Aggregation behavior of methacrylic acid/ethyl acrylate

copolymer in dilute solutions

S. Dai
a
, K.C. Tam
a,
*
, R.D. Jenkins
b
a
School of Mechanical and Production Engineering, Nanyang Technological University, Nanyang Avenue, Singapore 639798, Singapore
b
Union Carbide Asia Pacic Incorporation, Technical Center, 16 Science Park Drive, The Pasteur, Singapore 118227, Singapore
Received 22 June 1999; received in revised form 21 September 1999; accepted 5 January 2000
Abstract
A co-polymer consisting of methacrylic acid (MAA) and ethyl acrylate (EA) is commonly used as the polymer
backbone for a class of hydrophobically modied alkaline soluble emulsion (HASE) polymer. At alkaline pH, the
emulsion particle solubilizes, yielding a molecular structure that is currently not well understood. The chain confor-
mation of a model MAA/EA copolymer (designated as HASE107) in 0.1 M NaCl at pH of 9 was studied by dynamic
and static light scattering techniques. In dilute solutions, two decay modes in the distribution function are observed.
These two modes (referred to as the fast and slow modes) are attributed to the translational diusion of the unimers and
the aggregates. In order to isolate the aggregates, the HASE107 polymer was dissolved in a moderately good solvent
(tetrahydrofuran was chosen), where only a single diusion mode is observed. The results conrmed that the co-
polymers synthesized via emulsion polymerization technique are blocky, and in aqueous solutions, the blocky and more
hydrophobic EA segments associate to form aggregates consisting of a few polymer chains. 2000 Elsevier Science
Ltd. All rights reserved.
Keywords: Aggregation; Light scattering; Hydrophobic; Ethyl acrylate
1. Introduction
An associative polymer represents a class of polymers
that possesses surfactant-like properties. The polymer
usually consists of a hydrophilic backbone with hydro-
phobic groups located at the ends of the polymer chain
or distributed along the polymer backbone. Hence,
when the polymer dissolves in water, clusters of hydro-
phobic domains are formed yielding a network struc-
ture. Such a structure induces a large increase in the
solution viscosity, which gives rise to a viscous and often
elastic and gel-like uid. These associative polymers are
good candidates for thickening agents in environmen-
tally friendly coating applications. Interests in the eld
of associative polymers have received increasing atten-
tion in the last 1015 years [114].
A hydrophobically modied alkali soluble emulsion
(HASE) polymer is one type of a wide range of novel
synthetic associative thickeners [15]. This thickener
contains a backbone consisting of randomly distributed
methacrylic acid (MAA) and ethyl acrylate (EA)
monomers. Extended from the backbone is a small
proportion of hydrophobically modied water-insoluble
groups, usually between 13 mol%. Due to its structure,
the polymer, when dissolved in an alkaline aqueous so-
lution, induces a variety of interacting forces such as
hydrophobic, hydrogen bonding, electrostatic, etc. On a
macroscopic level, such interactions have a strong
bearing on the rheological properties of the polymer in
solution. Often, such a property can be easily quantied,
but it does not provide any insight into the nature of
European Polymer Journal 36 (2000) 26712677
*
Corresponding author. Present address: Department of
Mechanical Engineering, Massachusetts Institute of Technol-
ogy, 77 Massachusetts Avenue, Cambridge, MA 02139-4307,
USA. Fax: +65-791-1859.
E-mail address: mkctam@ntu.edu.sg (K.C. Tam).
0014-3057/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S0014- 3057( 00) 00022- 7
these interactions on a microscopic level. There is thus a
need to measure the behavior of the polymer molecules
at a microscopic level. Until now, several publications
on the rheological properties of this thickener [1621]
have been reported. Although many other techniques,
such as pulse gradient NMR, uorescence spectroscopy
and dynamic light scattering can be used to investigate
the microscopic behaviors of the HASE solutions, not
much has been published for this complicated system.
The HASE polymers are usually synthesized via the
emulsion polymerization technique. Whether the MAA
and EA are randomly distributed along the backbone is
still not known. The distribution of MAA and EA in the
backbone could signicantly aect the solution proper-
ties as well as the association mechanism. However,
from preliminary studies conducted at our laboratory, it
seems that some degree of blockiness in the EA mono-
mers may exist. Hence, a detailed study on the behaviors
of the model HASE polymer, without the hydropho-
bically modied group is essential for understanding the
association characteristics of HASE in aqueous solu-
tions.
