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Materials Science and Applied Chemistry

doi: 10.1515/msac-2016-0008

_______________________________________________________________________________________________ 2016/33

Synthesis and Characterization of Cationic Poly(N[3-Hexyldimethyl-Aminopropyl] Methacrylamide

Bromide) Water-Soluble Polymer
Wahiba Chaibi1, 2, Asma Ziane3, Zouaoui Benzehaim4, Lamia Bennabi5, Kaddour Guemra6
1, 36
Physical and Organic Macromolecular Chemistry Laboratory, Faculty of Science,
University "Djillali Liabes" of Sidi Bel-Abbes, Algeria
2
Scientific and Technical Research Center in Chemistry and Physics Analysis, Tipaza, Algeria
Abstract Water-soluble polymer, cationic poly(N-[3hexyldimethyl-aminopropyl]
methacrylamide
bromide)
(PHDAPMAA), is synthesized by radical polymerization and
studied in terms of its solubility, viscosity, surface tension and
conductivity. Viscometry and surface tension measurements
conrmed that intramolecular hydrophobic microdomains were
formed by the pendent alkyl chains. Conductivity of cationic
polymer in aqueous solution was determined. Variation of
conductivity versus concentration in investigated system exhibits
a typical polyelectrolyte behaviour.
Keywords Water-soluble polymer, hydrophobic association,
viscosity, surface tension, conductivity.

I. INTRODUCTION
In recent years, commercial applications of water-soluble
hydrophobically associating polymers have been introduced,
particularly, as dispersing agents, surface-modifiers, and in
textile, pharmaceutical and other related industries [1][6].
Among these polymers, hydrophobically associating
polyacrylamide (HAPAM) is especially attractive [7][10. It
is well known that there is intramolecular association and
intermolecular association in HAPAM aqueous solution due to
the presence of hydrophobic groups. Especially, cationic
polyacrylamides are a kind of important cationic
polyelectrolyte and are extensively used as flocculants for
liquid/solid separation, retention and drainage aids in
papermaking, flotation aids and demulsifiers for oil/water
clarification, as soil improvers and drainage aids, etc. [11]
13. Various cationic amphiphilic polymers like poly(N-3(dimethylamino)propyl] methacrylamide) [14], [15 have been
synthesized and studied for the same reasons. One additional
attractive feature of these cationic polymers is their ability to
allow the formation of intramolecular aggregates in presence
of water [16][19]. It is the so called polysoap that is similar
to surfactant in certain properties [20.
In the present study we report the synthesis and
characterization of cationic polymer poly(N-[3-hexyldimethylaminopropyl] methacrylamide bromide) [poly(HDAPMAA)] .
The present paper reports the viscometric, conductimetry
and properties of the cationic water-soluble polymer,
particularly, the effect of an inorganic salt (NaCl) on the
solution properties of poly(HDAPMAA). Detailed results of

the synthesis and solution behaviours of the polymers are

presented.
II. MATERIALS AND METHODS
A. Materials
Commercial N-3-(dimethylamino)propyl] methacrylamide
(DAPMAA, Aldrich) was distilled under reduced pressure
(8085 C, 0.2 mm Hg) in order to remove stabiliser under
argon atmosphere. 2,2'-Azobis (isobutyronitrile) (AIBN, Acros
Organics) was purified by recrystallization from methanol.
Hydroquinone (Aldrich) and 1-bromohexane (Aldrich) were
used as received.
B. Measurements
1

H NMR spectra were recorded using a Bruker Avance

instrument operated in CDCl3 at 300 MHz. IR spectra were
recorded in the range 4000400 cm1 for the synthesized
polymer (FTIR SCHIMADZU IRTF 8300 Spectrometer).
Conductivity measurements were performed with Inolab
Level1 model at 25 C 0.1, using platinum-black electrode
with an electrode constant of K = 0.80 cm1.Viscometric
measurements were carried out with a capillary viscometer
standard Ubbelohde with thermostatted bath at 30 C 0.1.
Surface tension was measured by plate method with Gibertini
TDS digital tensiometer at 25 C. All polymer solutions were
prepared by dissolution in water and maintained at 25 C.
C. Polymer Synthesis and Characterization: Synthesis of
Cationic Monomer
N-[3-Hexyldimethyl-aminopropyl methacrylamide bromide
(HDAPMAA) was synthesized via quaternization reaction
[21] of N-3-(dimethylamino) propyl] methacrylamide and
1-bromohexane. In a single-neck flask with a glass stopper
10 mL of acetonitrile was added to a mixture of 0.03 mol of
N-3-(dimethylamino)propyl] methacrylamide, 0.03 mol of
1-bromohexane and a small amount of inhibitor
(hydroquinone). The flask was closed under argon atmosphere
and heated at 50 C under magnetic stirring for about 72 h.
The solvents were then removed in vacuum below 40 C, and
the oily residue left to stand and washed several times with dry
diethyl ether. The synthetic route for HDAPMAA is shown in
Fig. 1. The monomer was characterized by 1H NMR
(300 MHz).

