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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 The samples are withdrawn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.
An extensive literature exists on the subject of the mainly two types of VAc emulsion polymers
emulsion polymerization of vinyl acetate. This is produced; a fine particle size (0.1-0.2 microns) grade
hardly surprising in view of the industrial importance by using anionic and/or nonionic emulsifiers and
of the polymer. Because of its good adhesion to a without a protective colloid and a large particle size
number of substrates, and to some extent because of (0.5-3 microns) emulsion which is often only
its cold flow, a large quantity is produced for use in stabilized by protective colloids such as polyvinyl
emulsion paints, adhesives and various textile alcohol (88% hydrolyzed) and hydroxyethylcellulose.
finishing1. Poly (vinyl acetate) is also used in floor The process of preparation of polyvinyl acetate
tile, chewing gum bases, paper coatings. In the textile using poly (vinyl alcohol) as the principle protective
field the polymer goes into bodying and stiffening colloid has been well described by Geddes3. Poly
agents, binders for pigments, fabric sizes, bonding (vinyl alcohol) plays an important role as a protective
agents for non-woven textiles, and as a material which colloid in the emulsion polymerization of vinyl
improves the abrasion resistance of the substrate. Its acetate. In general, the stabilizer of polymer
durability, transparency, flexibility, and stability to emulsions strongly affects not only the colloidal
weathering and sunlight are attributes that contribute properties but also the film properties. An emulsion
to its industrial acceptance2. In industry, exact stabilized with poly (vinyl alcohol) has many
repeatability of emulsion polymerization processes advantages over surfactants, including Newtonian
within narrow limits is desirable, which means that fluidity, superior primary wet tackiness, high strength
the final solids content should be constant within and creep resistant film properties. These phenomena
± 1%, the particle size, emulsion viscosity and stem from the existence of poly (vinyl alcohol) in
polymer average molecular mass should vary little emulsion, and therefore the chemical structure of poly
from batch to batch; and any residual monomer (vinyl alcohol) has a strong influence on the emulsion
should be maintained within minimum possible properties4. Poly(vinyl alcohol) is often used in vinyl
narrow limits. In order to achieve these conditions, acetate emulsion polymerization as a protective
the formulation of emulsion polymerization should colloid, but its role is complex and controversial since
not be subject to variations such as minor changes of it partakes in grafting reactions with the monomer,
raw materials or of operative conditions. There are influencing process mechanisms, and affecting the
SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY 35
colloidal properties of the latex. Furthermore, in sulphate and poly (vinyl alcohol) molecules that
industrial operations, the wide scatter of provides electro-steric stabilization. It was observed
macromolecular properties of the commercial types of that when sodium dodecyl sulphate was added, the
poly (vinyl alcohol) causes process irreproducibility. rate of polymerization, the average molecular mass
Carra et al.5 used different types of poly (vinyl and final latex viscosity increased. The earlier the
alcohol) to perform a series of polymerizations, and addition of sodium dodecyl sulphate, the more
compared their kinetics. A selective solubilization marked these increments. Earhart et al.10 conducted
procedure was applied to separate the three fractions infrared studies on the grafting reactions of poly
of poly(vinyl alcohol) in the final latex: free in the (vinyl alcohol). They studied the emulsion
water phase, physically adsorbed onto the polymer copolymerization of vinyl acetate and butyl acrylate
particles and chemically grafted. These results were with poly (vinyl alcohol) of different degree of
compared with those obtained from pure adsorption hydrolysis as the sole emulsifier. It was found that
measurements of polyvinyl alcohol onto ‘emulsifier- grafting reactions of the poly (vinyl alcohol) and the
free’ polyvinyl acetate dispersions. The rheological vinyl acetate in the aqueous phase affected the rates of
behaviour of the different latexes was also compared, individual monomer consumption and the overall
and the results were used to formulate a hypothesis on polymerization kinetics. The particle nucleation
the interaction mechanisms acting in these systems. mechanism in this system was also illustrated.
