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Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2015, 48, 23, 8451-8460
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Systematic Assessment of the Photochemical Stability of Photoinitiator-Derived Macromolecular Chain Termini

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† Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76128 Karlsruhe, Germany
‡ Institut für Biologische Grenzflächen (IBG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
§ Institute of Physical and Theoretical Chemistry, NAWI Graz, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria
*(C.B.-K.) E-mail: [email protected]
*(G.G.) E-mail: [email protected]
Cite this: Macromolecules 2015, 48, 23, 8451–8460
Publication Date (Web):November 20, 2015
https://doi.org/10.1021/acs.macromol.5b02127
Copyright © 2015 American Chemical Society
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Abstract

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The photostability of polymeric materials is crucial for their applicability, especially under potentially harsh environmental conditions. In the current study, the influence of methyl-substitution on the photochemical stability of photoinitiator-derived benzoyl end groups is systematically investigated by a combination of pulsed-laser polymerization and subsequent size exclusion chromatography coupled with electrospray ionization mass spectrometry (PLP–SEC–ESI–MS), chemically induced dynamic nuclear polarization–nuclear magnetic resonance spectroscopy (CIDNP–NMR), and density functional theory (DFT) calculations. Poly(methyl methacrylate)s (pMMA) were synthesized employing benzoin-type photoinitiators with systematically substituted benzoyl moieties (i.e., 2-methylbenzoin, 3-methylbenzoin, 4-methylbenzoin, 2,4-dimethylbenzoin, 2,6-dimethylbenzoin, 2,4,6-trimethylbenzoin, 2,3,5,6-tetramethylbenzoin, and 2,3,4,5,6-pentamethylbenzoin). Photoinduced cleavage of the photoinitiator-based end group (irradiation at 351 and 355 nm) occurs solely for polymeric species with benzoyl end groups carrying no or only one ortho-methyl substituent/s, whereas all of the other substitution patterns lead to stable chain termini. The theoretical calculations suggest that the different reactivity can be traced back to shifts of the n−π* transitions by approximately +0.25 eV. The current investigation unambiguously evidences that methylation in both ortho-positions of the benzoin-type photoinitiator critically enhances the photostability of the resulting polymer chain termini providing a clear instruction for photoinitiator design leading to polymers with stable chain termini.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.5b02127.

  • 1H NMR and SEC–ESI–MS spectra of 2, 4, 5, 9, 10, and 11; 1H NMR spectra of 1 and 3, Fx(i) plots of 1, 2, 9, and, 10; SEC–ESI–MS spectrum of 9 for the peak height evaluation; CIDNP–NMR data for polymers initiated by 2, 3, 4, 5, 9, 10, and 11; and DFT data, including the first five vertical excitations and the relevant molecular orbitals for 4-MBM and TMBM, the molecular orbitals of S1 and T1 for 4-MBM and TMBM, and the S1 singlet excitations for all calculated model compounds (PDF)

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Cited By

This article is cited by 7 publications.

  1. Jan Steinkoenig, Patrick A. J. M. de Jongh, David M. Haddleton, Anja S. Goldmann, Christopher Barner-Kowollik, and Kristian Kempe . Unraveling the Spontaneous Zwitterionic Copolymerization Mechanism of Cyclic Imino Ethers and Acrylic Acid. Macromolecules 2018, 51 (2) , 318-327. https://doi.org/10.1021/acs.macromol.7b02608
  2. Andrea Lauer, David E. Fast, Jan Steinkoenig, Anne-Marie Kelterer, Georg Gescheidt, and Christopher Barner-Kowollik . Wavelength-Dependent Photochemical Stability of Photoinitiator-Derived Macromolecular Chain Termini. ACS Macro Letters 2017, 6 (9) , 952-958. https://doi.org/10.1021/acsmacrolett.7b00499
  3. David E. Fast, Andrea Lauer, Jan P. Menzel, Anne-Marie Kelterer, Georg Gescheidt, and Christopher Barner-Kowollik . Wavelength-Dependent Photochemistry of Oxime Ester Photoinitiators. Macromolecules 2017, 50 (5) , 1815-1823. https://doi.org/10.1021/acs.macromol.7b00089
  4. Kristina Jovic, Tobias Nitsche, Christiane Lang, James P. Blinco, Kevin De Bruycker, Christopher Barner-Kowollik. Hyphenation of size-exclusion chromatography to mass spectrometry for precision polymer analysis – a tutorial review. Polymer Chemistry 2019, 10 (24) , 3241-3256. https://doi.org/10.1039/C9PY00370C
  5. Andrea Lauer, Jan Steinkoenig, Philipp Jöckle, Anne-Marie Kelterer, Andreas N. Unterreiner, Christopher Barner-Kowollik. Installing lactone chain termini during photoinduced polymerization. Polymer Chemistry 2018, 9 (24) , 3336-3341. https://doi.org/10.1039/C8PY00457A
  6. Ge Ding, Chuan Jing, Xiaozhuan Qin, Yulong Gong, Xueping Zhang, Shengtao Zhang, Ziping Luo, Hongru Li, Fang Gao. Conjugated dyes carrying N, N-dialkylamino and ketone groups: One-component visible light Norrish type II photoinitiators. Dyes and Pigments 2017, 137 , 456-467. https://doi.org/10.1016/j.dyepig.2016.10.034
  7. David E. Fast, Michal Zalibera, Andrea Lauer, Anna Eibel, Caroline Schweigert, Anne-Marie Kelterer, Martin Spichty, Dmytro Neshchadin, Dominik Voll, Hanna Ernst, Yu Liang, Kurt Dietliker, Andreas-Neil Unterreiner, Christopher Barner-Kowollik, Hansjörg Grützmacher, Georg Gescheidt. Bis(mesitoyl)phosphinic acid: photo-triggered release of metaphosphorous acid in solution. Chemical Communications 2016, 52 (64) , 9917-9920. https://doi.org/10.1039/C6CC05219C

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