The relation between chemical structure of branched amide nucleating agents and nucleation effect in isotactic polypropylene

Abstract

The relation between chemical structure of branched amide compounds as nucleating agents and the nucleation effect of them in isotactic polypropylene (iPP) was investigated through studying the crystallization and melting behavior of iPP nucleated with these nucleating agents by differential scanning calorimetry (DSC). The crystallization peak temperature (Tc) of nucleated iPP had different degrees of increase after the amide groups were introduced into the benzene ring. The nucleation efficiency of 1,3,5-benzenetrisamide was superior to that of terephthalamide due to the existence of benzamide. At the same time, the nucleation effect of different side chain-substituted amide compounds on iPP was investigated. The results showed that the crystallization peak temperature of iPP nucleated with ring-substituted amides was higher than that of iPP nucleated with chain-substituted amides, that of the 6-membered ring-substituted amides was better than that of the five-membered ring-substituted amides and that of the cyclohexyl group substitution was superior to that of the benzene ring. Besides, the amide compounds with different central group were also studied as iPP nucleating agents. The results show that the sequence of nucleating efficiency from high to low is six carbons > benzene >  ten carbons. In addition, the optimum contents of 1,3,5-benzenetricarboxylic acid tris(cyclopentylamine) (BTA-CP), 1,3,5-benzenetricarboxylic acid tris(tert-pentylamine) (BTA-TP) and 1,3,5-benzenetricarboxylic acid tris(iso-pentylamine) (BTA-IP) in iPP were 0.20 mass%, 0.20 mass% and 0.15 mass%, respectively. Under the optimum content of BTA-CP, BTA-TP and BTA-IP, the crystallization peak temperature of nucleated iPP was increased from 117.6 °C of pure iPP to 127.2°C, 125.7°C and 123.4 °C, respectively.

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

References

  1. 1.

    Zhang YF, Li D, Chen QJ. Preparation and nucleation effects of nucleating agent hexahydrophthalic acid metal salts for isotactic polypropylene. Colloid Polym Sci. 2017;295(10):1973–82.

    CAS  Article  Google Scholar 

  2. 2.

    Zhang YF, Hou HH, Guo LH. Effects of cyclic carboxylate nucleating agents on nucleus density and crystallization behavior of isotactic polypropylene. J Therm Anal Calorim. 2018;131(2):1483–90.

    CAS  Article  Google Scholar 

  3. 3.

    Liu L, Ren Z, Xiao C, He B, Dong H, Yan S, Wang Z. Epitaxially-crystallized oriented naphthalene bis (dicarboximide) morphology for significant performance improvement of electron-transporting thin-film transistors. Chem Commun. 2016;52(27):4902–5.

    CAS  Article  Google Scholar 

  4. 4.

    Zhang YF, Lin XF, Li Y, et al. Synergistic nucleation effect of calcium sulfate whisker and β-nucleating agent dicyclohexyl-terephthalamide in isotactic polypropylene. J Therm Anal Calorim. 2020;139(1):343–52.

    CAS  Article  Google Scholar 

  5. 5.

    Wittmann JC, Lotz B. Epitaxial crystallization of polymers on organic and polymeric substrates. Prog Polym Sci. 1990;15(6):909–48.

    CAS  Article  Google Scholar 

  6. 6.

    Libster D, Aserin A, Garti N. A novel dispersion method comprising a nucleating agent solubilized in a microemulsion, in polymeric matrix I. Dispersion method and polymer characterization. J Colloid Interface Sci. 2006;302(1):322–9.

    CAS  Article  Google Scholar 

  7. 7.

    Zhang YF, Chen H. Effects of nucleating agent 1, 3, 5-benzenetricarboxylic acid tris (cyclohexylamide) on properties and crystallization behaviors of isotactic polypropylene. Colloid Polym Sci. 2014;292(2):493–8.

    CAS  Article  Google Scholar 

  8. 8.

    Hou WM, Liu G, Zhou JJ, Gao X, Li Y, Li L, Zhao LQ. The influence of crystal structures of nucleating agents on the crystallization behaviors of isotactic polypropylene. Colloid Polym Sci. 2006;285(1):11–7.

    CAS  Article  Google Scholar 

  9. 9.

    Housmans JW, Gahleitner M, Peters GW, Meijer HE. Structure–property relations in molded, nucleated isotactic polypropylene. Polymer. 2009;50(10):2304–19.

    CAS  Article  Google Scholar 

  10. 10.

    Zhang YF, Luo XX, Zhu L, Yang XJ, Chang Y. Effects of α/β compound nucleating agents on mechanical properties and crystallization behaviors of isotactic polypropylene. J Macromol Sci Part B. 2012;51(12):2352–60.

