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Synthesis of a well-defined end-chain macrophotoinitiator of poly(ε − caprolactone) by combination of ring-opening polymerization and click chemistry

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Abstract

A novel well-defined end-chain functional macrophotoinitiator of poly(ε − caprolactone) (BPI-PCL) with controlled molecular weight and narrow molecular weight distribution was successfully synthesized by combination of ring opening polymerization (ROP) and “click chemistry”. The synthetic procedure for the preparation of a macrophotoinitiator involves three steps: (1) an azido-functionalized benzoin photoinitiator (BPI-N3) by transformation of a bromine-end group of BPI-Br compound into an azido group using NaN3; (2) an alkyne end-functionalized PCL (alkyne-PCL) precursor by ROP of ε − caprolactone (ε − CL) using propargyl alcohol as the initiator and stannous-2-ethylhexanoate (Sn(Oct)2) as the catalyst; and (3) BPI-PCL through “click reaction” between alkyne-PCL and BPI-N3 using Cu(I) as a catalyst. The 1H NMR, FTIR, UV–vis, fluorescence and gel permeation chromatography techniques were used to characterize the chemical structures of the intermediates and the target macrophotoinitiator. The obtained BPI-PCL macrophotoinitiator was used as a precursor in photoinitiated free radical promotedcationic polymerization to synthesize a poly(ε − caprolactone)-poly(cyclohexene oxide) (PCL-PCHO) block copolymer. The thermal behavior of the polymers was studied by differential thermal analysis and thermogravimetric analysis methods.

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Acknowledgments

The authors would like to thank Harran University's Scientific Research Council (HÜBAK) for financial support.

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Authors and Affiliations

  1. Science Faculty, Department of Chemistry, Harran University, Sanliurfa, 63190, Turkey

    Mustafa Degirmenci & Pinar Atuk Besli

  2. Vocational School of Diyarbakir, Dicle University, Diyarbakir, 21100, Turkey

    Nasrettin Genli

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  1. Mustafa Degirmenci
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  2. Pinar Atuk Besli
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  3. Nasrettin Genli
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Correspondence to Mustafa Degirmenci.

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Degirmenci, M., Besli, P.A. & Genli, N. Synthesis of a well-defined end-chain macrophotoinitiator of poly(ε − caprolactone) by combination of ring-opening polymerization and click chemistry. J Polym Res 21, 540 (2014). https://doi.org/10.1007/s10965-014-0540-2

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  • DOI: https://doi.org/10.1007/s10965-014-0540-2

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