Indian Journal of Chemical Technology

Vol. 17, January 2010, pp. 34-42

Increasing PVAc emulsion polymerization productivity-an industrial application

Ashwini Sood
Department of Chemical Engineering, Harcourt Butler Technological Institute, Kanpur 208 002, India
Email: sood.ashwini@rediffmail.com
Received 21 April 2009; revised 5 November 2009

A major objective in the operation of emulsion polymerization processes is that of faster and safer operation with
consistent polymer product quality. The reaction is very fast and highly exothermic. This puts a constraint on the speed of
the reaction, due to the limited heat removal capacity of the cooling jacket. The high viscosities of the latexes produced in
many industrial processes aggravate the heat-removal problems. A systematic, experimental study in a 50 L pilot reactor is
conducted where the monomer feed time is changed from 5.5 h to 2.5 h in various runs. The final samples are characterized
for various properties which include appearance of emulsion, %solids, particle size, viscosity, pH, free monomer, film
appearance and the application property which in this case is the bending length. The final viscosities are in the range of
300-500 poise. The reactor temperature during these runs could be safely controlled between 76-80°C. With decreasing
monomer feed time, the final product shows improved application property and lower viscosity. The samples are withdrawn
during the course of polymerization for two runs and analyzed for various properties. These provide fundamental
understanding about the polymerization process. In conclusion, 30% reduction in batch time is possible.

