Skip to main content
SpringerLink
Log in

Nonisothermal crystallization kinetics of isotactic polypropylene nucleated with a novel supported β-nucleating agent

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

The introduction of β-nucleating agent into isotactic polypropylene (iPP) is the most effective method to prepare β-iPP. In this paper, iPP nucleated with a novel highly efficient supported β-nucleating agent (NA100), calcium pimelate (CaHA) supported on the surface of nano-CaCO3, was prepared and its nonisothermal crystallization kinetic, melting characteristic, and crystallization activation energy are investigated and compared with those of pure iPP, nano-CaCO3 filled iPP, and β-nucleating agent CaHA nucleated iPP. The results indicate that addition of nano-CaCO3 increases the crystallization temperature of iPP and has no influence on the crystal form of iPP. iPP and nano-CaCO3 filled iPP mainly crystallize in the form of α-crystal. Although NA100 and CaHA induce iPP to mainly form β-crystal, NA100 nucleated iPP shows higher crystallization temperature, melting temperature, and β-phase content than that nucleated with CaHA without supports. Nonisothermal crystallization kinetic is well described by the equations of Avrami and Mo, and the crystallization activation energy was calculated from Kissinger’s method. It was found that the decreased crystallization activation energy is favorable to increase the crystallization rate and the content of β-crystal. Although the content of CaHA in 5 wt% NA100 nucleated iPP was less than that in 0.1 wt% CaHA nucleated iPP, the former formed more β-iPP than the latter, indicating that the β-nucleating agent CaHA supported on the surface of nano-CaCO3 exhibits higher efficiency for preparation of β-iPP than pure CaHA powder.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Dmytro B, Pierre P, Klaas R, Edwin B, Giovanni CA, Wim H de J. Crystallization under shear in isotactic polypropylene containing nucleators. Polymer. 2008;49:3076–83.

    Article  Google Scholar 

  2. Zhang YF. Isothermal crystallization behaviors of isotactic polypropylene nucleated with the third generation sorbitol derivative nucleating agents. J Macromol Sci Phys. 2008;47:891–9.

    Article  CAS  Google Scholar 

  3. Bai HW, Wang Y, Song B, Han L. Synergistic toughening effects of nucleating agent and ethylene-octene copolymer on polypropylene. J Appl Polym Sci. 2008;108:3270–80.

    Article  CAS  Google Scholar 

  4. Wang JB, Dou Q. Non-isothermal crystallization kinetics and morphology of isotactic polypropylene (iPP) nucleated with rosin-based nucleating agents. J Macromol Sci Phys. 2007;46:987–1001.

    Article  CAS  Google Scholar 

  5. Mai KC, Wang KF, Zeng HM. Multiple melting behavior of nucleated polypropylene. J Appl Polym Sci. 2003;88:1608–11.

    Article  CAS  Google Scholar 

  6. Wang KF, Mai KC, Zeng HM. Study on the thermal stability of heterogeneous nucleation effect of polypropylene nucleated by different nucleating agents. J Appl Polym Sci. 2002;83:1643–50.

    Article  Google Scholar 

  7. Wang KF, Mai KC, Zeng HM. Isothermal crystallization behavior and melting characteristics of injection sample of nucleated polypropylene. J Appl Polym Sci. 2000;78:2547–53.

    Article  CAS  Google Scholar 

  8. Varga J. β-modification of isotactic polypropylene: preparation, structure, processing, properties, and application. J Macromol Sci Phys. 2002;41:1121–71.

    Article  Google Scholar 

  9. Grein C. Toughness of neat, rubber modified and filled β-nucleated polypropylene: from fundamentals to applications. Adv Polym Sci. 2005;188:43–104.

    Article  CAS  Google Scholar 

  10. Garbarczyk J, Paukzta D. Influence of additives on the structure and properties of polymer. Polymer. 1981;22:562–4.

    Article  CAS  Google Scholar 

  11. Shi GY, Zhang JY, Jin HS. German Patent DE 3610644; 10 Feb 1986

  12. Shi GY, Zhang XD, Qiu Z. Crystallization kinetics of β-phase poly(propylene). Makromol Chem. 1992;193:583–91.

    Article  CAS  Google Scholar 

  13. Varga J, Schulek-Toth F, Pati M. Hungarian Patent 209132; 29 April 1992

  14. Feng JC, Chen MC, Huang ZT. Lanthanum stearate composite act as β-modification nucleating agent of isotatic polypropylene. Chem J Chin Univ. 2001;22:154–6.

