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Kinetics on the copolymerization of acrylonitrile with itaconic acid or methyl acrylate in dimethylsulfoxide by NMR spectroscopy

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Abstract

The free radical solution polymerization of acrylonitrile (AN) with itaconic acid (IA) or methyl acrylate (MA) was carried out in dimethylsulfoxide (DMSO) using 2 2'-azobisisobutyronitrile (AIBN) as the initiator. Based on the monomer conversion versus time data, the copolymerization rate was retarded by IA but promoted by MA. The monomer sequence distribution was characterized by 13C NMR to explain the significant difference in the copolymerization kinetics of the ANIA and AN-MA copolymers. The results of the copolymer composition curves and 13C NMR spectral analysis illustrated that the penultimate model was suitable for describing the copolymerization behavior of AN-IA, and the terminal and penultimate models were adequate for AN-MA. The penultimate reactivity ratios, r MA , were ~2 times higher than r IA , indicating that the reactivity of AN-terminated radical having MA as the preceding group was higher than that with IA. Then, the corresponding content of triads sequence AN-AN-AN (AAA) in the AN-MA copolymers was higher than those in the AN-IA copolymers. The appearance of new resonance signals of the quaternary and methyl carbon indicated a higher content of IA in copolymers. The higher IA concentrations the lower viscosity-average molecular weight of the polymers. The decrease in the molecular weight was correlated to the formation of the oligomers.

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References

  1. K. Sen, S. H. Bahrami, and P. Bajaj, J. Macromol. Sci. Pt. C-Polym. Rev., 36, 1 (1996).

    Article  Google Scholar 

  2. R. J. Diefendorf and E. Tokarsky, Polym. Eng. Sci., 15, 150 (1975).

    Article  CAS  Google Scholar 

  3. P. Bajaj, T. V. Sreekumar, and K. Sen, J. Appl. Polym. Sci., 86, 773 (2002).

    Article  CAS  Google Scholar 

  4. D. Godshall, P. Rangarajan, D. G. Baird, G. L. Wilkes, V. A. Bhanu, and J. E. McGrath, Polymer, 44, 4221 (2003).

    Article  CAS  Google Scholar 

  5. P. Bajaj, T. V. Sreekumar, and K. Sen, Polymer, 42, 1707 (2001).

    Article  CAS  Google Scholar 

  6. N. U. Nguyen-Thai and S. C. Hong, Macromolecules, 46, 5882 (2013).

    Article  CAS  Google Scholar 

  7. N. U. Nguyen-Thai and S. C. Hong, Carbon, 69, 571 (2014).

    Article  CAS  Google Scholar 

  8. Z. Fu, Y. Gui, S. Liu, Z. Wang, B. Liu, C. Cao, and H. Zhang, J. Appl. Polym. Sci., 131, DOI: 10.1002/app.40834 (2014).

  9. Z. Fu, Y. Gui, C. Cao, B. Liu, C. Zhou, and H. Zhang, J. Mater. Sci., 49, 2864 (2014).

    Article  CAS  Google Scholar 

  10. H. Zhang, L. Quan, and L. Xu, Fiber. Polym., 16, 263 (2015).

    Article  CAS  Google Scholar 

  11. J. Liu, Y. Huang, Y. Yuan, X. Zhang, Y. Wang, and C. Wang, Fiber. Polym., 15, 1583 (2014).

    Article  CAS  Google Scholar 

  12. V. A. Bhanu, P. Rangarajan, K. Wiles, M. Bortner, M. Sankarpandian, D. Godshall, T. E. Glass, A. K. Banthia, J. Yang, G. Wilkes, D. Baird, and J. E. McGrath, Polymer, 43, 4841 (2002).

