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The carbazole-bound ferrocenium salt as a specific cationic photoinitiator upon near-UV and visible LEDs (365–405 nm)

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Abstract

A carbazole-bound ferrocenium salt [i.e., (η6-Carbazole) (η5-cyclopentadienyl) iron hexafluorophosphate—FS] is proposed as an efficient photoinitiator for the cationic ring-opening polymerization of epoxides under air upon the exposure to a near-UV LED at 385 nm or a visible LED at 405 nm. When using this ferrocenium salt FS (0.2 wt%)/diphenyliodonium hexafluorophosphate or FS (0.2 wt%)/diphenyliodonium hexafluorophosphate/N-vinylcarbazole, final epoxide conversions of 55–66 % can be obtained after 800 s of irradiation at 385 or 405 nm. Reference cationic photoinitiators (i.e., diphenyliodonium hexafluorophosphate; 9-(4-hydroxyethoxyphenyl) thianthrenium hexafluorophosphate and triphenylsulfonium hexafluorophosphate) are unable to initiate the epoxide polymerization under the same conditions. The photochemical mechanisms for the formation of the initiating species are studied using steady-state photolysis, cyclic voltammetry, laser flash photolysis and electron spin resonance spin-trapping techniques. Molecular orbital calculations help to describe the absorption properties and the initiation step. The performance attained when using FS alone is really promising for applications under soft near-UV or visible light-emitting diode irradiation.

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Acknowledgments

JL thanks the Institut Universitaire de France for the financial support.

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Authors and Affiliations

  1. Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15, rue Jean Starcky, 68057, Mulhouse Cedex, France

    Jing Zhang, Pu Xiao & Jacques Lalevée

  2. Institut de Chimie Radicalaire ICR-UMR CNRS 7273, Aix-Marseille Université, équipe CROPS, case 542, avenue Escadrille Normandie-Niemen, 13397, Marseille Cedex 20, France

    Damien Campolo, Frederic Dumur & Didier Gigmes

  3. ENSCMu-UHA, 3 rue Alfred Werner, 68093, Mulhouse Cedex, France

    Jean Pierre Fouassier

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  1. Jing Zhang
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  2. Damien Campolo
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  3. Frederic Dumur
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  4. Pu Xiao
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Zhang, J., Campolo, D., Dumur, F. et al. The carbazole-bound ferrocenium salt as a specific cationic photoinitiator upon near-UV and visible LEDs (365–405 nm). Polym. Bull. 73, 493–507 (2016). https://doi.org/10.1007/s00289-015-1506-1

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