    CAS  Google Scholar 

  15. 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;86:531–9.

    Article  CAS  Google Scholar 

  16. Kotek J, Raab M, Baldrian J, Grellmann WJ. The effect of specific β-nucleation on morphology and mechanical behavior of isotactic polypropylene. J Appl Polym Sci. 2002;85:1174–84.

    Article  CAS  Google Scholar 

  17. Menyhárd A, Varga J, Molnár G. Comparison of different β-nucleators for isotactic polypropylene, characterisation by DSC and temperature- modulated DSC (TMDSC) measurements. J Therm Anal Calorim. 2006;83:625–30.

    Article  Google Scholar 

  18. Varga J, Mudra I, Ehrenstein GW. Highly active thermally stable β-nucleating agents for isotactic polypropylene. J Appl Polym Sci. 1999;74:2357–68.

    Article  CAS  Google Scholar 

  19. Dou Q. Effect of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator and crystallization temperature on the production of β crystal form in isotactic polypropylene. J Appl Polym Sci. 2008;107:958–65.

    Article  CAS  Google Scholar 

  20. Wang SW, Yang W, Xu YJ, Xie BH, Yang MB, Peng XF. Crystalline morphology of β-nucleated controlled-rheology polypropylene. Polym Test. 2008;27:638–44.

    Article  CAS  Google Scholar 

  21. Lezak E, Bartczak Z. Plastic deformation behavior of β phase isotactic polypropylene in plane-strain compression at elevated temperatures. J Polym Sci Polym Phys. 2008;46:92–108.

    Article  CAS  Google Scholar 

  22. Varga J, Menyhárd A. Effect of solubility and nucleating duality of N,N′-dicyclohexyl-2,6-naphthalene dicarboxamide on the supermolecular structure of isotactic polypropylene. Macromolecules. 2007;40:2422–31.

    Article  CAS  Google Scholar 

  23. Krache R, Benavente R, Lopez-Majada JM, Perena JM, Cerrada ML, Perez E. Competition between α, β and γ polymorphs in a β-nucleated metallocenic isotactic polypropylene. Macromolecules. 2007;40:6871–8.

    Article  CAS  Google Scholar 

  24. Xiao WC, Wu PY, Feng JC, Yao RY. Influence of a novel β-nucleating agent on the structure, morphology, and nonisothermal crystallization behavior of isotactic polypropylene. J Appl Polym Sci. 2009;111:1076–85.

    Article  CAS  Google Scholar 

  25. Zhao SC, Cai Z, Xin Z. A highly active novel β-nucleating agent for isotactic polypropylene. Polymer. 2008;49:2745–54.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  28. Bai HW, Wang Y, Liu L, Zhang JH, Han L. Nonisothermal crystallization behaviors of polypropylene with α/β nucleating agents. J Polym Sci Polym Phys. 2008;46:1853–67.

    Article  CAS  Google Scholar 

  29. Zhang YF, Xin Z. Isothermal crystallization behaviors of isotactic polypropylene nucleated with α/β compounding nucleating agents. J Polym Sci Polym Phys. 2007;45:590–6.

    Article  CAS  Google Scholar 

  30. Shentu BQ, Li JP, Gan TF, Weng ZX. Influence of N,N,N′,N′-tetraalkyl terephthalamide on isothermal crystallization kinetics and morphology evolution of polypropylene. Eur Polym J. 2007;43:3036–41.

    Article  CAS  Google Scholar 

  31. Zheng S, Xin Z, Dai GC. Application of β-form nucleating agent for polypropylene II. Non-isothermal crystallization kinetics of polypropylene nucleated by β-form nucleating agent. Huadong Ligong Daxue Xuebao/J East Chin Univ Sci Tech. 2006;32:16–9.

    CAS  Google Scholar 

  32. Zhang ZS, Wang CG, Yang ZG, Mai KC. Crystallization behaviors and melting characteristics of PP nucleated by a novel supported β-nucleating agent. Polymer. 2008;49:5137–45.

    Article  CAS  Google Scholar 

  33. Zhang ZS, Tao YJ, Yang ZG, Mai KC. Preparation and characteristics of nano-CaCO3 supported β-nucleating agent of polypropylene. Eur Polym J. 2008;44:1955–61.

    Article  CAS  Google Scholar 

  34. Tjong SC, Shen JS, Li RKY. Impact fracture toughness of β-form polypropylene. Scripta Metallurgicaet Materalia. 1995;33:503–8.

