Archive of SID

Iranian Polymer Journal

13 (6), 2004, 479-484

Synthesis of Partially Hydrolyzed

Polyacrylamide and Investigation of Solution
Properties (Viscosity Behaviour)
M. Ebrahim Zeynali, Ahmad Rabii*, and Habibollah Baharvand
Department of Colour, Resin and Surface Coatings, Iran Polymer and Petrochemical Institute,
P.O. Box: 14965/115, Tehran, I.R. Iran
Received 17 October 2003; accepted 12 May 2004

ABSTRACT

opolymer of sodium acrylate and acrylamide was prepared by free radical polymerization in solution. Molecular weight was determined using Ubbleohde viscometer. Various reduced viscosity measurement tests were conducted to characterize the viscosity behaviour of partially hydrolyzed polyacrylamide. Experiments show a
polyelectrolyte effect when reduced viscosity is plotted against polymer concentration.
The reduced viscosity is rising in salt free solution due to dilution. Salt addition to the polymer solution presents quite different results. The polyelectrolyte effect disappeared at
higher concentration of salt as a consequence of inhibiting the polyions from intramolecular expansion. The effect of different low molecular weight electrolytes on reduced viscosity of polymer solution was investigated. The intrinsic viscosity was obtained as a
function of charge density (degree of hydrolysis) on the backbone of the polymer chain.
It is observed that the intrinsic viscosity increases with increasing the percentage of ionic
carboxyl groups on the polymer molecules. The reduced viscosity of the polymer was
obtained in a solvent mixture of water and formamide.

Key Words:
polyelectrolyte;
reduced viscosity;
partially hydrolyzed
polyacrylamide;
intrinsic viscosity;
synthesis.

INTRODUCTION

(*)To whom correspondence should be addressed.

E-mail: a.rabii@ippi.ac.ir

Partially hydrolyzed polyacrylamide

is widely used in water treatment as
an anionic coagulant, in drilling
mud as a viscosifier and shale stabilizer and in enhanced oil recovery.
In enhanced oil recovery a dilute
aqueous solution of partially

hydrolyzed polyacrylamide is used

as a pushing fluid in the injection
wells to sweep oil in the reservoir
into the production well. Mobility
reduction or viscosity behaviour of
partially hydrolyzed polyacrylamide
polyelectrolyte solutions plays an

www.SID.ir

Zeynali M.E. et al.

Synthesis of
Archive
ofPartially
SID Hydrolyzed Polyacrylamide and...

important role in such applications. The properties of

polyelectrolytes in aqueous solutions have been widely
investigated in the past decade [1-8]. For polyelectrolyte solutions it was shown by Fuss and Strauss
many years ago that viscosity behaviours are significantly different than those of neutral polymers [9]. In
polyelectrolyte solutions, factors like chain conformation, orientation of the chains and entanglement
between different chains affect the flow properties of
these solutions [10]. The ionization of a flexible linear
polyelectrolyte markedly increases the viscosity of its
salt-free aqueous solution, often by several orders of
magnitude. This increase in viscosity has been
explained in terms of an unfolding of the polymer coil
due to the repulsion between the like-charges attached
to the coil [11]. Viscometric studies of polyelectrolyte
solutions are essential, as they provide clues to understanding the properties of these systems. In the present
paper the viscosity behaviour of polyelectrolyte solution was studied. Viscosity measurements were carried
out with samples of partially hydrolyzed polyacrylamide
covering a wide range of the degree of hydrolyses.

(21.2 g) aqueous solution was added into the reactor.

Nitrogen gas was bobbled for 30 min to remove oxygen
from the aqueous solution of monomers mixture. To
start the copolymerization reaction 0.05 g of sodium
metabisulphite and potassium persulphate in 20 mL of
water were added to the monomers mixture. The
copolymerization reaction was carried out at 60C
using a thermostated bath. During the reaction the reactor content was kept under a nitrogen atmosphere.
Degree of hydrolysis of copoly(acrylamide-sodium
acrylate) with 10-60% sodium acrylate was measured
[12] and adjusted initially by varying the acrylate content of monomer mixturs. At the end of copolymerization reaction the product was precipitated from aqueous
solution by the addition of methanol and dried in a vacuum oven at 50C. The chemical structure of partially
hydrolyzed polyacrylamide is as follow:
CH2

