Effect of Olefin-based Compatibilizers on the Formation of Cocontinuous Structure in Immiscible HDPE/iPP Blends

Abstract

In this work, the formation of cocontinuous structure in immiscible high density polyethylene/isotactic polypropylene (HDPE/iPP) blends was investigated for various olefin-based compatibilizers of distinct molecular architectures, including ternary random copolymer EPDM, olefin block copolymer (OBC), polypropylene-based OBC (PP-OBC), ethylene/a-olefin copolymer (POE), bottlebrush polymer poly(1-dodecene), and comb-like poly(propylene-co-high a-olefin) (PPO). The scanning electron microscopy results show that after adding OBC, PP-OBC, and POE copolymers, the finer droplet-in-matrix morphologies were obtained in 70/30 HDPE/iPP blend. Interestingly, for 70/30 HDPE/iPP blend with just 5 wt% of PPO copolymers, the phase inversion from droplet-in-matrix to cocontinuous morphology can be observed. It was proposed that the development of cocontinuous morphology contained the following steps: (1) interfacial saturation of compatibilizers and droplet deformation, (2) droplet-droplet coalescence, (3) continuity development, and (4) the formation of dual-phase continuity. Among the diverse copolymers studied in this work, PPO copolymer can be easily removed out of the interface during droplet coalescence and stabilize the curvature of minor fiber phase, facilitating the formation of cocontinuous morphology. In contrast, other olefin-based compatibilizers (EPDM, OBC, PP-OBC, and POE) exhibit the distinct steric repulsion effect to prohibit droplet coalescence. Moreover, the cocontinous interval varies with the compatibilizer architectures. Surprisingly, after adding 10 wt% of PPO copolymers, the cocontinuous interval was greatly broadened from HDPE/iPP range of 45/55–60/40 to that of 40/60–70/30.

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

References

  1. 1

    Hedegaard, A. T.; Gu, L.; Macosko, C. Effect of extensional viscosity on cocontinuity of immiscible polymer blends. J. Rheol.2015, 59, 1397–1417.

    CAS  Google Scholar 

  2. 2

    Lepers, J. C.; Favis, B. D. Interfacial tension reduction and coalescence suppression in compatibilized polymer blends. AlChE J.1999, 45, 887–895.

    CAS  Google Scholar 

  3. 3

    Li, J.; Favis, B. D. Characterizing co-continuous high density polyethylene/polystyrene blends. Polymer2001, 42, 5047–5053.

    CAS  Google Scholar 

  4. 4

    Shao, Y.; Dou, R.; Li, S. L.; Yin, B.; Yang, M. B. Morphology evolution and the tri-continuous morphology formation of a PVDF/PS/HDPE ternary blend in melt mixing. RSC Adv.2016, 6, 38803–38810.

    CAS  Google Scholar 

  5. 5

    Poothanari, M. A.; Abraham, J.; Kalarikkal, N.; Thomas, S. Excellent electromagnetic interference shielding and high electrical conductivity of compatibilized polycarbonate/polypropylene carbon nanotube blend nanocomposites. Ind. Eng. Chem. Res.2018, 57, 4287–4297.

    CAS  Google Scholar 

  6. 6

    Irwin, M. T.; Hickey, R. J.; Xie, S.; So, S.; Bates, F. S.; Lodge, T. P. Structure-conductivity relationships in ordered and disordered salt-doped diblock copolymer/homopolymer blends. Macromolecules2016, 49, 6928–6939.

    CAS  Google Scholar 

  7. 7

    Mcintosh, L. D.; Schulze, M. W.; Irwin, M. T.; Hillmyer, M. A.; Lodge, T. P. Evolution of morphology, modulus, and conductivity in polymer electrolytes prepared via polymerization-induced phase separation. Macromolecules2015, 48, 1418–1428.

    CAS  Google Scholar 

  8. 8

    Wang, J.; Reyna-Valencia, A.; Favis, B. D. Assembling conductive peba copolymer at the continuous interface in ternary polymer systems: morphology and resistivity. Macromolecules2016, 49, 5115–5125.

    CAS  Google Scholar 

  9. 9

    Li, L.; Miesch, C.; Sudeep, P. K.; Balazs, A. C.; Emrick, T.; Russell, T. P.; Hayward, R. C. Kinetically trapped co-continuous polymer morphologies through intraphase gelation of nanoparticles. Nano Lett.2011, 11, 1997–2003.

