Skip to main content

Polymer Blends and Composites

  • Living reference work entry
  • First Online:
Modern Magnetic Resonance

Abstract

In this chapter, first, the investigations of interpolymer interaction, miscibility, and composition change during phase separation for polymer blends are addressed. The hydrogen bonding between polymers is one of key interaction among the interpolymer interactions, causing the apparent lineshape change on 13C NMR spectrum. Based on the effects of 1H spin diffusion on 1H spin-lattice relaxation T 1, the miscibility on several nm or several tens of nm level is discussed. The close proximity between the component polymers revealed by two-dimensional 1H-1H exchange NMR is shown. Similarly, the phase separation process is discussed by the 1H spin diffusion behavior on T 1.

Second, the interaction between inorganic fillers and polymer and stability of the organic modifier treated on the clay surface for polymer nanocomposites are described. The interaction between filler surface and polymer is detected by two-dimensional heteronuclear correlation NMR measurement. The stability of the organic modifiers on the clay surface is clarified by the simple 1H MAS spectra. The paramagnetic source naturally containing in clay obscures the NMR signal, but it is useful to evaluate the stability of the organic modifiers.

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

Access this chapter

Institutional subscriptions

References

  1. Asano A, Takegoshi K. Polymer blends and miscibility, Chapter 10. In: Ando I, Asakura T, editors. Solid state NMR of polymers. The Netherlands: Elsevier Science BV; 1998. p. 351–414.

    Chapter  Google Scholar 

  2. Asano A, Eguchi M, Shimizu M, Kurotsu T. Miscibility and molecular motion of PMAA/PVAc blends investigated by high-resolution solid state CPMAS 13C NMR. Macromolecules. 2002;35:8819–24.

    Article  Google Scholar 

  3. Asano A. Hydrogen-bond interaction of PMAA/PVAc blends: a natural abundant two-dimensional 13C exchange NMR investigation. Polym J. 2004;36:23–7.

    Article  Google Scholar 

  4. Heffner A, Mirau PA. Identification of intermolecular interactions in 1,2-polybutadiene/polyisoprene blends. Macromolecules. 1994;27:7283–6.

    Article  Google Scholar 

  5. White JL, Mirau PA. Probing miscibility and intermolecular interactions in solid polymer blends using the nuclear Overhauser effect. Macromolecules. 1993;26:3049–54.

    Article  Google Scholar 

  6. Mirau PA, White JL. Solid-state NMR studies of intermolecular interactions in solid polymer blends. Magn Reson Chem. 1994;32:S23–9.

    Article  Google Scholar 

  7. Feng H, Feng Z, Ruan H, Shen L. A high-resolution solid-state NMR study of the miscibility, morphology, and toughening mechanism of polystyrene with poly(2,6-dimethyl-1,4-phenylene oxide) blends. Macromolecules. 1992;25:5981–5.

    Article  Google Scholar 

  8. Wolak J, Jia X, Gracz H, Stejskal EO, White JL, Wachowicz M, Jurga S. Polyolefin miscibility: solid-state NMR investigation of phase behavior in saturated hydrocarbon blends. Macromolecules. 2003;36:4844–50.

    Article  Google Scholar 

  9. Ngai KL, Roland CM. Unusual component dynamics in poly(ethylene oxide)/poly(methyl methacrylate) blends as probed by deuterium NMR. Macromolecules. 2004;37:2817–22.

    Article  Google Scholar 

  10. Takegoshi K, Hikichi K. Effects of blending on local chain dynamics and glass transition: polystyrene/poly(vinyl methyl ether) blends as studied by high-resolution solid-state 13C nuclear magnetic resonance spectroscopy. J Chem Phys. 1991;94:3200–6.

    Article  Google Scholar 

  11. Menestrel CLe, Kenwright AM, Sergot P, Lauprêtre F, Monnerie L. Carbon-13 NMR investigation of local dynamics in compatible polymer blends. Macromolecules. 1992;25:3020–6.

    Article  Google Scholar 

  12. VanderHart DL, Feng Y, Han CC, Weiss RA. Morphological characterization of blends of metal-sulfonated poly(styrene) and a methylated poly(amide) by solid state NMR. Macromolecules. 2000;33:2206–27.

    Article  Google Scholar 

  13. Linder M, Henrichs PM, Hewitt JM, Massa DJ. Use of carbon-carbon nuclear spin diffusion for the study of the miscibility of polymer blends. J Chem Phys. 1985;82:1585–98.

    Article  Google Scholar 

  14. Asano A, Takegoshi K, Hikichi K. 13C c.p./m.a.s. n.m.r. study on the miscibility and phase separation of a polystyrene/poly(vinyl methyl ether) blend. Polymer. 1994;35:5630–6.

