410 Pet.Sci.

(2010)7:410-415
DOI 10.1007/s12182-010-0086-9

Dispersion polymerization of anionic

polyacrylamide in an aqueous salt medium
Lu Jiao, Peng Bo , Li Mingyuan, Lin Meiqin and Dong Zhaoxia
Enhanced Oil Recovery Research Center, China University of Petroleum, Beijing 102249, China

© China University of Petroleum (Beijing) and Springer-Verlag Berlin Heidelberg 2010

Abstract: Anionic polyacrylamide dispersions were prepared by dispersion polymerization in

an aqueous salt medium, using acrylamide(AM) and acrylic acid(AA) as monomers and anionic
polyelectrolytes as stabilizer. Effects of salt concentration, and molecular weight and concentration of
stabilizers on the stability of the dispersions were investigated using a HAAKE rheometer and optical
microscopy. The results showed that stable anionic polyacrylamide dispersions, consisting of smooth,
spherical, polydisperse particles, could be obtained under the conditions of salt concentration ranging
from 26 wt% to 30 wt%, concentration of stabilizers from 1.2 wt% to 1.8 wt%, and intrinsic viscosity of
stabilizers from 2.98 dL·g-1 to 3.74 dL·g-1. The apparent viscosity of the stable dispersions changed very
little with the shear rate, showing Newton fluid behavior.

Key words: Dispersion polymerization, aqueous salt medium, stability, micromorphology, apparent
viscosity

1 Introduction chain length during polymerization. The precipitated

polymers form spherical micro-particles through aggregation
Polyacrylamide (PAM) is an important water-soluble and the particles are suspended in the medium by the
polymer. It can be used as a flocculant for water disposal, adsorption of stabilizer. There are several advantages of
strength additives for paper manufacture, oil displacement dispersion polymerization, such as no secondary pollution,
agents for enhanced oil recovery, and so on (Yan, 1998). high solid content and rapid dissolution (Fang et al, 2006).
At present, anionic polyacrylamide is synthesized Until now, most of the papers on dispersion polymerization
mainly by two methods, namely solution polymerization of hydrophilic monomer acrylamide mainly focus on an
and inverse emulsion/microemulsion polymerization. alcohol-water medium (Ray and Mandal, 1997; Ray and
Solution polymerization has been adopted commonly, but the Mandal, 1999; Ye et al, 2002; Guha and Mandal, 2004; Han
dissolution process of the dry powder is often tedious. When et al, 2004; Cui et al, 2002; Wang et al, 2005), and a few
dissolution of PAM is required, inverse microemulsion/ papers focus on dispersion polymerization of acrylamide
emulsion polymerization is chosen. This uses hydrocarbon as or of acrylamide with cationic monomer in an aqueous salt
the continuous phase and various surfactants as emulsifiers. medium (Cho et al, 2002; Song et al, 2003; Ye et al, 2003;
The main advantage of this method is that it can obtain high- Chen et al, 2006a; 2006b; Guo et al, 2007). Only a few papers
molecular weight anionic polyacrylamide and achieve high focus on dispersion polymerization of acrylamide and anionic
conversion rates during polymerization, and the anionic monomer acrylic acid (Liu et al, 2006; Liu et al, 2007).
polyacrylamide has good solubility. But it will result in In this paper, anionic polyacrylamide dispersions are
secondary pollution to the environment as it has organic synthesized by the dispersion polymerization method
solvents and emulsifiers added in the reaction system. with acrylamide as primary feedstock and acrylic acid as
Dispersion polymerization can be defined as a special secondary feedstock in a salt medium .
precipitation polymerization in which polymerization is The effects of salt concentration, molecular weight
carried out in the presence of a suitable stabilizer (Fang et and concentration of stabilizers on the stability of
al, 2006). Monomer, stabilizer, and initiator are dissolved anionic polyacrylamide dispersions were investigated by
in the aqueous medium before polymerization, and the pre- measurements of the apparent viscosity and the stability of
reaction system is a homogeneous solution. PAM polymer the anionic polyacrylamide dispersions and micromorphology
is precipitated from the aqueous medium due to its low observations.
solubility when the formed polymer chains reach critical
2 Experimental
*Corresponding author. email: [email protected] 2.1 Materials
Received November 18, 2009 Reagents used were: Acrylamide (AM) and ammonium
Pet.Sci.(2010)7:410-415 411