Laser light scattering is a powerful research tool for
studying the dilute solution properties of polymer sys-
tems. Two common approaches can be used, i.e., static
light scattering (SLS) [22] and dynamic light scattering
(DLS) [23,24]. Through the study of SLS, the weight
average molar mass (M
w
), second virial coecient (A
2
)
and the z-average radius of gyration (R
g
) can be ob-
tained. From DLS, the translational diusion coecient
(D), hydrodynamic radius (R
h
) and the polymer chain
conformation can be determined.
In this study, the laser light scattering technique is
chosen to investigate the association behaviors of
HASE107 in aqueous solutions with abundant salt.
HASE107 is a model MAA/EA copolymer and its
chemical structure is shown in Fig. 1. In addition, the
behavior of HASE107 in an organic solvent such as
tetrahydrofuran (THF), was examined. THF is a mod-
erately good solvent based on the comparison of the
solubility parameter (d) with the polymer (note: d(THF)
is 18.6 (MPa)
1=2
, d(PEA) is 19.8 (MPa)
1=2
and d(PMAA)
is 20.3 (MPa)
1=2
) [25]. Our experimental experiences in-
dicate that the polymer readily dissolves in THF.
2. Experiment
2.1. Materials and sample preparation
The copolymer, designated as HASE107, was syn-
thesized at Union Carbide using the emulsion poly-
merization technique. The details of the synthesis and
characterization of the polymer were described else-
where [19,26]. The molar ratio of the two monomers
(MAA/EA) is 1.
HASE107 in the latex form was dialyzed using a
cellulose membrane placed in the deionized water for
approximately four weeks. The water was changed every
week, and the cleaned latex was dried in the vacuum
oven at 80100C. The cellulosic dialysis membrane re-
moves molecules with a M
w
below 14,000. The dried
HASE107 sample was weighed and dissolved in THF or
0.1 M NaCl aqueous solutions to yield a stock solution
of 10 mg/ml. The reagents, NaCl and THF, were used as
received. Various concentrations of less than 10 mg/ml
were prepared by diluting the stock with either THF or
0.1 M NaCl. For samples in 0.1 M NaCl, AMP (2-
amino-2-methyl-propanol-1) was used to adjust the pH
to ~9. Prior to conducting the light scattering mea-
surements, the solutions were ltered through a 0.2 lm
lter in order to remove dust that may be present in the
test solutions. All the solutions were allowed to equili-
brate at room temperature for 24 h prior to testing.
2.2. Equipment
The Brookhaven BI-200SM goniometer system
equipped with a 522-channel BI9000AT digital multiple
s correlator was used. The light source is a power ad-
justable vertically polarized argon ion laser with the
wavelength of 488 nm. The measured temperature was
controlled at 25 0:1C using a Science/Electronic wa-
ter bath. The REPES inverse Laplace transform routine
[23] supplied with the GENDIST software package was
used to analyze the time correlation functions. The
probability of reject was set to 0.5.
3. Results and discussion
At a pH value less than 6, water is a poor solvent for
the HASE107 and the polymer exists in the form of a
latex dispersion. When the pH value was adjusted to
greater than 7, the MAA neutralizes and the polymer
begins to dissolve. Under this condition, water becomes
a selective solvent for HASE107. Due to the negative
charges present along the polymer backbone, the pres-
ence of a signicant electrostatic repulsive interaction
poses some diculties, when the system was investigated
using the light scattering technique [23]. Hence, a su-
cient amount of salt (0.1 M NaCl in this case) was added Fig. 1. The chemical structure of HASE107.
2672 S. Dai et al. / European Polymer Journal 36 (2000) 26712677
to the aqueous solution to shield the electrostatic inter-
action [23] in order to investigate the presence of any
hydrophobic interaction.
3.1. Static light scattering
SLS provides information on the time-averaged
properties of the system. The relationship between the
scattering intensity and the molecular properties is de-
scribed in Eq. (1):
KC
R
h
= 1
"

16p
2
n
2
R
2
g
sin
2
h
2

3k
2
#
1
M
w

2A
2
C

; (1)
where the constant quantity, K = 4p
2
n
2 on
oC

2
=N
A
k
4
;
Rayleigh ratio, R
h
= I
s
r
2
=I
i
sin
2
h; C is the polymer con-
centration; n is the refractive index for the solvent; h is
the measurement angle; k is the wavelength; N
A
is the
Avogadro constant; and (on=oC) is the refractive index
increment. The refractive index (n) and the refractive
index increment (on=oC) was determined using a dif-
ferential refractometer under normal light, where n =
1:4068 for 0.5 mg/ml HASE107 in THF at 298 K
and dn=dc = 0:2957 ml/g. In 0.1 M NaCl, n = 1:3342 for
0.5 mg/ml HASE107 and dn=dc = 0:2876 ml/g. As,
corrections were not made for the wavelength, the
magnitude of the M
w
and R
g
are only the apparent val-
ues.
