactions.

Charge-Transfer Complexes as New Inhibitors/Photoinitiators for On-Demand Amine/Peroxide Redox Polymerization.

Redox free-radical polymerizations have widespread applications but still clearly suffer from poor time control of the reaction. Currently, the workability (delay of the gel time) in redox polymerization after mixing is possible thanks to two main types of inhibitors (radical scavengers): phenols and nitroxides. Out of this trend, we propose in this work an alternative strategy for time delaying of the redox polymerization, which is based on charge-transfer complexes (CTCs). Thanks to iodonium salt complexation, the amine (here 4-N,N-trimethylaniline) is proposed to be stored in a CTC equilibrium and is slowly released over a period of time (as a result of the consumption of free amines by peroxides). This alternative strategy allowed us to double the gel time (e.g., from 60 to 120 s) while maintaining a high polymerization efficiency (performance comparable to reference nitroxides). More interestingly, the CTCs involved in this retarding strategy are photoresponsive under visible LED@405 nm and can be used on demand as photoinitiators, allowing (i) spectacular increases in polymerization efficiencies (from 50 °C without light to 120 °C under mild irradiation conditions); (ii) drastic reduction of the oxygen-inhibited layer (already 45% C=C conversion at a 2 µm distance from the top surface) compared to the nonirradiated sample (thick inhibited layer of more than 45 µm); and (iii) external control of the redox polymerization gel time due to the possible light activation.

New Synthetic Route to an Highly Efficient Photoredox Catalyst by Mechanosynthesis.

Photoredox catalysis based on the [Cu(neo)(DPEphos)]BF4 copper complex allowed getting a significant improvement of the polymerization performances (e.g., thick samples, coatings...) compared to that obtained with other benchmarked photoinitiators in both cationic (CP) and free radical polymerizations (FRP). Nevertheless, as for other copper complexes classically used as photoinitiators in polymer science, the synthesis of these complexes is carried out in a solvent; this fact remains an obstacle to their widespread use because of the cost associated with the use of a solvent and the complex synthesis procedure. In the present study, on the contrary, an outstanding efficient mechanosynthesis of [Cu(neo)(DPEphos)]BF4-purity ≥95% outranking the previous Cu(I) mechanosynthesis-allowed (i) to divide the synthesis time by 170-fold (as only 5 min is necessary to get the complex), (ii) to lower the environmental impact and cut the synthetic costs associated with solvent usage, and (iii) to access a new Cu(I) complex with a counteranion that is impossible to introduce under the traditional chemistry methods (e.g., I-). Reactivities of the mechanosynthesized copper complexes in resins (FRP and CP) confirmed the very high purity of the obtained copper complex by 1H nuclear magnetic resonance spectroscopy and high-resolution electrospray ionization mass spectrometry.

Novel Carbazole Skeleton-Based Photoinitiators for LED Polymerization and LED Projector 3D Printing.

Radical chemistry is a very convenient way to produce polymer materials. Here, an application of a particular photoinduced radical chemistry is illustrated. Seven new carbazole derivatives Cd1-Cd7 are incorporated and proposed as high performance near-UV photoinitiators for both the free radical polymerization (FRP) of (meth)acrylates and the cationic polymerization (CP) of epoxides utilizing Light Emitting Diodes LEDs @405 nm. Excellent polymerization-initiating abilities are found and high final reactive function conversions are obtained. Interestingly, these new derivatives display much better near-UV polymerization-initiating abilities compared to a reference UV absorbing carbazole (CARET 9H-carbazole-9-ethanol) demonstrating that the new substituents have good ability to red shift the absorption of the proposed photoinitiators. All the more strikingly, in combination with iodonium salt, Cd1-Cd7 are likewise preferred as cationic photoinitiators over the notable photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO) for mild irradiation conditions featuring their remarkable reactivity. In particular their utilization in the preparation of new cationic resins for LED projector 3D printing is envisioned. A full picture of the included photochemical mechanisms is given.

Development of Novel Photoinitiators as Substitutes of Camphorquinone for the LED Induced Polymerization of Methacrylates: A Bis-Silyl Ketone.