Keywords: Emulsion polymerization, Kinetics, Nucleation, Viscosity, Calculations

An extensive literature exists on the subject of the
emulsion polymerization of vinyl acetate. This is
hardly surprising in view of the industrial importance
of the polymer. Because of its good adhesion to a
number of substrates, and to some extent because of
its cold flow, a large quantity is produced for use in
emulsion paints, adhesives and various textile
finishing1. Poly (vinyl acetate) is also used in floor
tile, chewing gum bases, paper coatings. In the textile
field the polymer goes into bodying and stiffening
agents, binders for pigments, fabric sizes, bonding
agents for non-woven textiles, and as a material which
improves the abrasion resistance of the substrate. Its
durability, transparency, flexibility, and stability to
weathering and sunlight are attributes that contribute
to its industrial acceptance2. In industry, exact
repeatability of emulsion polymerization processes
within narrow limits is desirable, which means that
the final solids content should be constant within
± 1%, the particle size, emulsion viscosity and
polymer average molecular mass should vary little
from batch to batch; and any residual monomer
should be maintained within minimum possible
narrow limits. In order to achieve these conditions,
the formulation of emulsion polymerization should
not be subject to variations such as minor changes of
raw materials or of operative conditions. There are
mainly two types of VAc emulsion polymers
produced; a fine particle size (0.1-0.2 microns) grade
by using anionic and/or nonionic emulsifiers and
without a protective colloid and a large particle size
(0.5-3 microns) emulsion which is often only
stabilized by protective colloids such as polyvinyl
alcohol (88% hydrolyzed) and hydroxyethylcellulose.
The process of preparation of polyvinyl acetate
using poly (vinyl alcohol) as the principle protective
colloid has been well described by Geddes3. Poly
(vinyl alcohol) plays an important role as a protective
colloid in the emulsion polymerization of vinyl
acetate. In general, the stabilizer of polymer
emulsions strongly affects not only the colloidal
properties but also the film properties. An emulsion
stabilized with poly (vinyl alcohol) has many
advantages over surfactants, including Newtonian
fluidity, superior primary wet tackiness, high strength
and creep resistant film properties. These phenomena
stem from the existence of poly (vinyl alcohol) in
emulsion, and therefore the chemical structure of poly
(vinyl alcohol) has a strong influence on the emulsion
properties4. Poly(vinyl alcohol) is often used in vinyl
acetate emulsion polymerization as a protective
colloid, but its role is complex and controversial since
it partakes in grafting reactions with the monomer,
influencing process mechanisms, and affecting the
 SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY
colloidal properties of the latex. Furthermore, in
industrial operations, the wide scatter of
macromolecular properties of the commercial types of
poly (vinyl alcohol) causes process irreproducibility.
Carra et al.5 used different types of poly (vinyl
alcohol) to perform a series of polymerizations, and
compared their kinetics. A selective solubilization
procedure was applied to separate the three fractions
of poly(vinyl alcohol) in the final latex: free in the
water phase, physically adsorbed onto the polymer
particles and chemically grafted. These results were
compared with those obtained from pure adsorption
measurements of polyvinyl alcohol onto ‘emulsifier-
free’ polyvinyl acetate dispersions. The rheological
behaviour of the different latexes was also compared,
and the results were used to formulate a hypothesis on
the interaction mechanisms acting in these systems.
Gilmore et al.6,7 developed and validated a
mathematical model that accommodates the emulsion
polymerization of vinyl acetate stabilized with poly
(vinyl alcohol) in an isothermal semi-batch reactor. In
addition to the particle nucleation and growth
mechanisms governing ionically stabilized
polymerizations of relatively water-soluble
monomers, the model accounted for grafting onto the
poly (vinyl alcohol) backbone during nucleation, and
polymeric stabilization. The model predicted the
experimental conversion and particle size data with
reasonable accuracy. Model predictions of measurable
variables exhibited sensitivity to variables affecting
either primary un-grafted particle nucleation or
flocculation kinetics, but were relatively insensitive to
variables affecting poly (vinyl alcohol) grafting
reactions and the resulting primary grafted particle
concentration. Semi-batch simulations indicated that
independent increases in the vinyl acetate, poly (vinyl
alcohol), and initiator levels all increase the primary
grafted particle population. The styrene
minisuspension polymerization at 70ºC using AIBN
as initiator and poly (vinyl alcohol) and mixture of
poly (vinyl alcohol)–sodium dodecyl sulphate as
stabilizers was studied by Ramirez et al.8 and Ramirez
and Herrera-Ordonez9, focusing on the kinetic
behaviour of the process after the sodium dodecyl
sulphate was added. It was confirmed that the addition
of sodium dodecyl sulphate to the system initially
stabilized with poly (vinyl alcohol) highly enhances
the colloidal stability of the polymer particles because
of the association formed between sodium dodecyl
35
sulphate and poly (vinyl alcohol) molecules that
provides electro-steric stabilization. It was observed
that when sodium dodecyl sulphate was added, the
rate of polymerization, the average molecular mass
and final latex viscosity increased. The earlier the
addition of sodium dodecyl sulphate, the more
marked these increments. Earhart et al.10 conducted
infrared studies on the grafting reactions of poly
(vinyl alcohol). They studied the emulsion
copolymerization of vinyl acetate and butyl acrylate
with poly (vinyl alcohol) of different degree of
hydrolysis as the sole emulsifier. It was found that
grafting reactions of the poly (vinyl alcohol) and the
vinyl acetate in the aqueous phase affected the rates of
individual monomer consumption and the overall
polymerization kinetics. The particle nucleation
mechanism in this system was also illustrated.
Magallanes Gonzalez et al.11 performed GPC analysis
of the serum obtained after latex centrifugation and
found that high and low molecular mass oligomers are
formed during emulsion polymerization of vinyl