From the plot of KC=R
h
versus sin
2
(h=2) kC and
by extrapolating to zero angle and concentration, R
g
, A
2
can be obtained from the slopes and the M
w
is given by
the inverse of the intercept. Details of the SLS principle
can be found in the monograph by Flory [22] and Chu
[27].
The result of SLS for dilute HASE107 in 0.1 M NaCl
aqueous solutions at pH 9, 298 K is shown in Fig. 2.
From the Zimm plot, the calculated molecular weight,
M
w
is ~6.05 10
5
g/mol, while the radius of gyration,
R
g
~ 127 nm.
As mentioned above, HASE107 is a copolymer of
equal molar of MAA and EA. The solvent, THF is a
good non-polar solvent for both monomeric units and it
possesses a low dielectric constant [25]. The properties of
single polymer chains can be obtained by studying the
polymer in THF. Fig. 3 shows the Zimm plot for dilute
HASE107 in THF at 298 K. The results show that
M
w
= 6:23 10
4
g/mol; and R
g
= 41 nm.
By comparing the results obtained for the dilute
HASE107 in 0.1 M NaCl with those in THF, it is ap-
parent that both the molar mass and the radius of gy-
ration of HASE107 in 0.1 M NaCl solution is
signicantly higher. As the M
w
and R
g
obtained for the
HASE107 in the THF solutions represents those of a
single polymer chain, the results obtained for HASE107
in a 0.1 M NaCl solution suggests that aggregates con-
sisting of several polymer chains are present. Such ag-
gregates must have been formed by the association
between hydrophobic backbones, such as the blocky EA
segments, from the same or dierent polymer chains,
which gives rise to the increase in the molecular weight
and the radius of gyration.
3.2. Dynamic light scattering
Conversely, DLS measurements record the temporal
uctuations of the scattered light. The normalized in-
tensity auto-correlation function g
2
(t) can be converted
into normalized eld autocorrelation function g
1
(t) us-
ing the Siegert relations:
g
2
(t) = 1 b[g
1
(t)[
2
; (2)
where b is the coherence factor and g
1
(t) is described by
Fig. 2. SLS (Zimm plot) of dilute HASE107 in 0.1 M NaCl
aqueous solution at pH 9, 298 K. (Measurement angles range
from 30C to 120C; concentrations range from 0.49 to 1.54
mg/ml.)
Fig. 3. SLS (Zimm plot) of dilute HASE107 in THF at 298 K.
(Measurement angles range from 30C to 135C; concentra-
tions range from 0.455 to 2.20 mg/ml.)
S. Dai et al. / European Polymer Journal 36 (2000) 26712677 2673
g
1
(t) =
Z
w(C) exp(Ct) dC; (3)
w(C) is a continuous distribution function of decay rate
C, and the decay rate is the inverse of the decay time s.
By combining Eqs. (2) and (3), the decay time distri-
bution function can be obtained based on the measure-
ment of the temporary intensity uctuations.
In order to obtain the behavior of HASE107 single
chain, DLS measurement was carried out for HASE107
in THF at 298 K. The detection angles were varied from
45C to 90C. Under this condition, qR
g
is less than 1;
hence, the information obtained from DLS for dilute
polymer solutions corresponds to the translational mo-
tion of the polymer coil [23]. Fig. 4(a) shows the auto-
correlation functions of the intensity uctuations of
0.455 mg/ml HASE107 in THF at 298 K measured over
dierent detection angles. The autocorrelation function
shifts to the left, with the increase in the measurement
angles. Using the GENDIST software with the REPES
ILT routine, the decay time distribution function at each
detection angle was computed and plotted as shown in
Fig. 4(b). A single peak is observed in the distribution
function, where the decay time shifts to the left with
increasing angles. The properties of the auto-correlation
and distribution function as a function of measurement
angles are typical of the translational diusion mode.