    Article  Google Scholar 

  15. Miyoshi T, Takegoshi K, Hikichi K. High-resolution solid-state 13C nuclear magnetic resonance study of a polymer complex: poly(methacrylic acid)/poly(ethylene oxide). Polymer. 1996;37:11–8.

    Article  Google Scholar 

  16. Miyoshi T, Takegoshi K, Hikichi K. High-resolution solid state 13C n.m.r. study of the interpolymer interaction, morphology and chain dynamics of the poly(acrylic acid)/poly(ethylene oxide). Polymer. 1997;38:2315–20.

    Article  Google Scholar 

  17. Stejskal EO, Schaefer J, Sefcik MD, Mckay RA. Magic-angle carbon-13 nuclear magnetic resonance study of the compatibility of solid polymeric blends. Macromolecules. 1981;14:275–9.

    Article  Google Scholar 

  18. Asano A, Nishioka M, Takahashi Y, Kato A, Hikasa S, Iwabuki H, Nagata K, Sato H, Hasegawa T, Sawabe H, Arao M, Suda T, Isoda A, Mukai M, Ishikawa D, Izumi T. High impact properties of polyketone/polyamide-6 alloys induced by characteristic morphology and water absorption. Macromolecules. 2009;42:9506–14.

    Article  Google Scholar 

  19. Asano A, Kurotu T. 1H spin diffusion in PMLG/PVP blends as studied by CP/MAS 13C NMR. J Mol Struct. 1998;441:129–35.

    Article  Google Scholar 

  20. Clauss J, Schmidt-Rohr K, Spiess HW. Determination of domain sizes in heterogeneous polymers by solid-state NMR. Acta Polymer. 1993;44:1–17.

    Article  Google Scholar 

  21. Mirau PA. Chapter 4. In: A practical guide to understanding the NMR of polymers. Hoboken: Wiley; 2005. p. 248–335.

    Google Scholar 

  22. Hou S-S, Chen Q, Schmidt-Rohr K. Two-dimensional 13C NMR with 1H spin diffusion for characterizing domain sizes in unlabeled polymers. Macromolecules. 2004;37:1999–2001.

    Article  Google Scholar 

  23. Jia X, Wang X, Tonelli AE, White JL. Two-dimensional spin-diffusion NMR reveals differential mixing in biodegradable polymer blends. Macromolecules. 2005;38:2775–80.

    Article  Google Scholar 

  24. Amoureux J-P, Hu B, Trébosc J. Enhanced resolution in proton solid-state NMR with very-fast MAS experiments. J Magn Reson. 2008;193:305–7.

    Article  Google Scholar 

  25. Mafra L, Gomes JRB, Trébosc J, Rocha J, Amoureux J-P. 1H-1H double-quantum CRAMPS NMR at very-fast MAS (νR = 35 kHz): a resolution enhancement method to probe 1H-1H proximities in solids. J Magn Reson. 2009;196:88–91.

    Article  Google Scholar 

  26. Nishiyama Y, Frey MH, Mukasa S, Utsumi H. 13C solid-state NMR chromatography by magic angle spinning 1H T 1 relaxation ordered spectroscopy. J Magn Reson. 2010;202:135–9.

    Article  Google Scholar 

  27. Sun P, Dang Q, Li B, Chen T, Wang Y, Lin H, Jin Q, Ding D, An-C S. Mobility, miscibility, and microdomain structure in nanostructured thermoset blends of epoxy resin and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) triblock copolymers characterized by solid-state NMR. Macromoleules. 2005;38:5654–67.

    Article  Google Scholar 

  28. Wang X, Gu Q, Sun Q, Zhou D, Sun P, Xue G. Characterization of polymer compatibility by 1H dipolar filter solid-state NMR under fast magic angle spinning. Macromolecules. 2007;40:9018–25.

    Article  Google Scholar 

  29. He X, Liu Y, Zhang R, Wu Q, Chen T, Sun P. Unique interphase and cross-linked network controlled by different miscible blocks in nanostructured epoxy/block copolymer blends characterized by solid-state NMR. J Phys Chem C. 2014;118:13285–99.

    Article  Google Scholar 

  30. VanderHart DL, Prabhu VM, Lavery KA, Dennis CL, Rao AB, Lin EK. Thin-film solid-state proton NMR measurements using a synthetic mica substrate: polymer blends. J Magn Reson. 2009;201:100–10.

    Article  Google Scholar 

  31. Nieuwendaal RC, Snyder CR, Kline RJ, Lin EK, VanderHart DL, DeLongchamp DM. Measuring the extent of phase separation in poly-3-hexylthiophene/phenyl-C61-butyric acid methyl ester photovoltaic blends with 1H spin diffusion NMR spectroscopy. Chem Mater. 2010;22:2930–6.

