International audienceA short review on the role of photocatalysts in photopolymerization reactions is presented. A special emphasis is done on photoredox catalysts leading to i) high performance initiating systems for polymerization upon low light intensity for the use of light emitting diodes (LEDs) and/or visible light or ii) Controlled Radical PhotoPolymerization (CRP2) processes with formation/reactivation of dormant species triggered by light

Silyl glyoxylates are proposed here as a new class of high performance type I photoinitiators for free radical polymerization under air or in laminate (e.g., (meth)­acrylates) upon exposure to different near-UV (at 395 nm; at 405 nm) and blue (at 477 nm) LEDs. The new proposed photoinitiators can also be used in the presence of additives that can enhance their initiating ability: an iodonium salt and an amine or a phosphine. The silyl glyoxylate-based photoinitiating systems exhibit excellent polymerization performances upon blue LED light (at 477 nm) with exceptional bleaching properties compared to camphorquinone (CQ)-based systems. This can be highly worthwhile for the preparation of colorless polymers upon visible light. Real-time Fourier transform infrared spectroscopy (RT-FTIR) experiments are used to monitor the polymerization profiles. The involved chemical mechanisms are investigated by fluorescence, laser flash photolysis, electron spin resonance (ESR), and steady state photolysis experiments. Molecular orbital calculations are also carried out. The overall excited state processes and the chemical mechanisms involved in the initiation step are detailed.

The objective of this work was to propose a novel low migration additive (i.e. a phosphine) to overcome the oxygen inhibition in a camphorquinone (CQ) base photoinitiating system for the polymerization of methacrylates (e.g. a bisphenol A‐glycidyl methacrylate (Bis‐GMA)/triethyleneglycol dimethacrylate (TEGDMA) blend (70%/30% w/w)) upon exposure to a commercial blue light emitting diode centred at 477 nm. CQ/amine/phosphine derivative or CQ/amine/iodonium salt/phosphine derivative combinations were studied. Real‐time Fourier transform IR and photo‐DSC experiments were used to monitor the polymerization profiles. Remarkably, it was found that the addition of the new phosphine derivative to CQ/amine or CQ/amine/iodonium salt noticeably improved the rate of polymerization and the final conversion in air. A low migration was found for this additive as shown by HPLC experiments in agreement with a copolymerizable behaviour. No additional yellowing of the film was observed. Electron spin resonance spectrometry was used to detect the produced radicals. The overall chemical mechanisms are investigated and discussed. © 2016 Society of Chemical Industry

Diaryliodonium salts are well-established compounds in free radical chemistry and are already used as photoinitiators (free radical or cationic polymerization), but the presence of counter anions is a strong drawback. Indeed, a counter anion is always required (e.g., SbF6−) leading to potential toxicity issues or release of HF. In the present paper, counter anion-free and fluoride-free aryliodonium salts are proposed, that is, aryliodonium ylides (AY) are studied here as new and efficient additives for radical chemistry and an example is provided for the camphorquinone (CQ)/amine based photoinitiating systems (PISs) for the polymerization of thick (1.4 mm) and thin (20–13 µm) methacrylates under air and blue light irradiation. The newly proposed PISs, for example, CQ/amine/AY, presented excellent polymerization performances and good bleaching properties were obtained after polymerization. Real-time Fourier transform infrared spectroscopy (RT-FTIR) was used to monitor the photopolymerization profiles. The chemical mechanisms involved were investigated using electron spin resonance (ESR).

Iodonium sulfonates are proposed here as a new class of high‐performance coinitiators for camphorquinone (CQ)‐based systems for the polymerization of methacrylates under blue light irradiation. When combined with CQ, the new proposed coinitiators present excellent polymerization performances and are excellent candidates for the replacement of tertiary aromatic amines subjected to toxicological concerns in the well‐established CQ/amine photoinitiating system (PIS). Remarkably, good bleaching properties are obtained after polymerization. The use of the new PIS for dental adhesives is also investigated. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1664–1669

Photoinitiators exhibiting efficient thermally activated delayed fluorescence (TADF) are investigated.

New high performance photoinitiating systems for visible light exhibiting excellent bleaching properties and water solubility are proposed.

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