    CAS  Article  Google Scholar 

  11. 11.

    Zhao SC, Xin Z. Nucleation characteristics of the α/β compounded nucleating agents and their influences on crystallization behavior and mechanical properties of isotactic polypropylene. J Polym Sci Part B: Polym Phys. 2010;48(6):653–65.

    CAS  Article  Google Scholar 

  12. 12.

    Lotz B, Wittmann JC, Lovinger AJ. Structure and morphology of poly(propylenes): a molecular analysis. Polymer. 1996;37(22):4979–92.

    CAS  Article  Google Scholar 

  13. 13.

    Lotz B. A new ε crystal modification found in stereodefective isotactic polypropylene samples. Macromolecules. 2014;47(21):7612–24.

    CAS  Article  Google Scholar 

  14. 14.

    Padden FJ, Keith HD. Spherulitic crystallization in polypropylene. J Appl Phys. 1959;30(10):1479–84.

    CAS  Article  Google Scholar 

  15. 15.

    Kressler J. Gamma-phase of isotactic polypropylene. Polypropylene, 1999.

  16. 16.

    Varga J, Karger-Kocsis J. The occurence of transcrystallization or row-nucleated cylindritic crystallization as a result of shearing in a glass-fiber-reinforced polypropylene. Compos Sci Technol. 1993;48(1–4):191–8.

    CAS  Article  Google Scholar 

  17. 17.

    Varga J, Karger-Kocsis J. Rules of supermolecular structure formation in sheared isotactic polypropylene melts. J Polym Sci, Part B: Polym Phys. 2015;34(4):657–70.

    Article  Google Scholar 

  18. 18.

    Pantani R, Coccorullo I, Volpe V, Titomanlio G. Shear-induced nucleation and growth in isotactic polypropylene. Macromolecules. 2010;43(21):9030–8.

    CAS  Article  Google Scholar 

  19. 19.

    Byelov D, Panine P, Remerie K, Biemond E, Alfonso GC, deJeu WH. Crystallization under shear in isotactic polypropylene containing nucleators. Polymer. 2008;49(13–14):3076–83.

    CAS  Article  Google Scholar 

  20. 20.

    Zhang N, Zhang Q, Wang K, Deng H, Fu Q. Combined effect of β-nucleating agent and multi-walled carbon nanotubes on polymorphic composition and morphology of isotactic polypropylene. J Therm Anal Calorim. 2012;107(2):733–43.

    CAS  Article  Google Scholar 

  21. 21.

    Yi QF, Wen XJ, Dong JY, Han CC. A novel effective way of comprising a β-nucleating agent in isotactic polypropylene (iPP): polymerized dispersion and polymer characterization. Polymer. 2008;49(23):5053–63.

    CAS  Article  Google Scholar 

  22. 22.

    Varga J, Menyhárd A. Effect of solubility and nucleating duality of N, N’-dicyclohexyl-2,6-naphthalenedicarboxamide on the supermolecular structure of isotactic polypropylene. Macromolecules. 2007;40(40):2422–31.

    CAS  Article  Google Scholar 

  23. 23.

    Varley RJ, Dell’Olio M, Yuan Q, Khor S, Leong KH, Bateman S. Different β nucleants and the resultant microstructural, fracture, and tensile properties for filled and unfilled ISO polypropylene. J Appl Polym Sci. 2013;128(1):619–27.

    CAS  Article  Google Scholar 

  24. 24.

    Thierry A, Straupé C, Wittmann JC, Lotz B. Organogelators and polymer crystallisation. Macromol Symp. 2006;241(1):103–10.

    CAS  Article  Google Scholar 

  25. 25.

    Marco C, Gomez MA, Ellis G, Arribas JM. Activity of a β-nucleating agent for isotactic polypropylene and its influence on polymorphic transitions. J Appl Polym Sci. 2002;86(3):531–9.

    CAS  Article  Google Scholar 

  26. 26.

    Fanegas N, Gómez MA, Marco C, Jiménez I, Ellis G. Influence of a nucleating agent on the crystallization behaviour of isotactic polypropylene and elastomer blends. Polymer. 2007;48(18):5324–31.

    CAS  Article  Google Scholar 

  27. 27.

    Ma YJ, Xin M, Xu K, Chen M. A novel β-nucleating agent for isotactic polypropylene. Polym Int. 2013;62(5):744–50.

    CAS  Article  Google Scholar 

  28. 28.

    Kang J, Weng G, Chen Z, Chen J, Cao Y, Yang F, Xiang M. New understanding in the influence of melt structure and β-nucleating agents on the polymorphic behavior of isotactic polypropylene. RSC Adv. 2014;4(56):29514–26.

