J. Serb. Chem. Soc. 71 (1) 75–89 (2006)
JSCS – 3398
UDC
Original scientific paper
Chemical polymerization of aniline in phenylphosphinic acid
NICOLETA PLESU1*, GHEORGHE ILIA1, GEZA BANDUR2 and SIMONA POPA2
1Institute
of Chemistry of Romanian Academy, Mihai Viteazul Bul. 24, 300223-Timisoara,
Romani (e-mail: [email protected]) and 2University “Politehnica” Timisoara,
Bocsei No. 6, Timisoara, Romania
(Received 20 August 2004, revised 5 May 2005)
Abstract: The chemical polymerization of aniline was carried out in phenylphosphinic acid (APP) medium using ammonium peroxidisulphate as the oxidant agent,
at 0 ºC and 25 ºC. The yield of the polyaniline (PANI) was about 60–69 %. The polymerization process required an induction time 8–10 times greater than in other acids
(hydrochloric, sulfuric). The density determined for polymer sample shows that the
average density was 1.395 g cm–3 for PANI-salt and 1.203 g cm–3 for PANI-base.
The acid capacity of PANI depends on the synthesis parameters and maximum value
was 15.02 meq/g polymer. The inherent viscosity of the PANI was 0.662 dl/g at aniline/oxidant molar ratios >2 and 0 ºC. The oxidation state function of synthesis parameters was situated between 0.553–0.625 and was evaluated from UV-VIS and titration with TiCl3 data. The PANI was characterized by density, inherent viscosity,
conductivity, acid capacity, FTIR, UV-VIS and thermmogravimetric measurements.
Keywords: chemical oxidation, aniline, phenylphosphinic acid, conducting polymers, polyaniline
INTRODUCTION
Studies concerning the field of conducting polymers have opened up new and
attractive domains of applications, due to the possibility of the synthesis of this
new generation of polymers by methods which lead to products having the mechanical properties and attractive processability of traditional polymers combined
with the electrical and optical properties of electronic conductors.1-21
PANI is a conducting polymer which can easily be synthesized by both chemical and electrochemical methods. It seems to be the most studied conducting polymer due to its simple synthesis and its environmental stability. The general formula
of PANI presents the same structure in all cases and consists of a succession of reduced benzenoid nuclei and oxidized quinoid nuclei, but the diversity of the oxidation form affects the performance of the polymer and the reproducibility of the synthesis. The properties of PANI depend on the monomer/oxidant molar ratio, pH,
*
Coresponding author.
doi: 10.2298/JSC0511243G
75
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PLESU et al.
and reaction temperature, the nature of the employed acid, the mode of doping and
the structure of the monomer (presence of substituents). An important aspect of
PANI synthesis is the nature of the acid. The role of the acid dissociation constant
pKa is known; in PANI, the protonation equilibrium involves the quinoid nucleus
having two imine nitrogens with pKa1 = 1.05 and pKa2 = 2.55,6 therefore any acid
is suitable as a dopant if its pKa value lies in this range. Any acid having a pKa
around the value of the anilinium ion (pKa = 4.60) would be suitable as solvent and
prevents the overoxidation process.1 Thus, the properties of conductive PANI are
affected by the type of the employed dopant ion. The most preferred method for
synthesis is to use either hydrochloric or sulfuric acid with ammonium peroxydisulphat as oxidants.1–3,13–17 The synthesis has also been carried out in other organic acids.1,19,24 The use of large anions as dopants increases the solubility of
PANI.23,25 The conductivity of PANI is closely related to the redox state of the
polymer, the pH of the working medium and the type of the dopant anion.6 The
type of dopant anion affects the stability, electrical conductivity polymerization kinetics and the yield of the polymer.7 The synthesis and the characterization of
PANI doped with different anions are critical since many properties of the final
polymer are greatly influenced by the nature of the dopant ion.
In this study, the chemical polymerization of aniline was carried out in the
presence of aqueous APP solutions, not previously mentioned in the literature. The
PANI samples were characterized by FTIR, UV-VIS, density, inherent viscosity,
conductivity, acid capacity. The oxidation state of PANI samples was determined
by titration with TiCl3 solution and from UV-VIS data.
