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Direct Determination of Interchain Transfer Constants for Radical Polymerization of Benzyl Acrylate by RAFT Polymerization and Polymer Chromatography

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Abstract

Chain transfer reactions are important side reactions in the radical polymerization of acrylates. Discrimination between interchain and intrachain transfer is still a challenge for the study of interchain transfer. A prepolymer, poly(benzyl acrylate) with hydroxy terminals (HO-PBzA), was designed and used in the reversible addition-fragmentation chain transfer (RAFT) polymerization of BzA to measure the interchain transfer degree, with benzyl N-carbazole dithiocarbamate (BCBD) as the RAFT agent. Liquid chromatography at critical conditions was used to separate and measure interchain transfer products and then BzA interchain transfer constants (Ctr) at different temperatures determined without other kinetic parameters. Experimental results showed that experimental parameters in RAFT polymerization, except the high dosage of BCBD, had no significant effects on the measured Ctr, which showed good repeatability. The Ctr of benzyl acrylate at 100–120 °C was in the order of 1−2×10−4 and the activation energy of Ctr was at 31.1 kJ·mol−1.

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References

  1. T. Inui, E. Sato, and A. Matsumoto, RSC Adv., 4, 24719 (2014).

    Article  CAS  Google Scholar 

  2. J. Song, C. M. Thurber, S. Kobayashi, A. M. Baker, C. W. Macosko, and H. C. Silvis, Polymer, 53, 3636 (2012).

    Article  CAS  Google Scholar 

  3. S. Kar, D. Gupta, A. K. Banthia, and D. Ratna, Polym. Int., 52, 1332 (2003).

    Article  CAS  Google Scholar 

  4. S. L. Tomić, M. M. Babić, K. M. Antić, J. S. Jovašević Vuković, N. B. Malešić, and J. M. Filipović, Macromol. Res., 22, 1203 (2014).

    Article  Google Scholar 

  5. A. Veloso, W. García, A. Agirre, N. Ballard, F. Ruipérez, J. C. de la Cal, and J. M. Asua, Polym. Chem., 6, 5437 (2015).

    Article  CAS  Google Scholar 

  6. R. Balic, C. M. Fellows, and A. M. van Herk, Macromol. Res., 12, 325 (2004).

    Article  CAS  Google Scholar 

  7. S. Srinivasan, M. W. Lee, M. C. Grady, M. Soroush, and A. M. Rappe, J. Phys. Chem. A, 113, 10787 (2009).

    Article  CAS  Google Scholar 

  8. R. Guo, Y. Yao, S. Bai, Y. Wang, S. Shi, and J. Zhang, Polym. Chem., 8, 3560 (2017).

    Article  CAS  Google Scholar 

  9. A. N. Nikitin, R. A. Hutchinson, G. A. Kalfas, J. R. Richards, and C. Bruni, Macromol. Theory Simul., 18, 247 (2009).

    Article  CAS  Google Scholar 

  10. S. Hamzehlou, N. Ballard, Y. Reyes, A. Aguirre, J. M. Asua, and J. R. Leiza, Polym. Chem., 7, 2069 (2016).

    Article  CAS  Google Scholar 

  11. S. Laki, A. A. Shamsabadi, H. Riazi, M. C. Grady, A. M. Rappe, and M. Soroush, Ind. Eng. Chem. Res., 59, 2621 (2019).

    Article  Google Scholar 

  12. A. N. F. Peck and R. A. Hutchinson, Macromolecules, 37, 5944 (2004).

    Article  CAS  Google Scholar 

  13. N. Ballard and J. M. Asua, Prog. Polym. Sci., 79, 40 (2018).

    Article  CAS  Google Scholar 

  14. Y. W. Marien, P. H. M. Van Steenberge, K. B. Kockler, C. B. Kowollik, M. F. Reyniers, D. R. D’Hooge and G. B. Marin, Polym. Chem., 7, 6521 (2016).

    Article  CAS  Google Scholar 

  15. X. Yu and L. J. Broadbelt, Macromol. Theory Simul., 21, 461 (2012).

    Article  CAS  Google Scholar 

  16. H. Kattner and M. Buback, Macromolecules, 49, 3716 (2016).

    Article  CAS  Google Scholar 

  17. P. Castignolles, R. Graf, M. Parkinson, M. Wilhelm, and M. Gaborieau, Polymer, 50, 2373 (2009).

    Article  CAS  Google Scholar 

  18. G. Arzamendi and J. R. Leiza, Ind. Eng. Chem. Res., 47, 5934 (2008).

    Article  CAS  Google Scholar 

  19. S. Y. Yu-Su, F. C. Sun, S. S. Sheiko, D. Konkolewicz, H. I. Lee, and K. Matyjaszewski, Macromolecules, 44, 5928 (2011).

    Article  CAS  Google Scholar 

  20. C. Farcet, J. Belleney, B. Charleux, and R. Pirri, Macromolecules, 35, 4912 (2002).

    Article  CAS  Google Scholar 

  21. C. Former, J. Castro, C. M. Fellows, R. I. Tanner, and R. G. Gilbert, J. Polym. Sci., Part A: Polym. Chem., 40, 3335 (2002).

