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Efficiency of low-molecular-weight and high-molecular-weight alkoxyamines in the synthesis of polystyrene

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Abstract

The influence of the structure of high-molecular-weight alkoxyamines (obtained in situ from C-phenyl-N-tert-butylnitrone and 2-(benzylideneamino)-2-methyl-1-phenylpropanol-1-N-oxide) and their low-molecular-weight analogs on styrene polymerization in the temperature range 70—110 ° was analyzed. The controlled synthesis of polystyrene in the presence of low-molecular-weight alkoxyamines was revealed to occur most efficiently at 110 °. The use of high-molecular-weight alkoxyamines makes it possible to perform the controlled process under lower-temperature conditions (70—90 °), when the constant polymerization rate and linear increase in the molecular weight with conversion are observed, and the synthesis of polymers with fairly low polydispersity (Mw/Mn ~ 1.26) is also possible. The quantum chemical calculations showed that the energy of the C-ON bond in alkoxyamines is determined by the length of the chains at the nitroxide fragment rather than the structure of the substituents. It is found that the equilibrium dissociation constants of high-molecular-weight alkoxyamines are caused by both the structure of the nitroxide fragment and molecular weights.

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References

  1. D. Braun, H. Cherdron, M. Rehahn, H. Ritter, B. Voit, Polymer Synthesis: Theory and Practice Fundamentals, Methods, Experiments, Springer-Verlag, Berlin–Heidelberg, 2013, 402 p.

    Book  Google Scholar 

  2. Nitroxide Mediated Polymerization: from Fundamentals to Applications in Materials Science, Ed. D. Gigmes, The Royal Society of Chemistry, 2016, 500 p.

    Google Scholar 

  3. M. Yu. Zaremski, Polym. Sci., Ser. C, 2015, 57, 65.

    Article  CAS  Google Scholar 

  4. J. Nicolas, Y. Guillaneuf, C. Lefay, D. Bertin, D. Gigmes, B. Charleux, Prog. Polym. Sci., 2013, 38, 63.

    Article  CAS  Google Scholar 

  5. Y. Jing, A. Mardyukov, K. Bergander, C. G. Daniliuc, A. Studer, Macromolecules, 2014, 47, 3595.

    Article  CAS  Google Scholar 

  6. Y. Jing, M. Tesch, L. Wang, C. G. Daniliuc, A. Studer, Tetrahedron, 2016, 72, 7665.

    Article  CAS  Google Scholar 

  7. Y. Guillaneuf, P. Astolfi, D. Gigmes, S. R. A. Marque, P. Tordo, L. Grecci, D. Bertin, Macromolecules, 2007, 40, 3108.

    Article  CAS  Google Scholar 

  8. C. Detrembleur, C. Jérôme, J. Winter, P. Gerbaux, J.-L. Clement, Y. Guillaneuf, D. Gigmes, Polym. Chem., 2014, 5, 335.

    Article  CAS  Google Scholar 

  9. N. Ballard, M. Aguirre, A. Simula, A. Agirre, J. R. Leiza, J. M. Asua, S. Es, ACS Macro Lett., 2016, 5, 1019.

    Article  CAS  Google Scholar 

  10. Z. Zhu, G. Shan, P. Pan, RSC Adv., 2016, 6, 73842.

    Article  CAS  Google Scholar 

  11. G. Audran, R. Bikanga, P. Brémond, M. Edeleva, J. P. Joly, S. R. A. Marque, P. Nkolo, V. Roubaud, Org. Biomol. Chem., 2017, 15, 8425.

    Article  CAS  PubMed  Google Scholar 

  12. G. Gryn’va, L. M. Smith, M. L. Coote, Phys. Chem. Chem. Phys., 2017, 19, 22678.

    Article  PubMed  Google Scholar 

  13. G. Audran, E. Bagryanskaya, I. Bagryanskaya, M. Edeleva, S. R. A. Marque, D. Parkhomenko, E. Tretyakov, S. Zhivetyeva, Chemistry Select., 2017, 2, 3584.

    CAS  Google Scholar 

  14. V. Sciannamea, R. Jérôme, C. Detrembleur, Chem. Rev., 2008, 108, 1104.

    Article  CAS  PubMed  Google Scholar 

  15. E. V. Kolyakina, D. F. Grishin, Russ. Chem. Rev., 2009, 78, 535.

    Article  CAS  Google Scholar 

  16. M. V. Pavlovskaya, E. V. Kolyakina, V. V. Polyanskova, L. L. Semenycheva, D. F. Grishin, Russ. J. Appl. Chem., 2002, 75, 1868.

    Article  CAS  Google Scholar 

  17. M. Yu. Zaremski, A. P. Orlova, E. S. Garina, A. V. Olenin, M. B. Lachinov, V. B. Golubev, Polym. Sci., Ser. A, 2003, 45, 502.

    Google Scholar 

  18. D. F. Grishin, L. L. Semenycheva, S. A. Bulgakova, L. M. Mazanova, E. V. Kolyakina, Polym. Sci., Ser. A, 2003, 45, 305.

    Google Scholar 

  19. D. F. Grishin, L. L. Semenycheva, K. V. Sokolov, E. V. Kolyakina, Polym. Sci., Ser. B, 2000, 42, 189.

    Google Scholar 

  20. M. Yu. Zaremski, A. L. Reznichenko, Yu. V. Grinevich., E. S. Garina, M. B. Lachinov, V. B. Golubev, Polym. Sci., Ser. A, 2009, 47, 536—545.

