Acta Polyrnerica 41 (1990) Nr.

6
338 RALCHEVSKI, NIKOLOVA and ANGELOVA :
Rheological properties of acrylic latices

[lo]
- - CHAUDHARI,S. N. K., GOUNDEN,K. C., SRINIVASAN.G.. [14] KOTZ, J., LINOW, K.-J., PHILIPP, B., VOGL,O., und Hu,
und EKKUNDI,V. S. : J. Polymer Sci., Polymer Chem.’ Ed: L. P.: Polymer 27 (1986) 1574-1580.
26 (1987) 337-342. [15] PHILIPP, B., DAUTZENBERG, H., LINOW, K.-J., KOTZ, J . ,
R11 KOTZ.J.. LINOW.K.-J.. PHILIPP.B.. und DATJTZENBERG.
. >

Acta Polyrnerica 37 (1986) 108-114.

H.: .-
[12] PHILIPP, B., KOTZ,J., DAUTZENBERO, H., DAWYDOFF, W.,
und LINOW,K.-J.: Applied Polymer Analysis, im Druck.
[13] RINAUDO, M.: Polyelectrolytes. Dordrecht: D. Reidel
Publishing Company 1974, S. 157-193.
und DAWYDOFF,
[I61 DAUTZENBERG,
W.: Progr. Polymer Sci. 14 (1989) 9 1 -172.
H., ROTHER,G., LINOW,K.-J., und PHILIPP,
B.: Acta Polymerica 39 (1988) 157-164.
[17] MAEDA,H., und IKEDA,S. : Biopolymers 14 (1975) 1623.
Eingegangen am 29. Mai 1989

Rheological properties of acrylic latices

A. NIKOLOVA
Ts. RALCHEVSKI, and M. ANGELOVA
Higher Institute of Chemical Technology, Department “OXT”, 1156 Sofia/Rulgaria

The rheological properties of acrylic latices obtained by emulsion polymerization of ethyl acrylate, methyl methacry-
late, and methacrylic acid have been studied. These water dispersions are non-Newtonian pseudoplastic liquids, whose
apparent viscosity a t constant shear rate depends on the pH of the medium as well as on the amounts of the emulgator
and carboxylated agent used. The applicability of the DE-BROYN equation has been examined and the coefficient of
swelling has been determined.
Hheologische Eigenschaften yon Acrylat-Dispersionen
Die rheologischen Eigenschaften von durch Emulsionspolymerisation von Ethylacrylat, Methylmethacrylat und Acryl-
saure erhaltenen Acrylat-Dispersionen wurden untersucht. Diese waI3rigen Dispersionen sind Nicht-Newtonsche
pseudoplastische Flussigkeiten, deren scheinbare Viskositat bei konstanter Schergeschwindigkeit sowohl vom pH-Wert
des Mediums als auch von der Emulgatormenge und von der Menge des eingesetzten carboxylierten Agens abhangt. Die
Anwendbarkeit der ~ E - B ~ O ~ ~ - G l e i c h
wurde
u n g gepruft, und die Quellungskoeffizienten wurden bestimmt.
Peonosuuec~ueceoiicmsa axpunamnmx namemos
BCCJIeAOBaHO peOJI0rHqeCKOe IIOBeAeHMe aKpHJlaTHbIX JIaTeKCOB, IIOJIyqaeMbIX 3MyJIbCHOHHOfi IIOJIHMepH3aqHefi
3THnaKpHnaTa (EA), MeTHaMeTaKPHJIaTa (MMA) H MeTaKpHJIOdOa KHCJIOTbI. YCTaHOBJIeHO,YTO 3TM BOAHbIe AHcnep-
CHI4 FIBJIRIOTCFI HeHIOTOHOBCKHMH IICeBAOIIJIaCTHqeCKHMH XCHAKOCTFIMH, KaXCyWaFI BFI3KOCTb KOTOPbIX, npH IIOCTOHH-
HOfi CKOPOCTH CgBMra, 3aBHCHT KaK OT p H CpeAbI, T a K H OT KOJIMYeCTBa 3MyJIbraTOpa H ~ a p 6 0 ~ c ~ n ~ p y mWeHTa.
qero
nOATBepXneHa IIpHMeHHMOCTb YPaBHeHHFI AE-BPOfiHA H OIIpeAeJIeHbI 3HaYeHHtI K03@@HqHeHTaHa6yXaHHFI.

