7
84 Chem. Mater., Vol. 22, No. 3, 2010
Nesvadba et al.
H and C NMR spectra were recorded on a Bruker 300
1
13
Scheme 1. Redox Behavior of Nitroxide Radicals
1 13
spectrometer (300 MHz for H and 75.47 MHz for C).
Chemical shifts (δ) are given in parts per million downfield
from an internal Me Si standard, and J values are in hertz. IR
4
spectra were taken on Nicolet Magna-IR 750 spectrometer in
attenuated total reflectance (ATR) mode, and MS spectra were
taken on a Finnigan SSQ 710 apparatus. The electron spin
resonance (ESR) spectra were acquired on an X-Band Mini-
scope MS 2000 spectrometer (Magnettech, Germany). Size
exclusion chromatography (SEC) was carried out at a sample
1
9-21
22,23
23
polyoxetane, poly-
polyvinylether,
polyoxirane,
25,26
24
27
cellulose, or even DNA. On
28
allene, polyacetylene,
the other side, polymers substituted with nitroxides differ-
ent than TEMPO were prepared such as for example
poly(p-tert-butylaminoxy-styrene), polyacetylene, poly-
norbornene, or cellulose bearing 2,2,5,5-tetramethyl-1-pyr-
rolidinyloxy moieties
,2,5,5-tetramethyl-3-pyrroline-N-oxyls.
theoretical charge capacity of these new nitroxide polymers
did not significantly surpass that of PTMA. In fact, the
highest value (135 mA h g ) reached by poly(2,2,6,6-
tetramethylpiperidinyloxy-4-yl vinyl ether) is still lower
than that of the currently used LiCoO (about 140 mA
-1
concentration of 7 of 1 g L with degassed dimethylacetamide
-1
-
1
3
containing 3 g L LiBr and 6 g L CH COOH as eluent at a
29
-
1
flow rate of 0.5 mL min at 60 °C on a system consisting of a
GPCmax pump (Viscotek, Houston), a set of two columns
(GRAM 100, 300 mm ꢀ 8 mm, 10 μm, pore size 10 nm, and
GRAM 30, 300 mm ꢀ 8 mm, 10 μm, pore size 3 nm, Polymer
Standard Services, Germany), and a triple array detector TDA
2
6,27,30
or polyoxirane substituted with
2
3
2
However the
3
02 (Viscotek, Houston). The system was calibrated in the range
-
1
-1
of 1140-300 300 g mol with eight samples of poly(methyl
methacrylate) (Polymer Standard Services, Germany). Electro-
des for the use in coinlike test cells were prepared by coating
aluminum current collectors with a slurry consisting of pow-
dered nitroxide polymer 7a (20 wt %), graphite (TIMREX KS4,
TIMCAL SA, 34 wt %), carbon black (ENSACO 250, TIM-
CAL SA, 7 wt %), and binder (PVDF6020, Solvay SA, 39 wt %)
dissolved in N-methyl-2-pyrrolidone (NMP). After casting the
slurry by a doctor-blade method, the electrodes were dried for
19
2
-1
h g ). Moreover, the oxidation potential of nitroxides
attached to the above cited polymers was practically the
same as that of TEMPO (∼0.88 V vs NHE).
In this paper, we describe the synthesis of novel spiro-
bisnitroxides 6 and 6a containing two nitroxide groups
with significantly different oxidation potentials and very
1
2 h at 100 °C in vacuum and then transferred into an argon
-
1
high theoretical charge capacity of 174 and 173 mA h g
,
2
filled glovebox for cell assembly. Typical electrodes of 1.33 cm
geometric surface contained ca. 2 mg of nitroxide polymer. A
respectively (Scheme 2). Furthermore, 6 was transformed
into the polyacetylene polymers 7 and 7a of which the
latter was evaluated as a cathode material for organic
radical battery.
6
solution of LiPF (1M) in a 1:1 mixture of ethylene carbonate/
dimethyl carbonate (EC/DMC) or propylene carbonate (PC)
was used as electrolyte, and the counterelectrode was made from
lithium foil. Galvanostatic cycling was performed at 25 (( 0.1) °C
on a Batsmal battery measurement system (Astrol Electronic
AG). Cyclic voltammograms were measured at a sweep rate of
Experimental Section
Triacetonamine (>99%), was obtained from Ciba; all other
reagents and solvents (>99%) were purchased from Fluka and
-1
0.1 V s with an AMEL model 2049 potentiostat at 22 °C in
used as received. The catalyst [Rh(norbornadiene)(B(C
6 5 4
H ) )] was
acetonitrile containing 0.1M Bu NBF . Platinum wires wereused
4
4
0
2
prepared according ref 31, N,N -diprop-2-ynyl-oxalamide, accord-
ing to ref 32. The solid supported catalyst Fulcat 22B was obtained
from Laporte, England. Other acid catalysts will work too.
as the counter and working electrodes (20 mm ), a silver wire was
used as reference electrode, and potentials are given versus the
ferrocene/ferricenium (Fc) redox system.
