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Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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Tuning polymer melt fragility with antiplasticizer additives.

Robert A Riggleman1, Jack F Douglas, Juan J de Pablo

  • 1Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.

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|June 30, 2007
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Antiplasticizers lower polymer glass transition temperature but increase stiffness. These additives also enhance glass formation, making polymers stronger glasses with unique cooperative dynamics.

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Area of Science:

  • Polymer Science
  • Materials Science
  • Computational Chemistry

Background:

  • Antiplasticization is a phenomenon where additives can enhance polymer properties.
  • Understanding the molecular mechanisms behind antiplasticization is crucial for materials design.
  • Previous studies have explored various aspects of polymer-diluent interactions.

Purpose of the Study:

  • To develop and characterize a polymer-diluent model exhibiting antiplasticization.
  • To investigate the effects of antiplasticizers on polymer glass transition temperature and elastic moduli.
  • To analyze the impact of antiplasticizers on the glass-forming ability and cooperative dynamics of polymers.

Main Methods:

  • Molecular dynamics simulations were employed to model the polymer-diluent system.
  • Analysis included determining the glass transition temperature (Tg) and elastic moduli.
  • Characterization of glass formation involved fitting to the Vogel-Folcher-Tamman-Hesse equation and analyzing cooperatively rearranging regions (strings).

Main Results:

  • Antiplasticizer molecules decreased the glass transition temperature (Tg) but increased elastic moduli.
  • The polymer melt became a stronger glass-former with antiplasticizer addition.
  • String length showed weaker temperature dependence, and strings concentrated in antiplasticizer particles upon cooling.
  • Dynamic propensity correlated with molecular displacements, with antiplasticized systems showing larger fluctuations on smaller scales.

Conclusions:

  • Antiplasticizers significantly alter polymer properties, lowering Tg while enhancing stiffness and glass-forming ability.
  • The observed behavior of cooperatively rearranging regions provides insights into the Adam-Gibbs model of glass formation.
  • Structural indicators like dynamic propensity offer valuable correlations with molecular dynamics in antiplasticized polymer systems.