Journal of Industrial and Engineering Chemistry 16 (2010) 431–436

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Effects of agitation in emulsion polymerization of vinyl acetate, ethylene,

and N-methylol acrylamide
Yong-Hae Choi, Won-Ki Lee *
Division of Chemical Engineering, Pukyong National University, Busan 608-739, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: The emulsion polymerization of vinyl acetate monomer (VAM), ethylene and N-methylol acrylamide
Received 13 June 2009 (NMA) was carried out in a high pressure stirred reactor using an Rushton flat blade impeller at a
Accepted 18 December 2009 rotational speed of 300 rpm under a semi-batch polymerization process, which was subsequently grown
by the continuous addition of monomers (VAM, ethylene, and NMA). The particle diameters of the
Keywords: samples withdrawn during polymerization were determined by using capillary hydrodynamic
Emulsion polymerization fractionation (CHDF). Also, the number of particles was calculated from the data obtained by CHDF.
Particle distribution
Coagulum formation was studied. It was found that coagulum formation increased with increasing
Vinyl acetate-ethylene copolymer
Waterborne
conversion and auto-accelerated from ca. 20% conversion. The definition of coagulum in this research
Latex was presented. The coagulum formation pattern on the impeller was shown. Also, the flow pattern in the
reactor under the same geometrical configuration and operating conditions was simulated.
ß 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V.
All rights reserved.

1. Introduction
In emulsion polymerization, mixing, which results in the bulk
movement of the fluid, is very important for maintaining the
homogeneity of the reaction mass. Good mixing is essential to
prevent high local concentrations of added surfactants and water-
soluble monomers in the case of a semi-batch reaction where
certain components of the reaction are added continuously. These
effects are especially important in large volume reactors. Also,
mixing is essential to promote the mass transfer of monomer when
the monomer has relatively high water solubility. The shear
component of agitation is another important factor that strongly
influences coagulum formation in high-solids emulsion [1]. Shear
can accelerate coagulation through the development of fluid
velocity gradients, which can increase the force of collisions
between particles present in the reactor as well as the frequency of
the collisions.
Emulsion copolymers of vinyl acetate-ethylene emulsion are
widely used in adhesive, coating and nonwoven application
industry however this emulsion has a little lower water resistance,
so that various applications want grafting polymer like as N-
methylol acrylamide (NMA), it is widely used not only coating
application but also adhesive application [2]. NMA acts as a cross-
linking agent in the synthesis of reactive emulsion. For example,
* Corresponding author. Tel.: +82 051 629 6451.
E-mail address: wonki@pknu.ac.kr (W.-K. Lee).
Bonardi et al. [3–7] found that the NMA units were preferentially
located on the particle surface as strongly adsorbed or grafted
polymer. This study was applied of the approach method of the
agitation effects in emulsion copolymerization of n-butyl methac-
rylate and N-methylol acrylamide [8] at the vinyl acetate, ethylene
and N-methylol acrylamide polymerization. Agitation may affect
the degree of incorporation of the water-soluble NMA monomer in
the polymer particles. Therefore, emulsion properties such as
cross-link density and morphology can be affected by the agitation
conditions [9]. The purpose of this study are to research for trend
particles and grits by agitation and to be used the different impeller
and rpm to check for the trend of particles and grits.
2. Experimental
2.1. Materials
15 ppm mono-methyl ether of hydroquinone (MEHQ) inhibitor
was removed from vinyl acetate monomer (VAM, Samsung BP) by
passing the monomer through an inhibitor-removal column
(Sigma–Aldrich). Ethylene monomer (SK-Chemical) was used as
received. N-methylol acrylamide (NMA, Cytec) was received as a
48 wt% solution in water and was inhibited with 5 ppm of MEHQ.
Sodium lauryl sulfate (SLS, Dongnam chemical), potassium
persulfate (KPS, Decksung chemical), and sodium bicarbonate
(Decksung chemical) were used as surfactant, initiator, and buffer,
respectively. All of the chemicals except VAM were used as
received.

1226-086X/$ – see front matter ß 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2010.01.042
432 Y.-H. Choi, W.-K. Lee / Journal of Industrial and Engineering Chemistry 16 (2010) 431–436

Fig. 1. Schematic diagram of the experimental setup used to study the effect of agitation during emulsion copolymerization.