EXPERIMENTAL
Chemicals
Aniline freshly distilled and cooled at –4 ºC, phenylphosphinic acid (C6H5PH(O)OH, APP,
Aldrich), ammonium peroxidisulphate (Merck), ammonium hydroxide, N,N dimethylformamide
(DMF) were used.
Preparation of PANI-APP
PANI was obtained by oxidizing aniline in aqueous APP solutions with ammonium peroxidisulfate as the oxidizing agent. The molar ratio the aniline/oxidant (A/O) was 1; 1.33; 2 and 4, and aniline/APP ratio (A/APP): 1/1, 1/2, 1/3, 1/4 (1; 0.5, 0.33; 0.25), at 0 ºC and 25 ºC. The procedure was
the same for all preparation: first the aniline salt was formed by the dropwise addition of aniline (0.1
mol L–1) to an aqueous solution of APP, under continuous stirring and precooling. To this solution, a
precooled aqueous solution of ammonium peroxidisulfate (0.025 – 0.1 mol L–1) was added
dropwise under continuous stirring. After 24 h, the stirring was stopped, the PANI recovered by filtration, and washed several times with a dilute APP solution. The resulting PANI was dried in a dynamic vacuum for 24 h. The product was converted to PANI-base form with ammonium hydroxide.1
Characterization
The IR spectra were recorded in KBr pellets. The UV-VIS spectra were measured in DMF using a Specord M42 spectrophotometer. The conversion was calculated as the % crude product
(grams of dry polymer without purification ±100/ g aniline). The oligomer fractions (containing
POLYMERIZATION OF ANILINE IN PHENYLPHOSPHINE ACID
77
oligomeric and secondary products) were determined by the difference between % crede product
and the % dry polymer after purification. The yield (%) represents the grams of dry purified polymer
±100/g aniline.
The oxidation of aniline is exothermic, hence the temperature of the reaction mixture can be
used to monitor the progress of the reaction. The temperature-time profile is well reproducible and
was obtained using a high precision thermometer. It was possible to determine the induction time
from the temperature-time profile, as well as the maximum temperature. The induction time represents the time required to reach half of the total increase of temperature during the exothermal step.
The inherent viscosities of PANI samples doped with APP were determined as 0.01 % solutions in
97% sulfuric acid, using an Ubbelohde viscosimeter.. The density of PANI was determined by the
picnometer method, in decaline. The lectrical conductivities were measured on press pellets by the
two-probe method.
The acid capacity of the polymer was determined from the quantity of sodium hydroxide
(0.005 mol L–1) required for the titration of the polymer samples. PANI powder was suspended in
water and titrated with sodium hydroxide in a closed cell under nitrogen. The titration was performed very slowly, with incremental addition of 0.2–0.5 ml, with a delay of 15 min between two
consecutive additions, required for pH stabilization. The measurements were performed with a CG
841 SCHOTT pH meter, using a glass electrode, type SCHOTT GERATEN N 2041A. Three determinations were performed for each sample. The acid capacity, reported for 1 g of polymer, was determined from the neutralization curve.
The oxidation state of PANI was determined from the relative proportion of benzenoid and
quinoid rings in the polymer chains. This method is based on the quantity of hydrogen needed to
transform the quinoid rings into benzenoid rings (the conversion of emaraldine to leucoemeraldine).
Experimentally, it involves in the titration of PANI dissolved in acetic acid (80 %) with TiCl3. It is
known that the conversion of emeraldine to leucoemeraldine requires a theoretical quantity equal to
0.543 % H/gram emeraldin.22 The oxidation state was also determined from the UV-VIS absorbance
spectra of the polymers dissolved in DMF. Thermal analysis of the samples was performed using a
TG 209 (Netzsch) at a heating rate of 25 ºC/min in range 20 to 990 ºC, in a nitrogen atmosphere and a
DSC 204, (Netzsch) in a nitrogen atmosphere in range 20 to 500 ºC, with a heat rate 25 ºC/min.
RESULTS AND DISCUSSIONS
The oxidative polymerization of aniline in APP is an exothermal process. An
S-shape temperature-time dependence can be observed (Fig. 1). The oxidative
polymerization of aniline in acid media presents three distinctive steps. The first is
slow and independent of temperature. The active species in the polymerization
process are formed. The second step is faster and temperature dependent; the polymer is formed due to propagation. The post-polymerization step (third step) is also
temperature dependent, and the polymer undergoes protonation-deprotonation,
and oxidation-reduction processes.
