An experimental study of polymer diffusion in concentrated solution: Implications for diffusion in polymerization

Brian Hanley, Steven Balloge, Matthew Tirrell

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30 Scopus citations

Abstract

The Trommsdorf or gel effect in free radical polymerization is due to the fact that the termination reaction becomes strongly diffusion controlled above a critical concentration associated with the onset of molecular entanglements. Therefore, an understanding of polymer self-diffusion in entangled systems becomes essential to understanding the Trommsdorf effect. Our group has previously proposed a molecular model for the gel effect which uses a specific theory for polymer diffusion (reptation). The present work represents an experimental attack on the same problem. Experimental studies of polymer self-diffusion in entangled systems are scarce. Quasielastic light scattering from ternary systems composed of solvent(1)-polymer(2)-polymer(3), in which species (3) is isorefractive to the solvent (i.e. [formula omitted]), offers an attractive way to study the tracer diffusion coefficient of species (2) in a binary mixture of composition c3. In regimes of low momentum transfer [formula omitted] where q is the scattered wave vector and RGis the polymer radius of gyration, we have shown that the correlation function of the scattered electric field should decay with a single exponential decay time, given by (D22q2)–1 where D22(c2, c3) is the main ternary diffusion coefficient of component (2). Extrapolation to zero concentration of (2) at fixed concentration of (3) yields the tracer diffusion coefficient of (2) in the binary mixture of (1) and (3). The systems toluene(1)-polystyrene(2)-polymethylmethacrylate(3) [formula omitted] and toluene (1)-polystyrene(2)-polyvinylmethylether (3) [formula omitted] very nearly satisfy the above criteria. In both systems, we have found that the tracer diffusion coefficient of the polystyrene decreases with increasing concentration of the isorefractive polymer. Further studies have focused upon the dependence of the tracer diffusion coefficient upon polystyrene molecular weight, and upon the effect of incomplete index matching.

Original languageEnglish (US)
Pages (from-to)93-113
Number of pages21
JournalChemical Engineering Communications
Volume24
Issue number1-3
DOIs
StatePublished - Nov 1 1983

Keywords

  • Diffusion
  • Light scattering
  • Polymerization
  • Reptation
  • Trommsdorf effect

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