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

Emine Arman Kandirmaz; Efe N. Gencoglu; Nilhan Kayaman Apohan

Macromolecular Research, Vol.27, No.8, 756-763, August, 2019

DOI10.1007/s13233-019-7107-3 Export Citation

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

Emine Arman Kandirmaz, Efe N. Gencoglu, and Nilhan Kayaman Apohan^{1, †}

School of Applied Science, Printing Technology Department, Marmara University, 34722 Goztepe -Istanbul, Turkey
¹Department of Chemistry, Faculty of Art & Science, Marmara University, 34722 Goztepe-Istanbul, Turkey

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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.

Keywords:polymeric photoinitiator;photopolymerization;thioxanthone;migration;flexographic varnish

[References]

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Mishra MK, Yagci Y, Handbook of Radical Vinyl Polymerization, Marcel Dekker Inc., New York, 1998.
Pappas SP, UV Curing Science and Technolgy, Technology Marketing Corp., Norwalk, 1978.
Fouassier JP, Photoinitiation, Photopolymerization and Photocuring, Hanser Verlag, Munich, 1995.
Davidson RS, Exploring the Science, Technology and Applications of UV and EB Curing, SITA Technology Ltd., London, 1999.
Jiang XS, Yin J, Macromolecules, 37(21), 7850 (2004)
Jiang XS, Xu HJ, Yin J, Polymer, 46(24), 11079 (2005)
Aydin M, Arsu N, Yagci Y, Macromol. Rapid Commun., 24(12), 718 (2003)
Eren TN, Graff B, Lalevee J, Avci D, Prog. Org. Coat., 128, 148 (2019)
Cokbaglan L, Arsu N, Yagci Y, Jockusch S, Turro NJ, Macromolecules, 36(8), 2649 (2003)
Jiang XS, Xu HJ, Yin H, Polymer, 45(1), 133 (2004)
Jiang XS, Yin H, Polymer, 45(15), 5057 (2004)
Jiang XS, Yin J, Macromol. Rapid Commun., 25(6), 748 (2004)
Jiang XS, Yin J, J. Appl. Polym. Sci., 94(6), 2395 (2004)
Lago MA, de Quiroz ARB, Sendon R, Bustos J, Nieto MT, Perfecto Paseiro, Photoinitiators: A Food Safety Review Food Additives & Contaminants: Part A, 32, 5 (2015).
Sutter J, Dudler V, Meuwly R, Packaging Materials 8. Printing Inks for Food Packaging Composition and Properties of Printing Inks, ILSI-EUROPE, Belgium, 2011.
Rothenbacher T, Baumann M, Fugel D, Food Addit. Contam., 24, 438 (2007)
Dietliker K, Husler R, Birbaum JL, Ilg S, Villeneuve S, Studer K, Jung Y, Benkhoff J, Kura H, Matsumoto A, Oka H, Prog. Org. Coat., 58, 146 (2007)
Dadashi-Silab S, Aydogan C, Yagci Y, Polym. Chem., 6, 6595 (2015)
Avci D, Eren TN, Photopolym. Initiating Systems, 29, 131 (2018)
Wei J, Wang H, Jiang X, Yin J, Macromol. Chem. Phys., 207, 1752 (2006)
Jiang XS, Luo J, Yin J, Polymer, 50(1), 37 (2009)
Temel G, Arsu N, J. Photochem. Photobiol. A-Chem., 202, 63 (2009)
Akat H, Gacal B, Balta DK, Arsu N, Yagci Y, J. Polym. Sci. A: Polym. Chem., 48(10), 2109 (2010)
Tiantian L, Zhilong S, Hongjie X, Xuesong J, Xiaodong M, Jie Y, Chin. Chem. Lett., 43, 46 (2017)
Yamago S, Kayahara E, Yamada H, React. Funct. Polym., 69(7), 416 (2009)
Davis KA, Matyjaszewski K, Statistical, Gradient, Block, and Graft Copolymers by Controlled/Living Radical Polymerizations, Springer, Berlin, 2002.
Coessens V, Pintauer T, Prog. Polym. Sci, 26, 337 (2001)
Braunecker WA, Matyjaszewski K, Prog. Polym. Sci, 32, 93 (2007)
Matyjaszewski K, J. Macromol. Sci.-Pure Appl. Chem., 34, 1785 (1994)
Matyjaszewski K, Xia JH, Chem. Rev., 101(9), 2921 (2001)
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Oktay B, Demir S, Kayaman-Apohan N, Sci. Eng. C., 50, 386 (2015)
Temel G, Arsu N, Yagci Y, Polym. Bull., 57(1), 51 (2006)
Kandirmaz E, Apohan N, Gencoglu E, Prog. Org. Coat., 119, 36 (2018)
Aydin M, Arsu N, Yagci Y, Jockusch S, Turro NJ, Macromolecules, 38(10), 4133 (2005)
Smith CD, Grubbs H, Webster HF, Gungor A, Wightman JP, McGrath JE, High Perform. Polym., 3, 211 (1991)
Riley DJ, Thesis D, Synthesis and Characterization of Phosphorus Containing Polycarylene ether)s, Virgina Polytechnic Institute, 1997.
Beyler-Cigil A, Kahraman MV, Prog. Org. Coat, 101, 468 (2016)
Ciofini D, Striova J, Camaiti M, Siano S, Polym. Degrad. Stabil., 123, 47 (2016)
BS 4321:1969 Methods of test for printing inks (resistance of prints to various physical and chemical agents) Status: Superseded, Withdrawn (1969).
Akdemir ZS, Kayaman-Apohan N, Kahraman MV, Kuruca SE, Gungor A, Karadenizli S, J. Biomater. Sci., 22, 857 (2011)
Clemente I, Aznar M, Nerin C, Bosetti O, Food Addit. Contam Part A, 33, 703 (2016)

