LDPE and poly(1-butene) blends: Morphology, crystallinity and rheological properties

Document Type : Original research


Department of polymer processing, Iran Polymer & Petrochemical Institute, Tehran, 14977-13115, Iran


In this work, the compatibility and crystallinity of low density polyethylene (LDPE) and polybutene-1 (PB-1) blends were studied. Various blends of LDPE/PB-1 containing 5, 10 and 20 wt.% PB-1 were prepared in a corotating twin-screw extruder and characterized by scanning electron microscopy (SEM), shear oscillation rheology and wide-angle X-ray diffractometry (WAXD). A matrix-droplet morphology was observed in SEM images, indicating incompatibility of the two polymers in the solid state. Compared to neat LDPE, the relaxation spectra of the blends were broadened, and a slight increase in their relaxation times was observed. The relaxation time of the blends was enhanced by increasing PB-1 content, which was further proved by fitting rheological data in the Carreau-Yasuda model. Deviation of Cole-Cole diagrams from circular shape means that the blend samples were not miscible and the positive-deviation behavior of the complex viscosity and storage modulus from the mixing rule revealed the formation of strong interfacial interactions. The crystallinity of both LLDPE and PB-1 was decreased as a result of blending. The peaks attributed to the form II of PB-1 crystals were eliminated and the peaks related to LDPE were obviously weakened, suggesting to prevent crystallinity of polymers which is associated with a reduction in the total crystallinity percentage for the blend. The reduction of crystallinity was more pronounced in PB-1 phase.


