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On the rheology of ethylene-octene copolymers

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An Erratum to this article was published on 12 October 2005

Abstract

It has previously been shown that the plateau modulus, G pN , and thus the entanglement molecular weight, M e, of flexible polymers can be correlated to the unperturbed chain dimension, <R 2>o/M, and mass density, ρ, via the use of the packing length, p. For polyolefins, a method was recently proposed whereby knowledge of the average molecular weight per backbone bond, m b, allows <R 2>o/M and consequently G oN and M e to be estimated. This is particularly valuable for polyolefin copolymers since the melt chain dimensions are often unknown. This work corroborates these theoretical predictions by studying the rheology of a series of carefully synthesized ethylene/octene copolymers with varying octene content (19–92 wt%). Furthermore, the results reported herein also allow the advancement of rheological characterization techniques of polymer melts. For instance, based on the analysis of the linear viscoelastic properties of these copolymers, it has been found that several rheological parameters scale with the copolymer comonomer content. Analysis of the viscoelastic material functions in terms of the evolution of the phase angle, δ, as a function of the absolute value of the complex modulus, |G*|, (the so-called van Gurp-Palmen plots), provides a fast and reliable rheological means for determining the composition of ethylene/α-olefin copolymers. The crossover parameters, G co(=G′=G″) and gco(=1/ω co) also scale with copolymer composition.

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References

  • Carri GA, Winter HH (1997) Mapping of the relaxation patterns of polymers melts with linear flexible molecules of uniform length. Rheol Acta 36:330–344

    Article  Google Scholar 

  • Cocchini F, Nobile MR (2003) Constrained inversion of rheological data to molecular weight distribution for polymer melts. Rheol Acta 42:232–242

    Google Scholar 

  • Cole KS, Cole RH (1941) Dispersion and absorption in dielectrics. J Chem Phys 9:341–351

    Article  Google Scholar 

  • Doi M, Edwards SF (1986) The theory of polymer dynamics. Clarendon Press, Oxford

    Google Scholar 

  • Donald AM, Kramer EJ (1982) Effects of molecular entanglements on craze microstructure in glassy polymers. J Polym Sci Polym Phys Ed 20:899–909

    Article  Google Scholar 

  • Donald AM, Kramer EJ (1982) The competition between shear deformation and crazing in glassy polymers. J Mater Sci 17:1871–1879

    Article  Google Scholar 

  • Ferry JD (1980) Viscoelastic properties of polymers, 3rd edn. Wiley, New York

    Google Scholar 

  • Fetters LJ, Lohse DJ, García-Franco CA, Brant P, Richter D (2002) Prediction of melt state polyolefin rheological properties: the unsuspected role of the average molecular weight per backbone bond. Macromolecules 35:10096–10101

    Article  Google Scholar 

  • Fetters LJ, Lohse DJ, Richter D, Witten TA, Zirkel A (1994) The connection between polymer molecular weight, density, chain dimensions, and melt viscoelastic properties. Macromolecules 27:4639–4647

    Article  Google Scholar 

  • Graessley WW (1982) Entangled linear, branched and network polymer systems—molecular theories. Adv Polym Sci 47:67–117

    Article  Google Scholar 

  • Han CD, Kim J, Kim JK (1989) Determination of order-disorder transition temperature of block copolymers. Macromolecules 22:383–394

    Article  Google Scholar 

  • Harrel ER, Nakajima N (1984) Modified Cole-Cole plot based on viscoelastic properties for characterizing molecular architecture of elastomers. J Appl Polym Sci 29:995–1010

    Article  Google Scholar 

  • Ho J, Govaert L, Utz M (2003) Plastic deformation of glassy polymers: correlation between shear activation volume and entanglement density. Macromolecules 36:7398–7404

    Article  Google Scholar 

  • Krentsel BA, Kissin YV, Kleiner VJ, Stotskaya LL (1997) Polymers and copolymers of higher α-Olefins. Hanser Publishers, Munich, Vienna, New York

    Google Scholar 

  • Larson RG, Sridhar T, Leal GH, McKinley AE, Likhtman AE, McLeish TCB (2003). Definitions of entanglement spacing and time constants in the tube model. J Rheol 47:809–818