The obtained temperature-time profiles for the polymerization of aniline in
APP indicated a long induction period (8–10 times greater) compared to the synthesis under the same condition in AS or in other known acids, mentioned in the literature (hydrochloric, picric).8,14,20,23 The induction time was determined from
temperature-time dependence and represents the time required to reach half of the
total increase in the temperature during the exothermal step. Hence for the PANI
obtained with an aniline/oxidant ratio of 1.33 and an aniline/acid ratio of 1/2 at 0 ºC
in AS the induction time is 6.9 min and in APP in the same condition it was 65 min.
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PLESU et al.
Fig. 1. The temperature-time profile for aniline polymerization at an aniline/oxidant molar ratio
of 1.33 and an aniline/acid ratio of 1/2 in AS at 0 ºC, in APP at 0 ºC and 25 ºC (secondy-axis,
filled triangle).
With increasing synthesis temperature, the induction time decreases, hence, in
APP under the same conditions, but at 25 ºC, the induction time was 55 min.
The UV-VIS spectra recorded during the polymerization of aniline in APP
have an absorption peak at 720 nm. This peak appears after the induction period
necessary for the formation of the cation-radical species which initiate the polymerization (Fig. 2). The absorbance of this peak increases with time during the
evolution of the polymerization. The broad absorption band, which first appeared
between 700 and 840 nm, becomes narrower.
Fig. 2. The absorbance spectra during the polymerization of aniline on
an aniline/oxidant molar ratio of 2
and an aniline/APP molar ratio of 1/1
solution, at 0 ºC, after different times
of polymerization: 1- 80 min., 2- 85
min., 3- 90 min., 4- 100 min., 5- 115
min.
POLYMERIZATION OF ANILINE IN PHENYLPHOSPHINE ACID
79
The induction time depends on the synthesis parameters. Comparing the
absorbance at different APP concentrations, it can be seen that the polymerization
started fastest in the solution containing aniline and APP in a 1:1 ratio (Figs. 3, 4).
This is in accordance with the results of Lux,23 i.e., the polymerization is suppressed in more acidic media. This is mainly attributed to the protonation of aniline, which increases with increasing concentration. Thus, the degree of protonation of aniline is lowest at an aniline/APP ratio of 1:1 and is highest at an
aniline/APP ratio of 1:4 (Fig. 3).
Fig. 3. The absorbance versus at 720 nm time of polymerization at an aniline/oxidant molar ratio
of 1.33 and different aniline/APP molar ratios.
The degree of protonation of aniline increases with incresing APP concentration as a result of the slow formation of cation-radicals. The oxidation process of
protonated species is more difficult compared to the unprotonated ones, and decreases linearly with increasing oxidant concentration (decreasing of aniline/oxidant molar ratio).
With increasing amount of oxidant amount (decreasing aniline/oxidant molar
ratio) and decreasing quantity of acid in the solution (Figs. 5, 6), the polymerization
rate of aniline in APP solutions increases. The polymerization rate could be assessed
by the differential method in percent per minute, from % crede product versus time
profile, and was equal to the slope for a particular moment of the polymerization.
The IR spectra of PANI recorded in KBr pellets indicate the presence of five
characteristic peaks in all samples, at 1580 cm–1, 1490 cm–1, 1307 cm–1, 1145
cm–1 and 826 cm–1, which agrees with literature data.9,10,21
The peak at 3232 cm–1 of each curve is attributed to the N–H stretching vibrations. Its intensity is very sensitive to the concentration of APP, and increases with
incresing acid concentration. The peaks at 1580 and 1490 cm–1 are attributed to the
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PLESU et al.
Fig. 4. The induction time versus aniline/oxidant ratio for different aniline/APP molar ratios, at 0 ºC.
quinoid and benzenoid ring deformation, respectively, and are present in the samples
of PANI obtained by chemical synthesis. Their positions are independent of doping.
Fig. 5. Polymerization rate versus time for different aniline/oxidant molar ratios at an aniline/APP
molar ratio of 1/1, at 0 ºC.
