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

In Silico Design of Nitrocoumarins as Near-UV Photoinitiators: Toward Interesting Opportunities in Composites and 3D Printing Technologies

In this research, 31 nitrocoumarins (including 27 structures never reported in the literature) were designed through molecular orbital calculations and synthesized as high-performance near-UV–visible light photoinitiators of polymerization for a better understanding of their structure/reactivity/efficiency relationship. Based on their photoinitiating abilities examined during the free-radical polymerization (FRP) of acrylates, different coumarins examined in this work can be classified into three main categories: (1) very reactive ones (Coum6,7,11,12&26); (2) moderately reactive nitrocoumarins (Coum1,2,16,20,21,23,25,27&28); and (3) nitrocoumarins of low reactivity (Coum3,4,5,8,9,10,13,14,15,17,18,19,22,24,29,30&31). Different techniques were used in order to understand their photoinitiating abilities as well as the associated chemical mechanisms. The real-time Fourier transform infrared technique has been used to follow the polymerization profiles (reactive function conversion (FCs) vs irradiation time). Different two- and three-component photoinitiating systems based on nitrocoumarin/iodonium salt (or N-phenylglycine (NPG) or ethyl 4-(dimethylamino)benzoate) and nitrocoumarin/iodonium salt/NPG were examined for the FRP of acrylates or/and the cationic polymerization of epoxides upon irradiation with a light-emitting diode at 405 nm as an unharmed and inexpensive irradiation source. Moreover, cyclic voltammetry, fluorescence spectroscopy, UV–visible spectroscopy, and electron spin resonance techniques were also used to provide a full picture of the involved chemical mechanisms. Excellent polymerization performances (i.e., high final reactive FCs and also great rates of polymerization (Rp)) were obtained using these derivatives. Some applications in three-dimensional printing and composite synthesis are reported to highlight the interest of the proposed structures in modern technologies

In-silico based development of photoinitiators for 3D printing and composites: Search on the coumarin scaffold

In this work, the in-silico rational design of new photoinitiators by molecular modeling for specific wavelength (here 405 nm) and specific applications (3D printing, composites) is reported. A large number of (keto)coumarin derivatives were investigated by molecular modeling and their synthesis and more detailed photochemical investigations are based on obtaining structures having both excellent predicted light absorption properties @ 405 nm and high excited state energy levels (to ensure high photochemical reactivity). More particularly, four new families of coumarins were designed (4 of the 19 proposed coumarins were never synthesized (N2,M6,T1,T6)): the first family is based on Nitrocoumarins (N1-N6), the second one on Methoxybenzene-based coumarins and Ethoxycoumarins (M1-M6), the third one on Thiophene-based coumarins (T1-T6) and the last family studied concerns Alkyne-based coumarin (A1). The purpose of this work concerns the study of the photoinitiating ability of these compounds in different monomers for different polymerization processes (free radical, cationic) using FTIR technique. The different compounds reported in this work are very efficient to initiate the free radical polymerization of (meth)acrylates but also the cationic polymerization of epoxides upon mild irradiation conditions using a Light Emitting Diode (LED) at 405 nm as visible light source. Nitrocoumarins were identified as the best candidates for photoinitiation among the different families of coumarins investigated in this work. More precisely, nitrocoumarins are characterized by very good polymerization profiles, great final reactive function conversions (FC) and also high rates of polymerization (Rp). The electrochemical and pho-tochemical properties of the different compounds were also studied to get a deeper insight into the photo-chemical mechanisms supporting the initiation process. A full picture of the involved photochemical mechanisms is provided. Thanks to the astounding polymerization initiating ability of these coumarins, their use in 3D printing applications can be worthwhile. Remarkably, using these compounds, the preparation of photo-composites was possible even in difficult light penetration conditions resulting from the presence of fibers inside the resins

Mono vs. Difunctional Coumarin as Photoinitiators in Photocomposite Synthesis and 3D Printing

This work is devoted to investigate three coumarin derivatives (Coum1, Coum2, and Coum3), proposed as new photoinitiators of polymerization when combined with an additive, i.e., an iodonium salt, and used for the free radical polymerization (FRP) of acrylate monomers under mild irradiation conditions. The different coumarin derivatives can also be employed in three component photoinitiating systems with a Iod/amine (ethyl 4-dimethylaminobenzoate (EDB) or N-phenylglycine (NPG)) couple for FRP upon irradiation with an LED @ 405 nm. These compounds showed excellent photoinitiating abilities, and high polymerization rates and final conversions (FC) were obtained. The originality of this work relies on the comparison of the photoinitiating abilities of monofunctional (Coum1 and Coum2) vs. difunctional (Coum3) compounds. Coum3 is a combined structure of Coum1 and Coum2, leading to a sterically hindered chemical structure with a relatively high molecular weight. As a general rule, a high molecular weight should reduce the migration of initiating molecules and favor photochemical properties such as photobleaching of the final polymer. As attempted, from the efficiency point of view, Coum3 can initiate the FRP, but a low reactivity was observed compared to the monofunctional compound (Coum1 and Coum2). Indeed, to study the photochemical and photophysical properties of these compounds, different parameters were taken into account, e.g., the light absorption and emission properties, steady state photolysis, and fluorescence quenching. To examine these different points, several techniques were used including UV-visible spectroscopy, real-time Fourier Transform Infrared Spectroscopy (RT-FTIR), fluorescence spectroscopy, and cyclic voltammetry. The photochemical mechanism involved in the polymerization process is also detailed. The best coumarins investigated in this work were used for laser writing (3D printing) experiments and also for photocomposite synthesis containing glass fibers

Simultaneous initiation of radical and cationic polymerization reactions using the "G1" copper complex as photoredox catalyst: Applications of free radical/cationic hybrid photopolymerization in the composites and 3D printing fields.