    CAS  PubMed  Google Scholar 

  10. 10

    Sarazin, P.; Roy, X.; Favis, B. D. Controlled preparation and properties of porous poly(L-lactide) obtained from a co-continuous blend of two biodegradable polymers. Biomaterials2004, 25, 5965–5978.

    CAS  PubMed  Google Scholar 

  11. 11

    Trifkovic, M.; Hedegaard, A.; Huston, K.; Sheikhzadeh, M.; Macosko, C. W. Porous films via PE/PEO cocontinuous blends. Macromolecules2012, 45, 6036–6044.

    CAS  Google Scholar 

  12. 12

    Aravind, I.; Ahn, K. H.; Ranganathaiah, C.; Thomas, S. Rheology, morphology, mechanical properties and free volume of poly(trimethylene terephthalate)/polycarbonate blends. Ind. Eng. Chem. Res.2009, 48, 9942–9951.

    CAS  Google Scholar 

  13. 13

    Uthaipan, N.; Jarnthong, M.; Peng, Z.; Junhasavasdikul, B.; Nakason, C.; Thitithammawong, A. Micro-scale morphologies of EPDM/EOC/PP ternary blends: relating experiments to predictive theories of dispersion in melt mixing. Mater. Design2016, 100, 19–29.

    CAS  Google Scholar 

  14. 14

    Brown, H. R.; Char, K.; Deline, V. R.; Green, P. F. Effects of a diblock copolymer on adhesion between immiscible polymers 1. Polystyrene (PS)-PMMA copolymer between PS and PMMA. Macromolecules1993, 26, 4155–4163.

    CAS  Google Scholar 

  15. 15

    Fetters, L. J.; Lohse, D. J.; Richter, D.; Witten, T. A.; Zirkel, A. Connection between polymer molecular weight, density, chain dimensions, and melt viscoelastic properties. Macromolecules1994, 27, 4639–4647.

    CAS  Google Scholar 

  16. 16

    Li, J.; Ma, P. L.; Favis, B. D. The role of the blend interface type on morphology in cocontinuous polymer blends. Macromolecules2002, 35, 2005–2016.

    CAS  Google Scholar 

  17. 17

    Sundararaj, U.; Macosko, C. W. Drop breakup and coalescence in polymer blends: the effects of concentration and compatibilization. Macromolecules1995, 28, 2647–2657.

    CAS  Google Scholar 

  18. 18

    Scott, C. E.; Macosko, C. W. Morphology development during the initial stages of polymer-polymer blending. Polymer1995, 36, 461–470.

    CAS  Google Scholar 

  19. 19

    Zhang, C. L.; Feng, L. F.; Zhao, J.; Huang, H.; Hoppe, S.; Hu, G. H. Efficiency of graft copolymers at stabilizing co-continuous polymer blends during quiescent annealing. Polymer2008, 49, 3462–3469.

    CAS  Google Scholar 

  20. 20

    Mekhilef, N.; Favis, B. D.; Carreau, P. J. Morphological stability, interfacial tension, and dual-phase continuity in polystyrene-polyethylene blends. J. Polym. Sci., Part B: Polym. Phys.1997, 35, 293–308.

    CAS  Google Scholar 

  21. 21

    Ren, D.; Tu, Z.; Yu, C.; Shi, H.; Jiang, T.; Yang, Y.; Shi, D.; Yin, J.; Mai, Y. W.; Li, R. K. Y. Effect of dual reactive compatibilizers on the formation of co-continuous morphology of low density polyethylene/polyamide 6 blends with low polyamide 6 content. Ind. Eng. Chem. Res.2016, 55, 4515–4525.

    CAS  Google Scholar 

  22. 22

    Gersappe, D.; Harm, P. K.; Irvine, D.; Balazs, A. C. Contrasting the compatibilizing activity of comb and linear copolymers. Macromolecules1994, 27, 720–724.

    CAS  Google Scholar 

  23. 23

    Veenstra, H.; van Lent, B. J. J.; van Dam, J.; de Boer, A. P. Co-continuous morphologies in polymer blends with SEBS block copolymers. Polymer1999, 40, 6661–6672.

    CAS  Google Scholar 

  24. 24

    Wang, H.; Dong, W.; Li, Y. Compatibilization of immiscible polymer blends using in situ formed Janus nanomicelles by reactive blending. ACS Macro Lett.2015, 4, 1398–1403.