4
50 mL four neck flask was charged with triacetonamine
-Amino-2,2,6,6-tetramethyl-piperidine-4-carbonitrile (2). A
(
(
(
(
(
(
(
19) Koshika, K.; Sano, N.; Oyaizu, K.; Nishide, H. Chem. Commun.
009, 7, 836–838.
20) Suguro, M.; Iwasa, S.; Kusachi, Y.; Morioka, Y.; Nakahara, K.
Macromol. Rapid Commun. 2007, 28(18-19), 1929–1933.
21) Suguro, M.; Iwasa, S.; Nakahara, K. Macromol. Rapid Commun.
7
2
(155.2 g, 1 mol) and acetone cyanhydrin (154.4 g, 1.81 mol).
The suspension was stirred at 75-80 °C during 1 h, and the
acetone generated in the reaction was continuously distilled off.
The mixture was then cooled to room temperature, and 100 mL
of methyl-t-butyl ether were added. The slurry was cooled to
2
008, 29(20), 1635–1639.
22) Suga, T.; Yoshimura, K.; Nishide, H. Macromol. Symp. 2006, 245-
46, 416–422.
23) Oyaizu, K.; Suga, T.; Yoshimura, K.; Nishide, H. Macromolecules
008, 41, 6646–6652.
24) Zhang, X.; Li, H.; Li, L.; Lu, G.; Zhang, S.; Gu, L. Polymer 2008,
2
5 °C, filtered, washed with 150 mL cold methyl-t-butyl ether,
and dried to afford 149.7 g (82%) of 4-hydroxy-2,2,6,6-tetra-
2
49(16), 3393–3398.
methyl-piperidine-4-carbonitrile as white crystals, mp 134-
25) Qu, J.; Katsumata, T.; Satoh, M.; Wada, J.; Igarashi, J.;
Mizoguchi, K.; Masuda, T. Chem.;Eur. J. 2007, 13(28), 7965–
33
1
of this material were added to a methanolic solution of NH
36 °C (literature mp 136 °C). A 148.8 g portion (0.816 mol)
7973.
3
gas
(
26) Qu, J.; Fujii, T.; Katsumata, T.; Suzuki, Y.; Shiotsuki, M.; Sanda,
F.; Satoh, M.; Wada, J.; Masuda, T. J. Polym. Sci., Part A: Polym.
Chem. 2007, 45(23), 5431–5445.
(
230 g, 16.6% NH by weight), and the mixture was stirred at
3
room temperature during 19 h. The colorless solution was
evaporated at 10 mbar and a maximum of 25 °C to afford
163 g of crude 2 as a colorless oil slowly crystallizing on standing.
Sample recrystallized from hexanes had an mp 75-77 °C
(
(
(
(
27) Qu, J.; Khan, F. Z.; Satoh, M.; Wada, J.; Hayashi, H.; Mizoguchi,
K.; Masuda, T. Polymer 2008, 49(6), 1490–1496.
28) Qu, J.; Morita, R.; Satoh, M.; Wada, J.; Terakura, F.; Mizoguchi,
K.; Ogata, N.; Masuda, T. Chem.;Eur. J. 2008, 14(11), 3250–3259.
29) Suga, T.; Pu, Y.-J.; Kasatori, S.; Nishide, H. Macromolecules 2007,
3
4
1
3
(literature mp 75-76 °C). H NMR (CD OD): 4.7 (bs, 3H),
40, 3167–3173.
30) Qu, J.; Katsumata, T.; Satoh, M.; Wada, J.; Masuda, T. Macro-
molecules 2007, 40, 3136–3144.
(33) German Patent DE 91122, 1897. Chem. Abstr. 1906, 265353.
(34) Toda, T.; Morimura, S.; Mori, E.; Horiuchi, H.; Murayama, K.
Bull. Chem. Soc. Jpn. 1971, 44(12), 3445–3450.
(
(
31) Schrock, R. R.; Osborn, J. A. Inorg. Chem. 1970, 9(10), 2339–2343.
32) Reimlinger, H. Liebigs Ann. Chem. 1968, 713, 113–118.