persulfate, A.R. Grade, supplied by Guangdong Shantou and unstable (b) dispersions. In the unstable dispersion, the
Xilong Chemical Co., Ltd; Acrylic acid (AA) and sodium interface between particles and aqueous medium can not be
bisulfite, A.R. Grade, Beijing Yili Fine Chemicals Co., Ltd; distinguished. In the stable dispersion, there are amounts of
Sodium hydroxide, A.R. Grade, Beijing Modern Eastern Fine smooth-surfaced, spherical, polydisperse particles.
Chemicals Co., Ltd. Stabilizers with the same structure but
different molecular weights were prepared in the laboratory,
and the intrinsic viscosity ([η]) was determined in a 0.5 100

mol/L(NaCl) aqueous solution with an Ubbelhode capillary

Salt concentration
viscometer at 25.0 °C; Other reagents were all A.R. Grade 80
20 wt%

Apparent viscosity, Pa·s

and used as received. 22 wt%
60 24 wt%
2.2 Preparation and characterization 26 wt%
28 wt%
Acrylamide, acrylic acid, sodium hydroxide, salts, 40 30 wt%
stabilizer, and deionized water were added to a 500 mL four-
necked flask equipped with an anchor-like paddle stirrer, 20

a reflux condenser, and a nitrogen inlet. After purging

with nitrogen for half an hour at 30 °C in a water bath, 0

polymerization was initiated by injecting the water-soluble

initiator ammonium persulfate (APS) and NaHSO3 into the -20
10 100 1000
stirred reaction system. The polymerization was allowed
Shear rate, s-1
to proceed for 22 h and then the anionic polyacrylamide
dispersions were obtained. The apparent viscosity of the Fig. 1 Apparent viscosity of the anionic polyacrylamide dispersions
dispersions was measured at 25 °C with a HAAKE RS as a function of shear rate in aqueous medium with different salt
600 Rheometer (Thermo Haake Co., Ltd., Germany). concentrations
Conditions: monomer, 15wt%; molar ratio of AM/AA, 7:3; AA,
The micromorphology of the anionic polyacrylamide
neutralized by NaOH solution and neutralization degree reached 15%;
dispersions was observed using a XS-18 (304) biological intrinsic viscosity [η] of stabilizer, 3.74 dL·g-1; stabilizer, 1.5 wt%;
photomicroscope (Nanjing Jiangnan Photoelectric Co., Ltd., initiator 0.01 wt%
China).

