Jean Pierre Fouassier

Institut de Science des Matériaux de Mulhouse, Mulhousen, Alsace, France

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Publications (254)738.2 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: The utilization of visible lights for the fabrication of polymeric materials is recognized as a promising and environmentally friendly approach. This process relies on the photochemical generation of reactive species (e.g., radicals, radical cations, or cations) from well-designed photoinitiators (PIs) or photoinitiating systems (PISs) to initiate the polymerization reactions of different monomers (acrylates, methacrylates, epoxides, and vinyl ethers). In spite of the fact that metal complexes such as ruthenium- or iridium-based complexes have found applications in organic and polymer synthesis, the search of other low-cost metal-based complexes as PISs is emerging and attracting increasing attentions. Particularly, the concept of the photoredox catalysis has appeared recently as a unique tool for polymer synthesis upon soft conditions (use of light emitting diodes and household lamp). This highlight focuses on recently designed copper and iron complexes as PI catalysts in the application of photoinduced polymerizations (radical, cationic, interpenetrated polymer networks, and thiol-ene) or controlled radical polymerization under visible light irradiation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    Journal of Polymer Science Part A Polymer Chemistry 08/2015; DOI:10.1002/pola.27762 · 3.54 Impact Factor
  • Macromolecular Chemistry and Physics 08/2015; DOI:10.1002/macp.201500150 · 2.45 Impact Factor
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    ABSTRACT: Only one naphthalic anhydride derivative has been reported as light sensitive photoinitiator, this prompted us to further explore the possibility to prepare a new family of photoinitiators based on this scaffold. Therefore, eight naphthalic Naphthalic anhydride derivatives (ANH1-ANH8) have been prepared and combined with an iodonium salt (and optionally N-vinylcarbazole) or an amine (and optionally 2,4,6-tris(trichloromethyl)-1,3,5-triazine) to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources, that is, very soft halogen lamp (∼ 12 mW cm−2), laser diode at 405 nm (∼1.5 mW cm−2) or blue LED centered at 455 nm (80 mW cm−2). The ANH6 based photoinitiating systems are particularly efficient for the cationic and the radical photopolymerizations, and even better than that of the well-known camphorquinone based systems. The photochemical mechanisms associated with the chemical structure/photopolymerization efficiency relationships are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin-trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    Journal of Polymer Science Part A Polymer Chemistry 08/2015; DOI:10.1002/pola.27763 · 3.54 Impact Factor
  • Macromolecular Chemistry and Physics 07/2015; DOI:10.1002/macp.201500104 · 2.45 Impact Factor
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    ABSTRACT: Series of diketopyrrolopyrrole derivatives (DPPs) and indigo derivatives (IDGs) are synthesized and applied as photoinitiators (PIs) for the cationic polymerization (CP) of epoxides, the free radical polymerization (FRP) of acrylates or the thiol-ene polymerization under different lights (purple, blue, green, yellow, red LEDs and green laser diode). The photochemical mechanisms involved in the presence of these PIs and additives (iodonium salt (Iod), N-vinylcarbazole (NVK), amine (MDEA) or 2,4,6-tris(trichloromethyl)-1,3,5-triazine (R-Cl)) are investigated by steady state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques. Real-time infrared spectroscopy studies reveal that DPP4/Iod/NVK is very efficient for both CP and FRP and, compared to two references (Eosin-Y and camphorquinone), displays noticeably higher polymerization efficiencies. Panchromatic curable formulations exhibiting an almost constant photosensitivity from the blue to the red are proposed.
    06/2015; 4. DOI:10.1016/j.mtcomm.2015.06.007
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    ABSTRACT: Four novel onium salts (onium-polyoxometalate) have been synthesized and characterized. They contain a diphenyliodonium or a thianthrenium (TH) moiety and a polyoxomolybdate or a polyoxotungstate as new counter anions. Outstandingly, these counter anions are photochemically active and can sensitize the decomposition of the iodonium or TH moiety through an intramolecular electron transfer. The phenyl radicals generated upon UV light irradiation (Xe–Hg lamp) are very efficient to initiate the radical polymerization of acrylates. Cations are also generated for the cationic polymerization of epoxides. Remarkably, these novel iodonium and TH salts are characterized by a higher reactivity compared with that of the diphenyliodonium hexafluorophosphate and the commercial TH salt, respectively. Interpenetrating polymer networks can also be obtained under air through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend (monomer conversions > 65%). The photochemical mechanisms are studied by steady-state photolysis, cyclic voltammetry, and electron spin resonance techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015.
