Photoinitiators derived from natural product scaffolds: monochalcones in three-component photoinitiating systems and their applications in 3D printing

Chen, Hong; Noirbent, Guillaume; Sun, Ke; Brunel, Damien; Gigmès, Didier; Morlet‐Savary, Fabrice; Zhang, Yijun; Liu, Shaohui; Xiao, Pu; Dumur, Frédéric; Lalevée, Jacques

doi:10.1039/d0py00568a

Cited by 82 publications

(68 citation statements)

References 34 publications

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“…In 2020, the first ferrocenebased chalcones developed as photoinitiators of polymerization were reported for the first time (See chalcone 1-chalcone 6 in Figure 25). [302] It has to be noticed that if chalcones can be found in the Nature (fruits and flowers), [303] evidently, no ferrocene-based chalcones can be naturally found so that these structures are bioinspired and not biosourced. However, these structures remain of interest.…”

Section: Free Radical Polymerization Using Ferrocene-based Chalconesmentioning

confidence: 99%

Recent advances on ferrocene-based photoinitiating systems

Dumur

2021

European Polymer Journal

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Photoinitiators of polymerization with reversible electrochemical properties are actively researched as these molecules can advantageously be used in photocatalytic systems, enabling to reduce the photoinitiators content within the photocurable resins. In this field, ferrocene which is extensively used by electrochemists as a reference compound for cyclic voltammetry also exhibits a significant absorption in the visible range as well as a low oxidation potential so that this metallocene was used as a potential candidate for the design of photoinitiators of polymerization. Over the years, ferrocene has been examined in numerous polymerization processes going from anionic to cationic polymerizations, but also for the freeradical polymerization of acrylates or as a sacrificial electron donor in free radical polymerization processes. Parallel to this, the development of cheap, compact and energysaving irradiation setups based on light-emitting diodes (LEDs) have clearly favored the development of visible light photoinitiators and this technology has nowadays the potential to replace the well-established UV photopolymerization. In this review, an overview of the recent development of the ferrocene-based photoinitiating systems is provided. To evidence the interest of the ferrocene derivatives recently developed, comparisons with benchmark photoinitiators will be provided.

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Section: Free Radical Polymerization Using Ferrocene-based Chalconesmentioning

confidence: 99%

Recent advances on ferrocene-based photoinitiating systems

Dumur

2021

European Polymer Journal

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“…[ 6 ] However, at present, most of the Type I cleavage systems (e.g., hydroxyl‐ketone photoinitiators) and Type II H‐abstraction systems (e.g., benzophenone (BP)/amine) based on benchmark PIs can only be activated under UV irradiation and cannot be even used in the near UV–vis range, even if these wavelengths are now widely employed for the industrial production and scientific research. [ 7–9 ]…”

Section: Methodsmentioning

confidence: 99%

“…[6] However, at present, most of the Type I cleavage systems (e.g., hydroxyl-ketone photoinitiators) and Type II H-abstraction systems (e.g., benzophenone (BP)/amine) based on benchmark PIs can only be activated under UV irradiation and cannot be even used in the near UVvis range, even if these wavelengths are now widely employed for the industrial production and scientific research. [7][8][9] Nowadays, the irradiation @405 nm is the new standard in 3D printing for both stereolithography and digital light processing approaches. Therefore, search for new PISs perfectly matching the emission of LEDs is the focus of numerous research efforts.…”

Section: Doi: 101002/marc202000460mentioning

confidence: 99%

Novel Photoinitiators Based on Benzophenone‐Triphenylamine Hybrid Structure for LED Photopolymerization

Liu

Brunel

Sun

et al. 2020

Macromol. Rapid Commun.

