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The Synthesis of New Type II Polymeric Photoinitiator (thioxantone) via Atom Transfer Radical Polymerization and Their Curing and Migration Studies

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Abstract

Polymeric photoinitiators are widely used in ultraviolet (UV)-curable printing inks because of their low migration behavior. In this study, a new phenylphosphine oxide-polystyrene-thioxanthone (PPO-PSt-TX) polymeric photoinitiator was synthesized. Bis[(4-hydroxy)phenyl]phenyl phosphine oxide (BHPPO) that was synthesized by Grignard technique, was functionalized with 2-bromopropionyl bromide (atom transfer radical polymerization (ATRP) initiator) and then used in styrene polymerization. The bromine end-capped polystyrene was then reacted with 2-thioxanthone-thioacetic acid and final polymeric photoinitiator PPO-PSt-TX was obtained. Proton nuclear magnetic resonance (1H NMR), attenuated total reflectance- Fourier transform infrared spectroscopy (ATR-FTIR), gel permeation chromatography (GPC) and ultraviolet-visible spectroscopy (UV-Vis) confirmed the obtained structure. The curing characteristic of PPO-PSt-TX was compared with a standard flexographic printing varnish formulation containing thioxanthone (TX). The photopolymerization kinetics were determined by photo differential scanning calorimetry (Photo-DSC). The conversion of methylmethacrylate polymerization by using macrophotoinitiator is 78%. The migration behavior of PPO-PSt-TX was identified with liquid chromatography-mass spectrometry (LC-MS). It was shown that PPOPSt- TX macro photoinitiator is suitable for flexographic varnish and the migration level of photoinitiator is reduced by using polymeric photoinitiator.

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Referances

  1. K. Dietliker, Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, SITA Technology Ltd., London, 1991.

    Google Scholar 

  2. M. K. Mishra, Y. Yagci, Handbook of Radical Vinyl Polymerization, Marcel Dekker Inc., New York, 1998.

    Google Scholar 

  3. S. P. Pappas, UV Curing Science and Technolgy, Technology Marketing Corp., Norwalk, 1978.

    Google Scholar 

  4. J. P. Fouassier, Photoinitiation, Photopolymerization and Photocuring, Hanser Verlag, Munich, 1995.

    Google Scholar 

  5. R. S. Davidson, Exploring the Science, Technology and Applications of UV and EB Curing, SITA Technology Ltd., London, 1999.

    Google Scholar 

  6. X. Jiang and J. Yin, Macromolecules, 37, 7850, (2004).

    Article  CAS  Google Scholar 

  7. X. Jian, H. Xu, and J. Yini, Polymer, 46, 11079, (2005).

    Article  CAS  Google Scholar 

  8. M. Aydin, N. Arsu, and Y. Yagci, Macromol. Rapid Commun., 24, 718, (2003).

    Article  CAS  Google Scholar 

  9. T. N. Eren, B. Graff, J. Lalevee, and D. Avci, Prog. Org. Coat., 128, 148 (2019).

    Article  CAS  Google Scholar 

  10. L. Cokbaglan, N. Arsu, Y. Yagci, S. Jockusch, and N. J. Turro, Macromolecules, 36, 2649 (2003).

    Article  CAS  Google Scholar 

  11. X. Jiang, H. Xu, and J. Yin, Polymer, 45, 133 (2004).

    Article  CAS  Google Scholar 

  12. X. Jiang and J. Yin, Polymer, 45, 5057 (2004).

    Article  CAS  Google Scholar 

  13. X. Jiang and J. Yin, Macromol. Rapid Commun., 25, 748 (2004).

    Article  CAS  Google Scholar 

  14. X. Jiang and J. Yin, J. Appl. Polym. Sci., 94, 2395 (2004).

    Article  CAS  Google Scholar 

  15. M. A. Lago, A. Rodriguez-Bernaldo de Quiroz, R. Sendon, J. Bustos, and M. T. Nieto, Perfecto Paseiro, Photoinitiators: A Food Safety Review Food Additives & Contaminants: Part A, 32, 5 (2015).

    Google Scholar 

  16. J. Sutter, V. Dudler, and R. Meuwly, Packaging Materials 8. Printing Inks for Food Packaging Composition and Properties of Printing Inks, ILSI-EUROPE, Belgium, 2011.

    Google Scholar 

  17. T. Rothenbacher, M. Baumann, and D. Fügel, Food Addit. Contam., 24, 438 (2007).

    Article  CAS  PubMed  Google Scholar 

  18. K. Dietliker, R. Hüsler, J. L. Birbaum, S. Ilg, S. Villeneuve, K. Studer, T. Jung, J. Benkhoff, H. Kura, A. Matsumoto, and H. Oka, Prog. Org. Coat., 58, 146 (2007).

