himnos y marchas militares

Jhe-Yong Lin (林哲永), Hui-Min Wang (王惠民), Sheng-Huei Hsiao (蕭勝輝)*
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology,
1 Chunghsiao East Road, Section 3, Taipei 10608, Taiwan
E-mail: [email protected]
Abstract
A novel class of electroactive polyimides with ether-linked anthraquinone (AQ) units were prepared from the polycondensation reactions of a newly
synthesized CF3-containing AQ-dietheramine monomer with aromatic tetracarboxylic dianhydrides via a conventional two-step technique. The
fluorinated polyetherimides (PEIs) exhibited enhanced solubility and optical transparency and decreased dielectric constants because of increased free
volume caused by the CF3 substituents. Furthermore, the PEIs showed high thermal stability, with glass-transition temperatures of 263-312 oC and
decomposition temperatures in excess of 500 oC. These PEIs were also investigated by cyclic voltammetry and UV-visible spectroelectrochemistry.
Preliminary results reveal that these AQ-based PEIs are potentially useful as cathodically coloring red electrochromes.
Introduction
Experimental
What is electrochromism ?
A reversible color change takes place upon reduction (gain of electrons) or oxidation (loss of electrons).
Scheme 1. Synthetic route to CF3-containing AQ-dietheramine 3
www.gentex.com
http://www.siemens.com
http://wwwf.imperial.ac.uk
Polym. Eng. Sci. 2008, 48, 2224.
(a)
(b)
(c)
(d)
Himnos y Marchas Militares Vol.1
E. S. Lee et al. Sol. Energy Mater. Sol. Cells, 2002, 71, 465.
Suitable electron acceptor
Excellent electron mobility
Spectroelectrochemistry
Property comparison
S-H Hsiao, W-J Guo, C-L Chung, W-T Chen.
Eur. Polym. J. 2010, 46, 1878–1890.
S-H Hsiao,Y-R Kung. Polym. Int. 2013. 62, 573-580.
S-H Hsiao,Y-R Kung. Polym. Int. 2013, 62, 573-580.
Figure 1. (a) 1H NMR, (b) H-H COSY, (c) 13C NMR and (d) C-H HMQC spectra of monomer 3 in DMSO-d6 .
H-M Wang, S-H Hsiao. JPSA. 2011, 49, 337-351.
Results and Discussion
Thermal Properties
Basic Properties
Table 1. Inherent viscosity and solubility behavior of PEIs
Polymer
codea
5a-T
5a-C
5b-T
5b-C
5c-T
5c-C
5’c-C
5d-T
5d-C
5e-T
5e-C
5f-T
5f-C
Table 2. Thermal properties of PEIs
ηinh (dL/g)b
PAAd
1.21
1.01
0.94
0.89
0.77
0.85
Optical Properties
Solventsc,e
Polyimide
NMP
DMAc
DMF
0.51
0.76
---+-++
+-++++
-++
---+-++
--++++
-++
---+-++
--++++
+++
mDMSO
Cresol
------+---++
+----+-++++
+--++
+-
a T:
THF
---------+++
-++
polymer prepared by the thermal imidization method, C: by the chemical imidization method.
viscosity measured at a concentration of 0.5 dL/g in DMAc at 30 oC.
cSolvent: NMP: N-methyl-2-pyrrolidone; DMAc: N,N-dimethylacetamide; DMF: N,N-dimethylformamide; DMSO: dimethyl
sulfoxide; THF: tetrahydrofuran.
dPAA: Poly(amic acid).
eThe qualitative solubility was tested with 10 mg of a sample in 1 mL of stirred solvent.++, soluble at room temperature; +,
soluble on heating; +-, partially soluble; -, insoluble even on heating.
