Abstract
A one-step synthesis of a well-defined mid-chain functional macrophotoinitiator of a polystyrene-poly(ɛ-caprolactone) diblock copolymer (PSt-PI-PCL) was successfully performed at 110 °C using a novel dual-functional photoinitiator via simultaneous atom transfer radical polymerization and ring-opening polymerization (ROP). This dual-functional photoinitiator (Br-PI-OH), possessing a bromine group on one end and a hydroxyl group on the other, was synthesized by the reaction of the photoinitiator 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (HO-PI-OH) with 2-bromopropanoyl bromide. The two distinct polymerization reactions initiated by Br-PI-OH proceeded in a controlled manner without mutual interference. Elemental analysis and 1H-NMR, 13C-NMR and Fourier transform infrared spectroscopy (FT-IR) spectroscopy were used to characterize the chemical structure of Br-PI-OH. Characterization of the macrophotoinitiator PSt-PI-PCL was achieved using 1H-NMR, FT-IR, gel permeation chromatography, UV-vis and fluorescence spectroscopy.
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References
Bernaerts, Katrien V. & Du Prez, Filip E. Dual/heterofunctional initiators for the combination of mechanistically distinct polymerization techniques. Prog. Polym. Sci. 31, 671–722 (2006).
Wang, W. W., Ren, W. Y., Jiang, L. & Dan, Y. Synthesis and characterization of AB-type copolymers poly(L-lactide)-block-poly(methyl methacrylate) via a convenient route combining ROP and ATRP from a dual Initiator. J. Appl. Polym. Sci. 118, 2379–2388 (2010).
Mao, J., Ji, X. & Bo, S. Synthesis and pH/temperature-responsive behavior of PLLA-b-PDMAEMA block polyelectrolytes prepared via ROP and ATRP. Macromol. Chem. Phys. 212, 744–752 (2011).
Nasser-Eddine, M., Delaite, C., Hurtrez, G. & Dumas, P. Controlled one-step synthesis of a diblock copolymer. Eur. Polym. J. 41, 313–318 (2005).
Shin, S. J., Yu, Y. C., Seo, J. D., Cho, S. J. & Youk, J. H. One-Step Synthesis of poly(N-vinylpyrrolidone)-b-poly(L-lactide) block copolymers using a dual Initiator for RAFT polymerization and ROP. J. Polym. Sci. Part A: Poly. Chem. 52, 1607–1613 (2014).
Mecerreyes, D., Moineau, G., Dubois, P., Jerome, R., Hedrick, J. L., Hawker, C. J., Malmström, E. E. & Trollsas, M. Simultaneous dual living polymerizations: A novel one-step approach to block and graft copolymers. Angew. Chem. Int. Ed. 37, 1274–1276 (1998).
Hawker, C. J., Hedrick, J. L., Malmström, E. E., Trollsas, M., Mecerreyes, D., Moineau, G., Dubois, P. & Jerome, R. Dual living free radical and ring opening polymerizations from a double-headed initiator. Macromolecules 31, 213–219 (1998).
Öztürk, T., Göktaş, M. & Hazer, B. One-step synthesis of triarm block copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization. J. App. Polym. Sci. 117, 1638–1645 (2010).
Kang, H. U., Yu, Y. C., Shin, S. J. & Youk, J. H. One-step synthesis of block copolymers using a hydroxyl-functionalized trithiocarbonate RAFT agent as a dual initiator for RAFT polymerization and ROP. J. Polym. Sci. Part A: Poly. Chem. 51, 774–779 (2013).
Yu, Y. C., Li, G., Kang, H. U. & Youk, J. H. One-step synthesis of poly(alkyl methacrylate)-b-polyester block copolymers via a dual initiator route combining RAFT polymerization and ROP. Colloid. Polym. Sci. 290, 1707–1712 (2012).
Kryuchkov, M. A., Detrembleur, C. & Bazuin, C. G. Linear amphiphilic diblock copolymers of lactide and 2-dimethylaminoethyl methacrylate using bifunctional-initiator and one-pot approaches. Polymer 55, 2316–2324 (2014).
Corrales, T., Catalina, F., Peinado, C. & Allen, N. S. Free radical macrophotoinitiators:an overview on recent advances. J. Photochem. Photobiol. A Chem. 159, 103–114 (2003).
Yagci, Y., Mishra, M. K. Macroinitiators, in: Macromolecular Design: Concept and Practice (ed. Mishra, M. K.) Ch. 6, 229–264 (Polymer Frontiers International, inc., New York, NY, USA 1994)
Yagci, Y. Photoinitiating systems and their use in polymer synthesis. Macromol. Symp. 161, 19–36 (2000).