    Article  Google Scholar 

  • Lohse DJ, Milner ST, Fetters LJ, Xenidou M, Hadjichristidis N, Mendelson RA, García-Franco CA, Lyon MK (2002) Well-defined, model long chain branched polyethylene: part 2: melt rheological behavior. Macromolecules 35:3066–3075

    Article  Google Scholar 

  • Lomellini P, Rossi AG (1990) Effects of composition on the entanglement density in random copolymers. Makromol Chem 191:1729–1737

    Article  Google Scholar 

  • Marvin RS, Oser H (1962) A model for the viscoelastic behavior of rubberlike polymers including entanglements effects. J Res Natl Bur Stand 66B(4):171–180

    Article  Google Scholar 

  • Masuda T, Kitagawa K, Inoue T, Onogi S (1970) Rheological properties of anionic polystyrenes. II. Dynamic viscoelasticity of blends of narrow-distribution polystyrenes. Macromolecules 3:116–125

    Article  Google Scholar 

  • Masuda T, Kitagawa K, Onogi S (1970) Viscoelastic properties of Poly(Methyl Methacrylates) prepared by anionic polymerization. Polym J 1:418–424

    Article  Google Scholar 

  • Nobile MR, Cocchini F (2001) Evaluation of molecular weight distribution from dynamic moduli. Rheol Acta 40:111–119

    Article  Google Scholar 

  • Onogi S, Masuda T, Kitagawa K (1970) Rheological properties of anionic polystyrenes. I. Dynamic viscoelasticity of narrow-distribution polystyrenes. Macromolecules 3:109–116

    Article  Google Scholar 

  • Oser H, Marvin RS (1963) Effect of molecular weight on viscoelastic properties of polymers as predicted by a molecular theory. J Res Natl Bur Stand 67B(2):87–90

    Article  Google Scholar 

  • Prevorsek AC, De Bona BT (1981) On chain entanglement in high-Tg amorphous polymers. J Macromol Sci Phys B 19:605–622

    Article  Google Scholar 

  • Prevorsek AC, De Bona BT (1986) On chain entanglement in high-Tg amorphous polymers II. J Macromol Sci Phys B 25:515–543

    Article  Google Scholar 

  • Teerenstra MN, Steeman PAM, Iwens W, Vandervelden A, Suwier DR, Van Mele B, Koning CE (2003) On the entanglement density of different N-substituted alternating styrene-maleimide copolymers. e-Polymers no 045:1–12

    Google Scholar 

  • Trinkle S, Friedrich C (2001) Van Gurp-Palmen-plot: a way to characterize polydispersity of linear polymers. Rheol Acta 40:322–328

    Article  Google Scholar 

  • Trinkle S, Walter P, Friedrich C (2002) Van Gurp-Palmen plot II-classification of long chain branched polymers by their topology. Rheol Acta 41:103–113

    Article  Google Scholar 

  • Van Gurp M, Palmen J (1996) Time-temperature superposition for polymeric blends. In: Proceedings of the XII international congress on Rheology. Quebec City (Quebec), Canada, pp 134–135

    Google Scholar 

  • Van Gurp M, Palmen J (1998) Time-temperature superposition for polymer blends. Rheol Bull 67:5–8

    Google Scholar 

  • Wood-Adams PM, Dealy JM, deGroot AW, Redwine OD (2000) Effect of molecular structure on the linear viscoelastic behavior of polyethylene. Macromolecules 33:7489–7499

    Article  Google Scholar 

  • Wu S (1989) Chain structure and entanglements. J Polym Sci Polym Phys Ed 27:723–741

    Article  Google Scholar 

  • Ye Z, AlObaidi F, Zhu S (2004) Melt rheological properties of branched polyethylenes produced with Pd- and Ni-diimine catalysts, Macromol. Chem Phys 205:897–906

    Article  Google Scholar 

Download references

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Correspondence to César A. García-Franco.

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An erratum to this article is available at http://dx.doi.org/10.1007/s00397-005-0040-8.

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García-Franco, C.A., Harrington, B.A. & Lohse, D.J. On the rheology of ethylene-octene copolymers. Rheol Acta 44, 591–599 (2005). https://doi.org/10.1007/s00397-005-0441-8

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  • DOI: https://doi.org/10.1007/s00397-005-0441-8

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