    Journal of Polymer Science Part A Polymer Chemistry 04/2015; 53(8). DOI:10.1002/pola.27526 · 3.54 Impact Factor
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    ABSTRACT: Seven naphthalimide derivatives (NDP1-NDP7) with different substituents have been designed as versatile photoinitiators (PIs), and some of them when combined with an iodonium salt (and optionally N-vinylcarbazole) or an amine (and optionally chlorotriazine) are expected to exhibit an enhanced efficiency to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources (i.e., the LED at 385, 395, 405, 455, or 470 nm or the polychromatic visible light from the halogen lamp). Remarkably, some studied naphthalimide derivative based photoinitiating systems (PIS) are even more efficient than the commercial type I photoinitiator bisacylphosphine oxide and the well-known camphorquinone-based systems for cationic or radical photopolymerization. A good efficiency upon a LED projector at 405 nm used in 3D printers is also found: a 3D object can be easily created through an additive process where the final object is constructed by coating down successive layers of material. As another example of their broad potential, a NDP compound enveloped in a cyclodextrin (CD) cavity, leads to a NDP-CD complex which appears as a very efficient water-soluble photoinitiator when combined with methyldiethanol amine to form a hydrogel. The high interest of the present photoinitiator (NDP2) is its very high reactivity, allowing synthesis in water upon LED irradiation as a green way for polymer synthesis.The structure/reactivity/efficiency relationships as well as the photochemical mechanisms associated with the generation of the active species (radicals or cations) are studied by different techniques including steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin-trapping methods.
    Macromolecules 04/2015; 48(7):2054-2063. DOI:10.1021/acs.macromol.5b00201 · 5.93 Impact Factor
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    ABSTRACT: Isoquinolinone derivatives bearing amino- or nitro- substituent (IQNs) have been synthesized as photoinitiators and combined with various additives (i.e., iodonium salt, N-vinylcarbazole, amine or 2,4,6-tris(trichloromethyl)−1,3,5-triazine) to initiate ring-opening cationic polymerizations (CP) or free radical polymerizations under exposure to visible LEDs (e.g., LEDs at 405 nm or 455 nm, or cold white LED) or a halogen lamp. Compared to the well-known camphorquinone-based systems, the novel IQNs-based combinations employed here demonstrate higher efficiencies for the CP of epoxides. The photochemically generated reactive species (i.e., cations and radicals) from the IQNs-based systems have been investigated by steady state photolysis, cyclic voltammetry, fluorescence, laser flash photolysis, and electron spin resonance spin trapping techniques. The structure/reactivity/photoinitiating ability relationships of IQNs-based combinations are also discussed; the crucial role of the excited state lifetimes of the photoinitiators to ensure efficient quenching by additives is clearly underlined. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    Journal of Polymer Science Part A Polymer Chemistry 04/2015; DOI:10.1002/pola.27640 · 3.54 Impact Factor
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    ABSTRACT: N,N'-dibutylquinacridone (DBQA) is utilized here for the first time as a high-performance panchromatic photoinitiator for the cationic polymerization (CP) of epoxides, the free radical polymerization (FRP) of acrylates, the thiol-ene polymerization and the synthesis of interpenetrated polymer networks (epoxide/acrylate) under violet, blue, green and yellow lights (emitted from LED at 405 nm, 470 nm, 520 nm, or 594 nm, or laser diode at 532 nm). It confers a panchromatic character to the photopolymerizable matrices. Remarkably, the proposed DBQA based photoinitiating systems exhibit quite excellent efficiency (the final monomer conversion for multifunctional monomers at room temperature can reach 62% and 50% in CP and FRP, respectively) and appear as much more powerful than the camphorquinone or Eosin-Y containing reference systems for visible light. For green light, DBQA is much more reactive than the literature reference (Eosin-Y) and for blue light, a good reactivity is found compared with camphorquinone. The photochemical mechanisms are studied by molecular orbital calculations, steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015
    Journal of Polymer Science Part A Polymer Chemistry 03/2015; 53(14). DOI:10.1002/pola.27615 · 3.54 Impact Factor
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    ABSTRACT: A novel straightforward approach is proposed to generate in situ, under light activation and in aerated media, visible-light absorbing and well-defined titanium-based nanoparticles (NPs) in solution and in an epoxide matrix using titanium derivatives complexes/iodonium salt photoinitiating systems. The nature of the solvent and oxygen play a decisive role, and two mechanisms involved in these syntheses are operative, i.e photofragmentation/addition process (in toluene and isopropanol) and a photoinduced sol-gel reaction (in isopropanol).