    Article  CAS  Google Scholar 

  22. D. Boschmann and P. Vana, Macromolecules, 40, 2683 (2007).

    Article  CAS  Google Scholar 

  23. C. Plessis, G. Arzamendi, J. R. Leiza, J. M. Alberdi, H. A. S. Schoonbrood, D. Charmot, and J. M. Asua, J. Polym. Sci., Part A: Polym. Chem., 39, 1106 (2001).

    Article  CAS  Google Scholar 

  24. N. M. Ahmad, B. Charleux, C. Farcet, C. J. Ferguson, S. G. Gaynor, B. S. Hawkett, F. Heatley, B. Klumperman, D. Konkolewicz, P. A. Lovell, K. Matyjaszewski, and R. Venkatesh, Macromol. Rapid Commun., 30, 2002 (2009).

    Article  CAS  Google Scholar 

  25. N. M. Ahmad, F. Heatley, and P. A. Lovell, Macromolecules, 31, 2822 (1998).

    Article  CAS  Google Scholar 

  26. N. Ballard, S. Hamzehlou, and J. M. Asua, Macromolecules, 49, 5418 (2016).

    Article  CAS  Google Scholar 

  27. W. Radke, S. Lee, and T. Chang, J. Sep. Sci., 33, 3578 (2010).

    Article  CAS  Google Scholar 

  28. Y. Brun and P. Foster, J. Sep. Sci., 33, 3501 (2010).

    Article  CAS  Google Scholar 

  29. Y. Brun and P. Alden, J. Chromatogr. A, 966, 25 (2002).

    Article  CAS  Google Scholar 

  30. Y.-Z. Wei, R.-X. Zhuo, and X.-L. Jiang, J. Chromatogr. A, 1447, 122 (2016).

    Article  CAS  Google Scholar 

  31. Y. Wei, R. Zhuo, and X. Jiang, J. Sep. Sci., 39, 4305 (2016).

    Article  CAS  Google Scholar 

  32. M. I. Malik, P. Sinha, G. M. Bayley, P. E. Mallon, and H. Pasch, Macromol. Chem. Phys., 212, 1221 (2011).

    Article  CAS  Google Scholar 

  33. X. Jiang, P. J. Schoenmakers, X. Lou, V. Lima, J. L. van Dongen, and J. Brokken-Zijp, J. Chromatogr. A, 1055, 123 (2004).

    Article  CAS  Google Scholar 

  34. K. Kim, J. Ahn, M. Park, H. Lee, Y. J. Kim, T. Chang, H. B. Jeon, and H.-J. Paik., Macromolecules, 52, 7448 (2019).

    Article  CAS  Google Scholar 

  35. Y. Zhu, Y. Xue, X. Li, J. Zhang, and R. Guo, Polym. Chem., 10, 2073 (2019).

    Article  CAS  Google Scholar 

  36. R. Guo, M. Zhang, Y. Xue, and S. Zhang, Journal of Tianjin University Science and Technology, 54, 687 (2021).

    Google Scholar 

  37. J. Zhang, A. Dong, T. Cao, and R. Guo, Eur. Polym. J., 44, 1071 (2008).

    Article  CAS  Google Scholar 

  38. T. G. Ribelli, K. F. Augustine, M. Fantin, P. Krys, R. Poli, and K. Matyjaszewski, Macromolecules, 8, 7920 (2017).

    Article  Google Scholar 

  39. Y. Nakamura, R. Lee, M. L. Coote, and S. Yamago, Macromol. Rapid Commun., 37, 805 (2016).

    Article  CAS  Google Scholar 

  40. X. Li, Y. Xue, X, Ma, and R. Guo, Macromol. Chem. Phys., DOI: https://doi.org/10.1002/macp.202100074 (2021).

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Authors and Affiliations

  1. Department of Polymer Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, P. R. China

    Yang Xue, Xiaohua Li, Shixian Zhang & Ruiwei Guo

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  1. Yang Xue
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  2. Xiaohua Li
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  3. Shixian Zhang
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  4. Ruiwei Guo
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Correspondence to Ruiwei Guo.

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Supporting information

Information is available regarding the GPC spectra of RPBzAs with different DP0 (detected at 360 nm), 13C and 1H NMR spectra of HO-PBzA GPC spectra of HO-PBzA and LCCC of RPBzA with different MW (detected at 360 nm). The materials are available via the Internet at http://www.springer.com/13233.

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Xue, Y., Li, X., Zhang, S. et al. Direct Determination of Interchain Transfer Constants for Radical Polymerization of Benzyl Acrylate by RAFT Polymerization and Polymer Chromatography. Macromol. Res. 29, 477–486 (2021). https://doi.org/10.1007/s13233-021-9057-9

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  • DOI: https://doi.org/10.1007/s13233-021-9057-9

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