2.2. Emulsion synthesis and reaction kinetics
The emulsion was being synthesized in an 18 l high pressure
and temperature-controlled stirred reactor with two baffles. A
stirrer, which maintains a constant speed irrespective of changes in
the viscosity of the reaction fluid, was used to provide agitation.
The reactor lid had a sampling port for the injection of the initiator
and withdrawal of samples from a region next to the impeller
blade. The schematic diagram of the experimental setup is shown
in Fig. 1.
The recipe was used for the emulsion copolymerization of VAM,
ethylene and NMA is given in Table 1. The final solids content is ca.
55.61%. A mixture of VAM, SLS, NaHCO3, and deionized (DI) water
was heated to the reaction temperature (80 8C) with nitrogen
bubbling. The seeding stage reaction was continued for 60 min
after injection of the initiator solution. The mixture of KPS,
Table 1
VAM/ethylene/NMA emulsion polymerization recipe.
Stage Ingredient
NaHCO3, and DI water was added together into the reactor at the
beginning of the feeding stage reaction. Ethylene was fed using a
compressor from a bombe, precision syringe pump of NMA at a rate
of 3 ml/min. The aqueous feed, which was composed % of DI water/
NMA solution/SLS (18.31/5.03/0.55), it was using a syringe pump
at a rate of 0.29 ml/min. The reactions were carried out using an
10 cm Rushton agitator at a rotational speed of 300 rpm. About
20 ml of emulsion sample were withdrawn from the reactor at
30 min intervals during the feeding stage. Instantaneous conver-
sion was calculated to be greater than 94% from about 30 min into
the reaction onward. Hence, the semi-continuous batch polymeri-
zation was carried out under monomer-starved conditions.
3. Results and discussion
Fig. 2 shows the overall conversion as a function of time for the
feed stage reactions using the recipe shown in Table 1. The
beginning of the feed stage monomer conversion corresponded to
the conversion of the seed stage at 60 min. The conversions were
Mass (%)

Seeding stage 60 min, 55 8C Deionized water 24.79

VAM 35.50
SLS 0.89
KPS 0.07
NaHCO3 0.01

Feeding stage 150 min, 80 8C Deionized water 18.31

Mixture before feeding

VAM 6.27
Ethylene 8.12
SLS 0.34
NMA 5.03
SLS 0.55
KPS 0.10
Fig. 2. Overall conversion versus time behavior during the feed stage for the
NaHCO3 0.01
emulsion copolymerization of VAM/ethylene/NMA using the recipe in Table 1.
 Y.-H. Choi, W.-K. Lee / Journal of Industrial and Engineering Chemistry 16 (2010) 431–436 433

Table 2
Comparison of the particle size and number of particles of emulsion Run Number 2
prepared using the recipe given in Table 1.

Time Overall CHDF

(min) conv. (%)
Particle size (nm) Np (1015 dm3 H2O)

Dw Dn PDI

Seed 60 6.2 203.8 201.5 1.011 10.8

Feed 30 20.9 315.2 313.7 1.005 9.2
Feed 60 39.18 371.2 370.0 1.003 10.4
Feed 90 60.47 420.5 419.4 1.003 10.8
Feed 120 86.17 463.6 462.0 1.003 10.4
Feed 150 99.94 5222.2 518.1 1.008 9.2

determined by gravimetry. There was good agreement among the
conversion-time profiles for three runs of the reaction, which
indicates good reproducibility.
3.1. Particle size analysis and evolution of particle diameter
The particle size and size distribution in the final emulsion
obtained at the end of the seed stage as well as samples taken at
intervals of 30 min during the feed stage were measured by
capillary hydrodynamic fractionation (CHDF 1100, Matec Applied
Sciences).
Table 2 shows the weight-average diameter (Dw), the number-
average diameter (Dn), the polydispersity index (PDI (Dw/Dn)), and
the number of particles (Np) of emulsion Run Number 2 with
increasing time. The number of particles (Np, dm3 water) was
calculated using the following equation:
6rw M x Mx
Np ¼ ¼ 1:81  1021  3
prPD3n Dn
Fig. 3. Evolution of particle diameter (Dn) as a function of feed time in the semi-
batch emulsion copolymerization of VAM/ethylene/NMA.
particles with relatively large sizes. Therefore, the number of the
particles calculated based on the measured size can be artificially
smaller than the actual values.
Fig. 3 shows the evolution of particle size as a function of feed
time in the semi-batch emulsion copolymerization of VAM/
ethylene/NMA. The data obtained from CHDF is compared with
the theoretical curve, which is calculated from Eq. (2).
From Table 3 and Fig. 3, it can be seen that the calculated
diameter of the particles based on the seed particle size measured
by CHDF does not give accurate results with increasing conversion,
whereas the calculated diameter of particles based on the seed
particle size measured by CHDF gives good agreement with the
experimental values. This might be attributed to the existence of
the electrical double layer on the particle surface where its
thickness could be increased by adding the hydrophilic monomer
(1)
(NMA) in the feed stage.