    CAS  Google Scholar 

  25. 25

    Thomas, S.; Groeninckx, G. Reactive compatibilisation of heterogeneous ethylene propylene rubber (EPM)/nylon 6 blends by the addition of compatibiliser precursor EPM-g-MA. Polymer1999, 40, 5799–5819.

    CAS  Google Scholar 

  26. 26

    Harrats, C.; Omonov, T.; Groeninckx, G.; Moldenaers, P. Phase morphology development and stabilization in polycyclohexyl-methacrylate/polypropylene blends: uncompatibilized and reactively compatibilized blends using two reactive precursors. Polymer2004, 45, 8115–8126.

    CAS  Google Scholar 

  27. 27

    Galloway, J. A.; Jeon, H. K.; Bell, J. R.; Macosko, C. W. Block copolymer compatibilization of cocontinuous polymer blends. Polymer2005, 46, 183–191.

    CAS  Google Scholar 

  28. 28

    Pu, G.; Luo, Y.; Wang, A.; Li, B. Tuning polymer blends to cocontinuous morphology by asymmetric diblock copolymers as the surfactants. Macromolecules2011, 44, 2934–2943.

    CAS  Google Scholar 

  29. 29

    Pernot, H.; Baumert, M.; Court, F.; Leibler, L. Design and properties of co-continuous nanostructured polymers by reactive blending. Nat. Mater.2002, 1, 54.

    CAS  PubMed  Google Scholar 

  30. 30

    Bhadane, P. A.; Tsou, A. H.; Cheng, J.; Favis, B. D. Morphology development and interfacial erosion in reactive polymer blending. Macromolecules2008, 41, 7549–7559.

    CAS  Google Scholar 

  31. 31

    Yu, C.; Shi, D.; Wang, J.; Shi, H.; Jiang, T.; Yang, Y.; Hu, G. H.; Li, R. K. Y. Effect of a dual compatibilizer on the formation of co-continuous morphology of immiscible polymer blends. Mater. Design2016, 107, 171–177.

    CAS  Google Scholar 

  32. 32

    Mah, A. H.; Afzali, P.; Qi, L.; Pesek, S.; Verduzco, R.; Stein, G. E. Bottlebrush copolymer additives for immiscible polymer blends. Macromolecules2018, 51, 5665–5675.

    CAS  Google Scholar 

  33. 33

    Macosko, C. W.; Jeon, H. K.; Schulze, J. S. Block copolymers and compatibilization: reactively formed. in Encyclopedia of materials: science and technology. Buschow, K. H. J.; Cahn, R. W.; Flemings, M. C.; Ilschner, B.; Kramer, E. J.; Mahajan, S.; Veyssiere, P.; Eds. Elsevier, Oxford, 2001, pp 683–687.

    Google Scholar 

  34. 34

    Chaffin, K. A.; Knutsen, J. S.; Brant, P.; Bates, F. S. High-strength welds in metallocene polypropylene/polyethylene laminates. Science2000, 288, 2187–2190.

    CAS  PubMed  Google Scholar 

  35. 35

    Tian, Z.; Feng, L. F.; Fan, Z. Q.; Hu, G. H. Ethylene-propylene segmented copolymer as an in situ compatibilizer for impact polypropylene copolymer: an assessment of rheology and morphology. Ind. Eng. Chem. Res.2014, 53, 11345–11354.

    CAS  Google Scholar 

  36. 36

    Shanks, R. A.; Li, J.; Yu, L. Miscibility and co-continuous morphology of polypropylene—polyethylene blends. Pourdeyhimi, Behnam. In Imaging and image analysis applications for plastics, William Andrew Publishing, Norwich, NY, 1999, pp. 59–63.

    Google Scholar 

  37. 37

    Jang, G. S.; Jo, N. J.; Cho, W. J.; Ha, C. S. Isothermal crystallization behavior and properties of polypropylene/EPR blends nucleated with sodium benzoate. J. Appl. Polym. Sci.2002, 83, 201–211.

    CAS  Google Scholar 

  38. 38

    Teh, J. W.; Rudin, A.; Keung, J. C. A review of polyethylene-polypropylene blends and their compatibilization. Adv. Polym. Tech.1994, 13, 1–23.

    CAS  Google Scholar 

  39. 39

    Lin, Y.; Yakovleva, V.; Chen, H.; Hiltner, A.; Baer, E. Comparison of olefin copolymers as compatibilizers for polypropylene and high-density polyethylene. J. Appl. Polym. Sci.2009, 113, 1945–1952.