acetate using poly (vinyl alcohol) as surfactant, and
they remain in the aqueous phase. The quantitative
separation and characterization of the grafted water-
insoluble poly (vinyl alcohol) was also carried out. It
was concluded that grafting reactions do not occur on
all the poly (vinyl alcohol) chains. Only a small
fraction of the poly (vinyl alcohol) chains (about 21.8
wt%) participates in the grafting process. Egert et al.12
extended the work of Magallanes Gonzalez et al.
which was conducted on low solids content latexes to
high solid content latexes. Budhlall et al.13
investigated the role of grafting during the emulsion
polymerization of vinyl acetate with partially
hydrolyzed poly (vinyl alcohol) as an emulsifier and
potassium persulphate as an initiator. It was
concluded that particle nucleation was continuous and
was accompanied by extensive aggregation during the
particle growth stages. The final number of particles
was independent of the degree of blockiness of the
poly (vinyl alcohol). The amount of grafted poly
(vinyl acetate) were about the same in the final latexes
(37-39%). In these low solids recipes, grafting
appeared to be primarily a solution event, occurring
predominantly in the aqueous phase and not at the
particle/water interface, as was previously speculated.
The study showed that the hydrogen abstraction from
poly (vinyl alcohol) with the sulphate radical is the
fastest reaction, resulting in the grafting onto poly
36 INDIAN J. CHEM. TECHNOL., JANUARY 2010
(vinyl alcohol), while the initiation reaction resulting
mainly in homo-polymer is slower. The propagation
of the poly (vinyl acetate) radical in the aqueous
phase is a much slower reaction. The grafted
molecules coagulated with each other to become a
particle.
From an industrial perspective, one of the major
objectives in the operation of emulsion
polymerization processes is that of faster and safer
operation with consistent polymer product quality.
The polymerization reaction proceeds as a classical
double bond addition reaction initiated via a free-
radical mechanism. The reaction is very fast and
highly exothermic. This puts a constraint on the speed
of the reaction, due to the limited heat removal
capacity of the cooling jacket. With industrial reactors
becoming as big as 20 m3 (10 metric ton), this
limitation is of increasing importance in comparison
to lab scale reactors of a few 100 mL in volume. The
high viscosities of the latexes produced in many
industrial processes aggravate the heat-removal
problems. Semi-batch reactors are often used to carry
out strongly exothermic emulsion polymerization
reactions.
The aim of the present experimental study, in an
industrial 50 litre semi-batch pilot plant reactor
involving emulsion homo-polymerization of vinyl
acetate in the presence of poly (vinyl alcohol) as the
protective colloid, and potassium persulphate as the
initiator, is to demonstrate productivity improvement
in the process by increasing the monomer feed rate (or
reducing the monomer feed time). It is also shown
that these strategy can be used to control the particle
size and hence, the viscosity of the latexes. For new
as well as existing processes, first principles
understanding is essential for optimizing and
improving product quality and enhancing the
company’s cost position. Variations with time of the
% solids content, particle size, viscosity, pH, free
monomer content and the reactor temperature are
reported. Process knowledge of the variation of the
polymerization rate, total number of particles and
average number of radicals per particle during the
course of polymerization of this system is also
developed in this work.
Process description
Vinyl acetate is highly flammable, and its vapor is
explosive in most concentrations and hence safety
factors must be carefully considered. Vinyl acetate
has one of the highest heats of polymerization of the
common commercial monomers at 21 kcal/mol and it
has been emphasized3 that many recipes require alert
process operators, and appearance of the surface of
the emulsion (with regard to monomer pooling,
foams, or graininess due to entrained pockets of liquid
or vaporized vinyl acetate beneath the surface) can
indicate the need for prompt action. Many incidents
involving the runaway polymerization of vinyl acetate
monomer are known which have been reviewed by
Gustin15. In processes where the polymerization
initiator was dissolved in the monomer, the initiator
premix polymerized violently in the premix vessel. In
polymerization processes where vinyl acetate
monomer conversion ratio was not 100%, storages of
recycled monomers containing no polymerization
inhibitor and possibly some traces of polymerization
initiator exploded due to vinyl acetate monomer
violent bulk polymerization. Incidents happened
either in batch or semi-batch polymerization
processes in connection with wrong initiator
introduction.
In the laboratory, the polymerization is carried out
in a 250 mL to 2 l, three necked glass reactor
immersed in a constant temperature water bath at
typically 50 to 75°C and equipped with a reflux
condenser, a two bladed Teflon stirrer and a dropping
funnel. Deionised water, protective colloids and
emulsifiers and buffer are initially charged and
maintained under a constant agitation of 90-100 RPM
for 2 h to ensure solubilization of the poly (vinyl
alcohol). Then approximately 25% of the initiator
dissolved in deionised water is added, followed by
addition of 5% of the total monomer. The initiation
occurs after 10 min. This stage is called the ‘seeding
stage’. The remaining part of the monomer is then
added drop-wise over a period of 5-6 h. The
remaining 75% initiator is added in 3-12 parts after
every 30 min to 2 h. This stage of monomer addition
is called the ‘feeding stage’. After feeding, the batch
is held for 1 h at the temperature of reaction and then
cooled to 40-45°C and held for 30 min. The same
process is scaled up to pilot scale and plant scale
reactors.
The process that has been chosen can be described
as follows. Deionised water, along with poly (vinyl
alcohol) was charged in the reactor. The reactor was
heated to 90-95°C with the help of steam and held for
2 h. The monomer vinyl acetate was charged into the
monomer tank from the monomer storage tank. At 80-
82°C, sodium dodecyl sulphate (emulsifier) and
sodium bicarbonate (buffer) were added. The pH was
checked (7.5-8.2). If necessary, extra sodium
 SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY 37