    Chemical Communications 02/2015; 51(26). DOI:10.1039/C5CC01102G · 6.83 Impact Factor
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    ABSTRACT: Four different 2-amino-1H-benzo[de]isoquinoline-1,3(2H)-dione derivatives (NDNs) bearing nitro- or amino- substituents have been prepared and incorporated into photoinitiating systems together with an iodonium salt, N-vinylcarbazole, an amine or 2,4,6-tris(trichloromethyl)-1,3,5-triazine. The ring-opening cationic polymerization of epoxides as well as the free radical polymerization of acrylates upon exposure to various visible LEDs (e.g. LEDs at 405 nm, 455 nm or 470 nm) could be performed. Reactions under green or red light (e.g. laser diodes at 532 or 635 nm) are also feasible. Compared to the well-known camphorquinone-based systems, some of the novel NDN-based combinations employed here exhibit a much higher polymerization efficiency. A panchromatic behavior can also be observed with a specifically designed compound bearing two nitro groups (e.g. radical polymerization or thiol–ene processes can be promoted upon blue, green or red light). This outstanding performance paves the way to polymerization under soft conditions. Their photochemical properties and structure/efficiency relationships have been investigated using steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin trapping techniques.
    02/2015; 6(7). DOI:10.1039/C4PY01409J
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    ABSTRACT: A benzophenone-naphthalimide derivative (BPND) bearing tertiary amine groups has been developed as a high-performance photoinitiator in combination with 2,4,6-tris(trichloromethyl)-1,3,5-triazine or an iodonium salt for both the free radical polymerization (FRP) of acrylates and the cationic polymerization (CP) of epoxides upon exposure to near UV and visible LEDs (385–470 nm). BPND can even produce radicals without any added hydrogen donor. The photochemical mechanisms are studied by molecular orbital calculations, steady state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry and laser flash photolysis techniques. These novel BPND based photoinitiating systems exhibit an efficiency higher than that of the well-known camphorquinone-based systems (FRP and CP) or comparable to that of bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (FRP at λ ≤ 455 nm). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014
    Journal of Polymer Science Part A Polymer Chemistry 02/2015; 53(3). DOI:10.1002/pola.27451 · 3.54 Impact Factor
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    ABSTRACT: Six iron complexes (FeCs) with various ligands have been designed and synthesized. In combination with additives (e.g., iodonium salt, N-vinylcarbazole, amine, or chloro triazine), the FeC-based systems are able to efficiently generate radicals, cations, and radical cations on a near UV or visible light-emitting diode (LED) exposure. These systems are characterized by an unprecedented reactivity, that is, for very low content 0.02% FeC-based systems is still highly efficient in photopolymerization contrary to the most famous reference systems (Bisacylphosphine oxide) illustrating the performance of the proposed catalytic approach. This work paves the way for polymerization in soft conditions (e.g., on LED irradiation). These FeC-based systems exhibit photocatalytic properties, undergo the formation of radicals, radical cations, and cations and can operate through oxidation or/and reduction cycles. The photochemical mechanisms for the formation of the initiating species are studied using steady state photolysis, cyclic voltammetry, electron spin resonance spin trapping, and laser flash photolysis techniques. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014
    Journal of Polymer Science Part A Polymer Chemistry 01/2015; 53(1). DOI:10.1002/pola.27435 · 3.54 Impact Factor
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    ABSTRACT: Naphthalimide-phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N-vinylcarbazole, amine or 2,4,6-tris(trichloromethyl)-1,3,5-triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well-known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014
    Journal of Polymer Science Part A Polymer Chemistry 12/2014; 53(5). DOI:10.1002/pola.27490 · 3.54 Impact Factor
