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Polymerization of new aniline derivatives:

Cite this: RSC Adv., 2021, 11, 21006
synthesis, characterization and application as
sensors†
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Akhat G. Mustafin, *a Lyaysan R. Latypova,*a Anastasia N. Andriianova, *a

Ilnur N. Mullagaliev,b Shamil M. Salikhov,a Renat B. Salikhovb
and Gulsum S. Usmanovaa

This work is focused on modifying aniline monomers with various characteristics that allows one to study
the effect of the substituent on the respective polymer. A series of new polyaniline (PANI) derivatives based
on an ortho-substituted aniline derivative, 2-(1-methylbut-2-en-1-yl)aniline, were synthesized and
characterized. The structures and composition of the polymers that we synthesized were confirmed by
elemental analysis, proton nuclear magnetic resonance (1H NMR) spectroscopy, carbon nuclear
magnetic resonance (13C NMR) spectroscopy, Fourier-transform infrared spectroscopy (FT-IR), and
ultraviolet-visible spectroscopy (UV). Characterization by FT-IR and UV-visible spectroscopy techniques
indicated that the polymers exist in protonated emeraldine forms. Scanning electron microscope (SEM)
results revealed that the surface morphology of the resulting polymers changed from a heterogeneous
hierarchical to spherical structure upon changing the substituent in the aniline monomers. The polymers
are soluble in common organic solvents, so they can be used to make films. The electrical properties of
Received 29th March 2021
Accepted 28th May 2021
the polymers were studied and their high sensitivity to moisture and ammonia was demonstrated. The
results of the studies showed the prospects of using thin polymer films in the design of chemical
DOI: 10.1039/d1ra02474d
sensors. The impact of the substituent on the polymer characteristics is rationalized in terms of steric
rsc.li/rsc-advances and electronic effects.

properties. A review of literature data has shown that incorpo-

Introduction ration of substituents such as alkyl,15–17 alkoxy,18,19 and hydroxy
Polyaniline (PANI) is among the most famous representatives of groups20,21 at the ortho position of the aromatic ring has
the class of electrically conductive polymers. It has a unique set a benecial effect on the solubility of polymers. As a result,
of properties: redox activity, acid–base properties, electronic polymers can be soluble not only in high polarity but also in
and ionic conductivity, and high general stability and thermal medium polarity solvents. If sulfo groups are incorporated into
stability.1–4 For this reason, the polymer nds use in energy- the ring, the polymers become soluble in aqueous solutions.22
saving devices, for screening electromagnetic radiation, to The use of this method of PANI modication not only improves
obtain antistatic and electrically conductive coatings, and as its solubility but also favors the formation of uniform thin
a corrosion inhibitor.5–8 There is a signicant potential of PANI polymer lms.
application in medicine and heterogeneous catalysis.9–11 A Recently, lms of electrically conductive polyconjugated
considerable drawback of PANI, similarly to all conductive polymers in resistive sensors, which are used to determine
polymers, lies in its extremely low solubility in the majority of various toxic gases due to high sensitivity, relatively low cost,
typical solvents, which signicantly narrows the scope of its and simple design, were intensely studied.23–25
application.12–14 One of the ways to overcome these problems One of the main advantages of sensors based on electrically
involves the functionalization of PANI that makes it possible to conductive polyconjugated polymer lms is that they can
increase the solubility while retaining many of its important operate at room temperature.26
The most important feature that makes PANI a promising
material for sensors is that its chemical and optical properties
a
Ufa Institute of Chemistry of the Russian Academy of Sciences, Republic of change due to protonation (doping) and deprotonation
Bashkortostan, pr. Oktyabrya 71, Ufa 450054, Russia. E-mail: [email protected]
b
(dedoping) processes that occur when it interacts with compo-
Bashkir State University, Republic of Bashkortostan, Z. Validi St 32, Ufa, 450076,
nents that can change the oxidation state of the polymer. PANI
Russia
† Electronic supplementary information (ESI) available. See DOI:
derivatives are efficient materials for application in potentio-
10.1039/d1ra02474d metric and amperometric sensors for various gases (NH3, HCl,