Main Subjects

  1. Psomiadou E, Arvanitoyannis I, Biliaderis CG, Ogawa H, Kawasaki N (1997) Biodegradable films made from low density polyethylene (LDPE), wheat starch and soluble starch for food packaging applications: Part 2. Carbohydr Polym 33: 227-242
  2. Raj B (2004) Low density polyethylene/starch blend films for food packaging applications. Adv Polym Technol 23: 32-45
  3. Sängerlaub S, Reichert K, Sterra J, Rodler N, Von der Haar D, Schreib I, Stramm C, Gruner A, Voigt J, Raddatz H, Jesdinszki M (2018) Identification of polybutene-1 (PB-1) in easy peel polymer structures. J Polym Testing 65: 142-149
  4. Hsu TC, Geil PH (1990) Permanganic etching of polybutene. Polym Commun 31: 105-108
  5. Mohammadi RS, Zolali AM, Tabatabaei SH, Ajji A (2020) Nanoconfinement induced direct Formation of form I and III crystals inside in Situ formed poly(butene-1) nanofibrils. Macromolecules 53: 1346-1355
  6. Luciani L, Seppälä J, Löfgren B (1988) Poly1-butene: Its preparation, properties and challenges. Prog Polym Sci 13: 37-62
  7. Sängerlaub S, Reichert K, Sterr J, Rodler N, von der Haar D, Schreib I, Stramm C, Gruner A, Voigt J, Raddatz H, Jesdinszki M (2018) Identification of polybutene-1 (PB-1) in easy peel polymer structures. Polym Test 65: 142-149
  8. Robertson GL (2005) Food packaging: Principles and practice, 3rd ed,. CRC press, Taylor & Francis, London
  9. Nase M, Androsch R, Langer B, Baumann HJ, Grellmann W (2008) Effect of polymorphism of isotactic polybutene-1 on peel behavior of polyethylene/polybutene-1 peel systems. J Appl Polym Sci 107: 3111-3118
  10. Liebmann A, Schreib I, E. Schlözer R, Majschak J-P (2012) Practical case studies: Easy opening for consumer-friendly, peelable packaging. J Adhes Sci Technol 26: 2437-2448
  11. Stober P, Rist H (2004) Easy and safe to open. Kunststoffe Plast Europe 94: 66-69
  12. Nase M, Langer B, Grellmann W (2008) Fracture mechanics on polyethylene/polybutene-1 peel films. Polym Test 27: 1017-1025
  13. Aithani D, Lockhart H, Auras R, Tanprasert K (2006) Predicting the strongest peelable seal for ‘easy-open’packaging applications. J Plast Film Sheeting 22: 247-263
  14. Stober P, Rist H (2004) Leicht und gefahrlos öffnen. Kunststoffe 6: 66-69
  15. Nwabunma D, Kyu T (2008) Polyolefin blends, John Wiley & Sons, New Jersey
  16. Kopp S, Wittmann JC, Lotz B (1994) Epitaxial crystallization and crystalline polymorphism of poly (1-butene): Form I. Polymer 35: 916-924
  17. Kishore K, Vasanthakumari R (1986) Crystallization behaviour of polyethylene and i-polybutene-1 blends. Polymer 27: 337-343
  18. Shieh Y, Lee M, Chen S (2002) Interaction parameters of crystalline/crystalline polypropylene/ poly (butene-1) blends: Effect of molecular fractionation. J Polym Sci Pol Phys 40: 638-648
  19. Santamaria A, White JL (1986) Rheological properties, shrinkage and melt spinning instability of blends of linear polyolefins with low density polyethylene. J Appl Polym Sci 31: 209-224
  20. Morris BA (2016) The science and technology of flexible packaging, multilayer films from resin and process to end use, 2nd ed, Elsevier, 173–204
  21. Gahleitner M (2001) Melt rheology of polyolefins. Prog Polym Sci 26: 895-944
  22. Xu Y, Liu CG, Nie HR, He AH (2018) Fractionated and confined crystallization of polybutene-1 in immiscible polypropylene/polybutene-1 blends. chinese J Polym Sci 36: 859–865
  23. Ardakani F, Jahani Y, Morshedian J (2015) The impact of viscoelastic behavior and viscosity ratio on the phase behavior and morphology of polypropylene/polybutene-1 blends. J Vinyl Addit Technol 21: 94-101
  24. Salehiyan R, Yoo Y, Choi WJ, Hyun K (2014) Characterization of morphologies of compatibilized polypropylene/polystyrene blends with nanoparticles via nonlinear rheological properties from FT-rheology. Macromolecules 47: 4066-4076
  25. Xu L, Huang H, Chen Z, Wu X (2014) Effects of emulsion parameters on relaxation behaviors for immiscible polymer blends. J Appl Polym Sci 131: 39690
  26. Wang D, Li Y, Xie X, Guo B (2011) Compatibilization and morphology development of immiscible ternary polymer blends. Polymer 52: 191-200
  27. Dalsin SJ, Hillmyer MA, Bates FS (2015) Linear rheology of polyolefin-based bottlebrush polymers. Macromolecules 48: 4680-4691
  28. Ho K, Kale L, Montgomery S (2002) Melt strength of linear low-density polyethylene/lowdensity polyethylene blends. J Appl Polym Sci 85: 1408-1418
  29. Steffl T (2003) Rheological and film blowing properties of various low density polyethylenes and their blends, Ph.D. Thesis, Erlangen University, Nürnberg