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    ABSTRACT: Isoquinolinone derivatives (IQ) have been synthesized and combined with different additives (an amine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, an iodonium salt, or N-vinylcarbazole) to produce reactive species (i.e. radicals and cations) being able to initiate the radical polymerization of acrylates, the cationic polymerization of epoxides, the thiol-ene polymerization of trifunctional thiol/divinylether, and the synthesis of epoxide/acrylate interpenetrated polymer network IPN upon exposure to very soft polychromatic visible lights, blue laser diode or blue LED lights. Compared with the use of camphorquinone based systems, the novel combinations employed here ensures higher monomer conversions (∼50–60% vs. ∼15–35%) and better polymerization rates in radical polymerization. The chemical mechanisms are studied by steady-state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin trapping techniques. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014
    Journal of Polymer Science Part A Polymer Chemistry 12/2014; 53(4). DOI:10.1002/pola.27477 · 3.54 Impact Factor
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    ABSTRACT: Two naphthalimide derivatives (DMAENs) containing tertiary amine groups have been designed and synthesized. Upon exposure to near UV and visible LEDs (365 nm-455 nm), they lead to radicals without adding a hydrogen donor and, in combination with 2,4,6-tris(trichloromethyl)-1,3,5-triazine, an iodonium salt or N-vinylcarbazole, they produce radicals and cations. Compared to the well-known camphorquinone or bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide photoinitiator, the novel DMAENs containing photoinitiating systems are characterized by a very high reactivity for both the free radical polymerization of acrylates and the cationic polymerization of epoxides. This outstanding performance paves the way for polymerization in soft conditions (e.g. upon LED irradiation). The photochemical mechanisms are studied by Molecular Orbitals MO calculations, steady state photolysis, fluorescence, cyclic voltammetry, electron spin resonance spin trapping and laser flash photolysis techniques.
    Polymer 11/2014; 55(26). DOI:10.1016/j.polymer.2014.11.002 · 3.77 Impact Factor
  • Jean Pierre Fouassier · Jacques Lalevée
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    ABSTRACT: In this paper, we propose to review the ways to produce, through photopolymerization, interpenetrating polymer networks (IPN) based, e.g., on acrylate/epoxide or acrylate/vinylether blends and to outline the recent developments that allows a one-step procedure (concomitant radical/cationic polymerization), under air or in laminate, under various irradiation conditions (UV/visible/near IR; high/low intensity sources; monochromatic/polychromatic sources; household lamps/laser diodes/Light Emitting Diodes (LEDs)). The paper illustrates the encountered mechanisms and the polymerization profiles. A short survey on the available monomer systems and some brief examples of the attained final properties of the IPNs is also provided.
    Polymers 10/2014; 6(10):2588-2610. DOI:10.3390/polym6102588 · 2.51 Impact Factor
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    ABSTRACT: Two star-shaped tris(4-(thiophen-2-yl)phenyl)amine derivatives, namely tris(4-(5-(3-pentylthieno[3,2-b]thiophen-5-yl)thiophen-2-yl)phenyl) amine and tris(4-(5-(3-pentyl-2-(thiophen-2-yl)thieno[3,2-b]thiophen-5-yl) thiophen-2-yl) phenyl) amine, are developed as photoinitiators for radical and cationic polymerizations under near-UV and visible light-emitting diodes (LEDs) (e.g., 385, 405, and 455 nm). When used in combination with an iodonium salt (and optionally N-vinyl carbazole) or an amine/alkyl halide couples, they lead to excellent photoinitiating abilities for the polymerization of epoxides or (meth) acrylates under air. Compared with commercial photoinitiators, i.e., camphorquinone-based systems or bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, the novel photoinitiators exhibit noticeably higher polymerization efficiencies under air (epoxide conversions = 41-57% vs approximate to 0%, halogen lamp exposure; methacrylate conversions = 50-55% vs 44%, LED at 405 nm exposure; methacrylate conversions = 34-42% vs 0-8%, LED at 455 nm exposure). These systems are also interesting in overcoming oxygen inhibition. The photochemical mechanisms are studied by steady-state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques.