1. Introduction As seen from t h e table t h e particle size changes within

The acrylic latices possess exceptional good film-forming
properties and that explains the continuous increase of their
production in recent years [I] I n.comparison with poly(viny1
acetate) and poly(butadiene-co-styrene) latices the acrylic
latices have better coating characteristics [l , With respect
21.
to the rheological properties there are data in the reference lite-
rature only for the first ones of the above mentioned products
[3-61; the information about the acrylic latices is very scanty.
The purpose of the present work was to study the rheological
properties of acrylic latices obtained by emulsion polymeriza-
tion of ethyl acrylate (EA), methyl methacrylate (MMA) and
methacrylic acid (MA) [7, 81. The prevailing component in
the initial monomer mixture was the EA, and in this way
any change in the ratio EA:MMA may influence the flexi-
bility of the polymer chains [l21 , as well as the rheological
and physicomechanical properties of the obtained products. As
most suitable agent for involvement of free carboxylic groups
in the polymer chains we used MA [I2, , 71.
t h e range 40 t o 50 . m. Given these sizes, a n i m p o r t a n t
p a r t should b e played b y t h e colloidal-chemical interaction,
which results i n non-Newtonian flow of t h e latices a n d such
processes a s aggregation, structurizing, etc. T h e rheolo-
gical characteristics of t h e products were determined a t
20°C by “Brookfield LV” a n d “Rheotest RV2” r o t a r y
viscometers.
3. Results and discussion
T h e experimental d a t a for all latices studied by using
“Rheotest RV2” (cylinders S1 a n d S2) lie on a straight
line in double logarithmic coordinates (Figure 1 rmd Table
2). This shows there is no “slip effect a t t h e wall”, which
Table 1. Main characteristics of the latices

Initial ratio pH of
S . log2)
2. Experimental No.
of comonomers T,1) d, nonalka-
EA : MMA : MA mass lized
All latices were obtained by semicontinuous emulsion mass yo “C % m latex
polymerization i n accordance with t h e method described
i n detail i n our previous works [7, 81. An anionogen emul- 49.40
49.70
gator E-30 ( B u n a Werke, GDR) with a m e a n composition I 49.40
C,,H,,SO,Na was used. Ammonium persulphate i n a m o u n t
of 0.1 mass yo (in relation t o t h e water phase) was used as Determined by means of dilatometer type “UIP-70”, USSR
l)
initiator of t h e radical polymerization. Some m a i n charac- Determined by means. of electron microscope type “Philips
2,
teristics of t h e examined products a r e shown o n Table 1. EM 3 016”
 Acta Polyrnerica 41 (1990) Nr. 6
RALCHEVSKI,
NIKOLOVAand ANGELOVA: 339
Rheological properties of acrylic latices

similarly to the temperature invariant of viscosity described

102
in [lo]. The systematic deviation of the sour latex data can
Pa
be seen. Strong influence of the pH of the medium on theappa-
50 rent viscosity of the latices is expected. I t is illustrated in
Figure 4 with the three curves, corresponding to products
30 No. 1, 2 and 3 from Table 1, alkalized with 25% of water
20 solution of ammonia. It is obvious that the dependence has
an extreme character and the minimum of the curves
10' kJ
lies a t p H = 5 t o 7. This course of the curves is in accor-
dance with the established ideas about changes in the latex
5
globules with the increase of pH of the medium [Ill. The
3
2

5 10 20 50 lo2 200 500s-1103 14t

;Y

Fig. 1 . Double logarithmic anamorphoses of the flow curves of

acrylic latices with different values of dry substance S (see
Table 2 ) . 1 - 26.50 mass yo;2 - 29.20 mass yo;3 - 31.61 mass
%; 4 - 49.60 mass 76; 5 - 46.50 mass Yo; 6 - 49.60 mass %

permits a mathematical description of the flow curves by

following the binary parametric model of OSTWALD-DE-
WAELE[ l o l l ) :
t = kj* (1)
If we define the so-called apparent viscosity pa [lo] by
the equation:
p = t / y = kjn-1 (2)
it is typical that for pseudoplastic liquids ( n < 1)i t decreases
from po to pm as the shear rate grows (Figure 2 ) . The
parameters po and pm are the maximum and the minimum
Newtonian viscosity of the latex, respectively, and are
defined by the following expressions:

po =: lim pa ,urn= lirn pa (3)

Y-0 y->m

The determination of po and pm values of the acrylic latices

is certainly of technological and theoretical interest.
The rheological properties of the studied acrylic latices
are shown on Table 2 . The po values are determined on I I I I I I I 1 I

base of the empirical dependence [lo]: 0 2 4 6 8 I0 12 14 s-f 16

j.10*
Fig. 2. The interdependence between the apparent viscosity of
pa = 2 = ,uo exp (-at) (4) acrylic latices and shear rate a t different dry substance S. 1 -
P 49.60mass yo; 2 - 4 8 . 5 0 m a s s yo; 3 - 47.50 mass Yo; 4 -
by the method of least squares. 46.50 mass yo
In Figure 3 the rheological data of the acrylic latices are
shown as the interdependence between Ig (,u,Jpo)and lg ( j p o ) ,

1) For the meaning of the symbols see page 341.