  30. Liu C, Wang J, He J (2002) Rheological and thermal properties of m-LLDPE blends with mHDPE and LDPE. Polymer 43: 3811-3818
  31. Vtracki LA (1990) Polymer alloys and blends: thermodynamics and rheology, Hanser Publisher, New York
  32. Lyngaae-Jørgensen J, Utracki LA (2003) Structuring polymer blends with bicontinuous phase morphology. Part II: Tailoring blends with ultralow critical volume fraction. Polymer 44: 1661-1669
  33. Graebling D, Muller R, Palierne JF (1993) Linear viscoelasticity of incompatible polymer blends in the melt in relation with interfacial properties. J de Phys IV Colloque C7: 1525-1534
  34. Tschoegl NW (1971) A general method for the determination of approximations to the spectral distributions from transient response functions. J Rheologica Acta 10: 595-600
  35. Li R, Yu W, Zhou C (2006) Rheological characterization of droplet-matrix versus co-continuous morphology. J macromol Sci Pol Phys 45: 889-898
  36. Shao H, Wang S, Dong X, He A (2018) rheological behaviors of polypropylene/poly(1-butene) Blends. J Macromol Sci Phys 57: 608-623
  37. Wood-Adams PM, Dealy JM (1996) Use of rheological measurements to estimate the molecular weight distribution of linear polyethylene. J Rheol 40: 761-778
  38. Shi D, Hu G-H, Ke Z, Li RKY, Yin J (2006) Relaxation behavior of polymer blends with complex morphologies: Palierne emulsion model for uncompatibilized and compatibilized PP/PA6 blends. Polymer 47: 4659-4666
  39. Cho K, Lee BH, Hwang K, Lee H, Choe S (1998) Rheological and mechanical properties in polyethylene blends. Polym Eng Sci 38: 1969-1975
  40. Yu F, Zhang H, Zheng H, Yu W, Zhou C (2008) Experimental study of flow-induced crystallization in the blends of isotactic polypropylene and poly (ethylene-co-octene). Eur Polym J 44: 79-86
  41. Chopra D, Kontopoulou M, Vlassopoulos D, Hatzikiriakos SG (2002) Effect of maleic anhydride content on the rheology and phase behavior of poly (styrene-co-maleic anhydride)/poly (methyl methacrylate) blends. Rheol Acta 41: 10–24
  42. Zheng Q, Cao Y, Du M (2004) Dynamic rheological behavior of polypropylene filled with ultrafine powdered rubber particles 22: 363-367
  43. Graebling D, Muller R, Palierne JF (1993) Linear viscoelastic behavior of some incompatible polymer blends in the melt. Interpretation of data with a model of emulsion of viscoelastic liquids. Macromolecules 26: 320-329
  44. Wu DF, Zhang YS, Yuan LJ, Zhang M, Zhou WD (2010) Viscoelastic interfacial properties of compatibilized poly(ε-caprolactone)/polylactide blend. J Polym Sci Pol Phys 48: 756-765
  45. Xu L, Huang H (2012) Relaxation behavior of poly (lactic acid)/poly (butylene succinate) blend and a new method for calculating its interfacial tension. J Appl Polym Sci 125: E272-E277
  46. Xua Y, Ma Y, Liua C, Men Y, He A (2019) Crystallization of forms I′ and form II of polybutene-1 in stretched polypropylene/polybutene-1 blends. J Polymer 182: 121817
  47. Li R, Yu W, Zhou C (2006) Phase behavior and its viscoelastic responses of poly(methyl methacrylate) and poly(styrene-co-maleic anhydride) blend systems. Polym Bull 56: 455-466
  48. Chopra D, Kontopoulou M, Vlassopoulos D, Hatzikiriakos SG (2002) Effect of Maleic Anhydride Content on the rheology and phase behavior of poly(styrene-co-maleic anhydride)/ poly(methyl methacrylate) blends. Rheol Acta 41: 10-24
  49. Hong K, Spruiell JE (1985) The effect of certain processing variables on the form II to form I phase transformation in polybutene-1. J Appl Polym Sci 30: 3163-3188
  50. Stolte I, Androsch R (2014) Comparative study of the kinetics of non-isothermal melt solidification of random copolymers of butene-1 with either ethylene or propylene. Colloid Polym Sci 292: 1639-1647
  51. Schemm F, Van de Vliet F, Grasmeder J. Basell Polybutene-1: High performance polyolefin for plumbing appilcations
  52. Danusso F, Gianotti G (1963) The three polymorphs of isotactic polybutene-1: Dilatometric and thermodynamic fusion properties. Macromol Chem Phys 61: 139-156
  53. Miller RL, Holland VF (1964) On transformations in isotactic polybutene-1. J Polym Sci Pol Lett 2: 519-521
  54. Tosaka M, Kamijo T, Tsuji M, Kohjiya S, Ogawa T, Isoda S, Kobayashi T (2000) High-resolution transmission electron microscopy of crystal transformation in solution-grown lamellae of isotactic polybutene-1. Macromolecules 33: 9666-9672
  55. Srithep Y, Nealey P, Turng LS (2012) Rheological characterization of droplet-Matrix versus cocontinuous morphology. J Polym Eng Sci 53: 580-588
  56. Jing I, Harrison IR (1980) Crystallite size and lamellar thickness by X-ray methods. Methods Exp Phys 16: 128-184