Effect of a smectic liquid crystal polymer as new β-nucleating agent on crystallization structure, melting, and rheological behavior of isotactic polypropylene

Abstract

A smectic liquid crystal polysiloxane containing cholesteryl groups (SLCP-NA) was synthesized and used as a new kind of β-nucleating agent to induce the formation of β-crystal in isotactic polypropylene (iPP). The nucleating ability of SLCP-NA was investigated using wide-angle X-ray diffraction and differential scanning calorimetry. The content of SLCP-NA and crystallization temperature could lead to substantial changes to crystallization behavior of iPP. As the SLCP-NA content and crystallization temperature increased, the relative content of β-crystal (Kβ) tended to first increase and then decrease. The Kβ value reached a maximum value of 66.3% when the mass fraction of SLCP-NA and the crystallization temperature were 0.2 wt% and 120 °C, respectively. In addition, the rheological behavior of the iPP/SLCP-NA blends was studied. Exhilaratingly, a little mass fraction of SLCP-NA was found to greatly improve the flow ability of the blends, and the melt flow rate increased from 2.9 g/10 min of pure iPP to 43.9 g/10 min of the iPP blend with 0.3 wt% SLCP-NA. Moreover, the addition of SLCP-NA could decrease temperature sensitivity and increase shear sensitivity.

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References

  1. 1.

    Padden JFJ, Keith HD (1959) Spherulitic crystallization in polypropylene. J Appl Phys 30(10):1479–1484

    CAS  Article  Google Scholar 

  2. 2.

    Meille SV, Phillips PJ, Mezghani K et al (1996) α–γ disorder in isotactic polypropylene crystallized under high pressure. Macromolecules 29(2):795–797

    CAS  Article  Google Scholar 

  3. 3.

    Tjong SC, Shen JS, Li RKY (1996) Morphological behaviour and instrumented dart impact properties of β-crystalline-phase polypropylene. Polymer 37(12):2309–2316

    CAS  Article  Google Scholar 

  4. 4.

    Kawai T, Iijima R, Yamamoto Y et al (2002) Crystal orientation of β-phase isotactic polypropylene induced by magnetic orientation of N,N′-dicyclohexyl-2, 6-naphthalenedicarboxamide. Polymer 43(26):7301–7306

    CAS  Article  Google Scholar 

  5. 5.

    Fujiwara Y (1975) Double-melting behavior of beta phase of isotactic polypropylene. Colloid Polym Sci 253(4):273–282

    CAS  Article  Google Scholar 

  6. 6.

    Lovinger AJ, Chua JO, Gryte CC (1977) Studies on the α and β forms of isotactic polypropylene by crystallization in a temperature gradient. J Polym Sci Polym Phys 15(4):641–656

    CAS  Article  Google Scholar 

  7. 7.

    Varga J, Ehrenstein GW (1996) Formation of β-modification of isotactic polypropylene in its late stage of crystallization. Polymer 37(26):5959–5963

    CAS  Article  Google Scholar 

  8. 8.

    Ellis G, Gomez MA, Marco C (2004) Synchrotron infrared microscopy study of the crystalline morphology of the interphase in polypropylene/LCP-Fiber model composites. J Macromol Sci B 43(1):191–206

    Article  CAS  Google Scholar 

  9. 9.

    Sun X, Li H, Wang J et al (2006) Shear-induced interfacial structure of isotactic polypropylene (iPP) in iPP/fiber composites. Macromolecules 39(25):8720–8726

    CAS  Article  Google Scholar 

  10. 10.

    Byelov D, Panine P, Remerie K et al (2008) Crystallization under shear in isotactic polypropylene containing nucleators. Polymer 49(13):3076–3083

    CAS  Article  Google Scholar 

  11. 11.

    Varga J, Karger-Kocsis J (1996) Rules of supermolecular structure formation in sheared isotactic polypropylene melts. J Polym Sci Polym Phys 34(4):657–670

    CAS  Article  Google Scholar 

  12. 12.

    Leugering VHJ (1967) Einfluß der kristallstruktur und der überstruktur auf einige eigenschaften von polypropylen. Die Makromol Chem 109(1):204–216

    CAS  Article  Google Scholar 

  13. 13.

    Garbarczyk J, Paukszta D (1985) Influence of additives on the structure and properties of polymers. Colloid Polym Sci 263(12):985–990

    CAS  Article  Google Scholar 

  14. 14.

    Fujiyama M (1995) Structures and properties of injection moldings of β-crystal nucleator-added polypropylenes: part 1 effect of β-crystal nucleator content. Int Polym Proc 10(2):172–178

    CAS  Article  Google Scholar 

  15. 15.