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H2S, etc.) and in pH sensors.27–29 Therefore, the development of mmol) in ethyl acetate (150 mL). The mixture was stirred on
a technology for producing electrically conductive lms based a magnetic stirrer under hydrogen. Once the reaction
on PANI derivatives and for creating chemical sensors based completed (TLC monitoring), the reaction mixture was ltered
thereon is a problem of current interest. off and evaporated.
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Previously, we performed a study on the synthesis of a new 2-(1-Methylbutyl)aniline (3). Yield: 2.8 g (93%). 1H NMR
functionalized monomer, ortho-(1-methylbut-2-en-1-yl)aniline, (CDCl3, 500 MHz) d: 1.02 (3H, t, 3J ¼ 7.4 Hz, H-40 ), 1.34 (3H, d, 3J
followed by conversion into a polymer.30 The resulting poly- ¼ 6.8 Hz, H-50 ), 1.38–1.49 (2H, m, H-30 a, H-30 b), 1.60–1.67 (1H,
mer is soluble in NMP, DMF, DMSO and moderately soluble in m, H-20 b), 1.71–1.79 (1H, m, H-20 a), 2.84 (1H, m, H-10 ), 6.76 (1H,
CHCl3, acetone and THF. The presence of a double bond makes d, 3J6–5 ¼ 7.6 Hz, H-6), 6.89 (1H, t, 3J4–3 ¼ 7.6 Hz, H-4), 7.11 (1H,
it possible to involve this monomer in various chemical reac- t, 3J5–6 ¼ 7.6 Hz, H-5), 7.20 (1H, d, 3J3–4 ¼ 7.6 Hz, H-3). 13C NMR
tions followed by conversion to new polymeric products with (CDCl3, 500 MHz) d: 14.36 (C-40 ), 20.66 (C-50 ), 20.93 (C-30 ), 32.71
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physicochemical properties that differ from those of the orig- (C-10 ), 39.28 (C-20 ), 116.08 (C-6), 119.13 (C-4), 126.21 (C-3),
inal polymer. 126.45 (C-5), 132.07 (C-2), 143.63 (C-1).
The purpose of this work was to synthesize new functional General procedure for the synthesis of compounds 4 and 5.
monomers based on ortho-(1-methylbut-2-en-1-yl)aniline and Acetyl chloride (2.9 g, 37.2 mmol) was added with stirring in
study how the structure of the initial aniline derivatives affects small portions to a solution of compound 2 (3.0 g, 18.6 mmol) in
the properties of the resulting polymeric products. anhydrous CH2Cl2 (50 mL). The mixture was stirred for 6–7 h at
room temperature. Once the reaction completed (TLC moni-
toring), the reaction mixture was washed with a saturated
Materials and methods solution of NaHCO3 (3  40 mL) and extracted with CH2Cl2 (3 
Materials 30 mL). The extracts were combined and dried with MgSO4. The
Aniline was distilled under reduced pressure prior to use. solvent was removed under reduced pressure and the residue
Dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N,N- was separated on a column with Al2O3 (eluent: petroleum ether–
dimethylformamide (DMF), tetrahydrofuran (THF), toluene, EtOAc 7 : 1).
methanol (MeOH), chloroform (CHCl3), ethyl alcohol (EtOH), N-[2-(1-Hydroxy-1-methylbutyl)phenyl]acetamide (4) and N-{2-
ethyl acetate (EtOAc), benzene, acetonitrile (MeCN), methylene [1-methylbut-1-en-1-yl]phenyl}acetamide (5). Yields: 2.9 g (70%) of
chloride (CH2Cl2), petroleum ether, hexane, as well as penta-1,3- 4 and 0.6 g (17%) of 5. For 4, 1H NMR (CDCl3, 500 MHz) d: 0.79
diene were distilled prior to use. All the other chemicals were (3H, t, 3J ¼ 7.4 Hz, H-40 ), 1.17–1.32 (2H, m, H-30 a, H-30 b), 1.49
analytical grade reagents and were used as procured. 4-Chlor- (3H, s, H-50 ), 1.66–1.78 (2H, m, H-20 b, H-20 a), 2.02 (3H, s, Ac), 6.90