With increasing acid and oxidant concentrations, the experimental data show: a decrease in the intensity of the peak characteristic of benzenoid rings at 1500 cm–1; an increase of the intensity of the peaks due to the quinoid rings at 1375, 1150, 1560–1570,
1470–1490 and 1630 cm–1; a decrease of the intensity of peaks at 1630 cm–1, due to the
overoxidation process which results in a decay of the quinoid structure to decay and the
appearance of characteristic peaks of benzoquinone at 885, 944, 1080, 1313, 1654 cm–1.
POLYMERIZATION OF ANILINE IN PHENYLPHOSPHINE ACID
81
Fig. 6. Polymerization rate versus time for different aniline/APP molar ratios, for an aniline/oxidant molar ratio of 1.33, at 0 ºC.
The intensities of benzenoid and quinoid rings peaks in the IR spectra are,
qualitatively the same for an aniline/oxidant ratio situated in range 2 – 4. The employed aniline/acid ratio lay between 1/1 and 1/2. As a result, the PANI is obtained,
in the emeraldine form.
The UV-VIS spectra of PANI base were recorded in N,N-dimethylformamide.
The spectra allowed the detection of absorption maxima of polyaniline salt or base.
PANI was absorption maxima due to the p – p* transition of the benzenoid ring at
333 nm, characteristic for its most reduced form, i.e. polyleucoemeraldine; the p –
p* transition of the quinoid rings at 627 nm, characteristic for the partial oxidation
of PANI- polyleucoemeraldine form. Further oxidation to the fully oxidated form,
i.e., polypernigraniline, produces a blue shift of the p – p* transition of the quinoid
peak at 430 nm (due to the formation of a semiquinoidic nucleus) and a band at 844
nm (due to formation of an exiton centered on a quinoid nucleus).
The yield in PANI, conductivity, inherent viscosity and percent of hydrogen
per gram polymer required for the reduction of samples with TiCl3 at different aniline/oxidant ratios, and aniline/APP ratios are summarized in Table I.
The observed average yield was about 65 % in APP. The polymer yield increased almost linearly with decreasing aniline/oxidant ratio. The density of the
polymer samples had an average value of about 1.395 g cm–3 for the PANI-salt and
1.203 g cm–3 for the PANI-base. The viscosity decreased significantly when the
aniline/oxidant ratio was lower than 2. With increasing amount of oxidant in the reaction medium, the concentration of the formed radical cation formed increased
and the resulting polymer chains were shorter, hence the inherent viscosity decreased (Table I).
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PLESU et al.
TABLE I. The yield of PANI, conductivity, inherent viscosity and density of PANI in dependence of
the polymerization conditions
No.
sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
A/O* A/APP**
4
2
1.33
1
4
2
1.33
1
4
2
1.33
1
4
2
1.33
1
1/1
1/2
1/3
1/4
Yield %*
0 ºC
52.61
58.38
62.29
66.71
48.91
53.74
54.30
57.78
46.79
52.06
51.67
53.97
44.42
44.45
48.47
49.41
25 ºC
54.82
60.83
64.91
68.51
50.96
56.00
56.58
60.21
48.76
54.25
53.84
56.24
46.29
46.32
50.51
51.49
Conductivity S Inherent viscosDensity dL g–1
cm–1
ity dL g–1
0 ºC
25 ºC
0 ºC
25 ºC 0 ºC
25 ºC
0.07
0.06
0.625 0.601
0 ºC
25 ºC
0.49
0.39
0.589 0.547 1.395 1.438
0.56
0.44
0.567 0.495 1.395 1.396
0.78
0.62
0.494 0.465 1.396 1.427
1.92
1.06
0.638 0.582 1.398 1.431
1.15
0.91
0.612 0.577 1.387 1.452
0.62
0.49
0.582 0.535 1.391 1.456
1.10
0.87
0.523 0.502 1.395 1.458
1.68
1.07
0.655 0.598 1.399 1.451
0.89
0.70
0.632 0.519 1.396 1.460
1.89
1.10
0.588 0.519 1.394 1.453
0.92
0.73
0.547 0.515 1.396 1.457
0.44
0.35
0.662 0.598 1.398 1.461
1.25
0.99
0.645
0.54
1.395 1.458
1.80
1.11
0.592 0.488 1.396 1.460
1.45
1.03
0.554 0.452 1.396 1.458
*A/O – aniline/oxidant; ** A/APP – aniline/acid phenylphosphinic
Fig. 7. Conductivity of PANI samples versus induction time for different aniline/APP molar ratios, at 0 ºC.