bicarbonate was added to adjust the pH. At 78-80°C, Experimental Procedure

25% of potassium persulphate (initiator) dissolved in
deionised water was added and regular feeding of the
monomer was started. Feeding rate of the monomer
was 3 kg/h for 30 min and 5 kg/h for 5-6 h. Reactor
temperature is maintained at 76-80°C with the help of
cold water and chilled water, fed into the external
jacket. The reactor was also equipped with a reflux
condenser which provided evaporative cooling. 1/12 th
part of remaining initiator dissolved in deionised
water was added after every 30 min of regular
feeding. After monomer feeding was over, the last
shot of initiator was added and the batch held for 1 h
at 76-80°C. The cooling of the reactor was then
started and formaldehyde was added and the batch
was held for 30 min. It took about 30 min to empty
the reactor. The reactor was cleaned manually by
scrapping off the coagulum deposited during the
reaction, after every 5-6 batches. Due to proprietary
reasons, the commercial recipe can not be disclosed
but a typical recipe for this process is given in
Table 1. The product that was chosen was a
popular finishing agent that imparted body, handle
and stiffness to cotton, synthetic, blends, buckroms
and interlinings. The specifications for this product
are given in Table 2.
Thus, the total batch time comes to 9-10 h, out of
which 50-60% was the monomer feed time. It was
realized that since monomer is added very slowly or
drop-wise in the laboratory set-up; the delayed
addition of monomer translated into a very large
feeding time in the pilot-plant set-up during scale-up,
and therefore, reduction in batch time could be
achieved by feeding the monomer at faster rates,
while meeting the heat transfer and safety constraints.
This strategy was tested in a 50 L pilot plant reactor,
then newly constructed, in the plant of Jubilant
Organosys Limited, situated in Gajraula, Uttar
Pradesh, India. The above product was chosen as it
had the highest viscosity among all the homo-polymer
products that were being manufactured and thus,
provided the maximum limitation to heat transfer.
Since, the product specifications were not to be
disturbed, the initial seeding stage and initial feeding
of the monomer at slower rate for 30 min was not
changed in any of the runs; these stages define the
particle nucleation stage which determines most of the
end-use properties of the final product. It was decided
to change the feeding time of the monomer from 5 h
to 4 h to 3 h to 2 h. Thus, in different runs, the total
feed time of the monomer varied from 2.5 h to 5.5 h.
All the ingredients listed in Table 1 were used as
received, without any further purification.
The polymerization procedure has been described
above under process description. The pilot reactor
reaction volume was 50 L. It was jacketed and had
provisions for jacket heating with steam and cooling
with cold water and chilled water. It was also
provided with a reflux condenser which provided
evaporative cooling from the latent heat of
evaporation. The condensed monomer was cooled
further before return. The monomer fed into the
reactor from the storage tank at ambient temperature
also provided cooling. The reactor was equipped with
an agitator with provisions for two RPMs: 36 and 72.
All the runs were made at 72 RPM to overcome the
heat transfer limitations. The reactor was also
equipped with a temperature gauge and the
temperature was recorded manually at every 15 min
during a run. Monomer was fed into the reactor from
a storage tank and its flow rate was set using a valve
and measured using a rotameter.
The %solids (non-volatile content) was determined
gravimetrically by heating 1-2 g of the emulsion in an
oven at 105°C for 3 h. Viscosity of the emulsions was
measured at room temperature (~ 30°C) using a
Brookfield viscometer using spindles RVT 3-7.
Particle size of the emulsions was determined by the
use of disc centrifuge combined with light scattering.
The pH of the emulsions was measured using a pH
meter. Free monomer was measured through bromine
titration. General appearance of the emulsions was
observed
visually. Films were casted using 100 micron film
Table 1Typical recipe for polymerization
Ingredients Amount (% of total mass)
Deionised water 46.645
Vinyl acetate (monomer) 47.0
Poly (vinyl alcohol) (88% 5.0
hydrolyzed)
(protective colloid)
Potassium persulphate (initiator) 0.176
Sodium bicarbonate (buffer) 0.132
Formaldehyde (fungicide) 1.047
Table 2Specifications of the product
Property Nature/Value
Appearnce Milky white
Solid (%) 50±1
pH 4-6
Viscosity (poise) 300-500
Particle size (micron) 1-3
Film Hazy
Free monomer <3%
Application property Bending length
 38 INDIAN J. CHEM. TECHNOL., JANUARY 2010