opent-2-ene31 and 2-(1-methylbut-2-en-1-yl)aniline32 were ob- (1H, d, 3J6–5 ¼ 7.5 Hz, H-6), 7.01–7.04 (2H, m, H-3, H-5), 7.12
tained by known procedures. (1H, t, 3J4–5 ¼ 7.5 Hz, 3J4–3 ¼ 7.5 Hz, H-4). For 5, 1H NMR (CDCl3,
500 MHz) d: 0.87 (3H, t, 3J ¼ 7.5 Hz, H-40 ), 1.70–1.76 (2H, m, H-
30 a, H-30 b), 1.93 (3H, s, H-50 ), 2.10 (3H,s, Ac), 5.65 (1H, t, 3J20 –30 a ¼
Synthesis of the monomers 7.3 Hz, 3J20 –30 b ¼ 7.3 Hz, H-20 ), 6.59–7.06 (2H, m, H-3, H-4), 7.21
General procedure for the synthesis of compound 2. 2-(1- (1H, t, 3J5–4 ¼ 8.0 Hz, 3J5–6 ¼ 8.0 Hz, H-5), 8.27 (1H, d, 3J6–5 ¼
Methylbut-2-en-1-yl) aniline 1 (2 g, 12.4 mmol) was heated with 8.0 Hz, H-6). For 4, 13C NMR (CDCl3, 500 MHz) d: 14.12 (C-40 ),
KOH (0.7 g, 12.4 mmol) for 1 h in a steel reactor at 300
. The 16.92 (C-30 ), 21.74 (Ac), 27.97 (C-50 ), 44.28 (C-20 ), 80.70 (C-10 ),
reaction mixture was cooled to room temperature. The product 122.80 (C-6), 124.02 (C-3), 126.06 (C-5), 128.17 (C-4), 128.91 (C-
was decanted from the solid residue and washed with water (2 2), 138.30 (C-1), 160.08 (Ac). For 5, 13C NMR (CDCl3, 500 MHz)
 25 mL), extracted with EtOAc (2  15 mL), and dried with d: 14.03 (C-40 ), 22.62 (C-30 ), 24.79 (Ac), 25.07 (C-50 ), 120.09 (C-6),
MgSO4. The solvent was removed under reduced pressure. 123.81 (C-3), 127.60 (C-5), 128.12 (C-4), 131.33 (C-2), 131.94 (C-
2-(1-Methylbut-1-en-1-yl)aniline (2). Yield: 1.9 g (95%). 1H 10 ), 132.69 (C-20 ), 134.29 (C-1), 168.08 (Ac).
NMR (CDCl3, 500 MHz) d Z[E]: 1.04 [1.18] (3H, t, 3J ¼ 7.5 Hz, H- General procedure for the synthesis of compound 6. KOH
40 ), 1.92–1.98 [2.29–2.35] (2H, m, H-30 a, H-30 b), 2.07 [2.06] (3H, d, (2.9 g, 52.4 mmol) in MeOH (30 mL) was added to a solution of
4
J50 –20 ¼ 1.0 Hz, H-50 ), 3.78 (2H, br.s, NH2); 5.69 [5.61] (1H, dt, compound 4 (2.9 g, 13.1 mmol) in MeOH (20 mL) and the
3
J20 –30 a ¼ 7.5 Hz, 3J20 –30 b ¼ 7.5 Hz, 4J20 –50 ¼ 1.0 Hz, H-20 ), 6.79 [6.77] mixture was reuxed until the starting material was consumed
(1H, dd, 3J6–5 ¼ 8.1 Hz, 4J6–4 ¼ 1.5 Hz, H-6), 6.86 [6.84] (1H, dt, (TLC monitoring). A saturated NH4Cl solution was added to the
3
J4–5 ¼ 7.5, 3J4–3 ¼ 7.5 Hz, 3J4–6 ¼ 1.5 Hz, H-4), 7.05 [7.11] (1H, reaction mixture and the reaction products were extracted with
dd, 3J3–4 ¼ 7.5 Hz, 3J3–5 ¼ 1.3 Hz, H-3), 7.18 [7.15] (1H, ddd, 3J5–6 EtOAc (3  30 mL). The combined organic extracts were dried
¼ 8.1 Hz, 3J5–4 ¼ 7.5 Hz, 3J5–3 ¼ 1.3 Hz, H-5). 13C NMR (CDCl3, with MgSO4 and evaporated. The residue was chromatographed
500 MHz) d: 14.37 [14.28] (C-40 ), 22.62 [21.77] (C-30 ), 24.58 [24.59] on Al2O3 (petroleum ether–EtOAc 8 : 1).
(C-50 ), 115.05 [115.51] (C-6), 118.30 [118.35] (C-4), 127.74 2-(2-Aminophenyl)pentan-2-ol (6). Yield: 1.7 g (75%). 1H NMR
[127.56] (C-5), 128.85 [128.90] (C-3), 131.36 [132.37] (C-20 ), (CDCl3, 500 MHz) d: 0.91 (3H, t, 3J40 –30 ¼ 7.4 Hz, H-40 ), 1.16–1.24
131.63 [131.35] (C-10 ), 133.16 [133.11] (C-2), 142.91 [143.16] (C- (1H, m, H-30 a), 1.32–1.41 (1H, m, H-30 b), 1.62 (3H, s, H-50 ), 1.84–
1). 1.89 (1H, m, H-20 a), 1.95–2.0 (1H, m, H-20 b), 6.64 (1H, d, 3J6–5 ¼
General procedure for the synthesis of compound 3. Pd/C 7.5 Hz, H-6), 6.70 (1H, t, 3J5–6 ¼ 7.5 Hz, 3J5–4 ¼ 7.5 Hz, H-5), 7.04–
(10 mol%) was added to a solution of compound 1 (3.0 g, 18.6 7.07 (2H, m, H-4, H-5). 13C NMR (CDCl3, 500 MHz) d: 14.47 (C-

