Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions

Lale Nur Atici; Erhan Demirel; Umit Tunca; Gurkan Hizal; Hakan Durmaz

doi:10.1002/pola.27697

Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions

Lale Nur Atici, Erhan Demirel, Umit Tunca, Gurkan Hizal, Hakan Durmaz^*

^*Corresponding author for this work

Department of Chemistry

Istanbul Technical University

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

The brominated backbone of poly(oxanorbornene imide) (PONB) (PONB-Br) was functionalized with 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-acrylate, -epoxy, and poly (ethylene glycol) (PEG) yielding PONB-acrylate, PONB-epoxy, and PONB-PEG through the nitroxide radical coupling (NRC) reaction. Although an excess amount of functional-TEMPOs were used. The observed NRC efficiencies were found in the range of 7-25%. Notably, ¹H NMR spectra of all polymers exhibited a signal at 6.08 ppm after NRC reactions indicating rebuilding of the main chain double bond and further identified by ¹³C NMR analysis. The inevitable formation of double bond through the tendency of the recombination of the formed radicals was supported by a separate experiment conducted without utilizing functional-TEMPO. Besides, the versatility of the ROMP backbone further demonstrated by the introduction hetero functionality onto the polymer by a consecutive reactions.

Original language	English
Pages (from-to)	2381-2389
Number of pages	9
Journal	Journal of Polymer Science, Part A: Polymer Chemistry
Volume	53
Issue number	20
DOIs	https://doi.org/10.1002/pola.27697
Publication status	Published - 15 Oct 2015

Bibliographical note

Publisher Copyright:
© 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2381-2389.

Keywords

2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)
bromination
Controlled/living polymerization (CLP)
IR spectroscopy
nitroxide radical coupling (NRC)
poly (oxanorbornene imide) (PONB)
post-functionalization
ring-opening metathesis polymerization (ROMP) and NMR
UV spectroscopy

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title = "Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions",

abstract = "The brominated backbone of poly(oxanorbornene imide) (PONB) (PONB-Br) was functionalized with 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-acrylate, -epoxy, and poly (ethylene glycol) (PEG) yielding PONB-acrylate, PONB-epoxy, and PONB-PEG through the nitroxide radical coupling (NRC) reaction. Although an excess amount of functional-TEMPOs were used. The observed NRC efficiencies were found in the range of 7-25%. Notably, 1H NMR spectra of all polymers exhibited a signal at 6.08 ppm after NRC reactions indicating rebuilding of the main chain double bond and further identified by 13C NMR analysis. The inevitable formation of double bond through the tendency of the recombination of the formed radicals was supported by a separate experiment conducted without utilizing functional-TEMPO. Besides, the versatility of the ROMP backbone further demonstrated by the introduction hetero functionality onto the polymer by a consecutive reactions.",

keywords = "2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), bromination, Controlled/living polymerization (CLP), IR spectroscopy, nitroxide radical coupling (NRC), poly (oxanorbornene imide) (PONB), post-functionalization, ring-opening metathesis polymerization (ROMP) and NMR, UV spectroscopy",

author = "Atici, {Lale Nur} and Erhan Demirel and Umit Tunca and Gurkan Hizal and Hakan Durmaz",

note = "Publisher Copyright: {\textcopyright} 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2381-2389.",

year = "2015",

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doi = "10.1002/pola.27697",

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AU - Atici, Lale Nur

AU - Demirel, Erhan

AU - Tunca, Umit

AU - Hizal, Gurkan

AU - Durmaz, Hakan

PY - 2015/10/15

Y1 - 2015/10/15

N2 - The brominated backbone of poly(oxanorbornene imide) (PONB) (PONB-Br) was functionalized with 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-acrylate, -epoxy, and poly (ethylene glycol) (PEG) yielding PONB-acrylate, PONB-epoxy, and PONB-PEG through the nitroxide radical coupling (NRC) reaction. Although an excess amount of functional-TEMPOs were used. The observed NRC efficiencies were found in the range of 7-25%. Notably, 1H NMR spectra of all polymers exhibited a signal at 6.08 ppm after NRC reactions indicating rebuilding of the main chain double bond and further identified by 13C NMR analysis. The inevitable formation of double bond through the tendency of the recombination of the formed radicals was supported by a separate experiment conducted without utilizing functional-TEMPO. Besides, the versatility of the ROMP backbone further demonstrated by the introduction hetero functionality onto the polymer by a consecutive reactions.

AB - The brominated backbone of poly(oxanorbornene imide) (PONB) (PONB-Br) was functionalized with 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-acrylate, -epoxy, and poly (ethylene glycol) (PEG) yielding PONB-acrylate, PONB-epoxy, and PONB-PEG through the nitroxide radical coupling (NRC) reaction. Although an excess amount of functional-TEMPOs were used. The observed NRC efficiencies were found in the range of 7-25%. Notably, 1H NMR spectra of all polymers exhibited a signal at 6.08 ppm after NRC reactions indicating rebuilding of the main chain double bond and further identified by 13C NMR analysis. The inevitable formation of double bond through the tendency of the recombination of the formed radicals was supported by a separate experiment conducted without utilizing functional-TEMPO. Besides, the versatility of the ROMP backbone further demonstrated by the introduction hetero functionality onto the polymer by a consecutive reactions.

KW - 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)

KW - bromination

KW - Controlled/living polymerization (CLP)

KW - IR spectroscopy

KW - nitroxide radical coupling (NRC)

KW - poly (oxanorbornene imide) (PONB)

KW - post-functionalization

KW - ring-opening metathesis polymerization (ROMP) and NMR

KW - UV spectroscopy

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JO - Journal of Polymer Science, Part A: Polymer Chemistry

JF - Journal of Polymer Science, Part A: Polymer Chemistry

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Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions

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