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RAFT polymerization of isopropenyl boronate pinacol ester and subsequent terminal olefination: precise synthesis of poly(alkenyl boronate)s and evaluation of their thermal properties

Polymer Journal volume 53, pages 1167–1174 (2021)Cite this article

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Abstract

In this work, various types of chain-transfer agents (CTAs) were investigated in the reversible addition-fragmentation chain-transfer (RAFT) polymerization of isopropenyl boronate pinacol ester (IPBpin) toward not only precise synthesis of poly(IPBpin) but also elucidation of its feature as a monomer. CTAs suitable for conjugated monomers were found to be more compatible than those for nonconjugated monomers, likely due to the moderate stabilization of the growing radical by boron. This trend was supported by density functional theory-based calculations for energy balance between the growing IPBpin radical and the chain-transfer species to the CTA. The CTA-derived group at the ω-terminus of the obtained poly(IPBpin) was quantitatively converted into olefin under cobalt catalysis leading to improved stability, enabling evaluation of its well-defined structure by MALDI-TOF-MS and its thermal properties by DSC.

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References

  1. Rudin A, Choi P. The elements of polymer science & engineering. 3rd ed. Boston: Elsevier, Academic Press; 2013.

  2. Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, et al. Living free-radical polymerization by reversible addition-fragmentation chain transfer: the RAFT process. Macromolecules. 1998;31:5559–62.

    Article  CAS  Google Scholar 

  3. Moad G, Rizzardo E, Thang SH. Radical addition—fragmentation chemistry in polymer synthesis. Polymer. 2008;49:1079–131.

    Article  CAS  Google Scholar 

  4. Keddie DJ, Moad G, Rizzardo E, Thang SH. RAFT agent design and synthesis. Macromolecules. 2012;45:5321–42.

    Article  CAS  Google Scholar 

  5. Stenzel MH, Cummins L, Roberts GE, Davis TP, Vana P, Barner-Kowollik C. Xanthate mediated living polymerization of vinyl acetate: a systematic variation in MADIX/RAFT agent structure. Macromol Chem Phys. 2003;204:1160–8.

    Article  CAS  Google Scholar 

  6. Destarac M, Franck X, Charmot D, Zard SZ. Dithiocarbamates as universal reversible addition-fragmentation chain transfer agents. Macromol Rapid Commun. 2000;21:1035–9.

    Article  CAS  Google Scholar 

  7. Harrisson S, Liu X, Ollagnier J-N, Coutelier O, Marty JD, Destarac M. RAFT polymerization of vinyl esters: synthesis and applications. Polymers. 2014;6:1437–88.

    Article  Google Scholar 

  8. Nakabayashi K, Mori H. Recent progress in controlled radical polymerization of N-vinyl monomers. Eur Polym J. 2013;49:2808–38.

    Article  CAS  Google Scholar 

  9. Mori H, Ishikawa K, Abiko Y, Maki Y, Onuma A, Morishima M. Synthesis of triazole-based amphiphilic block copolymers containing carbazole moiety By RAFT polymerization. Macromol Chem Phys. 2012;213:1803–14.

    Article  CAS  Google Scholar 

  10. Nakabayashi K, Abiko Y, Mori H. RAFT polymerization of S-vinyl sulfide derivatives and synthesis of block copolymers having two distinct optoelectronic functionalities. Macromolecules. 2013;46:5998–6012.

    Article  CAS  Google Scholar 

  11. Mori H, Ookuma H, Nakano S, Endo T. Xanthate-mediated controlled radical polymerization of N-vinylcarbazole. Macromol Chem Phys. 2006;207:1005–17.

    Article  CAS  Google Scholar 

  12. Wan WM, Baggett AW, Cheng F, Lin H, Liu SY, Jäkle F. Synthesis by free radical polymerization and properties of BN-polystyrene and BN-poly(vinylbiphenyl). Chem Commun. 2016;52:13616–9.

    Article  CAS  Google Scholar 

  13. Thiedemann B, Gliese PJ, Hoffmann J, Lawrence PG, Sönnichsen FD, Staubitz A. High molecular weight poly(N-methyl-B-vinylazaborine)—a semi-inorganic B-N polystyrene analogue. Chem Commun. 2017;53:7258–61.

    Article  CAS  Google Scholar 

  14. van de Wouw HL, Lee JY, Klausen RS. Gram-scale free radical polymerization of an azaborine vinyl monomer. Chem Commun. 2017;53:7262–5.

    Article  Google Scholar 

  15. Nishikawa T, Ouchi M. An alkenyl boronate as a monomer for radical polymerizations: boron as a guide for chain growth and as a replaceable side chain for post-polymerization transformation. Angew Chem Int Ed. 2019;58:12435–9.