CH

CH2

CH

C O

C O

NH2

ONa

Scheme I

EXPERIMENTAL
Materials
Acrylamide, sodium chloride, calcium chloride, magnesium chloride, sodium hydroxide, sodium metabisulphite, potassium persulphate, formamide, and hydroquinone were obtained from Merck and Aldrich Co.
and used as received. Acrylic acid was vacuum distilled
at 50C in the presence of hydroquinone to separate the
inhibitor. Sodium acrylate was obtained by neutralization of acrylic acid using stoichiometric amount of
sodium hydroxide aqueous solution.
Copolymerization
Partially hydrolyzed polyacrylamide was prepared by
copolymerization of acrylamide and sodium acrylate. A
redox system including sodium metabisulphite and
potassium persulphate were used to initiate free radical
copolymerization. Copolymerization was conducted in
a 300-mL glass reactor equipped with a mechanical
stirrer. A typical formulation and preparation procedure
was as follow: 14 g of acrylamide was dissolved in 180
mL of water. The aqueous solution of acrylamide was
discharged into the glass reactor. 30% Sodium acrylate

480

Polar amide and ionic carboxylic groups impart

water solubility to the copolymer.

RESULTS AND DISCUSSION

Viscosity Measurement
The Ubbelohde capillary viscometer was used to measure the relative, specific and reduced viscosity of the
polymer solutions from the flow times of solutions.
The viscosity measurements were carried out at a constant temperature of 25C. The solution temperature
was controlled by a thermostat in a circulating bath and
monitored by a thermometer. A stopwatch with a resolution of 0.1s was used to measure the flow times. By
plotting the reduced viscosity (dL/g) of polymer solutions against concentration (g/dL), extrapolating to
infinite dilution and taking the intercept, the intrinsic
viscosity [] is determined. Reduced viscosity versus
concentration in the presence of various amounts of initiator is presented in Figure 1. Reduced viscosity is
directly proportional with the molecular weight. With
increasing the initiator concentration the molecular
weight decreases which results in decreasing the

Iranian Polymer Journal / Volume 13 Number 6 (2004)

www.SID.ir

Zeynali M.E. et al.

Archive
of SID

Synthesis of Partially Hydrolyzed Polyacrylamide and...

13.5

9.5

5.5

1.5

0.05

0.1

0.15

Concentration (g/dL)
Initiator concentration: 0.0088 mol/L ( ); Initiator concentration: 0.0066
mol/L ( ); Initiator concentration: 0.0044 mol/L ( ); Initiator concentration: 0.0022 mol/L (x).

Figure 1. Reduced specific viscosity vs. polymer concentration in the presence of 0.2 M sodium sulphate.

reduced viscosity. As it is expected the reduced viscosity decreases with increasing initiator concentration.
Molecular Weight Determination
Molecular weight was determined using MarkHouwink equation. For a partially hydrolyzed polyacrylamide polymer K and in Mark-Houwink equation change as a function of degree of hydrolysis.
Meiling et al. [13] described a simple method for determining molecular weight of partially hydrolyzed polyacrylamide using single point method of determination
of intrinsic viscosity. In another attempt to find a relationship between Mark-Houwink constants and degree
of hydrolysis, Wu et al. [14] obtained two empirical
polynomial equations for K and as functions of
degree of hydrolysis. In our experiments samples with
30% degree of hydrolysis have been used for molecular weight determination. For above samples K and
from polynomial equations are 2.2210-4 and 0.742,
respectively. Molecular weight as a function of initiator
concentration is presented in Figure 2. With increasing

initiator concentration the number of growing chains to

form polymer increase leads to lower molecular
weight.
The reduced viscosity is defined as sp/c = ( / c), where, and are the viscosity of polymer