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POLYMERIZATION OF ANILINE IN PHENYLPHOSPHINE ACID
The conductivity showed a small tendency to increase with increasingacid
concentration (Table I) and to decrease with increasing induction time (Fig. 7).
Higher values of the electrical conductivity were obtained in more acid media
(Table I). The conductivity increased with increasing proton concentration in the
aqueous acid media, due to the formation of doped polymer, and due to the existence of a remanent quantity of acid retained by the polymer chains.1,2,11 At aniline/oxidant molar ratios < 2, the inherent viscosity of the PANI samples was
higher (higher molar masses), and the conductivity should also be higher too, because the electrical conductivity increases with increasing polymer chain length. It
can be seen from the experimental data that the molar mass of PANI has almost no
effect on its electrical conductivity. Such a behavior was theoretically predicted for
the cases when the charges hop from one polymer chain to another. These hops are
faster in comparison to the life-time of the charge on the chain, i.e. when interchain
transport occurs more readily than intrachain transport and decreases with increasing reaction temperature.12,17
The oxidation state of PANI was estimated by calculating the intensity ratio of the
peaks at 620 nm and 320 nm (IQ/IB) for each UV-VIS spectrum of the polymer samples
and from the percentage hydrogen necessary to reduce the PANI samples (Table II).
TABLE II. The IQ/IB ratio, acidic capacity and percent of hydrogen per gram polymer, in dependence of the polymerization conditions
No.
sample
A/O*
A/APP**
1/1
IQ/IB
Mechiv/g polym
0 ºC
25 ºC
0 ºC
25 ºC
% H/g dry polymer
0 ºC
25 ºC
1
4
0.75
0.78
13.0
12.76
0.61
0.646
2
2
0.83
0.84
13.67
13.24
0.612
0.652
3
1.33
0.76
0.77
13.96
13.36
0.632
0.654
4
1
0.67
0.68
10.55
10.04
0.645
0.664
5
4
0.73
0.74
13.48
13.01
0.62
0.650
6
2
0.86
0.88
14.05
13.51
0.624
0.655
7
1.33
0.92
0.94
14.34
13.76
0.559
0.661
8
1
0.52
0.53
14.53
13.98
0.662
0.667
9
4
0.74
0.75
13.77
13.33
0.635
0.665
1/2
1/3
10
2
0.89
0.91
13.96
13.92
0.637
0.674
11
1.33
0.61
0.62
14.53
14.07
0.662
0.680
12
1
0.74
0.75
14.82
14.30
0.669
0.681
13
4
0.32
0.53
13.96
13.40
0.647
0.67
1/4
14
2
0.44
0.55
14.44
13.89
0.65
0.673
15
1.33
0.63
0.64
14.91
14.25
0.668
0.682
16
1
0.87
0.89
15.2
14.44
0.672
0.684
*A/O – aniline/oxidant; ** A/APP – aniline/acid phenylphosphinic
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PLESU et al.
The ratio of quinoid and benzenoid units (i.e. C=N/C–N) was calculated on
the basis of the following equation.
(1)
Larger quantities of oxidant favored the oxidation of the polymer chain and
enabled the formation of the polymer in an advanced slate of oxidation state
(pernigraniline) with an increased amount of quinoniminic rings.
The oxidation state (Y) of the obtained polymers was about 0.583 and both
methods of determination gave appropriate values and indicate that the PANI, synthesized in APP was obtained in the emeraldine state (Fig. 8).
Fig. 8. Oxidation states of PANI samples versus aniline/oxidant molar ratio at an aniline/APP molar ratio of 1/1.
The acid capacity of samples represent the quantity of base (meq.) necessary
for the neutralization of one gram of dry polymer and was determined from titration curves. With increasing quantity of oxidant and decreasing amount of acid, the
acidic capacity decreased (Table II).
