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Trans content in atactic polystyrene estimated by double-quantum solid-state NMR

M G Dunbar1, B M Novak, K Schmidt-Rohr

  • 1Department of Polymer Science and Engineering, University of Massachusetts, Amherst 01003, USA.

Solid State Nuclear Magnetic Resonance
|November 11, 1998
PubMed
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Solid-state NMR reveals the conformational statistics of atactic polystyrene. The study provides the first direct experimental estimate of the trans/gauche ratio in this polymer, finding a trans content of 68%.

Area of Science:

  • Polymer Science
  • Solid-State Nuclear Magnetic Resonance (NMR) Spectroscopy
  • Computational Chemistry

Background:

  • Atactic polystyrene (aPS) is a widely used amorphous polymer.
  • Understanding its conformational statistics is crucial for predicting material properties.
  • Previous studies relied on theoretical models with varying assumptions.

Purpose of the Study:

  • To experimentally determine the conformational statistics of atactic polystyrene.
  • To provide a direct measurement of the trans/gauche ratio in the polymer backbone.
  • To compare experimental findings with predictions from different theoretical models.

Main Methods:

  • Solid-state Nuclear Magnetic Resonance (NMR) spectroscopy was employed.
  • A sample of atactic polystyrene was selectively labeled with 13CH2 groups.

Related Experiment Videos

  • Double-quantum pulse sequences were utilized to isolate specific 13C-13C spin pairs.
  • Experiments correlated chemical-shift anisotropies to probe single and consecutive torsion angles.

    • Main Results:

    • The study determined a trans content of 68% (±10%) in atactic polystyrene.
    • This represents the first direct experimental estimation of the trans/gauche ratio.
    • The experimental trans content aligns well with rotational-isomeric-state models.
    • Results are inconsistent with atomistic models that incorporate packing effects.

    Conclusions:

    • Solid-state NMR provides a direct experimental method to probe polymer conformation.
    • The trans/gauche ratio in atactic polystyrene is accurately described by simpler models.
    • More complex atomistic models may require refinement to capture experimental realities accurately.