applicator on glass plates about 23 ×10 cm and dried compares the properties of the product obtained with a
overnight at ambient temperature in a dust free feed time of 5.5 h and 4.5 h. Both the runs were made
atmosphere. Clarity of the film was observed visually. on the same day and in the same reactor, back to back.
The bending length was measured as follows. 10% It can be seen that bending length obtained with feed
aqueous dispersions of the emulsions were made. time of 4.5 h was higher than that obtained with the
Pieces of similar dimensions (6 ×1 inch) were cut feed time of 5.5 h. Also the viscosity was lower for
from cotton cloth. These pieces were padded after the feed time of 4.5 h which could be attributed to
dipping them in the 10% aqueous dispersion by using larger particle size, and hence, larger interparticle
rollers. They were weighed. These pieces were dried distance.
in oven at 105°C for 5 min and again weighed. These
Then, it was decided to change the total monomer
pieces were then ironed and their bending length was
feed time to 3.5 h and 2.5 h. The comparison of the
measured using a bending meter.
key properties of final samples obtained with different
Results and Discussion feed times are given in Table 4. It can be seen that as
In the beginning the final product obtained with the the feed time is reduced, there is an improvement in
feed time of 5.5 h, manufactured in the 50 L pilot the application property i.e. bending length and there
plant reactor and 5 ton plant reactor was tested. The is decrease in the viscosity which is the result of
comparison of their properties is given in Table 3. As increase in the particle size (and hence larger
can be seen, the various properties are comparable. interparticle distance). It must be mentioned that latex
The viscosity of the pilot plant sample is higher than exhibit thixotropic behaviour i.e. their viscosity
the plant sample because in the pilot runs double the decreases with time at constant shear rate. In Table 5,
amount of poly (vinyl alcohol) (total mass percent the viscosities after 1 min and 5 min of shear at 30°C,
basis) was used as compared to plant runs. 20 RPM have been recorded with Brookfield
Then, it was decided to change the total feed time viscometer with 7RVT spindle. It can be seen that
of the monomer to 4.5 h in the pilot plant run. Table 4 viscosity decreases with time at constant RPM. All the
viscosities reported in this work (except those in the
third column of Table 5) were
measured after 1 min of shear at 30°C and 20 RPM.
Table 3Comparison of the properties of the Pilot plant sample In Fig. 1, the temperature of the reactor from the
and Plant sample start of monomer feeding to 1 h after the monomer
Property Nature/Value Nature/Value
Pilot plant sample Plant sample Table 5Effect of the duration of shear on the viscosity of final
Appearance Milky white Milky white samples of various runs
Viscosity (poise) 520 270 Run time (h) Viscosity after 1 min Viscosity after 5 min
Solids (%) 50.4 49.6 (poise) (poise)
Film properties Hazy, water sensitiveHazy, water sensitive Plant (5.5) 270 160
Particle size (micron) 2.09 2.09 Pilot (5.5) 520 420
pH 4.98 4.21 Pilot (4.5) 490 390
Free monomer (%) 0.22 0.43 Pilot (3.5) 400 320
Bending length (cm) 3.2 3.2 Pilot (2.5) 360 290
(10% aqueous
dispersion)
Table 4Key properties of final samples obtained with different
feed times
Property Nature/ Nature/ Nature/ Nature/
Value Value Value Value
Feed time (h) 5.5 4.5 3.5 2.5
Appearance Milky Milky Milky Milky
white white white white
Particle size (micron) 1.94 1.97 2.00 2.09
Viscosity (poise) 520 490 400 360
Solids (%) 50.40 49.69 50.18 50.61
pH 4.98 5.01 4.95 5.07 Fig. 1Variation of reactor temperature with time for runs with
Film appearance Hazy Hazy Hazy Hazy different monomer feed time. Feed time: Series 1, 2.5 h; Series 2,
Bending length (cm) 3.2 3.4 3.5 3.6 3.5 h; Series 3, 4.5 h; Series 4, 5.5 h
 SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY 39