Solubility tests in solvents such as NMP, DMF, DMSO indicated an enhanced
solubility of doped PANI samples obtained with APP compared with the samples
obtained in sulfuric acid (AS) under the same condition. The PANI samples synthesized at an aniline/oxidant molar ratio of 2, an aniline/acid molar ratio of 1/2, at
0 ºC had the highest solubility (Table II).
The increase in the solubility was attributed to the presence of the voluminous
phosphinate anion, the polymer-solvent interaction of which are much stronger
than polymer-polymer ones.
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POLYMERIZATION OF ANILINE IN PHENYLPHOSPHINE ACID
TABLE III. The solubility data of doped PANI samples obtained at an aniline/oxidant molar ratio of
2 and an aniline/acid molar ratio fo 1/2, at 0 ºC
Dopant
Solvent
NMP /
gL–1
DMF / gL–1
DMSO / gL–1
AS
–
0.042
0.006
APP
0.521
0.106
0.232
The thermal stability of polymers was studied by TGA and DSC; the TGA
curves for some samples are presented in Fig. 9.
In general the thermal behavior of PANI samples showed a characteristic
“three step” weight loss, as can be seen from the DSC curves illustrated in Fig. 10.
During heating up to 150 –C, weight losses due to the release of the residual
water present in all the PANI samples lie between 6 % for PANI-AS (Fig. 9 curve
A, B) and 9 % for PANI-APP (Fig. 9 curve C, D).
Fig. 9. Thermogravimetric curve for A: PANI-AS (A/O = 1.33. A/AS = 1/1, 0 ºC); B:
PANI-AS(A/O = 1, A/AS = 1/1, 0 ºC); C: PANI-APP (A/O = 1.33, A/APP = 1/1, 0 ºC); D:
PANI-APP (A/O = 1.33, A/PP = 1/2, 0 ºC) E: APP, F: PANI-AS (A/O = 2, A/AS = 1/1, 0 ºC).
Water molecules are able to occupy sites instead of dopants in polyanilin,
hence the residual water cannot be assumed to be humidity, because all the samples
were dried before the TG measurements. This phenomenom has also been observed by other authors.4,7,11,12–14
The weight loss in the temperature range 150 ºC to 400 ºC varied between 1 and
33 % for PANI samples obtained in AS and doped with HSO4– ions and 16 and 24 %
for PANI samples obtained in APP and doped with APP and are related to dopant
loss and degradation of the fomred oligomer chains formed. With increasing amount
of oxidant in the reaction medium, the polymer chains become shorter and the
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PLESU et al.
weight loss became higher. The use of large amounts of oxidant induces polymer
degradation. With increasing acid concentration, and temperature of synthesis, the
weight loss increases, due to the increasing content of dopant in the polymer samples. In the same temperature range, the PANI-APP samples showed two inflexion
points, corresponding to the decomposition of the dopant. APP (Fig. 9 curve E) remains stable up to 200 ºC, after which it starts decomposing gradually up to 410 ºC,
with two maximum decomposition rates at 239 ºC and 401 ºC and with a weight loss
of 61 % in this domain The maximum weight loss (24 %) was observed for the
PANI-APP obtained at an aniline/oxidant molar ratio = 1, an aniline/APP ratio = 1/2
and 25 ºC, and the minimum loss (16 %) was observed for the PANI-APP obtained at
an aniline/oxidant molar ratio = 1.33, an aniline/APP = 1/1 at 0 ºC.
In general, both the decomposition temperature and the weight loss are affected by the molar mass, and decrease with decreasing molar mass. For PANI synthesized in APP, the thermal stability decreases in a similar manner to that of PANI
Fig. 10. DSC curves for A: PANI-AS (A/O = 1.33, A/AS = 1/1, 0 ºC); B: PANI-AS(A/O = 1.
