ISSN 0965-545X, Polymer Science, Series A, 2018, Vol. 60, No. 2, pp. 127–133. © Pleiades Publishing, Ltd., 2018.

Original Russian Text © N.V. Zakharova, M.A. Simonova, A.R. Khairullin, A.P. Filippov, E.N. Danilovtseva, S.N. Zelinskii, V.V. Annenkov, 2018, published in Vysokomolekulyarnye
Soedineniya, Seriya A, 2018, Vol. 60, No. 2, pp. 102–109.

SOLUTIONS

Effect of pH on the Behavior of a Random Copolymer

of Acrylamide
N. V. Zakharovaa,*, M. A. Simonovaa, A. R. Khairullina, A. P. Filippova,
E. N. Danilovtsevab, S. N. Zelinskiib, and V. V. Annenkovb
aInstituteof Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, 199004 Russia
b
Limnological Institute, Siberian Branch, Russian Academy of Sciences, Irkutsk, 664033 Russia
*e-mail: na_zar@inbox.ru
Received May 2, 2017;
Revised Manuscript Received September 9, 2017

Abstract—A temperature- and pH-sensitive random copolymer of N-[3-(diethylamino)propyl]-N-methy-

lacrylamide] and N,N-diethylacrylamide was obtained. The copolymer contained 20 mol % of amine units
and had a molecular weight of 3.3 × 10 4. Buffer solutions containing 0.0102 g/cm3 of the synthesized copo-
lymer were studied in the pH range of 7–13.5 by light scattering and turbidimetry. At low temperatures, mac-
romolecules and large aggregates coexist in the solutions. The copolymer is temperature- and pH-sensitive in
the studied pH range. The temperature and the width of the phase separation interval increase with increasing
acidity of the medium.

DOI: 10.1134/S0965545X18020153

INTRODUCTION chloride, is commercially available and readily polym-

One of the main goals of chemistry is to establish
the dependence between properties and chemical
structures of substances. In this sense, polymers are a
much more complex system than low-molecular-
weight compounds. For binary polymers with differ-
ent numbers of units, for instance, the polymer prop-
erties will depend on the ratio of the units. When pre-
paring copolymers by the polymerization of mono-
mers, however, it is difficult and often even impossible
to obtain samples with the same degrees of polymer-
ization and polydispersity. Thus, when establishing a
correlation between the molecular-weight characteris-
tics and the properties of a given polymer, the depen-
dence of these properties on its molecular-weight
characteristics should also be considered.
The system can be simplified by preparing copoly-
mers via polymer-analogous reactions, which lead to a
change in the chemical nature of the units without
changing the length of the polymer chain. In this
regard, chemical reactions used in polymer modifica-
tions are subject to a number of requirements. These
reactions must be almost quantitative and proceed
without the formation of polymer by-products at a
sufficiently high rate and a moderate temperature, i.e.,
under the conditions that fully prevent the disruption
of the polymer main chain. An interesting reaction
that satisfies all of these requirements is the reaction
between acyl chlorides and amines. Despite the fact
that the simplest monomeric acyl chloride, acryloyl
erizes under the action of radical initiators [1], polyac-
ryloyl chloride has not yet been widely applied as a
starting polymer for polymer-analogous reactions.
Temperature- and pH-sensitive polymers are now
particularly interesting to scientists because of wide
possibilities of their application in various fields of
industry. These possibilities are associated with the
ability of these “smart” polymers to reversibly change
the hydrophilic–hydrophobic balance under changing
external conditions, which leads to conformational
rearrangements at the molecular level or to the forma-
tion of supramolecular structures [2–5]. A convenient
way to control the properties of polymers is to com-
bine temperature- and pH-sensitive monomers in one
macromolecule. This makes it possible to control the
processes of the formation and destruction of supra-
molecular structures and the intramolecular self-
organization and to regulate the association of such
polymers with low-molecular-weight compounds [6–
10].
The synthesis of temperature- and pH-sensitive
poly-N-[3-(diethylamino)propyl]-N-methylacrylamide
(PDEAP–MAA) is described in [11]. The behavior of
aqueous solutions (0.1 mol/L NaCl) of PDEAP–
MAA has been studied by microcalorimetry, potentio-
metric titration, turbidimetry, and light scattering. It
has been established that the phase separation tem-
perature depends on the polymer concentration and
pH. At c = 0.0005 g/cm3, for example, it decreases