    Article  Google Scholar 

  32. Nieuwendaal RC, Ro HW, Germack DS, Kline RJ, Toney MF, Chan CK, Agrawal A, Gundlach D, VanderHart DL, Delongchamp DM. Measuring domain sizes and compositional heterogeneities in P3HT-PCBM bulk heterojunction thin films with 1H spin diffusion NMR spectroscopy. Adv Funct Mater. 2012;22:1255–66.

    Article  Google Scholar 

  33. Asano A, Takegoshi K, Hikichi K. Solid-state NMR study of miscibility and phase-separation of polymer blend: polycarbonate/poly(methyl methacrylate). Polym J. 1992;24:555–62.

    Article  Google Scholar 

  34. Asano A. Polymer blends. In: Webb GA, editor. Modern magnetic resonance part I. Dordrecht: Springer; 2006. p. 627–31.

    Google Scholar 

  35. Miyoshi T, Takegoshi K, Terao T. 129Xe n.m.r, study of free volume and phase separation of the polystyrene/poly(vinyl methyl ether) blend. Polymer. 1997;38:5475–80.

    Article  Google Scholar 

  36. Pinnavaia TJ, Beall GW. Polymer-clay nanocomposites. Wiley: Chichester; 2000.

    Google Scholar 

  37. VanderHart DL, Asano A, Gilman JW. NMR measurements related to clay-dispersion quality and organic-modifier stability in nylon-6/clay nanocomposites. Macromolecules. 2001;34:3819–22.

    Article  Google Scholar 

  38. VanderHart DL, Asano A, Gilman JW. Solid state NMR investigation of paramagnetic nylon-6 clay nanocomposites. 1. Crystallinity, morphology, and the direct influence of Fe3+ on nuclear spins. Chem Mater. 2001;13:3781–95.

    Article  Google Scholar 

  39. VanderHart DL, Asano A, Gilman JW. Solid state NMR investigation of paramagnetic nylon-6 clay nanocomposites. 2. Measurement of clay dispersion, crystal stratification, and stability of organic modifiers. Chem Mater. 2001;13:3796–809.

    Article  Google Scholar 

  40. Bourbigot S, VanderHart DL, Gilman JW, Awad WH, Davis RD, Morgan AB, Wilkie CA. Investigation of nanodispersion in polystyrene–montmorillonite nanocomposites by solid-state NMR. J Polm Sci Part B: Polym Phys. 2003;41:3188–213.

    Article  Google Scholar 

  41. Gao Y, Zhang R, Lv W, Liu Q, Wang X, Sun P, Winter HH, Xue G. Critical effect of segmental dynamics in polybutadiene/clay nanocomposites characterized by solid state 1H NMR spectroscopy. J Phys Chem C. 2014;118:5606–14.

    Article  Google Scholar 

  42. Hou S-S, Bonagamba TJ, Beyer FL, Madison PH, Schmidt-Rohr K. Clay intercalation of poly(styrene-ethylene oxide) block copolymers studied by two-dimensional solid-state NMR. Macromolecules. 2003;36:2769–76.

    Article  Google Scholar 

  43. Schmidt-Rohr K, Rawal A, Fang X-W. A new NMR method for determining the particle thickness in nanocomposites, using T 2,H-selective X{1H} recoupling. J Chem Phys. 2007;126:054701–16.

    Article  Google Scholar 

  44. Rawal A, Urman K, Otaigbe JU, Schmidt-Rohr K. Detection of nanometer-scale mixing in phosphate-glass/polyamide-6 hybrids by 1H-31P NMR. Chem Mater. 2006;18:6333–8.

    Article  Google Scholar 

  45. Rawal A, Kong X, Meng Y, Otaigbe JU, Schmidt-Rohr K. Reduced crystallinity and mobility of nylon-6 confined near the organic-inorganic interface in a phosphate glass-rich nanocomposite detected by 1H-13C NMR. Macromolecules. 2011;44:8100–5.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Atsushi Asano .

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2017 Springer International Publishing AG

About this entry

Cite this entry

Asano, A. (2017). Polymer Blends and Composites. In: Webb, G. (eds) Modern Magnetic Resonance. Springer, Cham. https://doi.org/10.1007/978-3-319-28275-6_57-1

Download citation

  • DOI: https://doi.org/10.1007/978-3-319-28275-6_57-1

  • Received:

  • Accepted:

  • Published:

  • Publisher Name: Springer, Cham

  • Print ISBN: 978-3-319-28275-6

  • Online ISBN: 978-3-319-28275-6

  • eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics

Publish with us

Policies and ethics