A/AS = 1/1, 0ºC); C: PANI-APP (A/O = 1.33, A/APP = 1/1, 0ºC); D: PANI-APP (A/O = 1.33,
A/APP = 1/2, 0 ºC).
obtained in AS. For example, for PANI-AS obtained at an aniline/acid ratio of 1/1
and an aniline/oxidant molar ratio of 1.33, the temperature corresponding to Dm =
50 % was 988 ºC, and for PANI-APP it was 489.2 ºC. The 50 % (Dm = 50%) weight
loss for the PANI-AS samples obtained at an aniline/acid ratio of 1/1 and at an aniline /oxidant molar ratio of 1.33 and 2 occurs at higher temperatures (TDm=50%,)
988 ºC and 877 ºC, respectively. This is in accordance with the inherent viscosity
values which indicate a higher molar weight. It was observed that the decomposision process took place at higher temperature with increasing aniline/oxidant
molar ratio, due to the increase of molar weight, as evidenced by the inherent vis-
POLYMERIZATION OF ANILINE IN PHENYLPHOSPHINE ACID
87
cosity (Table I). For the sample synthesized at a higher temperature, 25 ºC, the 50
% (Dm = 50%) weight loss appears at a lower temperature comparing with the sample synthesized at 0 ºC; the differences registered were between 200 – 300 ºC. In
this case, the temperature assigned to the maximum decomposition rate varies
between 230 – 300 ºC, and decreases compared with the sample obtained at 0 ºC,
due to the decrease of molar weight.
All the PANI samples a first endothermic transition at aprox. 130 ºC, as can be
seen in Fig. 10.
These peaks correspond to the evaporation of water trapped inside the polymer or bonded to the polymer chain. The second and the third peak correspond to
endothermic transitions due to the loss of acid dopant (AS and APP) and due to the
decomposition of polymer chains starting around 400 ºC, respectively.
Comparing TGA data with DSC data, the appearance of an additional peak at
was noticed only for the PANI-APP samples obtained at 0 ºC about 240 ºC (Fig. 10
curve C, D) which does not correspond to the weight loss recorded on the
thermograms.
The presence of this peak can be assigned to the interaction of PANI and dopant, in this case APP, because this additional peak was not observed with the
PANI-AS samples. The maximum decomposition rates of weight loos observed on
the thermograms, occur at the same temperatures as endothermic peaks from the
DSC curves, which correspond similarly to the maximum decomposition rate.
CONCLUSIONS
The experimental data show that PANI having a conductivity of 1.5 Scm–1
could be synthesized in APP. The polymerization process had an induction time 8 –
10 times larger that in other common acids. The average yield was about 57 %. The
average density of the polymer samples was 1.395 g cm–3 for PANI-salt and 1.203
g cm–3 for PANI-base.
The acid capacity of the PANI samples lay between 13 – 15 meq./g polymer.
The PANI samples had maximum inherent viscosity values (0.625 – 0.662
dL/g) when synthesized at an aniline/oxidant molar ratio > 2.
The UV-VIS and titration with TiCl3 data show that the oxidation state of the
obtained polymer was about 0.58.
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PLESU et al.
IZVOD
HEMIJSKA POLIMERIZACIJA ANILINA U FENILFOSFINSKOJ
KISELINI
NICOLETA PLESU1, GHEORGHE ILIA1, GEZA BANDUR2 i SIMONA POPA2
1Institute of Chemistry of Romanian Academy, Mihai Viteazul Bul. 24, 300223-Timisoara, Romania
and 2University “Politehnica” Timisoara, Bocsei No. 6, Timisoara, Romania
Hemijska polimerizacija anilina izvedena je fenilfosfinskoj kiselini sa
amonijum-peroksidisulfatom kao oksidansom na temperaturema 25 i 0 ºC. Prinos
polianilina (PANI) iznosio je 60–69 %. Indukcioni period polimerizacije bio je
8–10 puta du`i nego u hlorovodoni~noj i sumpornoj kiselini. Gustina uzoraka polimera bila je 1,395 g cm–3 za PANI-so i 1,203 g cm–3 za PANI bazu. Kiselinski kapacitet
PANI zavisi od parametara sinteze i maksimalna vrednost iznosila je 15,02 meq./g
polimera. Viskoznost PANI iznosila je 0.662 dl/g pri molskim odnosima anilin/oksidans > 2 i na temperature 0 ºC. Funkcija oksidacionog stawa parametara sinteze je
izme|u 0,553 i 0,625, a odre|ena je na osnovu UV-VIS spektara i titracije sa TiCl3. PANI
je karakterisan merewima gustine, viskoznosti, provodqivosti i kiselinskim kapacitetom.
(Primqeno 20. avgusta 2004, revidirano 5. maja 2005)
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