solution and solvent, respectively. C is the polymer
concentration in g/dL. The reduced viscosity of the
salt-free polymer solution is shown in Figure 3 as a
function of polymer concentration. It is seen from
Figure 3 that the reduced viscosity increases with
decreasing polymer concentration. This typical polyelectrolyte behaviour which is usually observed in salt
free aqueous solutions occurs because the carboxylic
groups on the polymer chain can ionize in the polar solvent and the effective electrostatic repulsion makes this
polymer chain highly extended. This phenomenon was
also observed by Peiffer et al. [15], Liu et al. [16], and
Aseyev et al. [17] for different polyelectrolyte solutions.
For the higher molecular weight samples the
increase is followed by a rapid decrease at very low
concentrations [18]. The decrease probably remains
undetected in the lowest molecular weight sample,
because in this case measurement could not be performed at sufficiently low concentrations owing to the
comparatively low viscosity of these solutions. The
polyelectrolytes either cationic and anionic polymer
have special viscosity behaviour in comparison with
neutral polymer. Neutral polymers have the property
that reduce viscosity increases with the increase of
polymer concentration. The reduced viscosity of polyelectrolytes in a salt-free dilute aqueous solution is
more than tens of times as largest neutral polymers.
Reduced viscosity as a function of polymer concentration in the presence of 1 mol/L KI is presented in
Figure 4. The mechanism of the KI effect on reducing
the polyelectrolyte effect mainly is related to the reduc80
70

1.5 x 106

60

1.0 x 106

50
5.0 x

105
0

40
0

0.002

0.004

0.006

0.008

Initiator concentration (mol/L)

Figure 2. Molecular weight vs. initiator concentration.

0.010

0.05

0.10

0.15

Polymer concentration (g/L)

Figure 3. Reduced viscosity vs. polymer concentration at HD

= 30%.

481
www.SID.ir

Iranian Polymer Journal / Volume 13 Number 6 (2004)

Zeynali M.E. et al.

Synthesis of
Archive
ofPartially
SID Hydrolyzed Polyacrylamide and...

tion of double layer thickness on the polyelectrolyte

molecule. Due to high degree of ionization, KI reduces
the partial ionization of polyelectrolyte and eliminates
the polyelectrolyte effect at lower concentration. When
small molecule electrolyte is added to a polyelectrolyte
solution depending on the concentration the viscosity
behaviour changes. It is seen from Figure 4 that there is
not polyelectrolyte effect and viscosity does not
increase with decreasing polymer concentration, which
is in contrast with salt-free solution.
Figure 5 shows the effect that the mixed form
amide/water solvent system has on the reduced viscosity of partially hydrolyzed polyacrylamide. Increasing
the volume fraction of water produces a rise in the
reduced viscosity due to the expected increase in
hydrodynamic volume of the chain. The curve has a
minimum at 60% formamide content. With increasing
the formamide content after the minimum point again
the reduced viscosity increases as a result of rise in
hydrodynamic volume. Also by addition of formamide
the ionization of polyelectrolyte decreases. By varying
the solvent then important experimental parameters
such as dielectric constant and solvent can be varied.
The dielectric constant of formamide (109) is larger
than that of water (78.5). The dielectric constant has a
significant effect on the strength and range of electrostatic interactions.
Reduced viscosity was plotted as a function of salt
concentration in constant polymer concentration
(Figure 6). Ionic strength influence on viscosity was
determined by varying the salt type and concentration.
It is seen that reduced viscosity decreases significantly
with low molecular weight electrolyte addition. The
effect of divalent salts (CaCl2 and MgCl2) has been
16

120
80
40
0

20

40

60

80

100

120

Formamide content (%)

Figure 5. Reduced viscosity vs. formamide content in the formamide and water mixture.

investigated. The reduced viscosity decreases more by

Ca2+ than Mg2+ which can be ascribed to the fact that
Mg2+ is more soluble than Ca2+. Addition of a salt to
an aqueous solution of partially hydrolyzed polyacrylamide results in the screening of the electrostatic
repulsion between charges along the polymer chain
[19]. As a consequence addition of salt to polyelectrolytes solutions leads to a more pronounced decrease
in viscosity. At low ionic strength the coils are expanded due to intramolecular electrostatic repulsion, which
leads to higher hydrodynamic volume. On the other
hand introduction of salts which lowers both intra- and
intermolecular repulsion reduces the hydrodynamic
volume of the individual coil as well. In distilled water
the polymer has high viscosity typical of polyelectrolytes in aqueous media. At low ionic strength and
concentration the electrostatic repulsive forces dominate
the polymer solution behaviour and the polymer acts as
polyelectrolyte. No precipitation of the polymer has been
observed up to the highest concentrations of salts.
Dilute solution measurements can yield the intrinsic viscosity; an indication of the hydrodynamic volume of an isolated polymer chain in solution. Partially
hydrolyzed polyacrylamide molecules contain randomly distributed polar carboxyl groups and behave as a