    CAS  Google Scholar 

  40. 40

    Vervoort, S.; den Doelder, J.; Tocha, E.; Genoyer, J.; Walton, K. L.; Hu, Y.; Munro, J.; Jeltsch, K. Compatibilization of polypropylene-polyethylene blends. Polym. Eng. Sci.2018, 58, 460–465.

    CAS  Google Scholar 

  41. 41

    Eagan, J. M.; Xu, J.; Di Girolamo, R.; Thurber, C. M.; Macosko, C. W.; LaPointe, A. M.; Bates, F. S.; Coates, G. W. Combining polyethylene and polypropylene: enhanced performance with PE/PP multiblock polymers. Science2017, 355, 814–816.

    CAS  PubMed  Google Scholar 

  42. 42

    Xu, J.; Eagan, J. M.; Kim, S. S.; Pan, S.; Lee, B.; Klimovica, K.; Jin, K.; Lin, T. W.; Howard, M. J.; Ellison, C. J.; LaPointe, A. M.; Coates, G. W.; Bates, F. S. Compatibilization of isotactic polypropylene (iPP) and high-density polyethylene (HDPE) with iPP-PE multiblock copolymers. Macromolecules2018, 51, 8585–8596.

    CAS  Google Scholar 

  43. 43

    Tsou, A. H.; López-Barrón, C. R.; Jiang, P.; Crowther, D. J.; Zeng, Y. Bimodal poly(ethylene-cb-propylene) comb block copolymers from serial reactors: synthesis and applications as processability additives and blend compatibilizers. Polymer2016, 104, 72–82.

    CAS  Google Scholar 

  44. 44

    López-Barrón, C. R.; Tsou, A. H. Strain hardening of polyethylene/polypropylene blends via interfacial reinforcement with poly(ethylene-cb-propylene) comb block copolymers. Macromolecules2017, 50, 2986–2995.

    Google Scholar 

  45. 45

    Wang, X. Y.; Wang, Y. X.; Li, Y. S.; Pan, L. Convenient syntheses and versatile functionalizations of isotactic polypropylene containing plentiful pendant styrene groups with high efficiency. Macromolecules2015, 48, 1991–1998.

    CAS  Google Scholar 

  46. 46

    Zhang, D.; Pan, L.; Li, Y.; Wang, B.; Li, Y. Synthesis and reaction of anthracene-containing polypropylene: a promising strategy for facile, efficient functionalization of isotactic polypropylene. Macromolecules2017, 50, 2276–2283.

    CAS  Google Scholar 

  47. 47

    Wang, B.; Wang, Y. X.; Cui, J.; Long, Y. Y.; Li, Y. G.; Yuan, X. Y.; Li, Y. S. Cyclopolymerization of si-containing a, ω-diolefins by a pyridylamidohafnium catalyst with high cyclization selectivity and stereoselectivity. Macromolecules2014, 47, 6627–6634.

    CAS  Google Scholar 

  48. 48

    Graef, S. M.; Wahner, U. M.; van Reenen, A. J.; Brüll, R.; Sanderson, R. D.; Pasch, H. Copolymerization of propylene with higher a-olefins in the presence of the syndiospecific catalyst i-Pr(Cp)(9-Flu)ZrCl2/MAO. J. Polym. Sci., Part A: Polym. Chem.2002, 40, 128–140.

    CAS  Google Scholar 

  49. 49

    Pu, G.; Luo, Y.; Lou, Q.; Li, B. Co-continuous polymeric nanostructures via simple melt mixing of PS/PMMA. Macromol. Rapid Commun.2009, 30, 133–137.

    CAS  PubMed  Google Scholar 

  50. 50

    Willemse, R. C.; de Boer, A. P.; van Dam, J.; Gotsis, A. D. Co-continuous morphologies in polymer blends: a new model. Polymer1998, 39, 5879–5887.

    CAS  Google Scholar 

  51. 51

    Scott, C. E.; Macosko, C. W. Model experiments concerning morphology development during the initial stages of polymer blending. Polym. Bull.1991, 26, 341–348.

    CAS  Google Scholar 

  52. 52

    Willemse, R. C. Co-continuous morphologies in polymer blends: stability. Polymer1999, 40, 2175–2178.