A new photoinitiator based on a bis-silylketone (BSK) structure is proposed as a novel compound leading to highly efficient initiating silyl radicals for the polymerization of methacrylates (e.g., a bisphenol A-glycidyl methacrylate/triethyleneglycol dimethacrylate blend (70%/30% w/w)) upon exposure to a blue light emitting diode and a green laser diode. The polymerization profiles are recorded by real time Fourier transform IR (FTIR) spectroscopy. Absorption, fluorescence, electron spin resonance (ESR), and steady state experiments are used to investigate the involved chemical mechanisms. Molecular orbital calculations are also carried out. Remarkably, BSK efficiently works in the presence of an iodonium salt. The overall mechanism for the initiation step is clarified. This novel class of silyl radical generating photoinitiators is really promising for the photopolymerization of methacrylates, e.g., in dental materials.

Organic Electronics: An El Dorado in the Quest of New Photocatalysts for Polymerization Reactions.

Photoinitiated polymerization has been the subject of continued research efforts due to the numerous applications in which this polymerization technique is involved (coatings, inks, adhesives, optoelectronic, laser imaging, stereolithography, nanotechnology, etc.). More recently, photopolymerization has received renewed interest due to the emergence of 3D-printing technologies. However, despite current academic and industrial interest in photopolymerization methodologies, a major limitation lies in the slow rates of photopolymerization. The development of new photoinitiating systems aimed at addressing this limitation is an active area of research. Photopolymerization occurs through the exposure of a curable formulation to light, generating radical and/or cationic species to initiate polymerization. At present, photopolymerization is facing numerous challenges related to safety, economic and ecological concerns. Furthermore, practical considerations such as the curing depth and the competition for light absorption between the chromophores and other species in the formulation are key parameters drastically affecting the photopolymerization process. To address these issues, photoinitiating systems operating under low intensity visible light irradiation, in the absence of solvents are highly sought after. In this context, the use of photoredox catalysis can be highly advantageous; that is, photoredox catalysts can provide high reactivities with low catalyst loading, permitting access to high performance photoinitiating systems. However, to act as efficient photoredox catalysts, specific criteria have to be fulfilled. A strong absorption over the visible range, an ability to easily oxidize or reduce as well as sufficient photochemical stability are basic prerequisites to make these molecules desirable candidates for photoredox catalysis. Considering the similarity of requirements between organic electronics and photopolymerization, numerous materials initially designed for applications in organic electronics have been revisited in the context of photopolymerization. Organic electronics is a branch of electronics and materials science focusing on the development of semiconductors devoted to three main research fields; organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells (OSCs). The contribution of organic electronics to the field of electronics is important as it paves the way toward cheaper, lighter, and more energy efficient devices. In the present context of photopolymerization, materials that were investigated as photocatalysts were indifferently organic semiconductors used for transistors, charge-transport materials, and light-emitting materials used in electroluminescent devices or conjugated polymers and small molecule dyes for solar cells. In this Account, we summarize our latest developments in elaborating on photocatalytic systems based on these new classes of compounds. Through an in-depth understanding of the parameters governing their reactivities and our efforts to incorporate these materials into photoinitiating systems, we provide new knowledge and a valuable insight for future prospects.

A novel photoinitiating system producing germyl radicals for the polymerization of representative methacrylate resins: Camphorquinone/R3GeH/iodonium salt.

OBJECTIVES: The aim of our study is to find an amine free photoinitiating system (PIS) for the polymerization of representative dental methacrylate resins. A photoinitiating system (PIS) based on camphorquinone (CQ)/triphenylgermanium hydride/diphenyl iodonium hexafluorophosphate is proposed and compared to the conventional CQ/amine couple. The polymerization monitoring of thin (∼20µm) and thick (1.4mm) samples of a bisphenol A-glycidyl methacrylate (Bis-GMA)/triethyleneglycol dimethacrylate (TEGDMA) blend (70%/30% w/w) and of a urethane dimethacrylate (UDMA) upon exposure to a commercial blue LED centered at 477nm under air or in laminate is described. Finally, the impact of the photoinitiating system composition on the final polymer color is evaluated in detail. METHODS: FTIR and DSC experiments are used to record the photopolymerization profiles. ESR spectrometry and steady state photolysis are used to detect the produced radicals. Color measurements are carried out to determine the key parameters in the bleaching of the different dental formulations. RESULTS: The efficiency of the newly proposed PISs for the photopolymerization of BisGMA/TEGDMA and UDMA for thin (20µm) or for thick (1.4mm) samples upon exposure to a dental blue LED under air is excellent. It is noticeably higher than that of the CQ/amine reference couple. Excellent bleaching properties are also observed under irradiation in presence of the new PISs. A good correlation is found between the sample bleaching and the amount of Ph3GeH in the formulation. The excited state processes could be established. The overall chemical mechanisms for the initiation step were also clarified.

Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources.

Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

Photochemistry and radical chemistry under low intensity visible light sources: application to photopolymerization reactions.

The search for radical initiators able to work under soft conditions is a great challenge, driven by the fact that the use of safe and cheap light sources is very attractive. In the present paper, a review of some recently reported photoinitiating systems for polymerization under soft conditions is provided. Different approaches based on multi-component systems (e.g., photoredox catalysis) or light harvesting photoinitiators are described and discussed. The chemical mechanisms associated with the production of free radicals usable as initiating species or mediators of cations are reported.

Metal and metal-free photocatalysts: mechanistic approach and application as photoinitiators of photopolymerization.

In the present paper, the photoredox catalysis is presented as a unique approach in the field of photoinitiators of polymerization. The principal photocatalysts already reported as well as the typical oxidation and reduction agents used in both reductive or oxidative cycles are gathered. The chemical mechanisms associated with various systems are also given. As compared to classical iridium-based photocatalysts which are mainly active upon blue light irradiation, a new photocatalyst Ir(piq)2(tmd) (also known as bis(1-phenylisoquinolinato-N,C (2'))iridium(2,2,6,6-tetramethyl-3,5-heptanedionate) is also proposed as an example of green light photocatalyst (toward the long wavelength irradiation). The chemical mechanisms associated with Ir(piq)2(tmd) are investigated by ESR spin-trapping, laser flash photolysis, steady state photolysis, cyclic voltammetry and luminescence experiments.

On the synthesis, characterization and reactivity of N-heteroaryl-boryl radicals, a new radical class based on five-membered ring ligands.

The synthesis and physical characterization of a new class of N-heterocycle-boryl radicals is presented, based on five membered ring ligands with a N(sp(2) ) complexation site. These pyrazole-boranes and pyrazaboles exhibit a low bond dissociation energy (BDE; BH) and accordingly excellent hydrogen transfer properties. Most importantly, a high modulation of the BDE(BH) by the fine tuning of the N-heterocyclic ligand was obtained in this series and could be correlated with the spin density on the boron atom of the corresponding radical. The reactivity of the latter for small molecule chemistry has been studied through the determination of several reaction rate constants corresponding to addition to alkenes and alkynes, addition to O2 , oxidation by iodonium salts and halogen abstraction from alkyl halides. Two selected applications of N-heterocycle-boryl radicals are also proposed herein, for radical polymerization and for radical dehalogenation reactions.

Comparison of a new photosensitizer with erythrosine B in an AA/PVA-based photopolymer material.

Dyes often act as the photoinitiator PI/photosensitizer PS in photopolymer materials and are therefore of significant interest. The properties of the PI/PS used strongly influences grating formation when the material layer is exposed holographically. In this paper, the ability of a recently synthesized dye, D_1, to sensitize an acrylamide/polyvinyl alcohol (AA/PVA) based photopolymer is examined, and the material performance is characterized using an extended nonlocal photopolymerization-driven diffusion model. Electron spin resonance spin-trapping (ESR-ST) experiments are also carried out to characterize the generation of the initiator/primary radical, R(•), during exposure. The results obtained are then compared with those for the corresponding situation when using a xanthene dye, i.e., erythrosine B, under the same experiment conditions. The results indicate that the nonlocal effect is greater when this new photosensitizer is used in the material. Analysis indicates that this is the case because of the dye's (D_1) weak absorptivity and the resulting slow rate of primary radical production.