    Shi G, Zhang X (1992) Effect of β-nucleator content on the crystallization and melting behaviour of β-crystalline phase polypropylene. Thermochim Acta 205:235–243

    CAS  Article  Google Scholar 

  16. 16.

    Li JX, Cheung WL (1997) Pimelic acid-based nucleating agents for hexagonal crystalline polypropylene. J Vinyl Addit Technol 3(2):151–156

    CAS  Article  Google Scholar 

  17. 17.

    Varga J, Mudra I, Ehrenstein GW (1999) Highly active thermally stable β-nucleating agents for isotactic polypropylene. J Appl Polym Sci 74(10):2357–2368

    CAS  Article  Google Scholar 

  18. 18.

    Feng J, Chen M (2003) Effects of La3+ containing additive on crystalline characteristics of isotactic polypropylene. Polym Int 52(1):42–45

    CAS  Article  Google Scholar 

  19. 19.

    Krache R, Benavente R, Lopez-Majada JM et al (2007) Competition between α, β, and γ polymorphs in a β-nucleated metallocenic isotactic polypropylene. Macromolecules 40(19):6871–6878

    CAS  Article  Google Scholar 

  20. 20.

    Varga J, Stoll K, Menyhárd A et al (2011) Crystallization of isotactic polypropylene in the presence of a β-nucleating agent based on a trisamide of trimesic acid. J Appl Polym Sci 121(3):1469–1480

    CAS  Article  Google Scholar 

  21. 21.

    Hu JS, Sun J, Su D et al (2014) Effect of a nematic liquid crystalline polymer as highly active beta-nucleator on crystallization structure and morphology of isotactic polypropylene. Int J Polym Anal Charact 19(7):661–668

    CAS  Article  Google Scholar 

  22. 22.

    Varga J, Menyhard A (2007) Effect of solubility and nucleating duality of N,N′-dicyclohexyl-2, 6-naphthalenedicarboxamide on the supermolecular structure of isotactic polypropylene. Macromolecules 40(7):2422–2431

    CAS  Article  Google Scholar 

  23. 23.

    Marco C, Gomez MA, Ellis G et al (2002) Activity of a β-nucleating agent for isotactic polypropylene and its influence on polymorphic transitions. J Appl Polym Sci 86(3):531–539

    CAS  Article  Google Scholar 

  24. 24.

    Lu S, Lu YH, Sun J et al (2015) Study on the structure, melting, and nonisothermal crystallization behaviors of isotactic polypropylene with nematic liquid crystalline polymer as a new beta-nucleating agent. Polym Sci Ser A 57(1):67–75

    CAS  Article  Google Scholar 

  25. 25.

    Xu L, Zhang X, Xu K et al (2010) Variation of non-isothermal crystallization behavior of isotactic polypropylene with varying β-nucleating agent content. Polym Int 59(10):1441–1450

    CAS  Article  Google Scholar 

  26. 26.

    Xiao W, Wu P, Feng J (2008) Effect of β-nucleating agents on crystallization and melting behavior of isotactic polypropylene. J Appl Polym Sci 108(5):3370–3379

    CAS  Article  Google Scholar 

  27. 27.

    Zhang YF, Xin Z (2007) Isothermal crystallization behaviors of isotactic polypropylene nucleated with α/β compounding nucleating agents. J Polym Sci Polym Phys 45(5):590–596

    CAS  Article  Google Scholar 

  28. 28.

    Bai H, Wang Y, Song B et al (2009) Nucleating agent induced impact fracture behavior change in PP/POE blend. Polym Bull 62(3):405–419

    CAS  Article  Google Scholar 

  29. 29.

    Phillips A, Zhu PW, Edward G (2010) Polystyrene as a versatile nucleating agent for polypropylene. Polymer 51(7):1599–1607

    CAS  Article  Google Scholar 

  30. 30.

    Sun J, Li Q, Yao XJ et al (2013) Influence of two liquid crystalline polysiloxanes with different average molecular weight as new beta-nucleator on crystallization structure of isotactic polypropylene. Polym Bull 70(9):2519–2530

    CAS  Article  Google Scholar 

  31. 31.

    Qu N, Fu YZ, An F et al (2006) Study on mechanical properties and crystallization behavior of polypropylene and its blends modified by β crystalline form nucleating agent. Polym Plast Technol 45(5):637–640

    CAS  Article  Google Scholar 

  32. 32.

    Mormann W, Bröcher M (1999) Liquid crystalline thermosets by polymerization of mesogenic azomethine based diepoxides-influence of reaction rate on phase behaviour. Polymer 40(1):193–198

    CAS  Article  Google Scholar 

  33. 33.