Table 6Product properties during the course of polymerization for run with monomer feed time of 3.5 h

Time (h)
0.5 1.5 2.5 3.5 Final
Sample/Property
Appearance Milky white Free Milky white free Milky white Milky white Milky white
flowing emulsion flowing emulsion viscous emulsion viscous emulsion viscous emulsion
Solids (%) 6.86 26.46 43.49 51.04 51.14
Viscosity (poise) 1 90 500 500 620
Particle size (micron) - - 1.22 1.64 2.0
Free monomer (%) 0.14 0.29 0.50 0.25 0.21
Polymerization rate (kg/h) 2.6 14.3 18.3 14.35 0
Feed rate (kg/h) 6 15 15 14 0

Table 7Product properties during the course of polymerization for run with monomer feed time of 4.5 h
Time (h)
0.5 1.5 2.5 3.5 4.5 Final
Sample/Property
Appearance MWFFE* MWFFE MWVE** MWVE MWVE MWVE
Solids (%) 7.06 24.76% 34.78 39.88 48.30 50.72
Viscosity (poise) 1 140 500 720 1020 80
Particle size (μ)   0.98 1.28 1.66 1.84
Polymerization 2.6 12.2 10.4 9.6 12.8 0
Rate (kg/h)
Feed rate (kg/h) 6.0 11.0 11.0 11.0 11.0 0
*Milky white, free flowing emulsion
**Milky white, viscous emulsion