127
128 ZAKHAROVA et al.
from 95°С at pH 9 to 40°С at pH 11. At low tempera-
tures (T < 40°С), a bimodal distribution of particles by
dimensions has been detected by dynamic light scat-
tering in all the studied solutions. The hydrodynamic
radii of fast and slow modes differ by an order of mag-
nitude: 20–60 and 200–570 nm, respectively. Near
the cloud point, the sizes of large aggregates reach 2
μm.
Unfortunately, published data are scarce on struc-
turally similar random copolymers with double sensi-
tivity. However, the effect of copolymer components
on the characteristics of solutions is well reflected in a
series of studies [12–15] on aqueous solutions of linear
random copolymers of poly(isopropylacrylamide)
with maleic and methacrylic acids. It has been shown
that there are three types of particles in copolymer
solutions at room temperature: unimolecular micelles,
micelle-like structures, and large aggregates. The frac-
tion of micelle-like structures and aggregates increases
with decreasing concentration. The phase separation
temperature increases with increasing pH because the
number of charged groups increases with pH and,
consequently, the solubility improves. Differences in
the chemical structure of maleic and methacrylic acids
lead to a marked difference in the behavior of their
copolymers with N-isopropylacrylamide. The authors
believe that the reasons for this are the presence of a
hydrophobic methyl group in the comonomer of
methacrylic acid and different patterns of distribution
of hydroxyl groups in the macromolecules of the poly-
mers under comparison.
In [16], the concentration dependences of the
phase transition temperature have been established in
aqueous solutions of N,N-dimethylaminoethyl meth-
acrylate copolymers with N,N-butylacrylamide,
dodecyl acrylate, dodecyl methacrylate, N-(3-dime-
thylaminopropyl methacrylamide), and acrylic acid.
It has been shown that an addition of hydrophobic
comonomers (methacrylic esters, N-alkylacryl-
amides, and styrenes) leads to a decrease in the phase
transition temperature of copolymers. S.H. Yuk et al.
[17] have studied pH- and temperature-sensitive
copolymers of N,N-dimethylaminoethyl methacrylate
with ethyl acrylamide and their blocks. It has been
shown by optical transmission that the phase transi-
tion temperatures for all the copolymers are shifted by
four degrees in comparison with the homopolymer.
Study [18] reports the results of preliminary studies
on aqueous solutions of a random copolymer of N-[3-
(diethylamino)propyl]-N-methylacrylamide]
(DEAP–MAA) and N,N-diethylacrylamide (DEAA).
Buffer solutions (0.1 mol/L NaOH, pH 12.4) in which
the polymer concentration ranged from 0.0003 to
0.0102 g/cm3 was studied by light scattering and turbi-
dimetry. It was shown that a phase transition is
observed in the solutions of the random copolymer
under heating and that the temperatures of phase sep-
POLYMER SCIENCE, SERIES A
aration onset (T1) and end (T2) decrease with increas-
ing concentration of the copolymer.
The aim of the present work was to study the effect
that the pH of the medium has on the properties of
aqueous solutions with a fixed concentration of a ran-
dom copolymer obtained by modifying polyacryloyl
chloride under mild conditions. Another aim was to
demonstrate the synthesis and to study the properties
of aqueous solutions of a random copolymer contain-
ing basic amino groups and hydrophobic fragments.
EXPERIMENTAL
Synthesis of the Random Copolymer, Structural and
Molecular Weight Characteristics of the Polymer
The temperature- and pH-sensitive random copo-
lymer was synthesized by reacting polyacryloyl chlo-
ride with N,N-diethyl-N′-methyl-1,3-propanedi-
amine and diethylamine:
H Et NEt3
+ N N + NHEt2
n Et
Me
O Cl
y
x
Et
Et O N
O N N Et
Et
Me
N,N-diethyl-N′-methyl-1,3-propanediamine was
obtained according to the procedure [19]. For this
purpose, substances from Sigma Aldrich were pre-
pared as follows: 2,2-azo-bis-isobutyronitrile was
crystallized from ethanol before use, dioxane was dis-
tilled over sodium, and DMF was dried by shaking
with CuSO4 for 30 min and distilled at 5 mm Hg.
Polyacryloyl chloride was prepared as follows. A
solution of freshly distilled acryloyl chloride (20 g,
220.9 mmol) and 2,2-azo-bis-isobutyronitrile
(0.4011 g, 2.44 mmol) recrystallized from ethanol was
prepared under argon in dry dioxane (84.07 g). The
polymerization was carried out in a hermetically
sealed glass vessel at 60°C for three days. After cooling,
the reaction mixture was stored frozen at –20°C.
The random copolymer was prepared as follows. A
solution of polyacryloyl chloride (8.506 g) was poured
into an ice-water-cooled solution of N,N-diethyl-N′-
methyl-1,3-propanediamine (0.7799 g, 5.41 mmol),
diethylamine (1.5832 g, 21.65 mmol), triethylamine
(2.2334 g, 22.07 mmol), and 4.33 mL of dimethylfor-
mamide. The mixture was thoroughly stirred for 2 min
with vigorous shaking and left in a sealed vessel at
room temperature for 2.5 h. The resulting solution was
poured into 25 mL of water. The polymer was purified
from low-molecular-weight impurities by dialysis
through a cellophane membrane against water. The
resulting solution was concentrated under reduced
Vol. 60 No. 2 2018