3 Results and discussion Table 1 Stability of anionic polyacrylamide dispersions

Salt
3.1 Effect of salt concentration concentration, 20 22 24 26 28 30
wt%
The concentration of salt has a strong effect on the
stability of the dispersions. If the concentration is too low, Stability of
Unstable Unstable Unstable Stable Stable Stable
dispersions
the anionic polyacrylamide particles does not salt out easily
from the medium, and solution polymerization takes place. Conditions: monomer, 15 wt%; molar ratio of AM/AA, 7:3;
If the concentration is too high, the anionic polyacrylamide neutralization degree, 15%; Intrinsic viscosity [η] of stabilizer, 3.74
dispersions have lower thermodynamic stability, and it is dL·g-1; stabilizer, 1.5 wt%; initiator 0.01wt%
difficult to obtain stable dispersions.
Fig.1 shows the relationship between the apparent When the concentration of salt was relatively low (20-24
viscosity and shear rate of the anionic polyacrylamide wt%), part of the polymer salted out from the salt solution,
dispersions in an aqueous medium with different salt and some polymer remained in the salt solution. A network
concentrations. When the salt concentration was low (20- structure formed by tangled polymer molecule chains,
24 wt%), the apparent viscosity of the dispersions decreased leading to high apparent viscosity and undistinguished
gradually with increasing shear rate. At the same shear rate, micromorphology of the particles, hence the dispersion
the higher the salt concentration, the lower the apparent system was not stable. An increasing shear rate can destroy
viscosity of the dispersions. At high salt concentration (26- the network structure, so the system shows shear thinning.
30 wt%), the apparent viscosity of the dispersions was almost When the salt concentration was increased to a high value
unchanged with increasing shear rate, and at the same shear (26-30 wt%), the polymer particles would salt out entirely
rate, the apparent viscosity changed very little as the salt from the aqueous medium, forming a stable dispersion
concentration changed from 26 wt% to 30 wt%. because the stabilizer absorbed on the spherical particles and
The stability of the anionic polyacrylamide dispersions dispersed them. In this case, the apparent viscosity of the
is shown in Table 1. When the salt concentration was too dispersions is very low, and almost unchanged with the shear
low (20-24 wt%), the dispersions were not stable, and would rate. This result agrees well with that reported in literature
separate into layers within 10 hours. At high salt concentration (Zhou et al, 1987), namely, the more regular the disperse
(26-30 wt%), stable anionic polyacrylamide latex dispersions phase, the smaller the apparent viscosity and the more stable
were obtained. Fig. 2 shows the photographs of the stable (a) the dispersions.
412 Pet.Sci.(2010)7:410-415
Pet.Sci.(2010)7:410-415 413
414 Pet.Sci.(2010)7:410-415

Table 3 Stability of anionic polyacrylamide dispersions concentration affects the solubility of the formed polymers
in the aqueous medium. The lower the salt concentration,
Stabilizer [η],
dL·g-1
2.04 2.51 2.98 3.41 3.74 5.62 6.28 the higher the molecular weight of the polymers which will
Stability of be salted out and the smaller the amount of the salted-out
Unstable Unstable Stable Stable Stable Unstable Unstable polymer. So it is necessary to determine the suitable range
dispersions
Conditions: monomer, 15 wt%; molar ratio of AM/AA, 7:3; of salt concentrations for the balance between the expansion
neutralization degree, 15%; salt, 26 wt%; stabilizer, 10 wt%; initiator extent of stabilizer molecular chains and the efficient salting
0.01wt% out of the formed polymer to prepare stable dispersions. The
satisfactory salt concentration in this study is in the range of
When the intrinsic viscosity of the stabilizer was too 26-30 wt%.
low([η]=2.04 dL·g-1), the short molecular chains could not
inhibit aggregation between the particles through steric 4 Conclusion
hindrance and electrostatic repulsion. The particles could 1) Stable anionic polyacrylamide dispersions could be
easily stick to each other, forming irregular blocks. So the prepared under the conditions of salt concentration ranging
anionic polyacrylamide dispersion was unstable. Furthermore, from 26 wt% to 30 wt%, concentration of stabilizers from 1.2
the apparent viscosity of the dispersion was very high, and wt% to 1.8 wt%, and intrinsic viscosity of stabilizers from 2.98
showed shear thinning behavior. When the intrinsic viscosity dL·g-1 to 3.74 dL·g-1.
of the stabilizer was too high ([η] =5.62 dL·g-1), the long 2) The apparent viscosity of the stable dispersions was
molecular chains could be bridged between the particles almost unchanged with shear rate, and they behaved as
and the anionic polyacrylamide dispersion was also not Newtonian fluids.
stable. The stabilizer itself also contributed a lot to the high 3) The stable dispersions contained smooth-faced,
apparent viscosity of the dispersion. When the stabilizer with spherical, polydisperse particles.
suitable intrinsic viscosity was used ([η]=2.98-3.74 dL·g-1),
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