1 mol/L kl
12

70

50

30

0.05
0.10
concentration (g/L)

Figure 4. Reduced viscosity vs. concentration in the presence of 1 mol/L KI.

482

10
0

0.15

Salt concentration (mol/L)

( ) Nacl; ( ) CaCl2; ( ) MgCl2.

Figure 6. Reduced viscosity vs. salt concentration.

Iranian Polymer Journal / Volume 13 Number 6 (2004)

www.SID.ir

Zeynali M.E. et al.

Archive
of SID

Synthesis of Partially Hydrolyzed Polyacrylamide and...

polyelectrolyte in aqueous solution. The carboxyl

groups carry negative charges and polymer solution
becomes an anionic polyelectrolyte. Polyelectrolyte
properties originate from the combination of macromolecular and electrolyte behaviour. Because of the
repulsion forces between ionized carboxyl groups,
polymer chain extends and uncoils in the solution.
Therefore, the effective size or volume of the polymer
molecules increases which leads to larger hydrodynamic interactions between polymer chains and water molecules. This influences the transport properties of polyelectrolyte and increases its intrinsic viscosity.
The above analysis has been supported by our
experimental work as it is observed in Figure 7. With
increasing the hydrolysis degree (HD) or fraction of
ionizable carboxyl groups on the backbone of the polymer chain, the intrinsic viscosity increases. By increasing hydrolysis degree the intrinsic viscosity firstly rises
sharply due to the electrostatic repulsion between
charged groups along the polymer chains. In other
words, because of the repulsion forces between the negative charges (carboxyl groups), the original coiled molecules of partially hydrolyzed polyacrylamide uncoil as
hydrolysis proceeds, molecules become more extended,
thereby increasing the flocculation ability as well as viscosity of solutions [20]. Further increase in hydrolysis
degree leads to smoothness of the slope of the curve.
The height of the curve is strongly influenced by the
polymer concentration, the salt concentration, the chain
length and the molecular weight distribution [21]. It
must be noted that information discussed so far applies
7
6
5
4
3
2
1
0

20
40
Hydrolysis degree (%)

Figure 7. Intrinsic viscosity vs. hydrolysis degree.

60

to dilute solution. Very dilute solutions in water contain

only individual and unassociated polymer coils.

CONCLUSION
Partially hydrolyzed polyacrylamide was prepared by
free radical copolymerization in solution. The intrinsic
viscosity has been determined by extrapolating the
reduced viscosity to zero concentration. The effects of
solvent, salt type and concentration, degree of hydrolysis, and polymer concentration on viscosity have been
investigated. It was shown that the reduced viscosity of
salt-free solution of partially hydrolyzed polyacrylamide as a result of polymer chain expansion increases
with decreasing polymer concentration. In fact the polymer behaves like a polyelectrolyte in salt-free solution.
Adding low molecular weight electrolyte to the polymer
solution eliminates the polyelectrolyte effect and polymer behaves like a neutral macromolecule. The viscosity increases with increasing polymer concentration,
which is usually observed in neutral polymers. The
effect of dielectric constant on reduced viscosity was
studied by varying the solvent type and concentration. It
was found that reduced viscosity decreases with
increasing formamide content in the solvent mixture.