    Article  CAS  Google Scholar 

  13. A. R. Mahdavian, M. Abdollahi, and L. Mokhtabad, J. Macromol. Sci., Pure Appl. Chem., 43, 1583 (2006).

    Article  CAS  Google Scholar 

  14. A. R. Mahdavian and M. Abdollahi, J. Appl. Polym. Sci., 103, 3253 (2007).

    Article  CAS  Google Scholar 

  15. R. Devasia, C. P. Reghunadhan. Nair, and K. N. Ninan, Eur. Polym. J., 38, 2003 (2002).

    Article  CAS  Google Scholar 

  16. D. Renjith, C. P. Reghunadhan. Nair, P. Sivadasan, and K. N. Ninan, Polymer. Int., 54, 1110 (2005).

    Article  Google Scholar 

  17. J. V. Prasada, U. S. Satpathya, M. Jassala, A. Pantara, and S. Satisha, Int. J. Polym. Mater., 18, 105 (1992).

    Article  Google Scholar 

  18. J. S. Román and A. Gallardo, Polym. Eng. Sci., 36, 1152 (1996).

    Article  Google Scholar 

  19. G. Martińez, M. Sanchez-Chaves, E. L. Madruga, and C. Fernández-Monreal, Polymer, 41, 6021 (2000).

    Article  Google Scholar 

  20. A. S. Brar and R. Kumar, Eur. Polym. J., 37, 1827 (2001).

    Article  CAS  Google Scholar 

  21. M. L. Huggins, J. Am. Chem. Soc., 64, 2716 (1942).

    Article  CAS  Google Scholar 

  22. M. Bercea, S. Morariu, C. Ioan, S. Ioan, and B. C. Simionescu, Eur. Polym. J., 35, 2097 (1999).

    Article  Google Scholar 

  23. M. Takenaka and A. F. Johnson, Polymer, 35, 3899 (1994).

    Article  CAS  Google Scholar 

  24. T. Otsu and H. Watanabe, Eur. Polym. J., 29, 167 (1993).

    Article  CAS  Google Scholar 

  25. J. Miao, Z. Cheng, M. Zhou, and D. Pan, J. Macromol. Sci. Part A-Pure Appl. Chem., 49, 869 (2012).

    Article  CAS  Google Scholar 

  26. B. S. Krumgalz and J. G. M. Barthel, Z. Phys. Chemie., 142, 167 (1984).

    Article  CAS  Google Scholar 

  27. K. Plochocka, J. Macromol. Sci. Pt. C-Polym. Rev., 20, 67 (1981).

    Google Scholar 

  28. A. Kaim, J. Polym. Sci. Pol. Chem., 38, 846 (2000).

    Article  CAS  Google Scholar 

  29. M. Takenaka, A. F. Johnson, and K. Kamide, Polymer, 35, 3899 (1994).

    Article  CAS  Google Scholar 

  30. G. S. Kapur and A. S. Brar, J. Polym. Sci. Pol. Chem., 29, 479 (1991).

    Article  CAS  Google Scholar 

  31. P. Bajaj, T. V. Sreekumar, K. Sen, R. Kumar, and A. S. Brar, J. Appl. Polym. Sci., 88, 1211 (2003).

    Article  CAS  Google Scholar 

  32. P. Bajaj, T. V. Sreekumar, and K. Sen, J. Appl. Polym. Sci., 79, 1640 (2001).

    Article  CAS  Google Scholar 

  33. N. Han, X. Gao, R. Zhang, and X. Zhang, Polym. Compos., 34, 641 (2013).

    Article  CAS  Google Scholar 

  34. J. L. Koenig, “Chemical Microstructure of Polymer Chain”, p.39, Wiley-Interscience, New York, 1980.

    Google Scholar 

  35. H. J. Harwood, J. Polym. Sci. Pt. C-Polym. Symp., 25, 37 (1968).

    Article  Google Scholar 

  36. A. S. Brar, J. Polym. Sci. Pol. Chem., 30, 2549 (1992).

    Article  CAS  Google Scholar 

  37. K. Hatada, T. Kitayama, Y. Terawaki, H. Sato, R. Chûjô, Y. Tanaka, R. Kitamaru, I. Ando, K. Hikichi, and F. Horii, Polym. J., 27, 1104 (1995).

    Article  CAS  Google Scholar 

  38. C. P. Reghunadhan Nair, Macromolecules, 26, 47 (1993).

    Article  Google Scholar 

Download references

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Authors and Affiliations

  1. Changchun Hella Automotive Lighting Ltd., Changchun, 130033, P. R. China

    Tingting Zhou

  2. Engineering Research Center of Synthetic Resin and Special Fiber, Ministry of Education, Changchun University of Technology, Changchun, 130012, P. R. China

    Jing Wang, Mingyao Zhang, Zhongyu Fu, Xiaohui Xu & Baijun Liu

Authors
  1. Jing Wang
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  2. Mingyao Zhang
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  3. Zhongyu Fu
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  4. Tingting Zhou
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  5. Xiaohui Xu
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  6. Baijun Liu
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Correspondence to Mingyao Zhang.

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Wang, J., Zhang, M., Fu, Z. et al. Kinetics on the copolymerization of acrylonitrile with itaconic acid or methyl acrylate in dimethylsulfoxide by NMR spectroscopy. Fibers Polym 16, 2505–2512 (2015). https://doi.org/10.1007/s12221-015-5573-6

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  • DOI: https://doi.org/10.1007/s12221-015-5573-6

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