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Synthesis of novel photoreactive bis(dithiocarbonate) type xanthates as chain transfer agents and their use in MADIX polymerization of styrene

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Abstract

In this study, two novel photoactive xanthates, which bear a photoinitiator (PI) group in the middle and an S-alkyl dithiocarbonate group (–O–C(S)–S–R) at each of the two ends of the molecule, were synthesized as chain transfer agents (CTA) to be used in reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) polymerization. Having the same central photoinitiator group, two chain transfer agents (CTA-PI-CTA 1 and CTA-PI-CTA 2) differ from each other in their R leaving groups; C6H5–CH2– and C6H5–CH(COOEt)–, respectively. The structures of CTA-PI-CTAs were elucidated via elemental analysis and spectroscopic techniques, such as 13C NMR, 1H-NMR, and FT-IR. Styrene (St) was used as the model monomer in MADIX polymerization. Its RAFT/MADIX polymerization with these chain transfer agents successfully produced mid-chain functional polystyrene macrophotoinitiators (PSt-PI-PSt 1 and PSt-PI-PSt 2) with well-defined structures. The GPC, FT-IR, 1H-NMR, UV, and fluorescence spectroscopic studies revealed that low-dispersity polystyrenes with desired photoinitiator functionality in the middle of the chain were obtained. Finally, these macrophotoinitiators were used as prepolymers in photoinitiated free radical polymerization of methyl methacrylate (MMA) to obtain polystyrene-poly(methyl methacrylate) (PSt-PMMA) block copolymers.

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Acknowledgements

The authors acknowledge Harran University Scientific Research Project Coordination Unit (HÜBAP, Projects numbers: 15155 and 19319) for financial support.

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Authors and Affiliations

  1. Department of Chemistry, Science Faculty, Harran University, 63290, Sanliurfa, Turkey

    Zafer Uyar, Ozgur Ekmen, Ahmet Kalkan, Ulku Arslan, Mustafa Durgun & Mustafa Degirmenci

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  1. Zafer Uyar
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  2. Ozgur Ekmen
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  3. Ahmet Kalkan
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  4. Ulku Arslan
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  5. Mustafa Durgun
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  6. Mustafa Degirmenci
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Correspondence to Zafer Uyar or Mustafa Degirmenci.

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Uyar, Z., Ekmen, O., Kalkan, A. et al. Synthesis of novel photoreactive bis(dithiocarbonate) type xanthates as chain transfer agents and their use in MADIX polymerization of styrene. Polym. Bull. 79, 7635–7654 (2022). https://doi.org/10.1007/s00289-021-03873-w

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  • DOI: https://doi.org/10.1007/s00289-021-03873-w

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