For the translational diusion, the decay rates are
related to the translational diusion coecients D by
C = Dq
2
; (4)
where q is the scattering wave vector with expression,
q = 4pnsin(h=2)=k, where n is the refractive index of the
solvent, h is the measured angle and k is the wavelength
in vacuo.
The relationship of decay rate C and q
2
for 0.455 mg/
ml HASE107 in THF is shown in Fig. 5, and the decay
rate is proportional to the square of scattering vector.
From the results obtained from DLS, only the transla-
tional diusion of the single polymer chain was detected
for the dilute HASE107 in THF at 298 K. The above
results are similar to the results of previous studies on
dilute polymer in a good solvent [23,28].
Fig. 6 reveals the relationship of diusion coecients
and concentrations for dilute HASE107 in THF. The
diusion coecients do not change with increasing
concentrations, suggesting that the solution is in the
dilute regime, where the polymer chains are not inter-
acting with each other. From this gure, the diusion
coecient at innite dilute solution, D
0
, has a magnitude
of 0:16 10
10
m
2
/s.
From the StokesEinstein equation, the hydrody-
namic radius of HASE107 in THF solutions can be
determined:
D
0
=
kT
6pgR
h
; (5)
Fig. 4. (a) The eld autocorrelation function and (b) the decay
time distribution function of 0.45 mg/ml HASE107 in THF, at
298 K, and dierent measurement angles.
Fig. 5. The relationship of C and q
2
for 0.455 mg/ml HASE107
in THF at 298 K.
2674 S. Dai et al. / European Polymer Journal 36 (2000) 26712677
where k is the Boltzman constant, T is the absolute
temperature in Kelvin, g is the solvent viscosity and R
h
the polymer hydrodynamic radius, D
0
is the diusion
coecient at zero concentrations [23]. The hydrody-
namic radius, R
h
, was computed and found to be 29 nm.
Hence, the ratio of R
g
=R
h
is 1.45. This value indicates
that THF is a good solvent for HASE107 and the
polymer chain represents a Gaussian chain [23,29].
Next, DLS was carried out on dilute HASE107 in a
0.1 M NaCl solution. The decay time distribution
functions of 0.98 mg/ml HASE107 in 0.1 M NaCl at pH
9, 298 K, determined from REPES are shown in Fig. 7.
The distribution plots as shown, suggests that two main
decay modes are present, i.e. the fast mode and the slow
mode. The result resembles that of the dilute associative
polymer systems [14,2932]. With increasing measure-
ment angles, the two peaks shift to the shorter decay
time and they eventually merge. The merging of the
peaks at large angles is typical of DLS, because the de-
cay time is proportional to sin
1
(h=2).
As the decay rates and the square of scattering vec-
tors possess a linear relationship for these two decay
modes, they are related to the translational diusion of
two dierent components. According to the interpreta-
tion on the two-mode distribution for the dilute asso-
ciative polymer solutions [14,2932], both diusion
modes could be interpreted as follows. The fast mode
corresponds to the translational diusion of single
polymer chains or unimers and the slow mode is caused
by the diusion of the aggregates formed by several
polymer chains, through the intermolecular or intra-
molecular association between the EA blocks.
Fig. 8 shows the relationship between the diusion
coecient and the polymer concentration. It is clear that
the eect of the polymer concentration is more signi-
cant for the polymer in 0.1 M NaCl than in THF. By
extrapolating to zero concentration, the diusion coef-
cients at innite dilute solutions could be determined.
The diusion coecients for the fast and slow modes of
HASE107 in 0.1 M NaCl are 0:179 10
10
and
0:034 10
10
m
2
/s, respectively, (D
u
for HASE107 in
THF is 0:16 10
10
m
2
/s). The relationship for diusion
coecients and the polymer concentrations for unimers
and aggregates can be described by the following rela-
tionship:
D
u
= 0:179 10
10
0:8 10
12
C; (6)
D
a
= 0:034 10
10
0:3 10
12
C: (7)
The hydrodynamic radii of the single polymer chain and
the aggregates in 0.1 M NaCl aqueous solution at pH 9,
298 K are 14 and 73 nm, respectively. As the length of a
single polymer chain in 0.1 M NaCl is smaller than in
THF, the dierence is probably due to the fact that THF
Fig. 6. The relationship of translational diusion coecients
and concentrations for dilute HASE107 in THF at 298 K.
Fig. 7. The decay time distribution function of 0.98 mg/ml
HASE107 in a 0.1 M NaCl aqueous solution at 298 K, pH 9,
and dierent measurement angles.