where M is the total mass/water mass, x is the solids content of the

3.2. Coagulum characterization
emulsion, and rw (1 g/cm3) and rp (1.055 g/cm3) are densities of
water and polymer, respectively. A larger hydrodynamic volume
Coagulum formation studies were carried out using the same
might explain this difference. The theoretical particle sizes
recipes and operating conditions (10 cm agitator, 300 rpm). As
obtained for different feed times were calculated using Eq. (2).
described previously, coagulum formed in the emulsion was
The results were shown in Table 3.
measured by filtering the emulsion through a nylon mesh with a
 1=3 pore size of 100 mm. Also, the coagulum present in ca. 20 ml
M1 þ M2
F Fd ¼ DSd  (2) emulsion samples, which were withdrawn from the reactor at
M1
30 min intervals during the feed stage, was measured by vacuum
where DSd is the particle size of the final emulsion in the seed stage, filtering the emulsion through a filter paper with a pore size of
which is measured by CHDF, M1 is the total mass of BMA in the seed 11 mm. A smaller pore size was used because of detection of small
stage; M2 is the total mass of VAM/ethylene and NMA in the feed aggregated particles from the small amount of samples. Multi-
stage with changing time, and DFd is the theoretical particle size at plats (less than about 20 aggregated particles) passing through the
a given feed time. filter paper were not considered to be coagulum. The coagulum on
From the CHDF results presented in Table 2, it is also observed the baffles, impeller, and shaft were carefully scraped, collected,
that the particle number slightly decreased from about 80% washed, dried, and weighed. Table 4 shows the distribution of the
conversion onward. This might be due to shear-induced aggrega- coagulum in the emulsion and the reactor. Most of the coagulum is
tion of the particles. Another possible reason may be an artifact, formed on the agitator, shaft, and baffles. Although the amount of
which could be caused by an interaction between the fluent or the the coagulum in the emulsion is much smaller than that on the
wall of the CHDF column and the particle surface, in the case of agitator, shaft, and baffles, the influence of the mixing and the
shear on the coagulum in the emulsion may be considered in
further studies.
Table 3
Comparison of the experimental and theoretical particle sizes based on the recipe
given in Table 1.
Table 4
Seed Feed Feed Feed Feed Feed
Distribution of the coagulum amount in the emulsion and the reactor.
60 min 30 min 60 min 90 min 120 min 150 min
Emulsion ID Coagulum amount (g) Total coagulum (%)
Overall 6.2 20.9 39.18 60.47 86.17 99.94
conversion (%) Emulsion Agitator/shaft/baffles