2016 Wahiba Chaibi, Asma Ziane, Zouaoui Benzehaim, Lamia Bennabi, Kaddour Guemra. This is an open access article
licensed under the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), in the manner agreed
with De Gruyter Open.
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Materials Science and Applied Chemistry

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CH2

NH

95

NH

(CH2)3

70

(CH2)3

CH3

3500

3000

Fig. 1. The synthetic route for HDAPMAA.

2500
2000
Wavenumber cm-1

1500

1000

723.81

522.54
474.31
444.73
408.98

1077.71

CH3
CH3
(CH2)5

957.00
887.21

Br
1374.93
1337.40
1262.38
1202.11

1636.16

CH3

1526.71
1474.89

N
CH3

CH3CN

2954.27
2926.63
2863.91

+ CH3(CH2)5Br

3386.04

Transmittance [%]
90
85
80

CH2

CH3

T=500C; t=72h

75

CH3

500

Fig. 3. FTIR spectra of the polymer.

C:\Program Files\OPUS_65\MEAS\Ziane PC3C6.0

Ziane PC3C6

Instrument type and / or accessory

09/07/2012

Seite 1 von
1
FTIR spectra were obtained
using
a potassium bromide
(KBr) disc. The characteristic absorption bands of
PHDAPMAA units were observed at 3386.4 cm1 and
1635.5 cm1 due to the NH and NH-C=O vibration,
respectively. The area of the band at 2925.8 cm1 2856.4 cm1
was normalized using (CH2, CH3) stretching band of
PHDAPMAA.

Fig. 2. 1H NMR of the monomer HDAPMAA.

1

H NMR (CDCl3, in ppm): 0.86 (t, 3H, CH3 (H6), 1.25

(m, 4H,CH2 (H4,5), 1.32 (m, 2H, CH2 (H3), 1.65 (m, 2H
,CH2(H2), 1.97 (s, 3H, CH3(HC), 2.14 (m, 2H, CH2(H), 3.26
(s, 6H, N+-CH3), 3.44 (m, 2H, CH2(H), 3.65 (t, 2H, CH2(H)),
5.43 (s, 1H, HC=CCH3 CH2(Hb)), 5.93 (s, 1H, HC=C(Ha)),
7.99 (t, 1H, NH).
D. Synthesis
of
Cationic
Poly(N-[3-HexyldimethylAminopropyl]
Methacrylamide
Bromide)
[Poly(HDAPMAA)]
The polymer was prepared by radical polymerization using
AIBN (0.1 %) as initiator at 60 C. Monomer was degassed by
argon after the initiator was quickly introduced. The polymer
was purified by three cycles of dissolution-precipitation, from
chloroform into a large excess of heptane, to eliminate the
unreacted monomer. The resulting precipitates were filtered
off and dried at 60 C for 24 h to constant weight
(yield = 80 %).

Fig. 4. 1H NMR of cationic amphiphilic polymer.

1
H NMR (CDCl3, in ppm): 0.951.10 (Ha, CH3C and CH3CH2-), 1.151.60 (Hb, (CH2)n and CH2 main chain), 1.65
1.9 (Hf, N+-CH2-CH2), 2.002.20 (He, CH3N), 3.103.60 (Hc,
CH3-N+), 3.604.00 ( Hd, NHCH2).

III. RESULTS AND DISCUSSION

A. Solubility of Cationic Polymer
The solubilities of polymers were tested in some standard
solvents. The cationic polymer is soluble in water, methanol,
ethanol, acetonitrile and chloroform, but insoluble in heptane,
THF, ethyl acetate, benzene and dioxane.

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B. Viscosity Measurements

D. The Effect of Water Content

In order to obtain a concentration of [Cp] = 2.103 gmL1 of

polymer, a quantity of 0.04 g was dissolved in 20 mL of the
appropriate solvent using a graduated flask. The solution was
agitated using a magnetic bar for 15 min at ambient
temperature and filtered using usual filter paper.
The polymers displayed regular viscosity behaviour in
solution of chloroform for a large concentration, therefore
allowing to determine intrinsic viscosity. The intrinsic
viscosity then enabled to calculate the corresponding average
molecular weight by Mark-Houwink relationship, formerly
reported for very closely related polymers obtained from
acrylates containing tertiary amine groups. The average molar
mass of polymer, Mw = 8.61 103 gmol1, was determined by
the Mark-Houwink-Sakurada equation:

The objective of our study of the viscosimetric behaviour of

the polymer in ethanol as solvent in the presence of an
increasing proportion of water was to determine the exact
nature (intra- or intermolecular side chain aggregation) of the
micelle-like pseudo-phases. Fig. 6 shows the variations of the
reduced viscosity of the polymer solutions (0.002 gmL1) as a
function of water content in the water/ethanol mixture. The
maximum reduced viscosity was obtained in pure ethanol,
which is a good solvent. The addition of water, even in small
amounts, triggers a strong decrease of the reduced viscosity.
Thus, the hydrodynamic volume of the macromolecule in
solution was strongly reduced by folding effects. It can be well
explained by the hydrophobic effect responsible for the
intramolecular aggregation of the alkyl side chains.

