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Photoinitiation of multifunctional acrylates via ferrocene-alkyl chloride charge transfer complexes

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Abstract

The propensity for ferrocene-alkyl chloride charge transfer complexes (CTCs) to photoinitiate free-radical polymerization of multifunctional acrylates was determined using photodifferential scanning calorimetry. Also, the effects of varying ferrocene (ferrocene, methoxyferrocene, and cyanoferrocene) and alkyl chloride (dichloromethane and benzyl chloride) derivatives were evaluated with regard to the overall polymerization rate and conversion. Furthermore, relative polymerization rates of traditional free-radical Type I and Type II photoinitiators were compared to those of the ferrocene-alkyl chloride CTCs. Semi-empirical quantum mechanical analysis of the complexation reaction was performed using PM3, indicating a thermodynamic preference of complexations involving benzyl chloride, and corroborated the reported complexation mechanism. In order to explain the varying polymerization rates, the association constants for each complex were determined, whereupon complexation of each ferrocene derivative with dichloromethane was found to be more facile than similar complexation with benzyl chloride due to steric considerations. Substituent effects were more pronounced for the benzyl chloride complexes relative to those involving dichloromethane where steric constraints caused deviation from the expected effect. Thus, the cyanoferrocene-benzyl chloride CTC was determined to be the most effective photoinitiator examined with regard to semi-empirical analysis, complexation kinetics, and polymerization rate.

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References

  1. Pappas, SP, "Photoinitiation of Cationic and Concurrent Radical Cationic Polymerication", Prog. Org. Coat., 13, 35 (1985)

    Article  CAS  Google Scholar 

  2. Crivello, JV, Adv. Polym. Sci., 62, 1 (1984)

    Article  CAS  Google Scholar 

  3. Hoyle, CE, Clark, SC, Jönsson, S, Shimose, M, "Polymer, Photopolymerization Using Maleimides as Photoinitiators", 38, 5695 (1997)

    Article  CAS  Google Scholar 

  4. Clark, SC, Jönsson, S, Hoyle, CE, PMSE Polym Prepr, 37(2) 348 (1996)

    CAS  Google Scholar 

  5. Clark, SC, Hoyle, CE, Jönsson, S, Morel, F, Decker, C, RadTech ’98 North America Conf. Proc., 177 (1998)

  6. Miller, CW, Jönsson, S, Hoyle, CE, Hasselgren, C, Haraldsson, T, Shao, L, RadTech ’98 North America Conf. Proc., 182 (1998)

  7. Nguyen, CK, Cavitt, TB, Hoyle, CE, Kalyanaraman, V, Jönsson, S, In: Belfield, KD, Crivello, JV (eds.), A Mechanistic Description of the Sensitized N-Substituted Maleimide Initiated Photopolymerization of an Acrylate Monomer, Photoinitiated Polymerization, Vol. 27, American Chemical Society, Washington, D.C. (2003)

  8. Cavitt, TB, Phillips, B, Hoyle, CE, Nguyen, CK, Kalyanaraman, V, Jönsson, S, In: Belfield, KD, Crivello, JV (eds.), Photoinitiation of Acrylates via Sensitized Phthalimide Derivatives, Photoinitiated Polymerization, Vol. 41, American Chemical Society, Washington, D.C. (2003)

  9. Hoyle, CE, Cole, M, Bachemin, M, Kuang, W, Kalyanaraman, V, Jönsson, S, In: Belfield, KD, Crivello, JV (eds.), Photoinitiated Polymerization of Selected Thiol-ene System, Photoinitiated Polymerization, Vol. 52, American Chemical Society, Washington, D.C. (2003)

  10. Carlsson, I, Harden, A, Lundmark, S, Manea, A, Rehnberg, N, Svensson, L, In: Belfield, KD, Crivello, JV (eds.), Allyl Ethers in the Thiol-ene Reaction, Photoinitiated Polymerization, Vol. 65, American Chemical Society, Washington, D.C. (2003)

  11. Brand, JCD, Sneddon, W, "Electron-Transfer Spectra of Ferrocene",Trans. Faraday Soc., 53, 894 (1957)

    Article  CAS  Google Scholar 

  12. Nesmeyanov, AN, Vannikov, AV, Zver’kov, VA, Balabanova, LV, Shvekhgeimer, GA, Kochetkova, NS, Proc. Acad. Sci. USSR (Engl. Transl.), 240, 426 (1978)

  13. Traverso, O, Scandola, F, "Photooxidation of Ferrocene in Halocarbon Solvents", Inorg. Chim. Acta, 4, 493 (1970)

    Article  CAS  Google Scholar 

  14. Akiyama, T, Hoshi, Y, Goto, S, Sugimori, A, Bull. Chem. Soc. Jpn., 46, 1851 (1973)

    Article  CAS  Google Scholar 

  15. Tsubakiyama, K, Fujisaki, S, "Photosensitized Initiation of Vinyl Polymerization by a System of Ferrocene and Carbon Tetrachloride", J. Polym. Sci. B, 10, 341 (1972)