    CAS  Article  Google Scholar 

  29. 29.

    Kang J, Wang B, Peng H, Li J, Chen J, Gai J, Xiang M. Investigation on the dynamic crystallization and melting behavior of β-nucleated isotactic polypropylene with different stereodefect distribution-the role of dual-selective β-nucleation agent. Adv Polym Technol. 2014;25(1):97–107.

    CAS  Article  Google Scholar 

  30. 30.

    Varga J, Stoll K, Menyhárd A, Zs Horváth. Crystallization of isotactic polypropylene in the presence of a β-nucleating agent based on a trisamide of trimesic acid. J Appl Polym Sci. 2011;121:1469–80.

    CAS  Article  Google Scholar 

  31. 31.

    Horváth F, Gombár T, Varga J, Menyhárd A. Crystallization, melting, supermolecular structure and properties of isotactic polypropylene nucleated with dicyclohexyl-terephthalamide. J Therm Anal Calorim. 2017;128:925–35.

    Article  Google Scholar 

  32. 32.

    Xiao WC, Wu PY, Feng JC. Effect of β-nucleating agents on crystallization and melting behavior of isotactic polypropylene. J Appl Polym Sci. 2008;108(5):3370–9.

    CAS  Article  Google Scholar 

  33. 33.

    Zhang YF, Chen H, Liu BB, Gu YH, Li XX. Isothermal and non-isothermal crystallization of isotactic polypropylene nucleated with 1, 3, 5-benzenetricarboxylic acid tris (cyclohexylamide). Thermochim Acta. 2014;590:226–31.

    CAS  Article  Google Scholar 

  34. 34.

    Schmidt HW, Smith P, Blomenhofer M Polypropylene resin compositions. US Patent, US 7235191, 2007.

  35. 35.

    Blomenhofer M, Ganzleben S, Hanft D, Schmidt HW, Kristiansen M, Smith P, Hoffmann K. “Designer” nucleating agents for polypropylene. Macromolecules. 2005;38(9):3688–95.

    CAS  Article  Google Scholar 

  36. 36.

    Hanna LA, Hendra PJ, Maddams W, Willis HA, Zichy V, Cudby MEA. Vibrational spectroscopic study of structural changes in isotactic polypropylene below the melting point. Polymer. 1988;29(10):1843–7.

    CAS  Article  Google Scholar 

  37. 37.

    Kristiansen M, Smith P, Chanzy H, Baerlocher C, Gramlich V, McCusker L, Schmidt HW. Structural aspects of 1,3,5-benzenetrisamides-a new family of nucleating agents. Cryst Growth Des. 2009;9(6):2556–8.

    CAS  Article  Google Scholar 

  38. 38.

    Zhang YF, Zhou PZ, Guo LH, Hou HH. The relationship between crystal structure and nucleation effect of 1,3,5-benzenetricarboxylic acid tris(phenylamide) in isotactic polypropylene. Colloid Polym Sci. 2017;295(4):1–8.

    Google Scholar 

  39. 39.

    Nagarajan V, Pedireddi VR. Gelation and structural transformation study of some 1, 3, 5-benzenetricarbx amide derivatives. Cryst Growth Des. 2014;14(4):1895–901.

    CAS  Article  Google Scholar 

  40. 40.

    Xu T, Wang Y, Xu Y, Cao W, Liu C, Shen C. Crystallization behavior and nucleation analysis of isotactic polypropylene with a multiamide nucleating agent. Polym Test. 2014;36:62–8.

    CAS  Article  Google Scholar 

  41. 41.

    Abraham F, Schmidt HW. 1, 3, 5-benzenetrisamide based nucleating agents for poly (vinylidene fluoride). Polymer. 2010;51(4):913–21.

    CAS  Article  Google Scholar 

  42. 42.

    Abraham F, Ganzleben S, Hanft D, Smith P, Schmidt HW. Synthesis and structure-efficiency relations of 1, 3, 5-benzene trisamides as nucleating agents and clarifiers for isotactic poly (propylene). Macromol Chem Phys. 2010;211(2):171–81.

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by Hunan Provincial Natural Science Foundation of China (No. 2019JJ40294).

Author information

Affiliations

Authors

Corresponding author

Correspondence to Yue-Fei Zhang.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Xia, M., Zhang, Y. The relation between chemical structure of branched amide nucleating agents and nucleation effect in isotactic polypropylene. J Therm Anal Calorim (2020). https://doi.org/10.1007/s10973-020-09860-z

Download citation

Keywords

  • Branched amide compound
  • Structure
  • Nucleating agent
  • Nucleation effect
  • Isotactic iPP
  • Aliphatic C5