    Macromolecular Chemistry and Physics 10/2014; 216(2). DOI:10.1002/macp.201400403 · 2.45 Impact Factor
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    ABSTRACT: Although there have been many reports on photoinitiating systems adapted to visible lights for radical photopolymerization, the challenge for the design and development of photoinitiating systems for cationic photopolymerization or concomitant radical/cationic photopolymerization (for interpenetrating polymer network IPN synthesis) with visible lights still remains open. Particularly, the recent development of cheap and easily accessible LEDs operating upon soft visible light irradiations has opened new fields for polymer synthesis. Since 2011, many novel photoinitiating systems based on organic and organometallic compounds with excellent visible light absorption have emerged and exhibited outstanding photoinitiating abilities especially for cationic photopolymerization. In this review, recent progress (mainly from 2011 to early 2014) in applications of photoinitiators and sensitive photoinitiating systems under visible lights are reported. In addition, their relative efficiencies in the photopolymerization of different monomers are exemplified and discussed.
    Progress in Polymer Science 10/2014; 41. DOI:10.1016/j.progpolymsci.2014.09.001 · 26.85 Impact Factor
  • D.-L. Versace · J. Bourgon · E. Leroy · F. Dumur · D. Gigmes · J. P. Fouassier · J. Lalevée
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    ABSTRACT: [N,N′-Bis(salicylidene)-1,2-phenylenediamine]zinc(II) (ZnC) exhibits unexpected properties as a photoinitiator or additive for both free-radical photopolymerization reactions and in situ formation of Zn-based fillers under light activation and aerated conditions. The ZnC/2,2-dimethoxy-2-phenylacetophenone (DMPA) and ZnC/N-methyldiethanolamine (MDEA) couples are characterized by remarkable properties: (i) a photoinitiating efficiency for the radical polymerization of an acrylate matrix under air higher than that of a reference Type I photoinitiator such as DMPA (final conversion of 30–45% vs. 15%) and therefore a good ability to overcome the oxygen inhibition effect and (ii) a never reported in situ formation of Zn-based fillers (100 μm thick sticks) or composites. The photochemical properties of the ZnC are investigated by fluorescence and UV-visible spectroscopy and Electron Spin Resonance (ESR). The photodecomposition of ZnC under air is governed by either an addition of peroxyl radicals onto ZnC when associated with DMPA, or a H-abstraction mechanism when combined with MDEA. When using a ZnC/MDEA/silver salt photoinitiating system, a highly efficient polymerization of the acrylate matrix under air and a concomitant in situ production of Ag(0) NPs are observed.
    08/2014; 5(22). DOI:10.1039/C4PY00716F

Publication Stats

3k Citations
738.20 Total Impact Points

Institutions

  • 2014–2015
    • Institut de Science des Matériaux de Mulhouse
      Mulhousen, Alsace, France
    • University of New South Wales
      Kensington, New South Wales, Australia
  • 1996–2014
    • Université de Haute-Alsace
      • • Institut de Science des Matériaux de Mulhouse : IS2M
      • • Département de Chimie
      Mulhousen, Alsace, France
  • 1987–2013
    • French National Centre for Scientific Research
      Lutetia Parisorum, Île-de-France, France
  • 1997
    • Lamberti SpA
      Albizzate, Lombardy, Italy
  • 1988
    • University of Santiago, Chile
      • Departamento de Ingeniería Química
      Santiago, Region Metropolitana de Santiago, Chile