    Article  CAS  Google Scholar 

  35. Karger-Kocsis J, Varga J, Ehrenstein GW. Comparison of the fracture and failure behaviour of injection molded α- and β-polypropylene in high-speed three-point bending tests. J Appl Polym Sci. 1997;64:2059–66.

    Article  Google Scholar 

  36. Varga J. Melting memory effect of the β-modification of polypropylene. J Thermal Anal Calorim. 1986;31:165–72.

    Article  CAS  Google Scholar 

  37. Varga J. β-Modification of polypropylene and its two-component systems. J Thermal Anal Calorim. 1989;35:1891–912.

    Article  CAS  Google Scholar 

  38. Varga J, Garzó G, Ille A. Kristallisation, Umkristallisation und Schmelzen der. β-Modifikation des polypropylenes. Angew Makromol Chem. 1986;142:171–81.

    Article  CAS  Google Scholar 

  39. Shi GY, Cao YH, Zhang XD, Hong J, Hua XG. Multiple melting behavior of β-crystalline phase polypropylene. Chin J Polym Sci. 1992;10:319–27.

    CAS  Google Scholar 

  40. Zhang XD, Shi GY. The effect of a β-nucleator on the crystallization and melting behavior of ethylene/propylene random and block copolymer. Thermochim Acta. 1994;235:49–59.

    Article  CAS  Google Scholar 

  41. Varga J, Schulek-Toth F. Crystallization, melting and spherulitic structure of β-nucleated random propylene copolymers. J Therm Anal Calorim. 1996;47:941–55.

    Article  CAS  Google Scholar 

  42. Yuan Q, Jiang W, An L. Study of β-α recrystallization of the polypropylene. Colloids Polym Sci. 2004;282:1236–41.

    Article  CAS  Google Scholar 

  43. Avrami M. Kinetics of phase change: I general theory. J Chem Phys. 1939;7:1103–12.

    Article  CAS  Google Scholar 

  44. Avrami M. Kinetics of phase change: II transformation-time relation for random distribution of nuclei. J Chem Phys. 1940;8:212–24.

    Article  CAS  Google Scholar 

  45. Avrami M. Kinetics of phase change. III Granulation, phase change and microstructure. J Chem Phys. 1941;9:177–84.

    Article  CAS  Google Scholar 

  46. Jeziorny A. Parameters characterizing the kinetics of the non-isothermal crystallization of poly (ethylene terphthalate) determined by DSC. Polymer. 1978;19:1142–9.

    Article  CAS  Google Scholar 

  47. Yin JG, Mo ZS. Modern polymer physics. Beijing: Science Press; 2001. p. 101–125

  48. Liu JP, Mo ZS. Crystallization kinetics of polymers. Polym Bull. 1991;4:199–207.

    Google Scholar 

  49. Kissinger HE. Variation of peak temperature with heating rate in differential thermal analysis. J Res Nat’l Bureau Stand. 1956;57:217–21.

    CAS  Google Scholar 

  50. Zhang YF, Xin Z. Isothermal and nonisothermal crystallization kinetics of isotactic polypropylene nucleated with substituted aromatic heterocyclic phosphate salts. J Appl Polym Sci. 2006;101:3307–16.

    Article  CAS  Google Scholar 

  51. Jang GU, Cho WJ, Ha CS. Crystallization behavior of polypropylene with or without sodium benzoate as a nucleating agent. J Polym Sci Polym Phys. 2001;39:1001–16.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The work was supported by Natural Science Foundation of China (Grant No. 50573094, 50873115), Project of Science and Technology of Guangdong Province, China (Grant No. 0711020600002) and Doctoral Fund of Ministry of Education of China.

Author information

Authors and Affiliations

  1. Materials Science Institute, School of Chemistry and Chemical Engineering, Key Laboratory of Polymeric Composites and Functional Materials, the Ministry of Education, Sun Yat-sen University, Guangzhou, 510275, People’s Republic of China

    Zishou Zhang, Chunyan Chen, Chunguang Wang, Jieqi Guo & Kancheng Mai

  2. Department of Chemistry, College of Zhongshan, Guangdong, People’s Republic of China

    Chunyan Chen

Authors
  1. Zishou Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chunyan Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chunguang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jieqi Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Kancheng Mai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kancheng Mai.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, Z., Chen, C., Wang, C. et al. Nonisothermal crystallization kinetics of isotactic polypropylene nucleated with a novel supported β-nucleating agent. J Therm Anal Calorim 103, 311–318 (2011). https://doi.org/10.1007/s10973-010-0946-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-010-0946-y

Keywords

Search

Navigation