General theory for the diffusion of large molecules in amorphous polymers above Tg-recent developments

K. A. Mauritz, Christopher Coughlin, R. F. Storey

Research output: Contribution to journalConference articlepeer-review

Abstract

We have recently developed a largely free volume-based theory for the above-Tg diffusion of molecules that are large compared to the size of the chain segments of the host polymer. In the theory, the penetrant jump distance is a fraction of the molecular dimension along the jump direction and an increase in entropy accompanies the liberation of one penetrant translational degree of freedom after adjacent hole creation. The theory requires the penetrant's maximum cross-sectional areas that are perpendicular to the three principal axes of inertia that pass through its center-of-mass. Numerical methods for evaluating arbitrarily irregular areas for any large molecule were developed with the aid of theoretical conformational analysis. We present calculations of the diffusivities (D) of di-ni-alkylphthalate plasticizers in rubbery PVC and evaluate the results against corresponding experimental D's. We also discuss our incorporation of specific polymer-penetrant interactions to give the polymer a more distinct chemical identity in the model.

Original languageEnglish (US)
Pages (from-to)699-700
Number of pages2
JournalAmerican Chemical Society, Polymer Preprints, Division of Polymer Chemistry
Volume31
Issue number1
StatePublished - Apr 1 1990
EventPapers Presented at the Boston, Massachusetts Meeting of ACS 1989 - Boston, MA, USA
Duration: Apr 22 1989Apr 27 1989

All Science Journal Classification (ASJC) codes

  • Polymers and Plastics

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