Bulletin of the American Physical Society
APS March Meeting 2011
Volume 56, Number 1
Monday–Friday, March 21–25, 2011; Dallas, Texas
Abstract: C1.00026 : Synthesis of polymer brushes by surface-initiated controlled radical polymerization in the presence of free initiators. A Monte Carlo investigation
Author:
Simultaneous controlled radical polymerization from free and
surface-grafted
initiators is studied by means of computer simulations. We model
``truly
living'' reactions by neglecting chain termination and chain
transfer. We
study the competition between bulk- (i=b) and surface-initiated
(i=s)
polymers by monitoring the rates of polymerization
(d$<$N$>_{i}$/dt), the
average molecular weight ($<$N$>_{i})$, and the polydispersity index
(PDI$_{i})$ while varying the initiator grafting density ($\sigma
)$, the
fraction of surface based polymers ($\eta )$, and the initial
number of free
monomers (I$_{o})$. We find that
d$<$N$>_{B}$/dt$>$d$<$N$>_{S}$/dt and
that d$<$N$>_{S}$/dt decreases with increasing $\sigma $. The
difference
in polymerization rates between the bulk and surface
polymerizations results
in polymer populations with different $<$N$>$; this has
implications for the
experimental determination of $\sigma $ and $<$N$>_{S}$. Although
$\eta $
affects $<$N$>_{S}$ and $<$N$>_{B}$, it does not influence the
PDI. At a
specific $<$N$>_{i}$, the PDI$_{i}$ has a value independent of
$\eta $. In
addition, PDI$_{S}>$PDI$_{B}$; this difference increases with
increasing
$\sigma $. We therefore conclude that polymerization conditions
that yield
bulk polymers with low PDI do not guarantee the same PDI for the
surface-initiated polymers.
To cite this abstract, use the following reference: http://meetings.aps.org/link/BAPS.2011.MAR.C1.26
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