The first photochemical in situ production of Ti-based nanoparticles: a SH2 strategy using bis(cyclopentadienyl)titanium dichloride (Cp2TiCl2).

Bis(cyclopentadienyl)titanium dichloride (Cp2TiCl2) is a high performance additive under UV light activation for both i) radical photopolymerization reactions (when added to a Type I photo-initiator such as 2,2-dimethoxy-2-phenylacetophenone, the oxygen inhibition is reduced) and ii) a concomitant in situ photoinduced and oxygen mediated formation of Ti-based nanoparticles (diameters ranging from 45 to 220 nm). The photochemical properties of Cp2TiCl2 are investigated by steady state photolysis and electron spin resonance, and its photoinitiation ability checked. The nanoparticles (NPs) are well characterized by transmission electron microscopy. The high reactivity of Cp2TiCl2 under air is ascribed to a bimolecular homolytic substitution (the SH2 process is clearly demonstrated by density functional theory calculations and ESR experiments), which converts the peroxyls into new efficient initiating radicals. The photochemical in situ incorporation of Ti NPs has never previously been reported. The synthesis of metal nanoparticles by a SH2 approach instead of the reduction of a metal salt appears to be a promising original method.

Red-light-induced cationic photopolymerization: perylene derivatives as efficient photoinitiators.

Nine different perylene derivatives are prepared and their ability to initiate, when combined with an iodonium salt (and optionally N-vinylcarbazole), a ring-opening cationic photopolymerization of epoxides under very soft halogen lamp irradiation is investigated. One of them is particularly efficient under a red laser diode exposure at 635 nm and belongs now to the very few systems available at this wavelength. The photochemical mechanisms are studied by steady-state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques.

New core-pyrene π structure organophotocatalysts usable as highly efficient photoinitiators.

Eleven di- and trifunctional compounds based on a core-pyrene π structure (Co_Py) were synthesized and investigated for the formation of free radicals. The application of two- and three-component photoinitiating systems (different Co_Pys with the addition of iodonium or sulfonium salts, alkyl halide or amine) was investigated in detail for cationic and radical photopolymerization reactions under near-UV-vis light. The proposed compounds can behave as new photocatalysts. Successful results in terms of rates of polymerization and final conversions were obtained. The strong MO coupling between the six different cores and the pyrene moiety was studied by DFT calculations. The different chemical intermediates are characterized by ESR and laser flash photolysis experiments. The mechanisms involved in the initiation step are discussed, and relationships between the core structure, the Co_Py absorption property, and the polymerization ability are tentatively proposed.

A multicolor photoinitiator for cationic polymerization and interpenetrated polymer network synthesis: 2,7-di-tert-butyldimethyldihydropyrene.

For polymer synthesis upon visible light, actual photoinitiator operates in a restricted part of the spectrum. As a consequence, several photoinitiators are necessary to harvest all of the emitted visible photons. Herein, 2,7-di-tert-butyldimethyldihydropyrene is used for the first time as a multicolor photoinitiator for the cationic polymerization of epoxides. Upon addition of diphenyliodonium hexafluorophosphate and optionally N-vinylcarbazole, the originality of this approach is to allow efficient monomer conversions under various excitation light sources in the 360-650 nm wavelength range: halogen lamps, and light-emitting and laser diodes. The synthesis of an interpenetrated polymer network from an epoxide/acrylate blend using a red light at 635 nm is also feasible. The formed polymer material exhibits a photochromic character.

Light-harvesting organic photoinitiators of polymerization.

Two new photoinitiators with unprecedented light absorption properties are proposed on the basis of a suitable truxene skeleton where several UV photoinitiators PI units such as benzophenone and thioxanthone are introduced at the periphery and whose molecular orbitals MO can be coupled with those of the PI units: a red-shifted absorption and a strong increase of the molecular extinction coefficients (by a ≈ 20-1000 fold factor) are found. These compounds are highly efficient light-harvesting photoinitiators. The scope and practicality of these photoinitiators of polymerization can be dramatically expanded, that is, both radical and cationic polymerization processes are accessible upon very soft irradiation conditions (halogen lamp, LED…︁) thanks to the unique light absorption properties of the new proposed structures.