Wang, Y. L., Jiang, X. S. & Yin, J. A. Water-soluble supramolecular-structured photoinitiator between methylated b-cyclodextrin and 2,2-dimethoxy-2-phenylacetophenone. J. Appl. Polym. Sci. 105, 3819–3823 (2007).
Yagci, Y., Jockush, S. & Turro, N. J. Photoinitiated polymerization: advances, challenges, and opportunities. Macromolecules 43, 6245–6260 (2010).
Fouassier, J. P. & Lalevee, J. Photoinitiators for Polymer Synthesis: Scope, Reactivity and Efficiency, (Wiley-VCH Verlag GmbH & Co., KGaA, Weinheim, Germany, 2012)
Durmaz, Y. Y., Karagoz, B., Bicak, N. & Yagci, Y. Synthesis of block copolymers by combination of ATRP and photoiniferter processes. Polym. Int. 57, 1182–1187 (2008).
Durmaz, Y. Y., Tasdelen, M. A., Aydogan, B., Kahveci, M. U., Yagci, Y. Light Induced Processes for the Synthesis of Polymers with Complex Structures, The NATO Science For Peace and Security Programme (eds Khosravi, E., Yagci, Y. & Savelyev, Y.) Part 5, 329–341 (Springer, Dordrecht, the Netherlands, 2009)
Degirmenci, M., Sarac, M. A. & Genli, N. Synthesis and characterization of mid-chain macrophotoinitiator of poly(ɛ-caprolactone) by combination of ROP and click chemistry. Polym. Bull. 71, 1743–1755 (2014).
Degirmenci, M., Cianga, I., Hizal, G. & Yagci, Y. Synthesis, characterization and application of polymeric photoinitiators prepared by atom transfer radical polymerization and ring-opening polymerization. Poly. Preprints 43, 22–23 (2002).
Degirmenci, M. & Genli, N. Synthesis of well-defined telechelic macrophotoinitiator of polystyrene by combination of ATRP and click chemistry. Macromol. Chem. Phys. 210, 1617–1623 (2009).
Temel, G. & Arsu, N. One-pot synthesis of water-soluble polymeric photoinitiator via thioxanthonation and sulfonation process. J. Photochem. Photobiol. A: Chem. 202, 63–66 (2009).
Durmaz, Y. Y., Yilmaz, G. & Yagci, Y. N-alkoxy pyridinium ion terminated polystyrenes: a facile route to photoinduced block copolymerization. J. Poly.Sci.: Part A: Poly. Chem. 45, 423–428 (2007).
Degirmenci, M., Cianga, I. & Yagci, Y. Synthesis of well-defined polystyrene macrophotoinitiators by atom-transfer radical polymerization. Macromol. Chem. Phys. 203, 1279–1284 (2002).
Degirmenci, M., Alter, S. & Genli, N. Synthesis and characterization of well-defined mid-chain functional macrophotoinitiators of polystyrene by combination of ATRP and ‘‘click’’ chemistry. Macromol. Chem. Phys. 212, 1575–1581 (2011).
Degirmenci, M. Synthesis and characterization of novel well-defined end-functional macrophotoinitiator of poly(MMA) by ATRP. J. Macromol. Sci. Part A—Pure Appl. Chem. 42, 21–30 (2005).
Degirmenci, M., Hizal, G. & Yagci, Y. Synthesis and characterization of macrophotoinitiators of poly(ɛ-caprolactone) and their use in block copolymerization. Macromolecules 35, 8265–8270 (2002).
Degirmenci, M. Synthesis of novel well-defined end-functional macrophotoinitiator of poly(ɛ-caprolactone) by ring-opening polymerization. Polym. J. 36, 542–548 (2004).
Degirmenci, M., Besli, P. A. & Genli, N. Synthesis of a well-defined end-chain macrophotoinitiator of poly(ɛ−caprolactone) by combination of ring-opening polymerization and click chemistry. J. Polym. Res. 21, 540–549 (2014).
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The authors would like to thank the Harran University, Scientific Research Council (HÜBAK) for its financial support (Project no: 12157).
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Degirmenci, M., Gokkaya, C. & Durgun, M. One-step synthesis of a mid-chain functional macrophotoinitiator of a polystyrene-poly(ɛ-caprolactone) diblock copolymer via simultaneous ATRP and ROP using a dual-functional photoinitiator. Polym J 48, 139–145 (2016). https://doi.org/10.1038/pj.2015.93
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DOI: https://doi.org/10.1038/pj.2015.93