= KMwa,
40

Fig. 5 shows influence of temperature on reduced

viscosities of polymer solution in water. The reduced viscosity
increased with increasing temperature from 10 C to 30 C
and then decreased above 30 C.

-3

C. The Effect of Temperature

nred.10 (mL/g)

Where K = 1.08 105 mLg1 and a = 0.79 at T = 30 C [22].

35

30

25

2,5

20
0

2,0

20

40

60

80

100

1,5

Fig. 6. Variations of the reduced viscosity of the polymer solutions

([Cp] = 2.103 gmL1).

-3

nred.10 (ml/g)

water content %

1,0

E. Effect of Inorganic Salt Concentration on Viscosity of

Polymer Solution

0,5

0,0
10

20

30

40

50

60

T ( C)

Fig. 5. Variation of reduced viscosity as a function of temperature.

The results indicate that the increase of temperature was

favourable to intermolecular associations in a certain range of
temperature. This was due to the increase of endothermic
process of entropy for hydrophobic association at a low
temperature range [23].
However, increasing the temperature of the solution above
30 C led to a reduction of the solvent viscosity and hence an
increase in the mobility of the polymer chains while the
solubility of the polymer increased with temperature.

Fig. 7 shows the dependence of concentration on the

solution viscosity for polymer in deionized water and in 0.1 M
NaCl solution, respectively. In both cases almost the same
solution behaviour was observed. The reduced viscosities of
polymer in absence of NaCl solutions as a function of polymer
mass concentration Cp showed typical behaviour of
polyelectrolyte increasing with decreasing Cp. The reduced
viscosity of polymer solution decreased with salt addition of
0.051 M at a fixed polymer concentration.
In the presence of 1 M of NaCl, reduced viscosity linearly
varied with the polymer concentration. Extrapolation with null
concentration made it possible to determine the value of its
intrinsic viscosity [], which was about 300 mLg1.
The addition of salt increased the polarity of solvent, which
made the nonpolar hydrophobic groups to contract more
easily, leading to a reduction in the macromolecular chain size
and a decrease of solution viscosity.

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H2O
0.05M NacL
0.1NacL
0.5M NacL
1M NacL

-3

nred.10 (ml/g)

10

15

20

C.10 (g/ml)

Fig. 7. Variations of the reduced viscosity of the polymer solutions as a

function of NaCl concentration.
Fig. 9. Variation of the calculated molar conductance as a function of the
square root of polymer concentration.

F. Surface Tension Measurements

Fig. 8 shows the semi-logarithmic plots of the surface
tension as a function of LnCp. As is seen, the polymer
exhibited a nearly constant surface tension value at low
polymer concentrations which proves that molecular
adsorption at the water/air interface is very weak. This
adsorption became more prevalent when polymer
concentration became higher than 1.5102 gmL1 which was
regarded as the formation of microdomains.

66

Tensio sup (dyn/cm)

64

62

60

58

56

IV. CONCLUSION
Quaternary ammonium polymer was prepared by radical
polymerization of DAPMAA at 60 C. The monomer and
polymers were characterized by FTIR and 1H NMR. The
physico-chemical properties of cationic amphiphilic polymer
depended on the environmental parameters (temperature,
salinity, water content). Viscosity measurements were carried
out with aqueous solutions of a polymer and revealed
intramolecular associative properties. In particular, the
variation of the reduced viscosity of polymer solutions
reected the formation of hydrophobic micro-domains in
water. Surface tension method confirmed these observations,
while providing complementary information. The synthesized
polymers exhibited hydrophobic aggregation in water
characteristic of a general behaviour of polysoaps.
Conductivity measurements showed that polyelectrolyte
conductivity increases with decreasing concentration. Such
behaviour may be attributed to dissociated form of counter-ion
and their high mobility at infinite dilution.

54
-5,5

-5,0

-4,5

-4,0

-3,5

-3,0

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Wahiba Chaibi is a researcher at the Scientific and Technical Research

Center in Chemistry and Physics Analysis, Tipaza, Algeria. W. Chaibi
research activities include synthesis of amphiphilic comb polymers
(polysoaps) and study their behavior in aqueous medium, as well as synthesis
of amphiphilic block copolymers.
E-mail: Wahiba_chaibi@yahoo.fr
Asma Ziane is a PhD student at the Physical and Organic Macromolecular
Chemistry Laboratory, University "Djillali Liabes" of Sidi Bel-Abbes,
Algeria.
Zouaoui Benzehaim is a PhD student at the Physical and Organic
Macromolecular Chemistry Laboratory, University "Djillali Liabes" of Sidi
Bel-Abbes, Algeria.
Lamia Bennabi is an assistant professor at the Ibn Khaldoun University of
Tiaret, Algeria.
Kaddour Guemra is a professor at the Physical and Organic Macromolecular
Chemistry Laboratory, University "Djillali Liabes" of Sidi Bel-Abbes,
Algeria.

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