Table 2. Rheological properties of the latices

Designation
SIk p o . 102 APO

t
of the latex pH mass 0 0
(cf. Figure 1 ) Pa. s %
1 o 10.85 26.50 0.01 0.9 4.85 0.65 6.90 -0.8
-o.6
2 0 10.85 29.20 0.017 0.89 3.08 0.94 3.90
3 0 10.85 31.61 0.022 0.88 4.50 1.24 2.98 Fig. 3. Summarized dependence Ig (p,/po) = f(lg 9 . p o ) .The re-
4 0 10.85 49.60 0.324 0.72 4.80 14.90 2.50 sults shown refer to the data in Table 2. 1 - 26.50 mass yo;
5 a 10.50 46.50 1.43 0.49 5.50 30.54 2.30 2 - 29.20mass %; 3 - 31.61 mass %; 4 - 49.60mass %;
6 0 2.50 49.60 0.997 0.52 3.40 45.00 14.40 5 - 46.50 mass yo;6 - 49.60 mass yo
Acta Polymerica 41 (1990) Nr. 6
340 RALCHEVSKI, NIKOLOVAand ANGELOVA:
Rheological properties of acrylic latices

Table 3. The apparent viscosity o f the latex obtained i n the presence

f2 -
of different amounts of methacrylic acid

I I I I
Po3
No. of [MA] p H of the p H of the Apparent
the mass SOUr latex alkalized viscosityl)
10 -
sample latex mPa s

1 1 2.46 8.50 f 0.15 375

2 2 2.23 8.50 f 0.15 675
3 3 2.12 8.50 f 0.15 1040
8-
4 4 2.18 8.50 f 0.15 4510
s 5 5 2.20 8.20 f 0.152) 8200

6-

4-
ticles as a result of which the apparent viscosity in the pH
range of 5 to 7 is smallest. The further increasing of alkali-
nity, however, leads t o a neutralization process in which
2-
the carboxylic groups from the deeper layers of the globu-
I I I I les take part. At the same time the globules swell because of
2 4 6 8 10
the conversion of most of the -COOH groups into the more
PH
voluminous -COONH, groups and also because of their
Fig. 4. Change of the apparent viscosity (determined by Brook- hydratation. This process of hydratation is also accounted
field LV viscometer, spindle no. 2, 60 rpm) at alkalization of for by the fact t h a t the dissociation constants of the salt
acrylic latices. 1 - EA : M M A : M A = 60 : 37 : 3; 2 - EA:
MMA:MA=56:41:3;3 - EA:MMA:MA=53:44:3 groups are greater than the respective constants of the
- O H groups. The considerably increased effective vo-
lume of the latex globules causes the rapid growth of the
apparent viscosity a t pH > 7. The positioning of the cur-
ves on Figure 4 is in accordance with the concept of WESS-
LAU [I13 about the influence of the glass transition tempera-
ture of the polymer upon its tendency to swell in alkaline
42 - medium. As the amount of the “soft” component in the
copolymer (EA in our case) grows, its glass transition tem-
perature decreases which is confirmed b y the data shown
40 - on Table 1. The increased amount of EA leads t o greater
b
flexibility of the polymer chain. This facilitates all diffusion
phenomena resulting in redistribution of the salt groups
38 - and their quaternization and hydratation on the globule
surface. Thus a t determined value of pH the apparent vis-
cosity of latices obtained from monomer mixture with
higher content of EA is always higher.
36 - Table 3 contains the data about the apparent viscosity
of the products obtained from the mixture of EA:MMA
= 56: 41 with different amounts of MA. The apparent vis-
I I I I I I
cosity of the acrylic latices on the market seldom exceeds
0 2 4 6 8 10
PH
1800 mPa . s irrespective of their application [12]. For prac-
tical purposes the studied products should obviously not
Fig. 5. The influence of pH on surface tension. 1 - EA : M M A : contain MA more than 3 mass% regarding to the monomer
MA=60:37:3; 2 - E A : M M A : M A =56:41:3; 3 - E A :
M M A : M A = 53: 44: 3 mixture, and we have mentioned this fact in previous
works [a, 7, 81.
The experiments made with different amounts of the
conversion of the carboxylic groups into salt groups emulgator by using latex No. 2 (see Table 1)show t h a t the
(-COONH,) is accompanied with their accumulation on apparent viscosity of the latices grows along with the in-
the surface of the globules, owing t o their electrostatic creasing of the concentration of the emulgator in the system.
repulsion in the polymer matrix and also to the nonsolubi- The degree of adsorption saturation, determined by ad-
lity of the carboxylic links in the polymer chains. These sorption titration of the studied samples, does not exceed
changes usually affect the polymer layers close t o the glo- 31% [13]. Thus the data shown in Figure 6 can be explained
bule surface. The data on Figure 5 also testify t o such a solely with the growth of the effective volume of the latex
process of redistribution. particles along with an increase of the amount of the emul-
The decrease of the surface tension of the system is a gator added. Owing to the adsorption nonsaturation of
result of the desorption of emulgator molecules, displaced the products, the “external” thickening here is not of
by the salt groups accumulated on the surface. The de- importance.
sorption of voluminous hydrated molecules of the emulga- The interdependence between the apparent viscosity
tor leads to a decrease of the effective volume of latex par- of samples obtained from latex No. 2 (see Table 1) and the
 Acta Polyrnerica I 1 (1990) Nr. 6
RALCHEVSKI,NIKOLOVAand ANGELOVA: 341
Rheological properties of acrylic latices

