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Precise molecular weight determination and structure characterization of end-functionalized polymers: An NMR approach via combination of one-dimensional and two-dimensional techniques

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Abstract

We present here the application of one-dimensional and two-dimensional NMR techniques to characterize the structure of methoxyl end-functionalized polystyrenes (PS). The peaks in 1H-NMR spectra corresponding to main-chain, side-chain and chain-end groups are assigned by 1H-1H gCOSY, 1H-13C gHSQC and gHMBC spectra. For the first time, the spin-lattice relaxation time (T 1) of protons of the chain-ends is revealed to be affected more by polymer molecular weight (MW) than by the protons of the main-chains and the side-chains (almost independent from MW). As a result, a much higher delay time (d1) for chain-ends (d1 > 20T 1) is needed for quantitative NMR measurement when using end-group estimation method to obtain the MW of PS, which is in accordance with the value estimated by GPC. An improved method for the polymer MW determination is established, by combination of different NMR techniques to distinguish the peaks, and a large d1 setting to achieve quantitative NMR analysis.

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References

  1. Rinaldi, P.L., “NMR spectroscopy of polymers in solution and in the solid state, Vol. 834”, ed. by Cheng H.N., English A.D., ACS Symposium Series, American Chemical Society, Washington DC, 2002, P. 94

  2. Hatada, K. and Kitayama, T., “NMR spectroscopy of polymers”, Springer, New York, 2004

    Book  Google Scholar 

  3. Piserchia, A., Zerbetto, M., Salvia, M.V., Salassa, G., Gabrielli, L., Mancin, F., Rastrelli, F. and Frezzato, D.J., Phys. Chem., 2015, 119(34): 20100

    CAS  Google Scholar 

  4. Li, L., Zhang, B., Wyzgoski, F., Li, X., McCord, E.F. and Rinaldi, P.L., ACS Macro Lett., 2013, 2(2): 141

    Article  CAS  Google Scholar 

  5. Tanaka, K., Oouchi, M., Hayashi, F., Maeda, H. and Waki, H., Macromolecules, 2016, 49(15): 5750

    Article  CAS  Google Scholar 

  6. Luo, X., Xie, S., Huang, W., Dai, B., Lu, B. and Yan, D., Chinese J. Polym. Sci., 2016, 34(1): 77

    Article  CAS  Google Scholar 

  7. Li, L., Xiong, C. and Chen, D., Chinese J. Polym. Sci., 2016, 34(5): 594

    Article  CAS  Google Scholar 

  8. Li, X., McCord, E.F., Baiagern, S., Fox, P., Howell, J.L., Sahoo, S.K. and Rinaldi, P.L., Magn. Reson. Chem., 2011, 49(7): 413

    Article  CAS  Google Scholar 

  9. Gong, X., Hansen, E.W. and Chen, Q., Macromol. Chem. Phys., 2011, 212(10): 1007

    Article  CAS  Google Scholar 

  10. Ye, Y., Liu, X., Xu, G., Liu, M. and Li, C., Angew. Chem. Int. Ed., 2015, 54(18): 5328

    Article  CAS  Google Scholar 

  11. Hatada, K., Kitayama, T., Ute, K., Terawaki, Y. and Yanagida, T., Macromolecules, 1997, 30(22): 6754

    Article  CAS  Google Scholar 

  12. Sunder, A., Mülhaupt, R. and Frey, H., Macromolecules, 2000, 33(2): 309

    Article  CAS  Google Scholar 

  13. Päch, M., Zehm, D., Lange, M., Dambowsky, I., Weiss, J. and Laschewsky, A., J. Am. Chem. Soc., 2010, 132(25): 8757

    Article  Google Scholar 

  14. Boschet, F., Ono, T. and Ameduri, B., Macromol. Rapid Commun., 2012, 33(4): 302

    Article  CAS  Google Scholar 

  15. Ren, Y., Wei, Z., Leng, X., Wang, Y. and Li, Y., Polymer, 2015, 78: 51

    Article  CAS  Google Scholar 

  16. Chen, S., Chen, D., Lu, M., Zhang, X., Li, H., Zhang, X., Yang, X., Li, X., Tu, Y. and Li, C.Y., Macromolecules, 2015, 48(23): 8480