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General procedure for the synthesis of compound P-MB. The

compound was obtained from 2-(1-methylbutyl)aniline (1.0 g,
6.1 mmol), 1.7 g (7.6 mmol) of (NH4)2S2O8 and 0.2 mol L1 HCl
by the procedure used for synthesizing P-PA.
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Poly[2-(1-methylbutyl)aniline] (P-MB). Dark brown powder,

yield: 0.8 g (85%). 1H NMR (CDCl3, 500 MHz) d: 0.73–0.94 (m, H-
40 ), 1.10–1.34 (m, H-30 , H-50 ), 1.43–1.64 (m, H-20 ), 2.88–3.05 (m,
H-10 ), 6.95–7.51 (m, Ph). 13C NMR (CDCl3, 500 MHz) d: 14.19 (C-
Fig. 1 Calibration of humidity and ammonia sensors: (1) power supply 40 ), 20.71 (C-30 ), 21.60 (C-50 ), 33.48 (C-10 ), 39.75 (C-20 ), 125.68–
unit, (2) container with water or ammonia, (3) sealed cabinet, (4) 127.68 (C-3, C-5, C-6), 130.88 (C-2), 143.11 (C-4), 150.45 (C-1).
polymer film humidity sensor, (5) electronic hygrometer, (6) ammonia
General procedure for the synthesis of compound P-AP.
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sensor, (7) Arduino UNO, (8) display.

Monomer 6 (1.0 g, 5.6 mmol) was dissolved in water (15 mL) and
the solution was oxidized with ammonium persulfate (1.28 g,
40 ), 17.80 (C-30 ), 27.97 (C-50 ), 42.81 (C-20 ), 76.76 (C-10 ), 117.75 (C-
5.6 mmol) in water (15 mL). The reaction mixture was kept for
6), 117.77 (C-5), 126.69 (C-3), 128.08 (C-4), 129.99 (C-2), 145.41
24 h without disturbance at room temperature. Aer that, the
(C-1).
solution was ltered and washed with a large amount of
distilled water. Subsequently, the polymer was washed with
Synthesis of polymers a large amount of petroleum ether. The polymer was dried
under reduced pressure. For the doping procedure, the polymer
General procedure for the synthesis of compound P-PA.
was treated with 1 M HCl solution for 24 h. The powder was then
Monomer 2 (1.0 g, 6.2 mmol) was dissolved in 0.2 mol L1 HCl
ltered off, washed with petroleum ether and dried under
(50 mL) and the solution was oxidized with ammonium per-
vacuum.
sulfate (1.7 g, 7.5 mmol) in 0.2 mol L1 HCl (50 mL). The
Poly[2-(2-aminophenyl)pentan-2-ol] (P-AP). Dark brown
solution color changed from yellow to dark brown as the reac-
powder, yield: 0.6 g (60%).1H NMR (CDCl3, 500 MHz) d: 0.72–
tion progressed. Aer 24 h, the solution was ltered and washed
0.92 (m, H-40 ), 1.14–1.42 (m, H-30 ), 1.47–1.68 (m, H-50 ), 1.75–1.95
with a large amount of 0.2 mol L1 HCl. Subsequently, the
(m, H-20 ), 7.05–7.12 (m, H-6), 7.24–7.32 (m, H-5), 7.36–7.41 (m,
polymer was washed with a large amount of petroleum ether.
H-6). 13C NMR (CDCl3, 500 MHz) d: 14.21 (C-40 ), 17.50 (C-30 ),
The polymer was dried under reduced pressure.
28.32 (C-50 ), 43.72 (C-20 ), 76.55 (C-10 ), 123.27–130.17 (C-3, C-5, C-
Poly[2-(1-methylbut-1-en-1-yl)aniline] (P-PA). Dark brown
6) 137.16 (C-2), 139.54 (C-1).
powder, yield: 0.9 g (88%). 1H NMR (CDCl3, 500 MHz) d: 0.80–
1.03 (m, H-40 ), 1.67–1.92 (m, H-30 ), 1.98–2.08 (m, H-50 ), 5.60–5.74
(m, H-20 ), 7.01–7.35 (m, Ph). 13C NMR (CDCl3, 500 MHz) d: 14.01 Apparatus and characterization
(C-40 ), 22.75 (C-30 ), 25.32 (C-50 ), 127.65–130.23 (C-3, C-5, C-6, C- Proton (1H) and carbon (13C) nuclear magnetic resonance
10 ), 134.20 (C-20 ), 135.92 (C-2), 140.07 (C-4), 151.41 (C-1). (NMR) spectra were measured in CDCl3 using a Bruker Avance

Scheme 1 Synthesis of 2-(1-methylbut-2-en-1-yl)aniline derivatives followed by the production of PANIs.

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spectrouorophotometer in DMSO solution at 298 K. The

microstructure of nanoparticles was studied with a TESCAN
MIRA 3 LMH high-resolution scanning electron microscope
(SEM) equipped with a detector of scattered and backward
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scattered electrons. The survey was conducted at 10 kV accel-

erating voltage and under 103 Pa vacuum. For SEM analysis
a drop of the polymer solution was applied onto a substrate by
spin coating. For sensing study the sitall substrate was cleaned
in an ethanol solution and dried for 10 min in an oven at 50
C.
A polymer lm was applied on top of substrate by spin-coating
from a 0.1 M DMF solution. The spin time was 2 minutes, and
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the spin rates for three samples were 700 rpm. The following
equipment was used in the experiments to measure sensor
properties: MASTECH DC POWER SUPPLY HY3005D-2 power
supplies, a DMM 4020 multimeter as the ammeter, an Arduino
Fig. 2 FT-IR spectra of P-PA, P-MB and P-AP. Uno programmable controller, a display, as well as DHT-11 and
MQ135 sensors in Fig. 1.