Fig. 2Variation of %solids with time for the runs with monomer
feed time of 3.5 h (rectangles) and 4.5 h (diamonds)
feeding was stopped, for the runs with 5.5 h, 4.5 h, 3.5
h and 2.5 h feeding time, respectively, is given. As
can be seen, the temperature could be maintained
between 76-80°C during monomer feeding.
It was then decided to gain process understanding
by withdrawing samples during the course of the
run after every 0.5 to 1 h from the beginning of the
monomer feeding. The samples were quenched by
putting them in an ice-filled container and also by
adding hydroquinone. The samples were withdrawn
for two runs with monomer feed time of 3.5 h and 4.5
h and the various properties evaluated of these
samples are given in Tables 6 and 7. These runs were
conducted in 100 L pilot reactor. The sample size was
0.5 kg. The high viscosities of these runs were
attributed to the poly (vinyl alcohol) lot that was used
as it was reported that the same lot had given higher
viscosities in the plant runs also. It should be noted
that run with lower monomer feed time (3.5 h) gave
lower viscosities than the one with the higher feed
time (4.5 h). Since the particle size before 2.5 h could
not be measured, they were obtained by fitting a
linear regression line through the data for each of
these runs with intercept equal to zero (the particle
size at the start of monomer feed will be zero). The
plots are given in Fig. 2. As can be seen, the particle
grows at a faster rate at higher monomer feed rate as
expected. The variations of % solids with time, for
both the runs, are plotted in Fig. 3. In Fig. 4, the
variation of viscosity during the course of reaction is
plotted with respect to time, for both the runs. The
variation of viscosity with % solid, for both the runs,
40 INDIAN J. CHEM. TECHNOL., JANUARY 2010
Fig. 3Variation of particle size with time for the runs with
monomer feed time of 3.5 h (rectangles) and 4.5 h (diamonds)
Fig. 4Variation of viscosity with time for the runs with monomer
feed time of 3.5 h (rectangles) and 4.5 h (diamonds)
is plotted in Fig. 5. A second order polynomial curve
is fitted to the data points as shown in Fig. 5. The
polymerization rate was calculated as follows. During
every time interval, total mass of the recipe
components in the reactor till that time (mtot) was
calculated. Also, the mass of water (m ) and the
W
monomer fed (mM) was calculated. The mass of other
components (moc) was calculated from moc = mtot-
(mW + mM). The total solids in the reactor till that time
(msolid) were calculated from the measured value of
%solid and mtot as msolid = %solid/100×mtot. The mass
of polymer formed upto that time (m P) was calculated
from mP = msolid – moc. The mass of polymer formed
(ΔmP) in a given time interval (Δt) was calculated by
subtracting the mass of polymer formed after the end
of this time interval (mP)t+Δt from that formed after the
end of previous time interval (mP)t. The rate of
polymerization (RP) in a given time interval was
calculated from RP = ΔmP/Δt. The rate of
polymerization which provides information about the
Fig. 5Variation of viscosity with % solids for the runs with
monomer feed time of 3.5 h (rectangles) and 4.5 h (diamonds)
reaction kinetics of this process builds up during the
course of polymerization to a maximum after an
initial low value during the initial half hour when the
particles are being formed and falls to zero once the
monomer feeding is over. A comparison between the
rate of polymerization and feed rate can be also
obtained from Tables 6 and 7. It can be concluded that
initially the polymerization rate is slower than the
monomer feed rate and the unreacted monomer in this
stage leads to a higher polymerization rate than the
monomer feed rate sometimes during the course of
polymerization. In the remaining time, the
polymerization rate is more or less equal to the
monomer feed rate as is the characteristic of the
monomer-starved semi-batch operations.
In Table 8, the mass of solid formed at the end of a
given time duration (msolid), the particle size and the
number of particles are given, for the run with
monomer feed time of 3.5 h. The number of particles
(Np) were calculated using the formula: Np = msolid/(ρP
×π/6dp3 ). Here, ρP is the density of the polymer (=
1.15 g/cm3) and dp is the particle diameter. The
particle sizes at 0.5 h and 1.5 h were obtained from
the equation of the fitted regression line. In Fig. 6, the
variation of number of particles with time is plotted.
From initial trends, it can be concluded that a
coagulative nucleation mechanism is operative in this
process. As can be seen, there is continuous
coagulation during the course of polymerization and
even after monomer feeding is stopped. As the
particles grow there is a tendency to reduce the
surface area to maintain stability. The development of
viscosity during the course of polymerization is a
result of competition between increase in viscosity
due to increase in dispersed phase volume fraction
due to polymerization and decrease in viscosity due to
 SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY 41

decrease in total particle number as a result of Also, rate of polymerization, RP = kp[M]pn/NANp

coagulation. The extent of coagulation during a run
with a particular monomer feed time will depend on
the swelling of the polymer particles with the
monomer. The swelling will make the particles softer
and amenable to coagulation. The smaller the feed
time, the larger the monomer feed rate and larger the
monomer swelling. As a result, the ‘stickier’ the
particles16 or the softer the particles and the greater
the extent of coagulation. Thus, larger particles are
obtained with smaller monomer feed times as given in
Table 4. Also, the larger the particle size for nearly
the same %solids, the smaller the number of particles
and the greater the interspacing between them, and
hence, the smaller the viscosity. This trend is also
evident from Table 4.
No of particles ( 1017)
where kp is the propagation rate constant, [M] p is the
monomer concentration in the particle, n is the
average number of radicals per particle, NA is the
Avogadro’s number and Np is the total number of
particles in the reaction volume. Thus, one can
obtain the product kp[M]pn = RPNA/Np by using
the values of RP from Table 6, Np from Table 8 and
NA = 6.023×1023, for the run with the monomer feed
time of 3.5 h. These are given in Table 9. To
covert, RP in the units of gmol/s, the value of RP
given in Table 6 is multiplied by a factor
F=1000(g/kg)/[3600(s/h)×MWM(g/gmol)] where
MWM is the molecular mass of the monomer which
for the case of vinyl acetate is 86. Thus, F= 0.00323.
For vinyl acetate polymerization17, kp = 2×106 exp[-
(19000±2900)/RT] 1/gmols. The average temperature

