Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Perpendicular orientation between dispersed rubber and polypropylene molecules in an oriented sheet

Abstract

An immiscible blend of isotactic polypropylene (PP) and ethylene-butene-1 copolymer (EB) (PP/EB = 70/30) containing a small amount of N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide as a nucleating agent for β-form crystals was prepared by T-die extrusion. We successfully prepared an extruded sheet in which the orientation of the PP molecules is perpendicular to the deformation of the EB particles, i.e., the β-form crystals of PP are predominantly oriented perpendicular to the flow direction of the sheet plane (the transverse direction, TD), whereas the EB droplets are strongly deformed in the flow direction. It should be noted that EB barely affects the crystalline form and orientation of PP. This extraordinary structure provides unique mechanical anisotropy. The tear strength of the TD sample is significantly enhanced by the anomalous crack propagation in the machine direction (MD). Moreover, the anisotropy in tensile properties, such as the Young’s modulus, yield stress, strain at break, and dynamic tensile modulus, is reduced.

This is a preview of subscription content, access via your institution

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

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

References

  1. Bates FS, Fredrickson GH. Conformational asymmetry and polymer-polymer thermodynamics. Macromolecules. 1994;27: 1065–7.

    Article  CAS  Google Scholar 

  2. Yamaguchi M, Miyata H, Nitta K-H. Compatibility of binary blends of polypropylene with ethylene-α-olefin copolymer. J Appl Polym Sci. 1996;62:87–97.

    Article  CAS  Google Scholar 

  3. Weimann PA, Jones TD, Hillmyer MA, Bates FS, Londono JD, Melnichenko Y, Wignall GD, Almdal K. Phase behavior of isotactic polypropylene-poly(ethylene/ethylethylene) random copolymer blends. Macromolecules. 1997;30:3650–7.

    Article  CAS  Google Scholar 

  4. Carriere CJ, Silvis HC. The effects of short-chain branching and comonomer type on the interfacial tension of polypropylene-polyolefin elastomer blends. J Appl Polym Sci. 1997;66:1175–81.

    Article  CAS  Google Scholar 

  5. Yamaguchi M, Nitta K-H, Miyata H, Masuda T. Rheological properties for binary blends of i-PP and ethylene-1-hexene copolymer. J Appl Polym Sci. 1997;63:467–74.

    Article  CAS  Google Scholar 

  6. Yamaguchi M, Miyata H, Nitta K-H. Structure and properties for binary blends of isotactic polypropylene with ethylene-α-olefin copolymer. 1. Crystallization and morphology. J Polym Sci B Polym Phys. 1997;35:953–61.

    Article  CAS  Google Scholar 

  7. Thomann Y, Suhm J, Thomann R, Bar G, Maier RD, Mülhaupt R. Investigation of morphologies of one- and two-phase blends of isotactic poly(propene) with random poly(ethane-co-1-butene). Macromolecules. 1998;31:5441–9.

    Article  CAS  Google Scholar 

  8. Lohse DJ, Graessley WW. Thermodynamics of polyolefin blends. In: Paul DR, Bucknall CB editors. Ch. 8. John Wiley & Sons, New York, NY, USA:John Wiley & Sons;1999. p. 219–37.

  9. Yamaguchi M, Miyata H. Influence of stereoregularity of polypropylene on miscibility with ethylene-1-hexene copolymer. Macromolecules. 1999;32:5911–6.

    Article  CAS  Google Scholar 

  10. Yamaguchi M, Suzuki K-I, Miyata H. Structure and mechanical properties for binary blends of polypropylene and ethylene-1-hexene copolymer. J. Polym. Sci. B Polym Phys. 1999;37: 701–13.

    Article  CAS  Google Scholar 

  11. Bedia EL, Murakami S, Senoo K, Kohjiya S. Structural development and mechanical properties on immiscible and miscible blends from isotactic polypropylene and ethylene-1-hexene copolymers under uniaxial drawing. Polym (Guildf). 2002;43:749–55.

    Article  CAS  Google Scholar 

  12. Jones TD, Chaffin KA, Bates FS. Effect of tacticity on coil dimensions and thermodynamic properties of polypropylene. Macromolecules. 2002;35:5061–8.

    Article  CAS  Google Scholar 

  13. Pasquini N. Polypropylene morphology. In: Pasquini N, editor. Ch. 3. 2nd ed. Hanser, Munich, Germany:Hanser; 2005. p. 153–94.

  14. Lohse DJ. The Influence of chemical structure on polyolefin melt rheology and miscibility. J Macromol Sci Polym Rev. 2005;45: 289–308.

    Article  Google Scholar 

  15. Nitta KH, Yamaguchi M. Morphology and mechanical properties in iPP/polyolefin-based copolymer blend. In: Nwabunma D, Kyu T, editors. Ch. 9. New Jersey, USA: John Wiley & Sons; 2008. p. 224–68.

  16. Yang J, White JL. Crystallization behavior of polypropylene/ethylene-butene copolymer blends. J Appl Polym Sci. 2012;126:2049–58.

    Article  CAS  Google Scholar 

  17. Xu J, Mittal V, Bates FS. Toughened isotactic polypropylene: Phase behavior and mechanical properties of blends with strategically designed random copolymer modifiers. Macromolecules. 2016;49:6497–506.