    Article  CAS  Google Scholar 

  17. Wang, M., Wang, T., Yuan, K. and Du, J., Chinese J. Polym. Sci., 2016, 34(1): 44

    Article  Google Scholar 

  18. Chen, J., Chen, D., Huang, W., Yang, X., Li, X., Tu, Y. and Zhu, X., Polymer, 2016, 107: 29

    Article  CAS  Google Scholar 

  19. Seger, M.R. and Maciel, G.E., Anal. Chem., 2004, 76(19): 5734

    Article  CAS  Google Scholar 

  20. Farrar, T.C. and Becker, E.D., “Pulse and Fourier transform NMR”, Academic Press, New York, 1969

    Google Scholar 

  21. Pauli, G.F., Jaki, B.U. and Lankin, D.C., J. Nat. Prod., 2005, 68(1): 133

    Article  CAS  Google Scholar 

  22. Mambrini, G.P., Ribeiroa, C. and Colnago, L.A., Magn. Reson. Chem., 2012, 50(1): 1

    Article  CAS  Google Scholar 

  23. Heatley, F. and Wood, B., Polymer, 1978, 19(12): 1405

    Article  CAS  Google Scholar 

  24. Fang, T., Macromolecules, 1990, 23(21): 4553

    Article  CAS  Google Scholar 

  25. Roy, D., Basu, P.K., Raghunathan, P. and Eswaran, S.V., Magn. Reson. Chem., 2004, 42(1): 76

    Article  CAS  Google Scholar 

  26. Xu, Q., Chen, J., Huang, W., Qu, T., Li, X., Li, Y., Yang, X. and Tu, Y., Macromolecules, 2013, 46(18): 7274

    Article  CAS  Google Scholar 

  27. Nguyen, T.B.T., Nguyen, T.T.C., Tra, H.C., Nguyen, C.K. and Tran, N.Q., Int. J. Polym. Anal. Charact., 2015, 20(1): 57

    Article  CAS  Google Scholar 

  28. Wang, J.S. and Matyjaszewski, K., J. Am. Chem. Soc., 1995, 117(20): 5614

    Article  CAS  Google Scholar 

  29. Kato, M., Kamigaito, M., Sawamoto, M. and Higashimura, T., Macromolecules, 1995, 28(5): 1721

    Article  CAS  Google Scholar 

  30. Lutz, J.F. and Matyjaszewski, K., Macromol. Chem. Phys., 2002, 203(10-11): 1385

    Article  CAS  Google Scholar 

  31. Lutz, J.F. and Matyjaszewski, K., J. Polym. Sci., Part A: Polym. Chem., 2005, 43(4): 897

    Article  CAS  Google Scholar 

  32. Gao, L., Oh, J., Chang, T., Chen, D., Li, X., Yang, X., Tu, Y., Zhu, X. and Li, C.Y., Polymer, 2016, 101: 379

    Article  CAS  Google Scholar 

  33. Brandolini, A.J., Hills, D.D. and Vickers, T.J., “NMR spectra of polymers and polymer additives”, Marcel Dekker, Inc., New York, 2000

    Google Scholar 

  34. Kitayama, T., Hirano, T. and Hatada, K., Polym. J., 1996, 28(1): 61

    Article  CAS  Google Scholar 

  35. Bax, A., Freeman, R. and Kempsell, S.P., J. Am. Chem. Soc., 1980, 102(14): 4849

    Article  CAS  Google Scholar 

  36. Bodenhausen, G. and Ruben, D., J. Chem. Phys. Lett., 1980, 69(1): 185

    Article  CAS  Google Scholar 

  37. Huang, W., Wan, Y., Chen, J., Xu, Q., Li, X., Yang, X., Li, Y. and Tu, Y., Polym. Chem., 2014, 5(3): 945

    Article  CAS  Google Scholar 

  38. Bax, A. and Summers, M.F., J. Am. Chem. Soc., 1986, 108(8): 2093

    Article  CAS  Google Scholar 

  39. Simeral, L.S., Appl. Spectrosc., 1995, 49(3): 400

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China

    Dong-xue Chen, Ling-feng Gao, Xiao-hong Li  (李晓虹) & Ying-feng Tu  (屠迎锋)

Authors
  1. Dong-xue Chen
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  2. Ling-feng Gao
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  3. Xiao-hong Li  (李晓虹)
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  4. Ying-feng Tu  (屠迎锋)
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Corresponding authors

Correspondence to Xiao-hong Li  (李晓虹) or Ying-feng Tu  (屠迎锋).

Additional information

This work was financially supported by the National Natural Science Foundation of China (Nos. 21274099, 21305098 and 21474067) and the Priority Academic Program Development of Jiangsu High Education Institutions.

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10118_2017_1919_MOESM1_ESM.pdf

Precise Molecular Weight Determination and Structure Characterization of End-functionalized Polymers: An NMR Approach via Combination of One-dimensional and Two-dimensional Techniques

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Chen, Dx., Gao, Lf., Li, Xh. et al. Precise molecular weight determination and structure characterization of end-functionalized polymers: An NMR approach via combination of one-dimensional and two-dimensional techniques. Chin J Polym Sci 35, 681–692 (2017). https://doi.org/10.1007/s10118-017-1919-4

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  • DOI: https://doi.org/10.1007/s10118-017-1919-4

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