Table 1 The main absorption bands in FT-IR spectra and their

assignments
Results and discussion
Synthesis of samples
Bands and peaks (cm1) Assignments
2-(1-Methylbut-2-en-1-yl)aniline (1) was used as the starting
3350–3429 cm1 H-Bonded N–H groups compound. To obtain 2-(1-methylbut-1-en-1-yl)aniline (2),
2773–2968 cm1 C–H stretching of alkyl structures double bond isomerization was performed in the starting
1608–1616 cm1 Quinone-ring stretching compound by treatment with KOH at 300
C to give product 2
1504–1557 cm1 Aromatic C]C
in 98% yield. Catalytic hydrogenation of compound 1 on Pd/C
1368–1393 cm1 C–N stretching
1117–1138 cm1 ]N+–/–N+c– (10%) in ethyl acetate at room temperature gave 2-(1-methyl-
butyl)aniline (3) in 92% yield. 2-(2-Aminophenyl)pentan-2-ol
(6) was obtained due to an unusual reaction in the course of
compound 2 acylation with acetyl chloride. In this synthesis,
III spectrometer (500 MHz). Chemical shis are represented in we observed that yet another product, N-[2-(1-hydroxy-2-
parts per million downeld from tetramethylsilane as the methylbutyl)phenyl]acetamide (4), was formed along with N-
internal standard. FT-IR spectra were recorded between 200 and {2-[1-methylbut-1-en-1-yl]phenyl}acetamide (5). The content of
4000 cm1 in KBr pellets using a Specord M80 spectrometer. product 4 in the product mixture was 70%. The N-acetate
Elemental analysis was performed on a Euro-2000 CHNS(O) group was readily hydrolyzed upon reuxing compound 4 with
analyzer. UV-vis spectra were recorded on a Shimadzu Spec- KOH in methanol to give tertiary alcohol 6 in 75% yield
trophotometer 2600 in DMSO solution at 298 K, at wavelengths (Scheme 1). The structures of compounds 2, 3 and 6 were
ranging from 190 to 900 nm (slit width – 2.0 nm, scanning speed identied by 1H NMR and 13C spectra.
– fast), using a 1 cm thick quartz tube. Fluorescence spectral Chemical oxidative polymerization was carried out to
analysis was conducted using an RF-5301 PC Shimadzu synthesize PANI derivatives; monomers 2 (1 g, 6.2 mmol) and 3
(1 g, 6.1 mmol) were added to 0.2 mol L1 aqueous solution of

Table 2 Elemental analysis for the polymers synthesized

C (%) H (%) N (%) Cl (%) O (%) Total (%)

Polymera Calc. Found Calc. Found Calc. Found Calc. Found Calc. Found Calc. Found

P-PA 74.68 71.21 7.36 6.78 7.92 7.57 10.04 3.33 — — 100.00 88.89
P-MB 73.85 71.89 8.39 8.19 7.83 7.35 9.93 4.87 — — 100.00 92.30
P-AP 67.78 65.44 7.70 7.37 7.19 6.87 9.11 1.19 8.22 8.05 100.00 88.92
a
Repeat unit.

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Table 3 The solubility of substituted polyanilinesa temperature (20
C). The product was ltered off and washed
with a large amount of water followed by petroleum ether until
Form Film color Solubility
the ltrate became colorless. For the doping procedure, the
P-PA Dark-brown DMSO, DMF, NMP, polymer was treated with 1 M HCl solution for 24 h. The powder
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CHCl3, CH2Cl2, acetone was then ltered off, washed with petroleum ether, and dried
P-MB Dark-brown DMSO, DMF, NMP, CHCl3, under vacuum (Scheme 1).
CH2Cl2, acetone, EtOH, MeCN, THF
P-AP Dark-brown DMSO, DMF, NMP, CHCl3,
CH2Cl2, acetone, EtOH, MeCN, FT-IR spectra
THF, EtOAc, benzene, toluene
The structures of the polymers that we synthesized were
a
The solubility of polymers was measured using 100 mg of a sample in conrmed by FT-IR spectroscopy. One can see in Fig. 2 that the
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5 mL of a solvent.
spectra of poly[2-(1-methylbut-1-en-1-yl)aniline] (P-PA), poly[2-
(1-methylbutyl)aniline] (P-MB) and poly[2-(2-aminophenyl)
pentan-2-ol] (P-AP) samples exhibit peaks characteristic of
HCl (50 mL), and then the polymerization was conducted by PANI, in particular, the bands at 3032 cm1, 3245 cm1 and
dropwise addition of an ammonium persulfate solution 3038 cm1 corresponding to the stretching vibrations of the ]
(monomer/PSA ¼ 1.00/1.25) in 0.2 mol L1 aqueous solution of C–H bond. The absorption maxima in the regions of 3350 cm1,
HCl (50 mL) as the oxidant at 20
C for 24 h. Then the PANIs was 3420 cm1 and 3390 cm1 correspond to the vibrations of the
ltered and the precipitate was washed with petroleum ether –N–H bond. The presence of alkyl substituents in P-PA, P-MB
and 0.2 mol L1 HCl to remove aniline oligomers. Aer washing and P-AP is conrmed by the absorption of C–H bonds in the
and ltration, the solid was dried in vacuum to evaporate the ranges of 2773–2968 cm1, 2870–2957 cm1, and 2829–
solvent from the sample completely. 2961 cm1. The absorption maxima in the regions of
Monomer 6 (1 g, 5.6 mmol) was dissolved in 15 mL of 1616 cm1, 1608 cm1 and 1613 cm1 correspond to the
distilled water and the solution was oxidized with a solution of stretching vibrations of the C]N bond in the conjugated
ammonium persulfate (1.28 g, 5.6 mmol) in water. The poly- system. These absorption bands are consistent with the pres-
merization was continued for 24 h without disturbance at room ence of quinonediimine moieties in the polyaniline chain. The
intense narrow absorption maxima in the samples at