  21. D. F. Grishin, E. V. Kolyakina, M. V. Pavlovskaya, M. A. Lazarev, A. A. Shchepalov, in Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP, Ed. K. Matyjiaszewski. ACS Symposium Series, American Chemical Society, Washington DC, 2009, 1024, 95

    CAS  Google Scholar 

  22. V. Sciannamea, C. Guerrero-Sanchez, U. S. Schubert, J.-M. Catala, R. Jerome, C. Detrembleur, Polymer, 2005, 46, 9632.

    Article  CAS  Google Scholar 

  23. V. Sciannamea, J. M. Catala, R. Jerome, C. Detrembleur, J. Polym. Sci., Part A: Polym. Chem., 2007, 45, 1219.

    Article  CAS  Google Scholar 

  24. E. H. H. Wong, T. Junkers, C. Barner-Kowollik, J. Polym. Sci., Part A: Polym. Chem., 2008, 46, 7273.

    Article  CAS  Google Scholar 

  25. L. Zang, E. H. H. Wong, C. Barner-Kowollik, T. Junkers, Polymer, 2010, 51, 3821.

    Article  CAS  Google Scholar 

  26. E. Yoshida, Colloid Polym. Sci., 2010, 288, 7.

    Article  CAS  Google Scholar 

  27. Y. Guillaneuf, D.-L. Versace, D. Bertin, J. Laleve’e, D. Gigmes, J.-P. Fouassier, Macromol. Rapid Commun., 2010, 31, 1909.

    Article  CAS  PubMed  Google Scholar 

  28. A. N. Generalova, I. M. Asharchuk, V. P. Zubov, Russ. Chem. Bull., 2018, 67, 1759.

    Article  CAS  Google Scholar 

  29. E. H. H. Wong, T. Junkers, C. Barner-Kowollik, Polym. Chem., 2011, 2, 1008.

    Article  CAS  Google Scholar 

  30. J. P. Wu, C. W. Pan, K. E. Heiler, M. E. Ching, E. S. Tillman, Polymer, 2017, 127, 66.

    Article  CAS  Google Scholar 

  31. M. Du, C. Deng, X. Wu, H. Liu, H. Liu, Macromol. Chem. Phys., 2017, 218; DOI: 10.1002/macp.201700069.

    Google Scholar 

  32. S. Faucher, S. Zhu, J. Polym. Sci. Part A: Polym. Chem., 2007, 45, 553—565.

  33. E. Guegain, Y. Guillaneuf, J. Nicolas, Macromol. Rapid Commun., 2015, 36, 1227.

    Article  CAS  PubMed  Google Scholar 

  34. T. Fukuda, A. Goto, K. Ohno, Rapid Commun., 2000, 21, 151.

    Article  CAS  Google Scholar 

  35. Kratkii spravochnik fizikokhimicheskikh velichin [Brief Reference Book for Physicochemical Magnitudes], Eds A. A. Ravdel’ and A. M. Ponomareva, Izd. Ivan Fedorov, St. Petersburg, 2003, 218 pp. (in Russian)}.

    Google Scholar 

  36. R. Cuatepotzo-Díaza, M. Albores-Velascoa, E. Saldívar-Guerrab, F. B. Jime’neza, Polymer, 2004, 45, 815.

    Article  CAS  Google Scholar 

  37. Entsiklopediya polimerov [Polymer Encyclopedia], Ed. V. A. Kabanov, Sov. Entsiklopediya, Moscow, 1972, 1, 932 pp. (in Russian)}.

  38. Organic Syntheses, Interscience Publishers, New York–London, 1946–1952, 26–32.

  39. W. D. Emmons, J. Am. Chem. Soc., 1957, 79, 5739.

    Article  CAS  Google Scholar 

  40. U. Paulsen, B. Lindeke, Acta Pharm. Suec., 1978, 15, 264.

    CAS  PubMed  Google Scholar 

  41. J. C. Stowell, J. Org. Chem., 1971, 36, 3055.

    Article  CAS  Google Scholar 

  42. A. Weissberger, E. Proskauer, J. Riddick, E. Toops, Organic Solvents, Interscience Publishers, New York, 1955.

    Google Scholar 

  43. R. B. Grubbs, J. K. Wegrzyn, Q. Xia, Chem. Commun., 2005, 80.

    Google Scholar 

  44. B. G. Belen’kii, L. Z. Vilenchik, Khromatografiya polimerov [Chromatography of Polymers], Khimiya, Moscow, 1978, 344 pp. (in Russian).

    Google Scholar 

  45. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian 98, Rev. A.3, Pittsburgh, PA, 1998.

    Google Scholar 

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Authors and Affiliations

  1. Build. 5, 23 prosp. Gagarina, 603950, Nizhny Novgorod, Russian Federation

    E. V. Kolyakina, A. B. Alyeva, E. V. Sazonova, A. A. Shchepalov & D. F. Grishin

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  1. E. V. Kolyakina
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  2. A. B. Alyeva
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  3. E. V. Sazonova
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  4. A. A. Shchepalov
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  5. D. F. Grishin
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Correspondence to E. V. Kolyakina.

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Kolyakina, E.V., Alyeva, A.B., Sazonova, E.V. et al. Efficiency of low-molecular-weight and high-molecular-weight alkoxyamines in the synthesis of polystyrene. Russ Chem Bull 68, 1585–1598 (2019). https://doi.org/10.1007/s11172-019-2597-x

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  • DOI: https://doi.org/10.1007/s11172-019-2597-x

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