Document Type

Article

Publication Date

3-24-2009

Journal or Book Title

Macromolecules

Volume

42

Issue

6

First Page

1867

Last Page

1872

DOI

10.1021/ma8024909

Abstract

Here we report the kinetics of the surface-initiated atom transfer radical polymerization (ATRP) of styrene from the surface of functionalized montmorillonite clay as a function of graft density. Compared with analogous ATRP reactions with free initiator, we observe a seven-fold increase in the polymerization rate at the highest graft density, 1 chain/nm2, whereas bulk kinetics are recovered as the graft density is reduced. We hypothesize that this phenomenon is a consequence of local concentration heterogeneities that shift the ATRP equilibrium in favor of the active state and present a simple phenomenological kinetic model that accounts for our data. These findings present an important consideration relevant to the design of precisely defined molecular architectures from surfaces via surface-initiated ATRP.

Comments

Reprinted with permission from Macromolecules 42 (2009): 1867–1872, doi:10.1021/ma8024909. Copyright 2009 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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