A New Phosphine for Efficient Free Radical Polymerization under Air.

A new phosphine is proposed as efficient coinitiator for camphorquinone (CQ)-based photoinitiating systems for the free radical polymerization of (meth)acrylates. Remarkably, this new co-initiator can exhibit two functionalities: a phosphine moiety to overcome oxygen inhibition and an iodonium salt moiety as counter cation to initiate the polymerization process. Excellent polymerization performances in the presence of CQ for the free radical polymerization of methacrylates under blue light are observed, and amine-free systems can be easily developed from the proposed structure. The photopolymerization of composites is also investigated in the presence of the new phosphine (without iodonium counter cation) and very interesting depth of cure can be obtained from the new developed photoinitiating system after only 20 s of irradiation with a blue light-emitting diode.

Sulfinates and sulfonates as high performance co-initiators in CQ based systems: Towards aromatic amine-free systems for dental restorative materials.

OBJECTIVE: The aim of our study is to develop amine-free photoinitiating systems (PISs) for the polymerization of representative dental methacrylate resins under blue light irradiation. PISs based on camphorquinone (CQ)/sulfinate and CQ/sulfonate, eventually in combination with an iodonium salt, are proposed and compared to the well-established CQ/amine system. The polymerization performances of thick (1.4 mm) samples of different methacrylate blends upon exposure to a commercial blue LED centered at 477 nm under air are described. Finally, the performances of the new developed PISs are evaluated for dental composites application. METHODS: FTIR is used to monitor the photopolymerization profiles. ESR spectroscopy and electrochemical experiments are used to identify the radicals generated. Mechanical properties measurements and color stability measurements are carried out to determine the key properties of the dental composites prepared. RESULTS AND SIGNIFICIANCE: The performances of the new proposed PISs for the photopolymerization of thick (1.4 mm) samples of methacrylate upon exposure to a blue dental LED under air are excellent. Similar or better performances and bleaching properties are obtained with the new proposed amine-free systems compared to those reached with the CQ/amine reference system. Dental composites with excellent mechanical properties and exceptional color stability are obtained. The involved chemical mechanisms for the initiation step were also established.

1-Aryl-2-(triisopropylsilyl)ethane-1,2-diones: Toward a New Class of Visible Type I Photoinitiators for Free Radical Polymerization of Methacrylates.

1-Aryl-2-(triisopropylsilyl)ethane-1,2-diones (SEDs) are proposed here as a new class of visible Type I photoinitiators (PIs) for free radical polymerization under air upon exposure to blue (@455 nm) and green (@520 nm) LEDs. Remarkably, these new systems present good polymerization performances and excellent bleaching properties compared to camphorquinone-based systems, and transparent polymers are obtained upon visible light irradiation. Real-time Fourier transform infrared spectroscopy is used to monitor the polymerization profiles. Molecular orbital calculations are also carried out for a better understanding of the structure/reactivity relationship of the photoinitiators.

Aryliodonium Ylides as Novel and Efficient Additives for Radical Chemistry: Example in Camphorquinone (CQ)/Amine Based Photoinitiating Systems.

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).