1
Fig. 3 H NMR spectra of the monomers and the corresponding polyaniline in CDCl3.

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1510 cm1, 1557 cm1 and 1504 cm1 are consistent with the a pure polymer in the emeraldine oxidation state, as demon-
presence of a benzene ring and correspond to its pulsation strated by the comparison with the calculated values.
vibrations. Moreover, the presence of a benzene ring is consis-
tent with the absorption bands at 798 cm1, 755 cm1 and
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759 cm1 corresponding to the out-of-plane deformation Solubility

vibrations of the C–H bonds. The peaks at 1461 cm1,
As pointed out in the Introduction, the main purpose for
1496 cm1 and 1450 cm1 correspond to the N]N bonds. The
attaching alkyl chains to the polyaniline backbone was to
peaks at 1373 cm1, 1368 cm1 and 1393 cm1 correspond to
increase the poor solubility of unsubstituted polyaniline, espe-
the stretching vibrations of the C–N bonds. The absorption
cially in common organic solvents. Typically, when PANI doped
peaks at 1124 cm1, 1138 cm1 and 1117 cm1 are due to the
with mineral or organic acids is added to bipolar aprotic
vibrations of the –NH+] groups formed upon protonation of
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solvents such as DMSO or NMP, a fraction of the polymer

the PANI's molecular chain (Table 1). This is evidence of the
material (presumably oligomers or low molecular mass mate-
degree of electron delocalization and the nature of its electrical
rials) dissolves, but a residual mass is always present in the
conductivity. The spectra of the P-AP polymer contain bands in
mixture. Aer the successful synthesis of P-PA, P-MB and P-AP,
the region of 1368–1358 cm1 indicating the formation of
the solubility was determined in various organic solvents. P-PA
a tertiary alcohol. The peaks at 594–462 cm1, 536 cm1 and
and P-MB (dark-brown solution) readily dissolved in polar
541 cm1 correspond to various vibrations of the substituted
solvents such as DMSO, DMF, NMP and THF, as well as in less
rings. Thus, it follows from IR spectroscopy data that the
polar solvents such as chloroform, acetone, and acetonitrile,
structures of the polymers that we obtained are close to the
but were insoluble in benzene and toluene. It is noteworthy that
emeraldine structure.
P-AP (dark-brown solution) was soluble in all the organic
solvents tested (Table 3).
Thus, modifying the alkyl in the PANI side chain is an effi-
Elemental analysis cient method for enhancing the solubility of the polymer in
The results of elemental analysis are shown in Table 2. The total various types of solvents. Such a versatile solubility should be
of carbon, hydrogen, and nitrogen amounts in the polymers advantageous in the preparation of polymer lms for chemical
synthesized was over 90% in all cases. This is consistent with sensors.

Fig. 4 UV spectra (a), emission (b) and normalized excitation (c) photoluminescence spectra of the polymers in DMSO (102 g L1).

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Table 4 Optical characterization data of the polymers Optical properties

Absorption Studying the absorption spectra is the best way to perform

a comparative analysis of the effect of various structural factors
Sample l1 (nm) l2 (nm) lEx (nm) lEm (nm) Ega (eV) on the change in the molecular geometry of the polymer chain.33
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PPA30 285 — 430 500 1.91

It is known that in most cases, PANI and its derivatives manifest
P-MB 300 515 370 450 1.90 two absorption maxima in the regions of 300 and 600 nm cor-
P-AP 274 523 306 377 1.91 responding to the p–p* electron transition in the benzoid
P-PA 290 519 315 397 2.06 moiety and the n–p* electron transition in the quinoid moiety.33
a
Eg ¼ 1240/ledge Similarly to literature data, the PANI derivatives synthesized
exhibit two absorption peaks in the electronic spectra (Fig. 4a).
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The presence of a substituent at the aromatic ring of the poly-

