Reactions at polymer interfaces: Transitions from chemical to diffusion-control and mixed order kinetics

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1999 EDP Sciences
, , Citation B. O'Shaughnessy and D. Vavylonis 1999 EPL 45 638 DOI 10.1209/epl/i1999-00215-y

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Author affiliations

1 Department of Chemical Engineering, Columbia University 500 West 120th St., New York, NY 10027, USA

2 Department of Physics, Columbia University 538 West 120th St., New York, NY 10027, USA

Dates

  1. Received 24 April 1998
  2. Accepted 21 December 1998
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0295-5075/45/5/638

Abstract

We study reactions between end-functionalized chains at a polymer-polymer interface. For small chemical reactivities (the typical case) the number of diblocks formed, Script Rt, obeys 2nd-order chemically controlled kinetics, Script Rt ∼ t, until interfacial saturation. For high reactivities (e.g., radicals) a transition occurs at short times to 2nd-order diffusion-controlled kinetics, with Script Rt ∼ t/ln t for unentangled chains while t/ln t and t1/2 regimes occur for entangled chains. Long-time kinetics are 1st order and controlled by diffusion of the more dilute species to the interface: Script Rt ∼ t1/4 for unentangled cases, while Script Rt ∼ t1/4 and t1/8 regimes arise for entangled systems. The final 1st-order regime is governed by center-of-gravity diffusion, Script Rt ∼ t1/2.

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10.1209/epl/i1999-00215-y