Dn (nm) (CHDF) Run Number 1 0.43 2.56 0.64

Exper. 201.5 313.7 370 419.4 462 518.1 Run Number 2 0.42 2.11 0.54
Theoret. 201.5 316 380.1 427.8 466.7 501.9 Run Number 2 0.49 2.62 0.67
434 Y.-H. Choi, W.-K. Lee / Journal of Industrial and Engineering Chemistry 16 (2010) 431–436
Fig. 4. Fraction of coagulum formed in the withdrawn emulsion sample as a
function of feed time.
Fig. 5. Amount of coagulum present in the diluted emulsion as a function of the
added water.
Fig. 4 shows a plot of the fraction of the coagulum present in the
withdrawn emulsion samples as a function of time. However, the
filter paper was clogged by the emulsion with increasing solids
contents (increased conversion ratio). Thus, the emulsion was
diluted when the coagulum was measured.
Various amounts of water were added to 20 ml emulsion
samples in order to determine the appropriate degree of dilution.
Fig. 5 shows the amount of coagulum present in the diluted
emulsion as a function of the amount of added water. When the
solids content of the emulsion is lower than ca. 5%, the coagulum
amount was seen to reach a constant value. Fig. 6 shows the
evolution of the coagulum formation with increasing conversion in
the diluted emulsion. 150 ml water was added to the emulsion
samples. It can be seen that coagulum, which might be present as
Fig. 6. Evolution of coagulum as a function of conversion.
Fig. 7. Pattern formed by the coagulum on the blade of the agitator (a), simulated
flow pattern with a Rushton turbine blade (b), schematic three-dimensional views
of the trailing vortex pair (c) [10].
small aggregated particles, is generated around 20% conversion
from Fig. 4. Once a small amount of coagulum is formed, the
continued creation of coagulum may auto-accelerate with
increasing conversion as seen in Fig. 6. The kinetics of coagulation
is highly sensitive to small perturbations [11]. The pattern formed
by the coagulum on the blades of the agitator in experiment Run
Number 2 is shown in Fig. 7(a), and Fig. 7(b) shows a simulated
flow pattern in a reaction with the same geometrical configuration
and operating conditions used in our experiments.
It is observed that coagulum is formed on the back side of the
agitator blade. The pattern on the agitator blade indicates the
existence of a vortex flow near the agitator blade. The trailing
vortex pair exists behind each stirrer blade [12]. They found that
these vortexes are connected with high shear rates, which scale in
terms of the Reynolds number (Re = ND2r/m, where N is the
rotational speed, D is the diameter of the agitator, m is the viscosity
of the fluid, and r is the density of the fluid) of the flow. Coagulum
formation is proportional to the shear stress. Thus, the trailing
vortex behind the agitator blades can be the main locus for
coagulum formation.
3.3. Simulated flow patterns and analysis
A radial flow pattern is predominantly generated at the start of
mixing using a Rushton turbine impeller. The mixing time (fully
developed turbulent flow), which is generally equal to 4–5 times
the circulation time, is 3 s. A trailing vortex near the blade and a
little swirling around the shaft is observed because of high shear
generation. A combination of radial flow and axial flow is
generated with the pitched blade impeller. Aa true axial flow
pattern is generated early in the mixing and vortex formation
arising from velocity gradients in the fluid is not observed around
the impeller. This indicates that shear-induced coagulum forma-
tion should be decreased due to minimization of velocity gradients
of the fluid issuing from the impeller blade. The time for fully
 Y.-H. Choi, W.-K. Lee / Journal of Industrial and Engineering Chemistry 16 (2010) 431–436 435

Table 5
Evolution of particle diameter and number of particles at 300 rpm, 400 rpm, and 500 rpm using the 8 cm diameter fluid-foil impeller.

Time (min) 300 rpm 400 rpm 500 rpm

15 15
Size (nm) Np (10 dm 3
H2O) Size (nm) Np (10 dm 3
H2O) Size (nm) Np (1015 dm3 H2O)

Dv PDI Dv PDI Dv PDI

Seed 60 202 1.004 1.1 198 1.006 1.2 215 1.005 0.9
Feed 30 284 1.005 1.3 295 1.004 1.2 327 1.004 0.9
Feed 60 341 1.004 1.4 356 1.004 1.2 382 1.006 1.0
Feed 90 378 1.005 1.5 398 1.005 1.3 432 1.006 1.0
Feed 120 412 1.008 1.4 439 1.005 1.2 463 1.006 1.0
Feed 150 459 1.006 1.3 465 1.005 1.3 500 1.005 1.0

Table 6
Evolution of particle diameter and number of particles at 300 rpm, 400 rpm, and 500 rpm using the 8 cm diameter Rushton turbine impeller.

Time (min) 300 rpm 400 rpm 500 rpm

15 15
Size (nm) Np (10 dm 3
H2O) Size (nm) Np (10 dm 3
H2O) Size (nm) Np (1015 dm3 H2O)

Dv PDI Dv PDI Dv PDI

Seed 60 201 1.006 1.0 201 1.006 1.1 216 1.004 0.9
Feed 30 299 1.003 1.0 301 1.004 1.2 332 1.004 0.9
Feed 60 352 1.003 1.2 361 1.004 1.2 381 1.006 1.0
Feed 90 390 1.005 1.3 395 1.005 1.3 439 1.006 0.9
Feed 120 431 1.005 1.3 441 1.005 1.2 481 1.005 0.9
Feed 150 470 1.005 1.2 474 1.005 1.2 524 1.004 0.9