    Article  CAS  Google Scholar 

  16. van de Wouw HL, Lee JY, Awuyah EC, Klausen RS. A BN aromatic ring strategy for tunable hydroxy content in polystyrene. Angew Chem Int Ed. 2018;57:1673–7.

    Article  Google Scholar 

  17. van de Wouw HL, Awuyah EC, Baris JI, Klausen RS. An organoborane vinyl monomer with styrene-like radical reactivity: reactivity ratios and role of aromaticity. Macromolecules. 2018;51:6359–68.

    Article  Google Scholar 

  18. Makino H, Nishikawa T, Ouchi M. Elucidating monomer character of an alkenyl boronate through radical copolymerization leads to copolymer synthesis beyond the limitation of copolymerizability by side-chain replacement. ACS Macro Lett. 2020;9:788–93.

    Article  CAS  Google Scholar 

  19. Maki Y, Mori H, Endo T. Xanthate-mediated controlled radical polymerization of N-vinylindole derivatives. Macromolecules. 2007;40:6119–30.

    Article  CAS  Google Scholar 

  20. Sugihara S, Kawamoto Y, Maeda Y. Direct radical polymerization of vinyl ethers: reversible addition—fragmentation chain transfer polymerization of hydroxy-functional vinyl ethers. Macromolecules. 2016;49:1563–74.

    Article  CAS  Google Scholar 

  21. Sugihara S, Kawakami R, Maeda Y. Poly[di(ethylene glycol) vinyl ether]-stabilized poly(vinyl acetate) nanoparticles with various morphologies via RAFT aqueous emulsion polymerization of vinyl acetate. Polym J. 2021;53:309–21.

    Article  CAS  Google Scholar 

  22. Abreu CMR, Mendonca PV, Serra AC, Coelho JFJ, Popov AV, Gryn’ova G, et al. Reversible addition-fragmentation chain transfer polymerization of vinyl chloride. Macromolecules. 2012;45:2200–8.

    Article  CAS  Google Scholar 

  23. Oliveira M, Barbosa SB, Nele M, Pinto JC. Reversible addition-fragmentation chain transfer polymerization of vinyl acetate in bulk and suspension systems. Macromol React Eng. 2014;8:493–502.

    Article  CAS  Google Scholar 

  24. Sugihara S, Yoshida A, Kono T, Takayama T, Maeda Y. Controlled radical homopolymerization of representative cationicallypolymerizable vinyl ethers. J Am Chem Soc. 2019;141:13954–61.

    Article  CAS  Google Scholar 

  25. Coote ML, Henry DJ. Effect of substituents on radical stability in reversible addition fragmentation chain transfer polymerization: an ab initio study. Macromolecules. 2005;38:1415–33.

    Article  CAS  Google Scholar 

  26. Mori H, Yahagi M, Endo T. RAFT polymerization of N-vinylimidazolium salts and synthesis of thermoresponsive ionic liquid block copolymers. Macromolecules. 2009;42:8082–92.

    Article  CAS  Google Scholar 

  27. Soeriyadi AH, Boyer C, Burns J, Becer CR, Whittaker MR, Haddleton DM, et al. High fidelity vinyl terminated polymers by combining RAFT and cobaltcatalytic chain transfer (CCT) polymerization methods. Chem Commun. 2010;46:6338–40.

    Article  CAS  Google Scholar 

  28. Andrews RJ, Grulke EA. Glass transition temperatures of polymers. In: Brandrup J, Immergut EH, Eric A Grulke EA, editors. Polymer handbook. 4th ed. New York: John Wiley and Sons; 1999.

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Acknowledgements

We appreciate Mr. Takehiro Itami and Dr. Takaya Terashima for their kind advice. This work was partially supported by JSPS [KAKENHI grants 19K15622 (TN) and 17H06453 (MO)], the Mazda Foundation (TN), the Kyoto Technoscience Center (TN), the Masuya Memorial Foundation of the Promotion of Basic Research (TN), and the Hattori Hokokai Foundation (TN).

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  1. Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto, Japan

    Tomoaki Kanazawa, Tsuyoshi Nishikawa & Makoto Ouchi

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  1. Tomoaki Kanazawa
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  2. Tsuyoshi Nishikawa
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  3. Makoto Ouchi
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Correspondence to Tsuyoshi Nishikawa or Makoto Ouchi.

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Kanazawa, T., Nishikawa, T. & Ouchi, M. RAFT polymerization of isopropenyl boronate pinacol ester and subsequent terminal olefination: precise synthesis of poly(alkenyl boronate)s and evaluation of their thermal properties. Polym J 53, 1167–1174 (2021). https://doi.org/10.1038/s41428-021-00498-8

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