Influence of Macrocyclic Ligands on Ion Transport in Solid Polyelectrolytes
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INFLUENCE OF MACROCYCLIC LIGANDS ON ION TRANSPORT IN SOLID POLYELECTROLYTES
K. CHEN, K. DOAN, S. GANAPATHIAPPAN, M. RATNER AND D. F. SHRIVER Northwestern University, Department of Chemistry and Materials Research Center, 60208 Evanston, IL
ABSTRACT in
the cation transport
and crown ethers increase
Cryptands
phosphazene
Vibrational spectroscopy indicates that
and alkoxyaluminate polyelectrolytes.
the increased conductivity originates from reduced ion pairing.
Introduction salt
Polymer
complexes
have
been
in these materials, and there is substantially to
Ion aggregation appears to be strong
evidence that charged ion aggregates contribute
the conductivity
fundamental studies,
it
is
latter
consideration
The
electrolytes
containing polyether
agents
[4,5]. (crown
In
For both
[3].
applications
practical
and
desirable to reduce or eliminate the transport of ion
aggregates.
constant
from both
investigated
extensively
fundamental and applied viewpoints [1,2].
has
groups
led
to
to
the
achieve
a
synthesis favorable
of polydielectric
the present work we describe the influence of ion chelating
ethers,
and
cryptands)
properties of polyelectrolytes.
on
the
electrical
and
spectroscopic
Preliminary discussions of this work have been
published [6,7].
Experimental Polymers were synthesized as described in the literature samples of 15-crown-5 (l,4,7,10,13-pentaoxacyclopentadecane),
Commercial
[4]. 2,
and cryptand1, were used
2.2.2(4,7,13,16,21,24-hexaoxa-l,10-diazabicyclo[8.8.8]hexacosane), after extended prepared in to
an N2 atmosphere by adding weighed amounts of the chelating ligand
the polyelectrolyte
solvent.
or
polymer salt
After removal of solvent
complex
under vacuum,
dried under high vacuum and stored in properties
Samples were
evacuation to remove water and dissolved gases.
an N2 -filled
in
acetonitrile
the
glove box.
and spectra were determined as previously described
1
or methanol
sample was extensively
2
Mat. Res. Soc. Symp. Proc. Vol. 210. @1991 Materials Research Society
The dielectric [7].
212
Results and Discussion The influence of C-2.2.2 on the conductivity of polyphosphazene sulfonates and polyalkoxyaluminates
shown in
is
Upon addition of C-2.2.2,
Table I.
ty of the polyphosphazene of magnitude,
sulfonates,
increases by approximately one order
3,
a much larger increase for polyalkoxyaluminates,
whereas there is
the poly-alkoxyaluminate than in
This may be due to tighter ion pairing in
4.
the
The conductivi-
conductivities of both polyelectrolytes increase significantly.
the phosphazene sulfonates.
O(C 2 H40) 2 cH3
O(C2H40)2CH33 I
II iP = Ny 0C 2 H4 SO
"-P=
N'x ) O(C2 H4 0) 2 CH3
3
OC2 H4 0CH 3 Nan-+OAI(OC 2 H4-+n OC2 H4OCH 3
No
4
3 Table I.
Conductivity Data of Polyelectrolytes without Crypt-2.2.2 1
Polyelectrolyte
with and
a cm- S (80 No C-2.2.2
'C) C-2.2.2 added'
1.7 1.9 2.9 1.5
8.3 1.6 1.9 9.2
polyphosphazeneb x x x x
-
0.2 0.14 0.1 0.04
x x x x
10-6 10-6 10-6 10-6
x x x x
10-6 10
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