developed mixing is 5 s for the pitched blade. Some dead zones are lowest turbulence. Therefore, a higher collision frequency between
observed near the blade in the case of the Rushton turbine particles using the Rushton impeller led to larger particle size.
impeller. The zones may be caused by trailing vortices, which can It was observed that the seed particle sizes for both impeller
have a major effect on coagulum formation. types were very similar at 300 rpm and 400 rpm, whereas at
500 rpm, the size was much larger than at the other speeds. The
3.4. Effect of extent of agitation on the particle size and particle seed particle size also differed with impeller diameter. The number
number of particles decreased with increasing impeller diameter and
speed. There are two possible explanations for this. One involves
Tables 5–7 show the volume-average diameter (Dv), the the shear stress and its effect on the homogeneous-coagulative
polydispersity index (PDI = Dw/Dn), and the number of particles nucleation mechanism. The latter involves the precipitation of
(Np) of the emulsions synthesized under different agitation growing radicals (primary precursors) to form nuclei as well as the
conditions. aggregation of nuclei that were already generated unstably
From the CHDF results, mono-disperse particles are observed (precursors). More nuclei (precursors) can aggregate in the
for each sample with increasing time. The particle size of the beginning of the seed stage by the induced high shear stress
emulsion increased with the degree of agitation for both impeller (500 rpm), which is proportional to the square of the impeller
types and smaller numbers of particles were produced at higher speed and, eventually, the number of particles is decreased. The
impeller speeds. The particle sizes of the emulsions synthesized second explanation involves the distribution of the surfactant. The
using the Rushton impeller, are generally larger than those higher agitation intensity produces smaller droplet sizes and thus
prepared using the fluid-foil impeller, most notably for the final more droplets. As a result, the surface area of monomer droplets is
emulsions. This is because the Rushton turbine impeller is more increased, resulting in more surfactant adsorption. Fewer surfac-
dominant in shear than the fluid-foil impeller. Velocity-time tant molecules are thus available to stabilize the nucleated
profiles for three different impellers (Rushton turbine, pitched polymer particles. Hence, higher agitation produces a smaller
blade (458), and fluid-foil impeller), which indicate the degree of number of particles. However, to fully explain the mechanism
turbulence [13]. The Rushton turbine impeller produced the during the entire polymerization, a combination of the two
highest turbulence, while the fluid-foil impeller produced the explanations might be in order, namely, fluid mechanics (i.e.,
hydrodynamic and colloidal interactions) and surface science (i.e.,
adsorbed surfactant on particles).
With increasing impeller speed, especially for the Rushton
Table 7
turbine impeller at 500 rpm, the coagulation rate is seen to change
Evolution of particle diameter and number of particles at 300 rpm using the 6 cm
diameter Ruton turbine impeller. with time. The several rate stages in the stirred tank coagulation
phenomena. The primary rate stage was associated with collisions
Time (min) 300 rpm
among small particles [14]. The secondary stage displayed an
Size (nm) Np (1015 dm3 H2O) accelerated coagulation rate with large, porous particles resulting.
Dv PDI The collision efficiency is enhanced by penetration of fluid flow
into the aggregates which attain large porosities [15]. Also, the
Seed 60 199 1.006 1.2
Feed 30 298 1.004 1.2 capture efficiency in hete-coagulation (collisions between dissim-
Feed 60 352 1.004 1.3 ilar size particles), is much higher than in homo-coagulation [16].
Feed 90 382 1.006 1.5 Therefore, coagulum formation is affected not only by static
Feed 120 425 1.006 1.4
factors, but also by dominantly dynamic factors such as large
Feed 150 458 1.005 1.3
particle size.
436 Y.-H. Choi, W.-K. Lee / Journal of Industrial and Engineering Chemistry 16 (2010) 431–436
4. Conclusions
The number of particles was found to decrease with increasing
degree of agitation, and was correlated to impeller diameter,
speed, and type. Two explanations are being considered. First, the
higher agitation intensities produce an increased surface area of
monomer droplets, affecting surfactant adsorption. Thus, higher
agitation can produce smaller numbers of particles because fewer
surfactant molecules are available to stabilize the nucleated
polymer particles. Second, these results might be explained by
shear stress and the homogeneous-coagulative nucleation
mechanism. This mechanism is not confined only to the
precipitation of growing radicals to form nuclei, but also the
aggregation of nuclei that were previously generated. More nuclei
will be aggregated in the beginning of the seed stage by induced
high shear stress and, subsequently, the number of particles is
decreased.
It was found that coagulum formation increased with time and
impeller speed. Most of the coagulum is formed on the impeller,
shaft, and baffles. With increasing rotational speed of the impeller,
the differences in the amounts of coagulum in the emulsions
between the different RPM were seen to increase. This is because a
trailing vortex is created by the high velocity gradient for the
Rushton turbine impeller.
Acknowledgment
This work was supported by the Pukyong National University
Research Abroad Fund in 2008 (PS-2008-052).
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