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Divergent chain growth of poly(dithiocarbonate)s through arylmethyl triflate-mediated ring-opening polymerization of cyclic dithiocarbonate

Polymer Journal volume 55, pages 571–580 (2023)Cite this article

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Abstract

Benzyl triflate (BnOTf) was demonstrated as a new initiator in cationic ring-opening polymerization (ROP) of cyclic dithiocarbonate, yielding poly(dithiocarbonate) with a benzylated chain end. BnOTf was generated in situ from benzyl bromide and silver trifluoromethanesulfonate (AgOTf). Several arylmethyl triflates were prepared from 1,4-bis(bromomethyl)benzene, 1,3,5-tris(bromomethyl)benzene, and 1,2,4,5-tetrakis(bromomethyl)benzene. These triflates were used for the synthesis of polymeric architectures, such as two-armed linear polymers and tri- and tetra-armed polymers. The number of polymer arms was related to the number of arylmethyl triflate groups bound in the initiators through divergent chain propagation. The chain length of each arm was adjusted with initiators at theoretical concentrations considering the number of substituted triflates and confirmed via 1H NMR analysis of the prepared polymers. The lengths agreed with the results determined by the number-average molecular weights retrieved from gel permeation chromatography analysis. A symmetric structure of the aromatic cores and low polydispersities of the prepared polymers were suggested for divergent chain propagation. Fluorescent dye-attached polymers were prepared through ROP, and the presence of cores retrieved from the initiators was verified.

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References

  1. Cowie JMG, Valeria A. Polymers chemistry and physics of modern materials. 3rd edn., Boca Raton: Taylor & Francis, 2007.

  2. Grubbs RB, Grubbs RH. 50th anniversary perspective: living polymerization-emphasizing the molecule in macromolecules. Macromolecules. 2017;50:6979–97.

    Article  CAS  Google Scholar 

  3. Bingham MN, Abousalman-Rezvani Z, Collins K, Roth PJ. Thiocarbonyl chemistry in polymer science. Polym Chem 2022;13:2880–01.

    Article  CAS  Google Scholar 

  4. Dey A, Haldar U. Block PDe. Copolymer synthesis by the combination of living cationic polymerization and other polymerization methods. Front Chem 2021;9:644–47.

    Article  Google Scholar 

  5. Darensbourg DJ, Andreatta JR, Jungman MJ, Reibenspies JH. Investigation into the coupling of cyclohexene oxide and carbon isulfide catalyzed by (salen)CrCl. Selectivity for the production of copolymers vs. cyclic thiocarbonates. Dalton Trans. 2009; 8891–99.

  6. Tang Y, Pina-Hernandez C, Niu Q, Nie J, Cabrini S. A novel high-refractive index episulfide-thiol polymer for nanoimprinting optical elements. J Mater Chem C. 2018;6:8823–31.

    Article  CAS  Google Scholar 

  7. Nakano K, Tatsumi G, Nozaki K. Synthesis of sulfur-rich polymers: copolymerization of episulfide with carbon disulfide by using [PPN]Cl/salph)Cr(III)Cl system. J Am Chem Soc. 2007;129:15116–17.

  8. Nuyken O, Pask SD. Ring-opening polymerization-an introductory review. Polym. 2013;5:361–403.

    Article  Google Scholar 

  9. Gleede T, Reisman L, Rieger E, Mbarushiman PC, Rupar PA, Wurm FR. Aziridines and azetidines: building blocks for polyamines by anionic and cationic ring-opening polymerization. Polym Chem 2019;10:3257–83.

    Article  CAS  Google Scholar 

  10. Krishnamurthy S, Yoshida Y, Endo T. Cationic ring-opening polymerization of a five membered cyclic dithiocarbonate having a tertiary amine moiety. Polym Chem 2022;13:267–74.

    Article  CAS  Google Scholar 

  11. Do JY, Shin SB, Jeong SM, Jung M. Ring-opening polymerization of cyclic 1,3-oxathiolane-2-thione promoted by neighboring sulfide group and ring contraction. Eur Polym J 2020;131:109689.

    Article  CAS  Google Scholar 

  12. Choi W, Sanda F, Endo T. Dependence of ring-opening reaction of five-membered dithiocarbonates on cationic catalyst: control of isomerization and polymerization. Macromolecules 1998;31:2454–60.

    Article  CAS  Google Scholar 

  13. Kim CG, Son MJ, Do JY. Cationic living polymerization of cyclic dithiocarbonates involving sulfide-migration. Eur Polym J 2021;156:110611.

    Article  CAS  Google Scholar 

  14. Oike H, Imaizumi H, Mouri T, Yoshioka Y, Uchibori A. Designing unusual polymer topologies by electrostatic self-assembly and covalent fixation. J Am Chem Soc. 2000;122:9592–99.

    Article  CAS  Google Scholar 

  15. Laali K. Electrophilic benzylation and nitration of 2,6-dimethylanisole, 2,6-dimethylphenol, and 2,6-diisopropylphenol. Isomer distribution and mechanistic considerations. J Org Chem. 1985;50:3638–40.

    Article  CAS  Google Scholar 

  16. Allison-Logan S, Karimi F, Sun Y, McKenzie TG, Nothling MD, Bryant G, et al. Highly living stars via core-first photo-RAFT polymerization: exploitation for ultra-high molecular weight star synthesis. ACS Macro Lett. 2019;8:1291–95.

    Article  CAS  PubMed  Google Scholar 

  17. Yang DP, Oo MNNL, Deen GR, Li Z, Loh XJ. Nano-star-shaped polymers for drug delivery applications. Macromol Rapid Commun 2017;38:1700410.

    Article  Google Scholar 

  18. Hasneen A, Kim SJ, Paik H. Synthesis and characterization of low molecular weight poly(methyl acrylate)-b-polystyrene by a combination of ATRP and click coupling method. Macromol Res 2007;15:541–46.

    Article  CAS  Google Scholar 

  19. Chesnokov GA, Topchiy MA, Dzhevakov PB, Gribanov PS, Tukov AA, Khrustalev VN, et al. Eight-membered-ring diaminocarbenes bearing naphthalene moiety in the backbone: DFT studies, synthesis of amidinium salts, generation of free carbene, metal complexes, and solvent-free copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Dalton Trans. 2017;46:4331–45.

    Article  CAS  PubMed  Google Scholar 

  20. Callaghan S, Flanagan KJ, O’Brien JE, Senge MO. Short-chained anthracene strapped porphyrins and their endoperoxides. Eur J Org Chem. 2020;2020:2735–44.

    Article  CAS  Google Scholar 

  21. Nallasivam JL, Fernandes RA. A cascade aza-cope/aza-prins cyclization leading to piperidine derivatives. Eur J Org Chem. 2015;2015:2012–22.

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (No. NRF-2019R1F1A1060583).

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  1. Department of Chemical Materials, Pusan National University, Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, 46241, Republic of Korea

    Chi Gwan Kim, Hyo Jo Jeong & Jung Yun Do

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  1. Chi Gwan Kim
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Correspondence to Jung Yun Do.

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Kim, C.G., Jeong, H.J. & Do, J.Y. Divergent chain growth of poly(dithiocarbonate)s through arylmethyl triflate-mediated ring-opening polymerization of cyclic dithiocarbonate. Polym J 55, 571–580 (2023). https://doi.org/10.1038/s41428-022-00745-6

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