    Horváth F, Gombár T, Varga J, Menyhárd A (2017) Crystallization, melting, supermolecular structure and properties of isotactic polypropylene nucleated with dicyclohexyl-terephthalamide. J Therm Anal Calorim 128(2):925–935

    Article  CAS  Google Scholar 

  34. 34.

    Zhou PZ, Zhang YF, Lin XF (2018) Thermal stability of nucleation effect of different β-nucleating agents in isotactic polypropylene. J Therm Anal Calorim 132(3):1845–1852

    CAS  Article  Google Scholar 

  35. 35.

    He B, Lin XF, Zhang YF (2018) Effect of a novel compound nucleating agent calcium sulfate whisker/β nucleating agent dicyclohexyl-terephthalamide on crystallization and melting behavior of isotactic polypropylene. J Therm Anal Calorim 132(2):1145–1152

    CAS  Article  Google Scholar 

  36. 36.

    Su Z, Dong M, Guo Z et al (2007) Study of polystyrene and acrylonitrile-styrene copolymer as special β-nucleating agents to induce the crystallization of isotactic polypropylene. Macromolecules 40(12):4217–4224

    CAS  Article  Google Scholar 

  37. 37.

    Su ZQ, Chen XN, Yu ZZ et al (2009) Morphological distribution of polymeric nucleating agents in injection-molded isotactic polypropylene plates and its influence on nucleating efficiency. J Appl Polym Sci 111(2):786–793

    CAS  Google Scholar 

  38. 38.

    Li Q, Zhang X, Li J et al (2014) A highly effective reactive liquid crystal for the improved β-nucleation of isotactic polypropylene. Polym Eng Sci 54(9):2112–2120

    CAS  Article  Google Scholar 

  39. 39.

    Habibpour S, Zabihirad J, Mohammadi N et al (2016) Modeling of polystyrenic nanoparticles driven β-trans-crystalline efficiency in isotactic polypropylene. RSC Adv 6(76):72500–72509

    CAS  Article  Google Scholar 

  40. 40.

    Hu HS, Zhang BY, Sun K, Li QY (2003) Side chain cholesteric liquid crystalline elastomers: synthesis and phase behaviour. Liq Cryst 30(11):1267–1275

    CAS  Article  Google Scholar 

  41. 41.

    Jones AT, Aizlewood JM, Beckett DR (1964) Crystalline forms of isotactic polypropylene. Die Makromol Chem 75(1):134–158

    Article  Google Scholar 

  42. 42.

    Wang TT, Nishi T (1977) Spherulitic crystallization in compatible blends of poly (vinylidene fluoride) and poly (methyl methacrylate). Macromolecules 10(2):421–425

    CAS  Article  Google Scholar 

  43. 43.

    Li JX, Cheung WL, Jia D (1999) A study on the heat of fusion of β-polypropylene. Polymer 40(5):1219–1222

    CAS  Article  Google Scholar 

  44. 44.

    Varga J, Ille A, Fujiwara Y (1990) β, α-Bifurcation of growth during the spherulitic crystallization of polypropylene. Period Polytech Chem 34(4):255

    CAS  Google Scholar 

  45. 45.

    Varga J (1986) Melting memory effect of the β-modification of polypropylene. J Therm Anal Calorim 31(1):165–172

    CAS  Article  Google Scholar 

  46. 46.

    Lotz B, Fillon B, Thierry A et al (1991) Low Tc growth transitions in isotactic polypropylene: β to α and α to smectic phases. Polym Bull 25(1):101–105

    CAS  Google Scholar 

  47. 47.

    Sukananta P, Bualek-Limcharoen S (2003) In Situ modulus enhancement of polypropylene monofilament through blending with a liquid-crystalline copolyester. J Appl Polym Sci 90:1337–1346

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This study was supported by Fundamental Research Funds for the Central Universities (N160504001), Doctor Start Funding of Liaoning Province (201601379), Strengthening the Police Force with Science and Technology Foundation Works Special of Ministry of Public Security (2017GABJC14), and Central Public Welfare Research Institutes of basic research special operations (CA268).

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Correspondence to Bai Wang or Jianshe Hu.

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Liu, Y., Yao, X., Fan, C. et al. Effect of a smectic liquid crystal polymer as new β-nucleating agent on crystallization structure, melting, and rheological behavior of isotactic polypropylene. Polym. Bull. 76, 2915–2929 (2019). https://doi.org/10.1007/s00289-018-2505-9

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Keywords

  • Liquid crystal polymer
  • β-Nucleating agent
  • Isotactic polypropylene
  • Crystallization structure
  • Rheological behavior