WOS:000469902800007International audienceThis investigation presents the use of a photoredox catalyst "G1" as a photoinitiating system for free radical/cationic hybrid polymerization under mild irradiation conditions. The G1 system (G1/iodonium salt/N-vinylcarbazole), can simultaneously initiate the free radical and cationic polymerization reactions upon exposure to a visible (405 nm) light from a Light Emitting Diode (LED) source. The multicomponent G1 system is able to simultaneously generate radical and cationic species through a catalytic photoredox process. The curing of thin samples (25 mu m), thick samples (1.4 mm) as well as the manufacture of hybrid system/glass fibers composites ( 2 to 4 mm thickness) was realized and the influence of the ratio of cationic/radical monomer blends on the polymerization kinetics was studied. The use of G1 in visible light photoinitiating system for the access to composites and 3D printing experiments was particularly outlined. G1 was also shown to have low levels of migration from the cured materials. When compared to reference materials ("F1", a similar copper complex and an anthracene derivative, dibutoxy anthracene), G1 showed better polymerization efficiency. The initiation efficiency was investigated through the real-time Fourier transform infrared (RT-FTIR) spectroscopy and optical pyrometry. Dynamical Mechanical Analysis has been used to determine the glass temperature transition of the cured hybrid system as a complementary technique

Household LED irradiation under air: cationic polymerization using iridium or ruthenium complex photocatalysts:

Household LED bulbs are used to promote the ring-opening photopolymerization of epoxides in the presence of a photocatalyst (here tris(2-phenylpyridine)iridium [Ir(ppy)(3)] or tris(1,10-phenanthroline)ruthenium(II) [Ru(phen) (3) (2+) ] complex) and a silyl radical source. Remarkably, even under this very soft irradiation (light intensity lower than 10 mW/cmA(2)), excellent polymerization profiles are obtained i.e., this is the first reported use of such very convenient irradiation devices for photopolymerization processes. The role of the silane and other hydrogen donors is outlined

Photoinduced modification of the natural biopolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) microfibrous surface with anthraquinone-derived dextran for biological applications

A straightforward and versatile method for immobilizing polysaccharides on the surface of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) electrospun fibers is developed with the objective of designing a new functional biomaterial having a significant effect on cell proliferation. The approach relies on a one-step procedure: UV grafting of a photosensitive dextran (AQ-Dext) on the surface of PHBHV fibers according to a "grafting onto" method, with the use of an anthraquinone derivative. The photografting is conducted through a photoinduced free radical process employing an anthraquinone-based photosensitizer in aqueous medium. Under appropriate conditions, AQ-Dext reacts with C-H sigma-bonds of the polymer substrate (PHBHV) to produce a semianthraquinone radical according to an H-abstraction reaction. This radical recombines together with the alkylradical (R-center dot) formed at the surface of PHBHV fibers via the oxygen atom of the anthraquinone photolinker. The photochemical mechanism of the AQ-Dext photolysis is entirely described for the first time by an electron spin resonance technique and laser flash photolysis. The modified PHBHV microfibrous scaffolds are extensively characterized by water contact angle measurements, XPS analysis and atomic force microscopy, confirming the covalent grafting of dextran on PHBHV fibers. Finally, a primary investigation demonstrates that dextran modified PHBHV fibers are permissive for optimized cell colonization and proliferation. The cell morphologies are described by SEM micrographs, revealing a significant affinity and favorable interactions for adherence of human mesenchymal stem cells (hMSCs) on scaffolds provided by dextran chemical structure. Moreover, the proliferation rate of hMSCs increases on this new functionalized biomaterial associated with a higher extra-cellular matrix production after 5 days of culture in comparison with native PHBHV fibers

Silyloxyamines as sources of silyl radicals: ESR spin-trapping, laser flash photolysis investigation, and photopolymerization ability:

Two silyloxyamines derived from 8-(pentamethyldisilyloxy)-julolidine and diethyl 3-(pentamethyldisilyloxy)-aniline are proposed as new sources of silyl radicals. The decomposition mechanism, excited state processes and the radical generation are explored by steady state photolysis, laser flash photolysis (LFP), electron spin resonance (ESR), and MO calculations. The Si-Si bond cleavage is clearly demonstrated. The formation of a radical cation on the amine moiety is also observed. Moreover, these compounds work as efficient Type I and Type II photoinitiators (PI) of free radical photopolymerization (FRP). Copyright (C) 2010 John Wiley & Sons, Ltd

Thermal Initiators as Additives for Photopolymerization of Methacrylates upon Blue Light

Free radical polymerization is often performed by thermal initiation but also more and more by light-assisted polymerization processes. This second approach allows the polymerization to be carried out under mild conditions (under air, upon blue light exposure, under low light intensity). The aim and the originality of the present paper is to perform photopolymerization in the presence of a thermal initiator, i.e., we can take advantage of the exothermicity of the photopolymerization process to decompose the thermal initiator, leading to enhanced polymerization rates. The performance of the photoinitiating system is discussed in the present study based on real-time Fourier-transform infrared spectroscopy measurements (following the C=C bond content evolution vs. time) and by thermal imaging experiments. Mechanisms of the new system proposed in this work are also fully detailed using cyclic voltammetry, electron spin resonance (ESR) spin trapping, and UV-visible absorption properties