[Referenced By]

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

[2] Mishra MK, Yagci Y, Handbook of Radical Vinyl Polymerization, Marcel Dekker Inc., New York, 1998.

[3] Pappas SP, UV Curing Science and Technolgy, Technology Marketing Corp., Norwalk, 1978.

[4] Fouassier JP, Photoinitiation, Photopolymerization and Photocuring, Hanser Verlag, Munich, 1995.

[5] Davidson RS, Exploring the Science, Technology and Applications of UV and EB Curing, SITA Technology Ltd., London, 1999.

[6] Jiang XS, Yin J, Macromolecules, 37(21), 7850 (2004)

[7] Jiang XS, Xu HJ, Yin J, Polymer, 46(24), 11079 (2005)

[8] Aydin M, Arsu N, Yagci Y, Macromol. Rapid Commun., 24(12), 718 (2003)

[9] Eren TN, Graff B, Lalevee J, Avci D, Prog. Org. Coat., 128, 148 (2019)

[10] Cokbaglan L, Arsu N, Yagci Y, Jockusch S, Turro NJ, Macromolecules, 36(8), 2649 (2003)

[11] Jiang XS, Xu HJ, Yin H, Polymer, 45(1), 133 (2004)

[12] Jiang XS, Yin H, Polymer, 45(15), 5057 (2004)

[13] Jiang XS, Yin J, Macromol. Rapid Commun., 25(6), 748 (2004)

[14] Jiang XS, Yin J, J. Appl. Polym. Sci., 94(6), 2395 (2004)

[15] Lago MA, de Quiroz ARB, Sendon R, Bustos J, Nieto MT, Perfecto Paseiro, Photoinitiators: A Food Safety Review Food Additives & Contaminants: Part A, 32, 5 (2015).

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

[17] Rothenbacher T, Baumann M, Fugel D, Food Addit. Contam., 24, 438 (2007)

[18] Dietliker K, Husler R, Birbaum JL, Ilg S, Villeneuve S, Studer K, Jung Y, Benkhoff J, Kura H, Matsumoto A, Oka H, Prog. Org. Coat., 58, 146 (2007)

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

[20] Avci D, Eren TN, Photopolym. Initiating Systems, 29, 131 (2018)

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

[22] Jiang XS, Luo J, Yin J, Polymer, 50(1), 37 (2009)

[23] Temel G, Arsu N, J. Photochem. Photobiol. A-Chem., 202, 63 (2009)

[24] Akat H, Gacal B, Balta DK, Arsu N, Yagci Y, J. Polym. Sci. A: Polym. Chem., 48(10), 2109 (2010)

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

[26] Yamago S, Kayahara E, Yamada H, React. Funct. Polym., 69(7), 416 (2009)

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

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

[29] Braunecker WA, Matyjaszewski K, Prog. Polym. Sci, 32, 93 (2007)

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

[31] Matyjaszewski K, Xia JH, Chem. Rev., 101(9), 2921 (2001)

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

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

[34] Temel G, Arsu N, Yagci Y, Polym. Bull., 57(1), 51 (2006)

[35] Kandirmaz E, Apohan N, Gencoglu E, Prog. Org. Coat., 119, 36 (2018)

[36] Aydin M, Arsu N, Yagci Y, Jockusch S, Turro NJ, Macromolecules, 38(10), 4133 (2005)

[37] Smith CD, Grubbs H, Webster HF, Gungor A, Wightman JP, McGrath JE, High Perform. Polym., 3, 211 (1991)

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

[39] Beyler-Cigil A, Kahraman MV, Prog. Org. Coat, 101, 468 (2016)

[40] Ciofini D, Striova J, Camaiti M, Siano S, Polym. Degrad. Stabil., 123, 47 (2016)

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

[42] Akdemir ZS, Kayaman-Apohan N, Kahraman MV, Kuruca SE, Gungor A, Karadenizli S, J. Biomater. Sci., 22, 857 (2011)

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