Fig. 8. The relationship of translational diusion coecients
and concentrations for dilute HASE107 in a 0.1 M NaCl
aqueous solution, 298 K, pH 9.
S. Dai et al. / European Polymer Journal 36 (2000) 26712677 2675
is a better solvent. Hence, the volume of the polymer
chain is higher and less compact. The aggregates are
formed by several polymer chains, which give rise to the
larger value of hydrodynamic radius. In addition, the
ratio of R
g
=R
h
= 1:75, which means that aggregates
formed by several polymer chains are in the forms of
draining Gaussian chains. Some hydrophobic associa-
tion junctions are formed inside these aggregates.
3.3. Association behaviors of HASE107 in 0.1 M NaCl
solutions
Both the SLS and the DLS suggest that associations
are present for HASE107 in aqueous solutions. The
association mechanism of HASE107 in 0.1 M NaCl
aqueous solutions is more complicated than that for the
end-capped water-soluble polymers. For the end-capped
water-soluble system (such as HEUR), the hydrophobic
group is located at both ends of the polymer, with the
hydrophilic segments separating them. For HEUR
polymer with strong hydrophobes, association occurs in
the form of ower micelles according to the closed-
association mechanism [1,7,14,3033].
For the present system, the association mechanism is
much more complicated. First, the hydrophilic groups in
the polymer contain charges induced by the carboxylate
groups. The electrostatic repulsive interaction gives rise
to the sti backbone. Although addition of salt shields
some of the electrostatic interaction, the hydrophilic
segments are not as exible, when compared to poly
(ethylene oxide) (PEO). Secondly, the hydrophobic
groups are randomly distributed along the hydrophilic
backbone, and not situated at both ends. Thirdly, the
hydrophobicity of the EA is not very strong. The asso-
ciation mechanism should be much more complicated
than that of the end-capped polymer. Based on the
above analysis, the combination of sti water-soluble
backbone and the low hydrophobicity of the water-
insoluble groups causes the polymer to associate ac-
cording to the open association mechanism.
From the results of DLS, it is clear that the aggre-
gates and the unimers exist at the same time. Due to the
open association, more and more polymer chains would
associate into the larger aggregates, when the concen-
tration is increased. With the increase in the number of
polymer chains in the aggregate, the electrostatic inter-
action would increase. When the number of polymer
chains increases to an optimum value (i.e., the hydro-
phobic and electrostatic force is in equilibrium), the
unimer would no longer be incorporated into the ag-
gregate. Due to the lower hydrophobic nature of EA
(compared to hydrophobic groups such as the C12 or
C16 alkyl chains), the blockiness of EA must be su-
ciently long for it to be hydrophobic enough to induce
the formation of EA bundles as shown in Fig. 9. This
schematic description illustrates the manner in which the
EA blocks associate to form aggregates consisting of a
few polymer chains, which are in equilibrium with the
unimers. As indicated by DLS results, the aggregates
exhibit a fairly broad distribution in sizes as are typical
of structure formed by the open association mechanism.
4. Conclusion
The copolymer of MAA and EA in 0.1 M NaCl at
pH 9 was studied by SLS and DLS. The results show
that light scattering is a sensitive tool for studying the
static and dynamic properties of associative polymer
solutions. From DLS, two-peak distributions were ob-
served. Both peaks are due to the translational diu-
sions, where the fast and the slow modes are attributed
to the diusion of the un-associated polymer chains or
the unimers and the diusion of the polymer aggregates,
respectively. The static and the dynamic studies reveal
that association between the EA blocks occurs in the
aqueous solution. This is the rst reported evidence that
the MAA/EA copolymer produced by emulsion poly-
merization is blocky and the EA blocks are hydrophobic
enough to induce association with other EA blocks from
other polymer chains.
Acknowledgements
One of the authors (S.D.) acknowledges the nancial
support provided by the university. We appreciate the
support and enthusiasm of Dr. Dave Bassett in this re-
search collaboration between the NTU and Union
Carbide. We also acknowledge the nancial support
provided by the National Science and Technology
Board of Singapore and the Ministry of Education.
Fig. 9. The microstructure of dilute HASE107 in 0.1 M NaCl
aqueous solutions at pH 9.
2676 S. Dai et al. / European Polymer Journal 36 (2000) 26712677
In addition, we thank Professors Wyn Brown and Mitch
Winnik for their helpful suggestions.
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