    CAS  Google Scholar 

  53. 53

    Yu, Y.; Zhang, B.; Wang, Y.; Qi, G.; Tian, F.; Yang, J.; Wang, S. Co-continuous structural electrolytes based on ionic liquid, epoxy resin and organoclay: effects of organoclay content. Mater. Design2016, 104, 126–133.

    CAS  Google Scholar 

  54. 54

    Hu, Y. T.; Pine, D. J.; Leal, L. G. Drop deformation, breakup, and coalescence with compatibilizer. Phys. Fluids2000, 12, 484–489.

    CAS  Google Scholar 

  55. 55

    Milliken, W. J.; Leal, L. G. The Influence of surfactant on the deformation and breakup of a viscous drop: the effect of surfactant solubility. J. Colloid Interf. Sci.1994, 166, 275–285.

    CAS  Google Scholar 

  56. 56

    Chang, K.; Morse, D. C. Diblock copolymer surfactants in immiscible homopolymer blends: interfacial bending elasticity. Macromolecules2006, 39, 7397–7406.

    CAS  Google Scholar 

  57. 57

    Jang, S. G.; Kim, B. J.; Hawker, C. J.; Kramer, E. J. Bicontinuous block copolymer morphologies produced by interfacially active, thermally stable nanoparticles. Maoromeluceles2011, 44, 9366–9373.

    CAS  Google Scholar 

  58. 58

    Macosko, C. W. Morphology development and control in immiscible polymer blends. Macromol. Sym.2000, 149, 171–184.

    CAS  Google Scholar 

  59. 59

    Taylor, G. I. The viscosity of a fluid containing small drops of another fluid. Proceedings of the Royal Society of London. Series A, Containing Papers of a Mathematical and Physical Character1932, 138, 41–48.

    CAS  Google Scholar 

  60. 60

    Taylor, G. I. The formation of emulsions in definable fields of flow. Proceedings of the Royal Society of London. Series A, Containing Papers of a Mathematical and Physical Character1934, 146, 501–523.

    CAS  Google Scholar 

  61. 61

    Souza, A. M. C.; Demarquette, N. R. Influence of coalescence and interfacial tension on the morphology of PP/HDPE compatibilized blends. Polymer2002, 43, 3959–3967.

    CAS  Google Scholar 

  62. 62

    Fredrickson, G. H. Surfactant-induced lyotropic behavior of flexible polymer solutions. Macromolecules1993, 26, 2825–2831.

    CAS  Google Scholar 

  63. 63

    Subbotin, A.; Saariaho, M.; Ikkala, O.; ten Brinke, G. Elasticity of comb copolymer cylindrical brushes. Macromolecules2000, 33, 3447–3452.

    CAS  Google Scholar 

  64. 64

    Saariaho, M.; Subbotin, A.; Szleifer, I.; Ikkala, O.; ten Brinke, G. Effect of side chain rigidity on the elasticity of comb copolymer cylindrical brushes: a Monte Carlo simulation study. Macromolecules1999, 32, 4439–4443.

    CAS  Google Scholar 

  65. 65

    Liang, H.; Cao, Z.; Wang, Z.; Sheiko, S. S.; Dobrynin, A. V. Combs and bottlebrushes in a melt. Macromolecules2017, 50, 3430–3437.

    CAS  Google Scholar 

  66. 66

    Wintermantel, M.; Gerle, M.; Fischer, K.; Schmidt, M.; Wataoka, I.; Urakawa, H.; Kajiwara, K.; Tsukahara, Y. Molecular bottlebrushes. Macromolecules1996, 29, 978–983.

    CAS  Google Scholar 

  67. 67

    Willis, J. M.; Caldas, V.; Favis, B. D. Processing-morphology relationships of compatibilized polyolefin/polyamide blends. J. Mater. Sci.1991, 26, 4742–4750.

    CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21574097).

Author information

Affiliations

Authors

Corresponding authors

Correspondence to Zhe Ma or Yue-Sheng Li.

Electronic Supplementary Information

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Yang, F., Pan, L., Du, H. et al. Effect of Olefin-based Compatibilizers on the Formation of Cocontinuous Structure in Immiscible HDPE/iPP Blends. Chin J Polym Sci (2020). https://doi.org/10.1007/s10118-020-2433-7

Download citation

Keywords

  • Compatibilizer
  • polyolefin
  • Cocontinuous structure
  • Droplet-coalescence
  • Phase inversion