1 mer resulted in a hypsochromic shi of the absorption maxima
H NMR spectroscopy studies
(by 10–20 nm) in the electronic spectra relative to those of
Additional information about the structures of monomers and
unsubstituted PANI. The observed changes are due to the steric
polymers was obtained from NMR spectra. Interestingly,
effect of bulky substituents, the presence of which favors an
displacement and hydrogenation of the double bond, as well as
increase in the torsion angle between the aromatic rings and
the presence of a hydroxy group in the polymers, made these
a decrease in the degree of conjugation (Table 4).16 It was found
samples soluble in polar solvent such as CHCl3, which enabled
that in the series of PANI derivatives in question, the presence
us to record their NMR spectra. The NMR spectra of monomers
of a hydroxy group in the substituent of P-AP favors the largest
and polymers recorded in CDCl3 are shown in Fig. 3.
shi in the absorption maximum due to a greater steric effect
Analysis of the 1H NMR spectra recorded at 500 MHz showed
compared to Alk-substituted PANI derivatives (P-MB, P-PA) that
that aromatic protons in the starting monomers appeared in the
manifest smaller hypsochromic shis. Comparative analysis of
d 6.71–7.17 range as sharp peaks with clearly visible coupling
literature data on other alkyl-substituted PANI derivatives
constants, while the corresponding signals in the polymers were
conrms the above regularities.16,30,33
shied downeld to the region of d 7.06–7.62 and appeared as
Previously, unsubstituted PANI was found to have lumines-
broadened lines. The signals of the H-4 proton at 7.0 ppm and
cent properties with a quantum yield of 0.1 only NMP solution,34
of –NH2 at 3.80 ppm from the monomers disappear in 1H NMR
whereas the luminescence quantum yields of substituted PANI
aer polymerization. The protons of the methylene groups in
derivatives are much higher.35 In addition, the luminescent
the side chains are expected to appear at 0.72–5.74 ppm.

Fig. 5 PLE map of the solutions of P-AP (a), P-PA (b) and P-MB (c).

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properties of the resulting material can be controlled by rigidity.36 However, the opposite picture is observed for all the
changing the synthesis conditions and by varying the doping PANI derivatives studied, namely, incorporation of a bulky alkyl
agent. In view of this, uorescence studies of new PANI deriv- substituent increases the luminescence intensity. It was found
atives are very important. At the same time, analysis of changes previously that a PANI polymer should contain more than two
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in the excitation and emission spectra would make it possible to sequentially linked benzenoid moieties to make photo-
estimate the effect of the substituent on the structure of the luminescence observable.38 Thus, the highest luminescence
polymer chain and on the optical properties of the compounds intensity is demonstrated by undoped PANI in fully reduced
being studied. form. Analysis of the set of the PANI derivatives presented in
Fig. 4b shows the excitation and emission spectra of P-AP, P- this work allows one to make the assumption that incorporation
MB and P-PA recorded in DMSO solutions at room temperature. of an alkyl substituent complicates the oxidation of the amino
The uorescent properties of conjugated polymers can be group to an imino group.33 This assumption is conrmed by the
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explained in terms of the band theory of semiconductors.36 On increase in the photoluminescence intensity with an increase in
exposure to radiation, electrons pass from the valence band of the substituent volume, that is, in accordance with the steric
a conjugated polymer to the conduction band and then migrate hindrance that it exerts.
back to the polymer chain. An excited electron and an oppo- The photoluminescence excitation–emission maps (PLE)
sitely charged hole attract each other and undergo recombina- were studied for the series of PANI derivatives obtained in Fig. 5.
tion to emit a photon.37 According to the general concept of the One can see from the PLE maps that the position of the pho-
photoluminescence of compounds comprising a system of toluminescence maximum does not depend on the excitation
conjugated bonds, incorporation of a substituent into the wavelength and shis with an increase in the substituent
aromatic system should have resulted in a decrease in the volume, which also allows one to make the assumption that the
luminescence intensity due to a decrease in the structure

Fig. 6 SEM images of the polymers.

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steric effect has an inuence on the position of the photo-

emission maximum.

Scanning electron microscopy

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The structural exibility and the dependence of physicochem-

ical properties on the synthesis conditions are considered to be
among the most important PANI properties. They make it
possible to identify the structure–property relationship for
nanosized materials and develop potential applications adapt-
ed for various types of morphologies, depending on the prop-
erties required.39
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Fig. 6 shows the results of scanning electron microscopy. The