REFERENCES
1. Jousset S., Bellissent H., and Galin J.C., Polyelectrolytes
of high charge density in organic solvent: Synthesis and
viscometric behavior, Macromolecules, 31, 4520-4530
(1998).
2. Rinaudo M., Milas M., Jouon N., and Borsali R., On some
original properties of dilute polyelectrolyte solutions at
low salt content: Sodium hyaluronate example, Polymer,
34, 3710-3715 (1993).
3. Muller-Nedebock K.K., and Vilgis T.A., Dynamics of
dense polyelectrolyte solutions, Macromolecules, 31,
5898-5903 (1998).
4. Antonietti M., Briel A., and Forster S., Quantitative
description of the intrinsic viscosity of branched polyelectrolytes, Macromolecules, 30, 2700-2704 (1997).
5. Leibler L. and Pezron E., Viscosity behaviour of polymer
solutions in the presence of complexing ions, Polymer, 29,
1105-1109 (1988).

483
www.SID.ir

Iranian Polymer Journal / Volume 13 Number 6 (2004)

Zeynali M.E. et al.

Synthesis ofofPartially
Archive
SID Hydrolyzed Polyacrylamide and...

6. Ennari J., Elomaa M., and Sundholm F., Modelling a

polyelectrolyte system in water to estimate the ion-conductivity, Polymer, 40, 5035-5041 (1999).
7. Vishalakshi B., Ghosh S., and Kalpagam V., The effects of
charge density and concentration on the composition of
polyelectrolyte complexes, Polymer, 34, 3270-3275
(1993).
8. Dobrynin A.V., Colby R.H., and Rubintein M., Scaling
theory of polyelectrolyte solutions, Macromolecules, 28,
1859-1871 (1995).
9. Sukpisan J., Kanatharana J., Sirivat A., and Wang S.Q.,
The specific viscosity of partially hydrolyzed polyacrylamide solutions: Effects of degree of hydrolysis, molecular weight, solvent quality and temperature, J. Polym. Sci.,
Part B: Polym. Phys., 36, 743-753 (1998).
10. Vink H., Rheology of dilute polyelectrolyte solutions,
Polymer, 33, 3711-3716 (1992).
11. Darskus R.L., Jordan D.O., Kurucev T., and Martin M.L.,
Concentration dependence of the reduced viscosity of
dilute aqueous polyelectrolyte solutions, J. Polym. Sci.,
Part A: Polym. Chem., 3, 1941-1948 (1965).
12. Zeynaly M.E. and Rabii A., Alkaline hydrolysis of polyacrylamide and properties study of poly(acrylamide-cosodium acrylate), Iran. Polym. J., 11, 269-275 (2002).
13. Ye M., Han D., and Shi L., Studies on determination of
molecular weight for ultra-high molecular weight partially hydrolyzed polyacrylamide, J. Appl. Polym. Sci., 60,
317-322 (1996).
14. Wu X.Y., Hunkeler D., Hamielec A.E., Pelton R.H., and
Woods D.R., Molecular weight characterization of
poly(acrylamide-co-sodium acrylate), 1. Viscometry, J.
Appl. Polym. Sci., 42, 2081-2093 (1991).
15. Peiffer D.G. and Lundberg R.D., Solution properties of
ion-containing polymers in polar solvents, J. Polym. Sci.,
Polym. Chem. Ed., 22, 1757-1773, 1984.
16. Liu X., Hu O., and Tong Z., Viscosity behavior of polyelectrolyte copolymers containing sulfonate groups in
mixed organic solvents, J. Polym. Sci., Part B: Polym.
Phys., 35, 1433-1438 (1997).
17. Aseyev V., Klenin S.I., and Tenhu H., Conformational
changes of a polyelectrolyte in mixtures of water and acetone, J. Polym. Sci., Part B: Polym. Phys., 36, 1107-1114
(1998).
18. Cohen J., Priel Z., and Rabin Y., Viscosity of dilute polyelectrolyte solutions, J. Chem. Phys., 88, 7111-7115
(1988).
19. Shalaby S.W., McCormick C.L., and Butler G.B., Water-

484

soluble Polymer, Am. Chem. Soc., Washington, DC, Ch. 5

(1991).
20. Buscall R., Corner T., and Stageman J.F., Polymer
Colloids, Elsevier, Appl. Sci., London and NewYork, Ch.5
(1985)
21. Stahl G.A. and Schulz D.N., Water-soluble Polymer for
Petroleum Recovery, Plenum, New York and London,
Ch.1 (1986).

Iranian Polymer Journal / Volume 13 Number 6 (2004)

www.SID.ir