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In this study, a new generation of photoinitiator (PI) based on hybrid structures combining benzophenone and triphenylamine is proposed. Remarkably, these photoinitiators (noted monofunctional benzophenone‐triphenylamine (MBP‐TPA) and trifunctional benzophenone‐triphenylamine (TBP‐TPA)) are designed and developed for the photopolymerization under light‐emitting diodes (LEDs). Benzoyl substituents connected with triphenylamine moiety contribute to the excellent absorption properties which results in both high final conversions and polymerization rates in free radical photopolymerization (FRP). Remarkably, TBP‐TPA owning trifunctional benzophenone group exhibits a better Type II PI behavior than well‐known 2‐isopropylthioxanthone for photopolymerization under LED@365 and 405 nm irradiation. FRP and cationic photopolymerization of TBP‐TPA‐based systems are applied on 3D printing experiments, and good profiles of the 3D patterns are observed. The high molecular weight of TBP‐TPA associated with it trifunctional character can also be very interesting for a better migration stability of PIs that is a huge challenge. The development of this new generation of photoinitiators based on benzophenone hybrid structures is a real breakthrough. It reveals that the novel versatile photoinitiators based on benzophenone‐triphenylamine hybrid structures have great potentials for future industrial applications (e.g., 3D printing, composites, etc.).

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“…Considering that no natural chalcones comprise a ferrocene unit, the six chalcones examined in this work can be considered as bioinspired photoinitiators. [167] Interestingly, when incorporated in three-component chalcone/Iod1/EDB (1.5 wt%/1.5 wt%/1.5 wt%) systems (where EDB stands for ethyl 4dimethylaminobenzoate), for the polymerization of a PEG-diacrylate resin, final monomer conversions ranging between 30% for chalcone 22 to 80% for chalcones 1 and 6 respectively after 200 s of irradiation at 405 nm in laminate. Surprisingly, ferrocene-based chalcones proved to be efficient photoinitiators for thin films but not for thick films for which tacky polymers were obtained.…”

Section: Ferrocene-based Chalconesmentioning

confidence: 99%

Recent advances on iron-based photoinitiators of polymerization

Dumur

2020

European Polymer Journal

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With regards to the environmental and safety concerns raised nowadays by the polymer industry, polymerization processes requiring light as the activation source are currently knowing a revival of interest after decades of disinterest. Recent progresses in photopolymerization are notably sustained by the development of new polymerization application namely 3D and 4D printing enabling an unprecedented access to structures of incredible complexity. Parallel to the manufacturing process, the polymer material itself and its composition are also facing numerous questions concerning their environmental and human health impacts. Beyond the monomers, the different additives introduced in the resin can also be potentially toxic so that a great deal of efforts is currently done to develop new photoinitiators with a toxicity assessed as being insignificant. In this field, iron-based metal complexes are candidates of choice due to the clinical demonstration of their very low toxicities. Among iron complexes, ferrocene is among the most widely studied iron-based metallocene. Due to its unique and reversible electrochemical properties as well as their absorption centred in the visible range, numerous photoinitiators have been developed with ferrocene or its oxidized form i.e. ferrocenium. Parallel to this, the remarkable electrochemical properties of ferrocenium made it an excellent candidate for its incorporation in photoinitiating systems. However, interest for iron-based photoinitiators was not limited to ferrocene and ferrocenium, and Schiff base complexes were also successfully used as initiators of polymerization. In this review, an overview of the different iron-based photoinitiating systems reported to date is presented. More precisely, if iron-based photoinitiators are developed since 50 years, a special focus will be done on photoinitiators designed for recent polymerization conditions, namely, under visible light and low light intensity.

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Photoinitiators derived from natural product scaffolds: monochalcones in three-component photoinitiating systems and their applications in 3D printing

Abstract:
Design of new photoinitiators based on natural Chalcone scaffold.

Cited by 82 publications

References 34 publications

Recent advances on ferrocene-based photoinitiating systems

Recent advances on ferrocene-based photoinitiating systems

Novel Photoinitiators Based on Benzophenone‐Triphenylamine Hybrid Structure for LED Photopolymerization

Recent advances on iron-based photoinitiators of polymerization

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Photoinitiators derived from natural product scaffolds: monochalcones in three-component photoinitiating systems and their applications in 3D printing

Abstract: Design of new photoinitiators based on natural Chalcone scaffold.

Cited by 82 publications

References 34 publications

Recent advances on ferrocene-based photoinitiating systems

Recent advances on ferrocene-based photoinitiating systems

Novel Photoinitiators Based on Benzophenone‐Triphenylamine Hybrid Structure for LED Photopolymerization

Recent advances on iron-based photoinitiators of polymerization

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Abstract:
Design of new photoinitiators based on natural Chalcone scaffold.