f4 r Table 4 . Values of the coefficient of swelling K

1- Viscosity I K
C alkalized alkalized
sour latex latex
kg m-3 P a . s .lo3 Pa. s .lo3
I
0.26 2.91 3.04 1.05 1.09
0.27 3.30 3.31 1.12 1.13
0.30 4.03 4.00 1.17 1.18
0.31 5.01 4.86 1.24 1.28
0.32 5.79 5.75

The following fact confirms the validity of the DE BROYN

equation, especially in the range of large polymer concentra-
I 1 a I I J tion: The calculated value of K is 1.36 (C = 0.49 I ~ g r n - ~ ) .
0.4 0.6 0.8 1.0 mass-% 1.4 This value is in agreement with the value of K = 1.37 which
cE l was predetermined by the light scattering method [13].
Fig. 6. The influence of amount of emulgator on the apparent
viscosity of the alkalized latices
List of symbols
C concentration, kg/m3
k coefficient of consistency, P a * sn
K coefficient of swelling
n power-law index
Po, P m apparent viscosity for i, +- 0 and i, CU, respectively,
Pa. s
PC dynamic viscosity of the medium, P a . s
qj volume part of the polymer in the dispersion
Z shear stress, P a
i shear rate, s-l
TB glass transition temperature, "C
4% particle size, m
S dry substance, mass yo

References

111 MAREK,O., and TOMKA,M. : Acrylic Polymers (in Russian).

I I I I Moskva/Leningrad: Khimiya 1966.
26 28 30 32 moss YO 36 [2] ANGELOVA, M., BALOVA,S., TOMOVA, R., and RALCHEVSKI,
C Ts. : Khimiya i Industria (1987) no. 9, 396.
Fig. 7. The interdependence of apparent viscosity and polymer r31 KUSNEZOV.
L ,
V. L., and LEBEDEV.A. V.: Kauchuk i Rezina
concentration of diluted samples (see Table 4) (1962) no. 1, 16.
.~
141 KUSNEZOV,
V. L., and LEBEDEV,A. V.: Kauchuk i Rezina
(1963) no. 7, 7.
polymer concentration before and after the alkalization is [5] KOSAREVA,V. A., and TSAREV,0. P.: Zh. Prikl. Khim.
(1982) no. 4 , 803.
shown in Figure 7. All viscosity values belong t o the second [6] KUSNEZOV,V. L., LEBEDEV,A. V., and EZRIELEV,A. I.:
Newton range of the flow curves, i.e., in a physical sense Kauchuk i Rezina (1967) no. 5, 6.
they correspond to the previously defined viscosity p,. [7] VOYNOVA, S., RALCHEVSKI, Ts., CHERNEVA, A., and ANGE-
These viscosity values are very close to each other a t one LOVA,M.: Avtor. svid. P R D no. 70776 (21. 06. 1985).
[8] RALCHEVSPI,Ts., VOYNOVA, S., and ANGELOVA, M.: Acta
and the same polymer concentration and different pH values Polymerica 39 (1988) 555.
of the medium. Therefore the absence of a parallel course [9] RHEOTEST2, Gebrauchsanleitung, V E B Prufgeratewerk
of the two curves does not allow in this case the determina- Medingen.
tion of the coefficient of swelling K in the same manner a s l.l O l-VINOORADOV,G. B.. and MALKIN, L. YA.: Rheoloev -" of
Polymers (in'Russian). Moskva: Khirniya 1977.
proposed in [6] concerning butadiene-styrene latices. The [ l l ] WESSLAU,H . : Makromol. Chemie 69 (1963) 220.
values of K for alkalized and sour latices calculated by the [12] BASF-Erzeugnisse. 4 . Aufl., p. 57.
DE BROYNequation [13] NEJMAN, R. E. : Practical Course of Colloid Chemistry (in
Russian). Moskva: Vyssh. Shkola 1972.
P C
p, =
1 - 2.591 + 1.54912 (5)
Received May 18, 1989
where p = K . C, are shown in Table 4. -4ccepted J u h ~15, 1989