    Article  CAS  Google Scholar 

  16. Kaeriyama, K, "Photocatalyzed Polymerization of Epichlorohydrin", J. Polym. Sci. Polym. Chem. Ed, 14, 1547 (1976)

    Article  CAS  Google Scholar 

  17. Kaeriyama, K, Shimura, Y, "Photopolymerization with the Use of Titanocene Dichoride as Sensitizer",J. Polym. Sci. Polym. Part A-1 Polym. Chem., 10, 2833 (1972)

    Article  CAS  Google Scholar 

  18. Harrigan, RW, Hammond, GS, Gray, HB, "Photochemistry of Titanocene(IV) Derivatives", J. Organomet. Chem., 81, 79 (1974)

    Article  CAS  Google Scholar 

  19. Tsai Z-T, Brubaker CH, "Photolysis of Titanocene Dichloride", J. Organomet. Chem, 166, 199 (1979)

    Article  CAS  Google Scholar 

  20. Yang, DB, Kutal, C, In: Pappas, SP (ed.), Radiation Curing: Sci. and Tech., Vol. 21 Plenum Press, New York (1992)

  21. Kutal, C, Yamaguchi, Y, Ding, W, Sanderson, CT, Li, X, Gamble, G, Amster, IJ, In: Belfield, KD, Crivello, JV (eds.), Harvesting the Fields of Inorganic and Organometallic Photochemistry for New Photoinitiators, Photoinitiated Polymerization, Vol. 332, American Chemical Society, Washington D.C. (2003)

  22. Sanderson, CT, Palmer, BJ, Morgan, A, Murphy, M, Dluhy, RA, Mize, T, Amster, J, Kutal, C, "Classical Metallocenes as Photoinitiators for the Anionic Polymerization of an Alkyl 2-Cyanoacrylate", Macromolecules, 35, 9648 (2002)

    Article  CAS  Google Scholar 

  23. Ding, W, Sanderson, CT, Conover, RC, Johnson, MK, Amster, J, Kutal, C, "Characterization of the Low-Energy Electronic Excited States of Benzoyl-Substituted Ferrocenes", Inorg. Chem., 42(5) 1532 (2003)

    Article  CAS  Google Scholar 

  24. Fish, RW, Rosenblum, M, "A Convenient Synthesis of Some Haloferrocenes", J. Org. Chem., 30, 1253 (1965)

    CAS  Google Scholar 

  25. Nesmejanow, AN, Ssasonowa, WA, Drosd, VN, "Synthese von Ferrocenderivaten mittels bor- und halogensubstituierter Ferrocene", Chem. Ber., 93, 2717 (1960)

    Google Scholar 

  26. Graham, JJ, Lindsey, V, Parshall, W, Peterson, L, Whitman, GM, "Some Acyl Ferrocenes and Their Reactions", J. Am. Chem. Soc., 79, 3416 (1957)

    Article  CAS  Google Scholar 

  27. Broadhead, GD, Osgerby, JM, Pauson, PL, “Ferrocene Derivatives. Part V. Ferrocenealdehyde.” J. Chem. Soc., 650 (1958)

  28. Wayne, CE, Wayne, RP, Photochemistry, Oxford University Press, Oxford (2002)

    Google Scholar 

  29. Benesi, HA, Hildebrand, JH, "Spectrophotometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons", J. Am. Chem. Soc., 71, 2703 (1949)

    Article  CAS  Google Scholar 

  30. Scott, RL, Proc. Int. Cong. on Co-ordination Compounds, Vol. 265, Amsterdam (1955)

  31. Scott RL, Recl. Trav. Chim. Pays Bas Belg., 75 787 (1956)

    CAS  Google Scholar 

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Acknowledgments

The authors would like to express their appreciation to both The Welch Foundation and to the Office of Research and Sponsored Programs at Abilene Christian University for funding this research and to Charles E. Hoyle at The University of Southern Mississippi for use of the photo-DSC.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Abilene Christian University, ACU Box 28132, Abilene, TX, 79699-8132, USA

    Julie A. Anderson, Evan Hardgrove, T. Brian Cavitt & Perry C. Reeves

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  1. Julie A. Anderson
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  2. Evan Hardgrove
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  3. T. Brian Cavitt
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  4. Perry C. Reeves
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Correspondence to T. Brian Cavitt.

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Presented at e|5: UV and EB Technical Expo and Conference, sponsored by RadTech International North America, May 4, 2004, Charlotte, NC.

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Anderson, J.A., Hardgrove, E., Cavitt, T.B. et al. Photoinitiation of multifunctional acrylates via ferrocene-alkyl chloride charge transfer complexes. J Coat Technol Res 4, 43–49 (2007). https://doi.org/10.1007/s11998-007-9008-1

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