    Article  CAS  Google Scholar 

  19. S. Dadashi-Silab, C. Aydogan, and Y. Yagci, Polym. Chem., 6, 6595 (2015).

    Article  CAS  Google Scholar 

  20. D. Avci and T. N. Eren, Photopolym. Initiating Systems, 29, 131 (2018).

    Article  Google Scholar 

  21. J. Wei, H. Wang, X. Jiang, and J. Yin, Macromol. Chem. Phys., 207, 1752 (2006).

    Article  CAS  Google Scholar 

  22. X. Jiang, J. Luo, and J. Yin, Polymer, 50, 37 (2009).

    Article  CAS  Google Scholar 

  23. G. Temel and N. Arsu, J. Photochem. Photobiol. A: Chem., 202, 63 (2009).

    Article  CAS  Google Scholar 

  24. H. Akat, B. Gacal, D. K. Balta, N. Arsu, and Y. Yagci, J. Polym. Sci., Part A: Polym. Chem., 48, 2109 (2010).

    Article  CAS  Google Scholar 

  25. L. Tiantian, S. Zhilong, X. Hongjie, J. Xuesong, M. Xiaodong, and Y. Jie, Chin. Chem. Lett., 43, 46 (2017).

    Google Scholar 

  26. S. Yamago, E. Kayahara, and H. Yamada, React. Funct. Polym., 69, 416 (2009).

    Article  CAS  Google Scholar 

  27. K.A. Davis and K. Matyjaszewski, Statistical, Gradient, Block, and Graft Copolymers by Controlled/Living Radical Polymerizations, Springer, Berlin, 2002.

    Book  Google Scholar 

  28. V. Coessens and T. Pintauer, Prog. Polym. Sci., 26, 337 (2001).

    Article  CAS  Google Scholar 

  29. W. A. Braunecker, and K. Matyjaszewski, Prog. Polym. Sci., 32, 93 (2007).

    Article  CAS  Google Scholar 

  30. K. Matyjaszewski, J. Macromol. Sci. Pure Appl. Chem., 34, 1785 (1994).

    Article  Google Scholar 

  31. K. Matyjaszewski and J. H. Xia, Chem. Rev., 101, 2921 (2001).

    Article  CAS  PubMed  Google Scholar 

  32. K. Matyjaszewski, Controlled/Living Radical Polymerization: From Synthesis to Materials, American Chemical Society, Washington DC, 2006.

    Book  Google Scholar 

  33. B. Oktay, S. Demir, and N. Kayaman-Apohan, Sci. Eng. C., 50, 386 (2015).

    Article  CAS  Google Scholar 

  34. G. Temel, N. Arsu, and Y. Yagci, Polym. Bull., 57, 51 (2006).

    Article  CAS  Google Scholar 

  35. E. Kandirmaz, N. Apohan, and E. Gençoğlu, Prog. Org. Coat., 119, 36 (2018).

    Article  CAS  Google Scholar 

  36. M. Aydin, N. Arsu, Y. Yagci, S. Jockusch, and N. J. Turro, Macromolecules, 38, 4133 (2005).

    Article  CAS  Google Scholar 

  37. C. D. Smith, H. Grubbs, H. F. Webster, A. Gungor, J. P. Wightman, and J. E. McGrath, High Perform. Polym., 3, 211 (1991).

    Article  CAS  Google Scholar 

  38. D. J. Riley, Ph. D. Thesis, Synthesis and Characterization of Phosphorus Containing Polycarylene ether)s, Virgina Polytechnic Institute, 1997.

    Google Scholar 

  39. A. Beyler-Çiğil and M. V. Kahraman, Prog. Org. Coat., 101, 468 (2016).

    Article  CAS  Google Scholar 

  40. D. Ciofini, J. Striova, M. Camaiti, and S. Siano, Polym. Degrad. Stab., 123, 47 (2016).

    Article  CAS  Google Scholar 

  41. BS 4321: 1969 Methods of test for printing inks (resistance of prints to various physical and chemical agents)_Status: Superseded, Withdrawn (1969).

    Google Scholar 

  42. Z. S. Akdemir, N. Kayaman-Apohan, M. V. Kahraman, S. Erdem Kuruca, A. Güngör, and S. Karadenizli, J. Biomater. Sci., 22, 857 (2011).

    Article  CAS  Google Scholar 

  43. I. Clemente, M. Aznar, C. Nerín, and O. Bosetti, Food Addit. Contam. Part A, 33, 703 (2016).

    CAS  Google Scholar 

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Acknowledgments

This work was supported by Marmara University, Commission of Scientific Research Project (M.U.BAPKO) under grant FEN-C-DRP-120514-0163. The authors would like to thank Prof.Dr. Duygu Avcı for their valuable help in photo DSC studies.

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Authors and Affiliations

  1. School of Applied Science, Printing Technology Department, Marmara University, 34722, Goztepe -Istanbul, Turkey

    Emine Arman Kandirmaz & Efe N. Gençoğlu

  2. Department of Chemistry, Faculty of Art & Science, Marmara University, 34722, Goztepe-Istanbul, Turkey

    Nilhan Kayaman Apohan

Authors
  1. Emine Arman Kandirmaz
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  2. Efe N. Gençoğlu
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  3. Nilhan Kayaman Apohan
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Correspondence to Nilhan Kayaman Apohan.

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Kandirmaz, E.A., Gençoğlu, E.N. & Kayaman Apohan, N. The Synthesis of New Type II Polymeric Photoinitiator (thioxantone) via Atom Transfer Radical Polymerization and Their Curing and Migration Studies. Macromol. Res. 27, 756–763 (2019). https://doi.org/10.1007/s13233-019-7107-3

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  • DOI: https://doi.org/10.1007/s13233-019-7107-3

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