supramolecular structure of the samples obtained differs
signicantly from the structure of PANI and its alkyl derivatives Fig. 7 Plots of the conductivity of P-PA, P-AP and P-MB films on the
studied previously.39 Unsubstituted PANI obtained in the clas- air humidity.
sical way has a brillar structure, whereas its ortho-substituted
derivatives are most commonly characterized by a globular
morphology comprising distinct spheres.39 Similarly to the humidity is due to an increase in the mobility of the doping ion
samples studied previously, the P-AP and P-PA polymers ob- that is weakly bound to the polymer chain through van der
tained have a globular morphology, in contrast to P-MB which Waals forces.42 As the environment humidity increases, the
has a heterogeneous hierarchical structure. polymer lm absorbs moisture, which results in polymer
The observed difference between the supramolecular struc- swelling followed by unfolding of the compact spiral-shaped
tures formed by the polymers may be due to the nature of the polymer chain. The formation of a more aligned structure of
reacting monomer and the effect of the substituent at the the PANI derivative favors the charge transfer along the polymer
aromatic ring in the polymer chain. chain.43 It is also assumed that saturation of the polymer with
moisture is accompanied by the formation of a complex due to
Mw determination of polymers the transfer of an unshared electron pair from the nitrogen
Molecular weights of the polymers P-MB and P-AP were ob- atom in the polymer to water molecules.43 The results of
tained by gel permeation chromatography analyses. The measuring the current–voltage characteristics conrm the
samples were dissolved in THF. Weight average MW (Mw) varies assumption that the mobility of charge carriers along individual
from 59 796 to 67 268 g mol1. Table 5 summarizes the Mw, polymer chains and across adjacent chains is high due to the
number average MW (Mn), and polydispersity index (PDI) of geometrically ordered, closely packed structure of the polymer
these samples. chains.44
On the other hand, the polymer chains within the micro-
The sensing properties of polymers aggregated P-MB polymer lm were much less ordered and
less densely packed, which resulted in a greater number of
An important advantage of PANI and its derivatives that allows
structural defects that apparently improve the sensitivity to
one to use them in various elds of technology is that their
ammonia vapor (Fig. 7 and 8). The P-MB lm had the largest
physicochemical parameters depend on the chemical compo-
roughness (Table 6).
sition of the environment.40 Gas sensors are considered to be
one the promising applications of PANI-based polymers.41 In
view of this, the P-MB, P-AP and P-PA polymers obtained were
used as sensitive materials in resistive sensors. The results are
presented in Fig. 7 and 8.
Based on SEM results, it is assumed that P-PA (Fig. 7) should
have the best response to chemicals in air because it has a more
developed surface. P-PA showed the highest lm conductivity in
humid air (Fig. 8). Presumably, an increase in the electrical
conductivity of a polymer lm with an increase in the ambient

Table 5 Molecular characteristics of the polymers

Sample Mn (g mol1) Mw (g mol1) PDI

P-MB 31 454 67 268 2.1

P-AP 22 353 59 796 2.7 Fig. 8 Plots of the conductivity of P-PA, P-AP and P-MB films on the
concentration of ammonia vapor.

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Table 6 Surface roughness parameters of samples aminophenyl)pentan-2-ol]. The polymers vary in solubility,
depending on the chemical structure of the substituents. The
Compound P-PA P-MB P-AP
PANI derivatives presented here demonstrated a high photo-
Average roughness Ra, nm 1.7 2.5 3.7 luminescence intensity. The changes in the emission spectra
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Root-mean-square roughness Rq, 2.4 3 4.7 made it possible to estimate the effect of structural factors on
nm the molecular geometry of the polymers obtained. However, the
electrical conductivity of modied polyanilines is lower than
that of pure PANI due to the smaller conjugation length. The
considerable increase in the solubility of the presented series of
polymers, i.e., P-MB, P-AP and P-PA, made it possible to form
homogeneous thin lms and use them as active layers in
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resistive gas sensors. Varying the substituents in the polymer

structure resulted in sensors with various sensitivity to the
ambient humidity and ammonia concentration. The greatest
response to the moisture variation was obtained for the sensor
based on P-PA. The quality of the lm surface plays an impor-
tant role in the sensor properties of polymers; therefore, the
PANI derivatives were studied by AFM and SEM. It was found
that the polymer with the smallest roughness was most sensi-
tive to the environment quality.
Thus, a detailed study of a number of PANI derivatives with
different substituents showed that the physicochemical prop-
erties of the resulting polymers can be tuned, which makes it
possible to use them in various elds of organic electronics.

Conflicts of interest
Fig. 9 Atomic force microscopy of the surface of polymer films.
The authors declare that they have no known competing
nancial interests or personal relationships that could have
It is well known that PANI doping with HCl results in an appeared to inuence the work reported in this paper.
increase in electrical conductivity. Upon protonation, neutral
PANI molecules acquire protons to form positively charged local Acknowledgements
centers located on the nitrogen atoms, which facilitate the
motion of valence electrons from one such center to another, This work was supported by the Ministry of Science and Higher
thus causing the hopping conductivity. When PANI reacts with Education of the Russian Federation as part of the state task no.
ammonia, the molecules of the latter absorb protons from PANI AAAA-A19-119020890014-7.
to form energetically favorable ammonium (NH4+). As a result,
PANI dedoping occurs. Notes and references
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