bInherent
Electrochemical Properties
Polymer Tg
codea ( oC )b
Td at 5 %
weight loss
( oC )c
Table 3. Optical properties of the PEIs
Td at 10 %
weight loss
( oC ) c
Polymer code
Char yield
N2
Air
N2
Air
(wt %)d
5a
312
513
507
558
535
54
5b
289
565
557
595
587
56
5c
275
545
540
577
571
53
5d
263
547
541
580
574
53
5e
276
451
493
492
521
50
5f
281
536
531
557
552
51
5’f
285
565
549
592
578
56
Imidization
methoda
Blank
5a
5b
5c
5d
5e
5f
Kapton
5’f
E1/2Red,1
－
(T)
－
－
－
－
42
47
45
－
20.7
12.4
7.3
5.8
1.3
2.0
-
(C)
-0.6
(T)
－
－
－
－
-3.8
-3.2
－
12.3
－
66.2
52.3
43.1
30.3
36.0
99.7
-
L*
(C)
0.3
－
－
－
－
26.7
22.1
－
57.1
(T)
－
64.4
75.9
75.2
82.3
80.8
81.0
-
(C)
96.5
－
－
－
－
84.5
85.6
－
64.5
(T)
－
429
425
423
417
425
462
-
(C)
－
－
－
－
－
423
425
－
490
(T)
－
539
539
537
521
506
534
-
(C)
－
－
－
－
－
473
468
－
580
polymer prepared by the thermal imidization method, C: by the chemical imidization method. b The color parameters were
calculated according to a CIE LAB equation. L* is the lightness, where 100 means white and 0 implies black. A positive a* means a red
color, and a negative a* indicates a green color. A positive b* means a yellow color, and a negative b* implies a blue color.
c Absorption edge from the UV–vis spectra of the polymer thin films.
a All
the polymer films were heated at 300 oC for 1 h to DSC and TGA experiments.
b Midpoint temperature of the baseline shift on the second DSC heating trace (rate= 20 oC/min) of the sample after quenching
from 400 to 50 oC (rate= 20 oC/min) in nitrogen.
c Decomposition temperature at which a 10% weight loss was recorded by TGA at a heating rate of 20 oC/min.
d Residual weight % at 800 oC at a scan rate 20 oC /min in nitrogen.
5f-C
5’f-C
5’f
Polyimide Films
(a)
(b)
Spectroelectrochemistry
(c)
Bandgaps
(eV)
Reduction potential (V)
EonsetRed
－
47
43
44
48
43
41
-
(C)
b*
λ at 80%
transmission
(nm)
Table 5. Electrochromic properties of PEI 5d
Code
λmaxabs λonsetabs
(T)
a*
λ0
(nm)c
a T:
Figure 2. TGA and DSC curves of PEI 5c
at a heating rate of 20 oC/min.
Table 4. Redox potentials and energy levels of PEIes
Thin film (nm)
Color coordinatesb
Film thickness
(μm)
E1/2Red,2 E1/2Red,3 E1/2Red,4 E1/2Red,5
5a
341
365
-0.64
-0.71
-1.19
5b
340
364
-0.59
-0.68
-1.03
-1.22
5c
336
359
-0.60
-0.68
-0.81
-1.10
5d
339
362
-0.54
-0.69
-1.15
-1.31
5e
353
382
-0.52
-0.65
-0.81
-0.99
5f
348
393
-0.46
-0.66
-1.01
-1.13
5g
-
-
-0.60
-0.65
-1.25
Polymer
Egopt
3.40
3.41
-1.28
-1.64
3.45
3.43
-1.29
(d)
(e)
(f)
λmaxa
(nm)
Δ%T
Response timeb
ΔODc
tc (s)
tb (s)
5d
563
36
5.0
7.9
0.199
aWavelength of absorption maximum.
bTime for 90% of the full-transmittance change.
cOptical Density (ΔOD) = log[T
bleached /Tcolored ],
dQ is ejected charge, determined from the in situ experiments.
d
eColoration efficiency (CE) =ΔOD/Q .
d
(a)
Qdd(mC/cm2)
CEe(cm2/C)
1.74
114
(b)
3.25
Figure 5. Spectroelectrochemistry of 5d
thin film on the ITO-coated glass substrate
in 0.1 M Bu4NClO4/ DMF under negative
potential scanning.
3.16
-
5g
Figure 3. Cyclic voltammograms of model compound 5g (1x10-3 M) in 0.1 M
Bu4NClO4/ DMF at a scan rate of 100 mV/s.
Figure 4. Cyclic voltammograms of the cast films of PEIs (a) 5a, (b) 5b, (c) 5c, (d) 5d, (e) 5e and (f) 5f
in 0.1 M Bu4NClO4/ DMF at a scan rate of 50mV/s.
Figure 6. Potential step absorptiometry of the cast film of 5d on the ITO-glass slide (coated area: 1.0 cm2)(in DMF
with 0.1M Bu4NClO4 as the supporting electrolyte)by applying a potential step (a) 5d at potential 0.0 V ~ -1.25 V and
cycle time 12 s, and (b) optical switching for 5d at λmax = 563 nm as the applied voltage was stepped between 0.0 V
and -1.25 V (vs. Ag/AgCl).
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