    Article  CAS  Google Scholar 

  18. Lin Y, Chen H, Chan C-M, Wu J. High impact toughness polypropylene/CaCO3 nanocomposites and the toughening mechanism. Macromolecules. 2008;41:9204–13.

    Article  CAS  Google Scholar 

  19. Wiwattananukul R, Fan B, Yamaguchi M. Improvement of rigidity for rubber-toughened polypropylene via localization of carbon nanotubes. Comp Sci Technol. 2017;141:106–12.

    Article  CAS  Google Scholar 

  20. Feng Y, Jin X, Hay JN. Effect of nucleating agent addition on crystallization of isotactic polypropylene. J Appl Polym Sci. 1998;69:2089–95.

    Article  CAS  Google Scholar 

  21. 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 

  22. Jang G-S, Cho W-J, Ha C-S. Crystallization behavior of polypropylene with or without sodium benzoate as a nucleating agent. J Polym Sci B Polym Phys. 2001;39:1001–16.

    Article  CAS  Google Scholar 

  23. 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 

  24. Zhu P-W, Tung J, Phillips A, Edward G. Morphological development of oriented isotactic polypropylene in the presence of a nucleating agent. Macromolecules. 2006;39:1821–31.

    Article  CAS  Google Scholar 

  25. Liu M, Guo B, Du M, Chen F, Jia D. Halloysite nanotubes as a novel β-nucleating agent for isotactic polypropylene. Polym (Guildf). 2009;50:3022–30.

    Article  CAS  Google Scholar 

  26. Kerscha M, Schmidtb HW, Altstädta V. Influence of different beta-nucleating agents on the morphology of isotactic polypropylene and their toughening effectiveness. Polym (Guildf). 2016;98:320–6.

    Article  Google Scholar 

  27. Romankiewicz A, Sterzynski T, Brostow W. Structural characterization of α- and β-nucleated isotactic polypropylene. Polym Int. 2004;53:2086–91.

    Article  CAS  Google Scholar 

  28. 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 B. 2012;51:2352–60.

    Article  CAS  Google Scholar 

  29. Phulkerd P, Arayachukeat S, Huang T, Inoue T, Nobukawa S, Yamaguchi M. Melting point elevation of isotactic polypropylene. J Macromol Sci B. 2014;53:1222–30.

    Article  CAS  Google Scholar 

  30. Uchiyama Y, Iwasaki S, Ueoka C, Fukui T, Okamoto K, Yamaguchi M. Molecular orientation and mechanical anisotropy of polypropylene sheet containing N,N’-dicyclohexyl-2,6-naphthalenedicarboxamide. J Polym Sci B Polym Phys. 2009;47:424–33.

    Article  CAS  Google Scholar 

  31. Yamaguchi M, Fukui T, Okamoto K, Sasaki S, Uchiyama Y, Ueoka C. Anomalous molecular orientation of isotactic polypropylene sheet containing N,N’-dicyclohexyl-2,6-naphthalenedicarboxamide. Polym (Guildf). 2009;50:1497–504.

    Article  CAS  Google Scholar 

  32. Yamaguchi M, Irie Y, Phulkerd P, Hagihara H, Hirayama S, Sasaki S. Plywood-like structure of injection-moulded polypropylene. Polym (Guildf). 2010;51:5983–9.

    Article  CAS  Google Scholar 

  33. Phulkerd P, Nobukawa S, Uchiyama Y, Yamaguchi M. Anomalous mechanical anisotropy of β form polypropylene sheet with N,N’-dicyclohexyl-2,6-naphthalene- dicarboxamide. Polym (Guildf). 2011;52:4867–72.

    Article  CAS  Google Scholar 

  34. Phulkerd P, Hagihara H, Nobukawa S, Uchiyama Y, Yamaguchi M. Plastic deformation behavior of polypropylene sheet with transversal orientation. J Polym Sci B Polym Phys. 2013;51: 897–906.

    Article  CAS  Google Scholar 

  35. Phulkerd P, Hirayama S, Nobukawa S, Inoue T, Yamaguchi M. Structure and mechanical anisotropy of injection-molded polypropylene with a plywood structure. Polym J. 2014;46:226–33.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  37. Grein C, Gahleitner M. On the influence of nucleation on the toughness of iPP/EPR blends with different rubber molecular architectures. Express Polym Lett. 2008;2:392–7.

    Article  CAS  Google Scholar 

  38. Chen Y, Yang S, Yang H, Zhang M, Zhang Q, Li Z. Toughness reinforcement in carbon nanotube-filled high impact polypropylene copolymer with β‑nucleating agent. Ind Eng Chem Res. 2016;55:8733–42.

    Article  CAS  Google Scholar 

  39. Sato S, Maeda T, Yamaguchi M. Control of chain orientation in blends of polypropylene and polybutene-1. Macromol Mater Eng. 2017;302:1600413–1600421.

    Article  Google Scholar 

  40. Li JX, Cheung WL, Jia D. A study on the heat of fusion of β-polypropylene. Polym (Guildf). 1999;40:1219–22.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Panitha Phulkerd.

Ethics declarations

Conflict of interest

The authors declare that they have no competing financial interests.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Phulkerd, P., Funahashi, Y., Ito, A. et al. Perpendicular orientation between dispersed rubber and polypropylene molecules in an oriented sheet. Polym J 50, 309–318 (2018). https://doi.org/10.1038/s41428-017-0017-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-017-0017-3

Search

Quick links