In situ production of visible light absorbing Ti-based nanoparticles in solution and in a photopolymerizable cationic matrix

Lalevée, Jacques; Poupart, Romain; Bourgon, Julie; Fouassier, Jean Pierre; Versace, Davy‐Louis

doi:10.1039/c5cc01102g

Cited by 7 publications

(5 citation statements)

References 41 publications

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“…356−358 In a quite similar approach, they investigated a series of different Ti-based complexes containing Ti−O bonds as additives toward reduction of oxygen inhibition for the free radical polymerization initiated by a bisacylphosphine oxide photoinitiator, as well as photochemical generation of metallic nanoparticles. 359,360 The key to these systems is the formation of metal-based radical compounds which act as peroxyl radical scavengers, and multiple addition of peroxyl radicals leads to the formation of metal nanoparticles.…”

Section: Polymer-metal Nanocomposites Bymentioning

confidence: 99%

“…Thus, significant enhancement of the rate of polymerization in the presence of oxygen was achieved by the added organometallic compounds being used as additives to Type I photoinitiators. The interaction of the peroxyl radicals with the organometallic compounds through a bimolecular homolytic substitution reaction led to the formation of metal-based structures, which finally resulted in the generation of metallic nanoparticles embedded in the polymeric matrix. − In a quite similar approach, they investigated a series of different Ti-based complexes containing Ti–O bonds as additives toward reduction of oxygen inhibition for the free radical polymerization initiated by a bisacylphosphine oxide photoinitiator, as well as photochemical generation of metallic nanoparticles. , The key to these systems is the formation of metal-based radical compounds which act as peroxyl radical scavengers, and multiple addition of peroxyl radicals leads to the formation of metal nanoparticles.…”

Section: Polymer-metal Nanocomposites By Photoinduced Electron Transf...mentioning

confidence: 99%

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Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

2016

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Photochemical reactions, particularly those involving photoinduced electron transfer processes, establish a substantial contribution to the modern synthetic chemistry, and the polymer community has been increasingly interested in exploiting and developing novel photochemical strategies. These reactions are efficiently utilized in almost every aspect of macromolecular architecture synthesis, involving initiation, control of the reaction kinetics and molecular structures, functionalization, and decoration, etc. Merging with polymerization techniques, photochemistry has opened up new intriguing and powerful avenues for macromolecular synthesis. Construction of various polymers with incredibly complex structures and specific control over the chain topology, as well as providing the opportunity to manipulate the reaction course through spatiotemporal control, are one of the unique abilities of such photochemical reactions. This review paper provides a comprehensive account of the fundamentals and applications of photoinduced electron transfer reactions in polymer synthesis. Besides traditional photopolymerization methods, namely free radical and cationic polymerizations, step-growth polymerizations involving electron transfer processes are included. In addition, controlled radical polymerization and "Click Chemistry" methods have significantly evolved over the last few decades allowing access to narrow molecular weight distributions, efficient regulation of the molecular weight and the monomer sequence and incredibly complex architectures, and polymer modifications and surface patterning are covered. Potential applications including synthesis of block and graft copolymers, polymer-metal nanocomposites, various hybrid materials and bioconjugates, and sequence defined polymers through photoinduced electron transfer reactions are also investigated in detail.

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Section: Polymer-metal Nanocomposites Bymentioning

confidence: 99%

Section: Polymer-metal Nanocomposites By Photoinduced Electron Transf...mentioning

confidence: 99%

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

2016

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“…These systems under air and upon exposure to a low-intensity UV light activation result in simultaneous formation of Ti-based NPs. More recently, the synthesis of visible-light-absorbing Ti-based NPs in a polyether film has been demonstrated using UV light irradiation of a titanium isopropoxide/(4-methylphenyl)[4-(2-methylpropyl) phenyl]-hexafluorophosphate (Iod) couple under air and in a cationic monomer film.…”

Section: Introductionmentioning

confidence: 99%

Well-Defined Titanium Complex for Free-Radical and Cationic Photopolymerizations under Visible Light and Photoinduction of Ti-Based Nanoparticles

et al. 2019

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A quinoline-derived titanium complex (TiQ) is shown here to possess remarkable photosensitizing properties when treated with an iodonium salt (Iod) to initiate, under visible light irradiation, (i) the free-radical photopolymerization of acrylate monomer in aerated/laminate conditions, (ii) the cationic photopolymerization of epoxy monomer under air, and (iii) the in situ formation of Ti-based nanoparticles (NPs) inside coatings. The photochemical properties of the TiQ/Iod photoinitiating system have been probed by electron paramagnetic resonance, laser flash photolysis, and real-time Fourier transform infrared spectroscopy, which provide an insight into the possible radical/cationic pathways. The microstructural properties of the photosynthesized Ti-based NPs have been investigated by bright-field conventional transmission electron microscopy and high-angle annular dark-field scanning transmission electron microscopy. The macroscopic mechanical properties of the resulting nanocomposite reveal that the generation of these Ti-based NPs in a polyacrylate/polyether blend matrix leads to an increase of mechanical resistance by toughening the matrix.

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“…This new photoinduced process gave the opportunity to tune the functionality of the polymer surface and consequently to control its wettability as a function of the irradiation time. Additionally, Versace et al used a titanium (iso)propoxide/iodonium salt as an alternative photoinitiating system to synthesize visible-light absorbing Ti-based nanoparticles (NPs) in cationic photopolymerizable films [48]. EPR spin trapping with PBN evidenced the formation of phenyl radicals (a N = 14.1 G and a H = 2.1 G in tert-butylbenzene) and the corresponding peroxyl radicals (PhOO • , a N = 13.6 G and a H = 1.6 G) under air.…”

Section: Carbon-centred Radical Spin Adducts Of Pbnmentioning

confidence: 99%

Electron Paramagnetic Resonance Spin Trapping (EPR–ST) Technique in Photopolymerization Processes

2022

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To face economic issues of the last ten years, free-radical photopolymerization (FRP) has known an impressive enlightenment. Multiple performing photoinitiating systems have been designed to perform photopolymerizations in the visible or near infrared (NIR) range. To fully understand the photochemical mechanisms involved upon light activation and characterize the nature of radicals implied in FRP, electron paramagnetic resonance coupled to the spin trapping (EPR–ST) method represents one of the most valuable techniques. In this context, the principle of EPR–ST and its uses in free-radical photopolymerization are entirely described.

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In situ production of visible light absorbing Ti-based nanoparticles in solution and in a photopolymerizable cationic matrix

Cited by 7 publications

References 41 publications

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

Well-Defined Titanium Complex for Free-Radical and Cationic Photopolymerizations under Visible Light and Photoinduction of Ti-Based Nanoparticles

Electron Paramagnetic Resonance Spin Trapping (EPR–ST) Technique in Photopolymerization Processes

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