for the run with the monomer feed time of 3.5 h can
be taken as 78°C or 351 K. Substituting R = 8.314
J/gmolK at this temperature and taking activation
energy as 19000 J/gmol, one gets kp =
2974.485 l/gmols or 2974485 cm3/gmols. Also, for
vinyl acetate polymerization, maximum monomer
volume fraction inside particle when aqueous phase
is saturated with monomer, фmax = 0.91327. This
can be multiplied by the density of monomer (ρM =
0.9317 g/cm3) and then divided by the molecular mass
Fig. 6Variation of number of particles with time for run with
monomer feed time of 3.5 h of the monomer (MWM = 86) to give the maximum
monomer concentration in the particle, [M]p,max = 0.01
gmol/cm3. Thus, dividing kp[M]pn by kp[M]p,max, one
Table 8Variation with time of total solids, particle size and can get nmin, the minimum number of average number
number of particles during the course of polymerization for the
run with monomer feed time of 3.5 h of radicals per particle. Here, it has been assumed that
the particles are having
Time (h) Total soilds Particle size No. of particles maximum saturated monomer concentration but under
(micron) monomer-starved conditions, [M]p < [M]p,max and
hence,
0.5 3611 0.216 5.97×1017 through these calculations, we can get the lower
bound
1.5 18007 0.648 4.63×1017 of n (Table 9). It can be concluded that during most
part
2.5 36345 0.648 3.33×1017 of the polymerization (except the initial 0.5 h),
3.5 50788 1.64 1.92×1017 Smith-Ewart case 3 kinetics is observed (n> 0.5). This
final 50788 2.00 1.06×1017 can be attributed to large particle sizes ~ 1 micron.
Table 9Variation with time of minimum number of the average number of radicals per particle during the course of polymerization for
the run with monomer feed time of 3.5 h
Time Rp Rp Np kp[M]pn nmin
duration (h) (kg/h) (kg/h)
0-0.5 2.6 0.0084 5.97×1017 8475 0.28
0.5-1.5 14.3 0.0462 4.63×1017 60100 2.02
1.5-2.5 18.3 0.0591 3.33×1017 106895 3.59
2.5-3.5 14.35 0.0464 1.92×1017 145556 4.89
42 INDIAN J. CHEM. TECHNOL., JANUARY 2010
3.5-final 0 0 1.06×1017 0 0
 SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY
Conclusions
Through a systematic, experimental study on a
pilot reactor, it is shown that the monomer feed time
could be safely decreased from 5.5 h to 2.5 h; thus,
decreasing the total batch time by 30%. Reducing the
monomer feed time gives an improvement in the
application property which in this case was the
bending length. Also, it leads to product with larger
particle size and as a result with lower viscosity. The
reactor temperature during these runs could be safely
controlled between 76-80°C. The effect of decreased
monomer feed time on the particle size and viscosity
was attributed to presence of coagulation during the
course of polymerization.
A fundamental understanding of the
polymerization behaviour was provided by analyzing
the samples withdrawn during the course of
polymerization for various properties. The rate of
polymerization, the number of particles and the
minimum number of average radicals per particle
during the course of polymerization were calculated
using these measurements. The polymerization rate
was compared with the monomer feed rate. It was
found that initially the polymerization rate is slower
than the monomer feed rate and the unreacted
monomer in this stage leads to a higher
polymerization rate than the monomer feed rate
sometimes during the course of polymerization. In the
remaining time, the polymerization rate is more or
less equal to the monomer feed rate as is the
characteristic of the monomer-starved semi-batch
operations. The number of particles was found to
initially increase and then decrease with time which
indicates the presence of significant coagulation
throughout the polymerization, even after the
stoppage of monomer feeding. It was also found that
during most of the polymerization, Smith-Ewart
case 3 kinetics is followed due to large size of the
particles ~ 1 micron.
Nomenclature
kp = Propagation rate constant
mM = Mass of monomer fed
moc = Mass of other components
mP = Mass of polymer formed
msolid = Mass of total solids
mW Mass of water
MWM = Molecular weight of monomer
43
[M]p = Monomer concentration in the particle
n = Average number of radicals per particle
NA = Avogadro’s Number
NP = Number of particles
R = Universal gas constant
RP = Rate of polymerization
t = Time
T = Temperature
ρM = Density of monomer
ρP = Density of polymer
ф = Monomer volume fraction in the particle
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