Gilmore et al.6,7 developed and validated a Magallanes Gonzalez et al.11 performed GPC analysis
mathematical model that accommodates the emulsion of the serum obtained after latex centrifugation and
polymerization of vinyl acetate stabilized with poly found that high and low molecular mass oligomers are
(vinyl alcohol) in an isothermal semi-batch reactor. In formed during emulsion polymerization of vinyl
addition to the particle nucleation and growth acetate using poly (vinyl alcohol) as surfactant, and
mechanisms governing ionically stabilized they remain in the aqueous phase. The quantitative
polymerizations of relatively water-soluble separation and characterization of the grafted water-
monomers, the model accounted for grafting onto the insoluble poly (vinyl alcohol) was also carried out. It
poly (vinyl alcohol) backbone during nucleation, and was concluded that grafting reactions do not occur on
polymeric stabilization. The model predicted the all the poly (vinyl alcohol) chains. Only a small
experimental conversion and particle size data with fraction of the poly (vinyl alcohol) chains (about 21.8
reasonable accuracy. Model predictions of measurable wt%) participates in the grafting process. Egert et al.12
variables exhibited sensitivity to variables affecting extended the work of Magallanes Gonzalez et al.
either primary un-grafted particle nucleation or which was conducted on low solids content latexes to
flocculation kinetics, but were relatively insensitive to high solid content latexes. Budhlall et al.13
variables affecting poly (vinyl alcohol) grafting investigated the role of grafting during the emulsion
reactions and the resulting primary grafted particle polymerization of vinyl acetate with partially
concentration. Semi-batch simulations indicated that hydrolyzed poly (vinyl alcohol) as an emulsifier and
independent increases in the vinyl acetate, poly (vinyl potassium persulphate as an initiator. It was
alcohol), and initiator levels all increase the primary concluded that particle nucleation was continuous and
grafted particle population. The styrene was accompanied by extensive aggregation during the
minisuspension polymerization at 70ºC using AIBN particle growth stages. The final number of particles
as initiator and poly (vinyl alcohol) and mixture of was independent of the degree of blockiness of the
poly (vinyl alcohol)–sodium dodecyl sulphate as poly (vinyl alcohol). The amount of grafted poly
stabilizers was studied by Ramirez et al.8 and Ramirez (vinyl acetate) were about the same in the final latexes
and Herrera-Ordonez9, focusing on the kinetic (37-39%). In these low solids recipes, grafting
behaviour of the process after the sodium dodecyl appeared to be primarily a solution event, occurring
sulphate was added. It was confirmed that the addition predominantly in the aqueous phase and not at the
of sodium dodecyl sulphate to the system initially particle/water interface, as was previously speculated.
stabilized with poly (vinyl alcohol) highly enhances The study showed that the hydrogen abstraction from
the colloidal stability of the polymer particles because poly (vinyl alcohol) with the sulphate radical is the
of the association formed between sodium dodecyl fastest reaction, resulting in the grafting onto poly
36 INDIAN J. CHEM. TECHNOL., JANUARY 2010
(vinyl alcohol), while the initiation reaction resulting common commercial monomers at 21 kcal/mol and it
mainly in homo-polymer is slower. The propagation has been emphasized3 that many recipes require alert
of the poly (vinyl acetate) radical in the aqueous process operators, and appearance of the surface of the
phase is a much slower reaction. The grafted emulsion (with regard to monomer pooling, foams, or
molecules coagulated with each other to become a graininess due to entrained pockets of liquid or
particle. vaporized vinyl acetate beneath the surface) can
From an industrial perspective, one of the major indicate the need for prompt action. Many incidents
objectives in the operation of emulsion involving the runaway polymerization of vinyl acetate
polymerization processes is that of faster and safer monomer are known which have been reviewed by
operation with consistent polymer product quality. Gustin15. In processes where the polymerization
The polymerization reaction proceeds as a classical initiator was dissolved in the monomer, the initiator
double bond addition reaction initiated via a free- premix polymerized violently in the premix vessel. In
radical mechanism. The reaction is very fast and polymerization processes where vinyl acetate monomer
highly exothermic. This puts a constraint on the speed conversion ratio was not 100%, storages of recycled
of the reaction, due to the limited heat removal monomers containing no polymerization inhibitor and
capacity of the cooling jacket. With industrial reactors possibly some traces of polymerization initiator
becoming as big as 20 m3 (10 metric ton), this exploded due to vinyl acetate monomer violent bulk
limitation is of increasing importance in comparison polymerization. Incidents happened either in batch or
to lab scale reactors of a few 100 mL in volume. The semi-batch polymerization processes in connection
high viscosities of the latexes produced in many with wrong initiator introduction.
industrial processes aggravate the heat-removal In the laboratory, the polymerization is carried out in
problems. Semi-batch reactors are often used to carry a 250 mL to 2 l, three necked glass reactor immersed in
out strongly exothermic emulsion polymerization a constant temperature water bath at typically 50 to
reactions. 75°C and equipped with a reflux condenser, a two
The aim of the present experimental study, in an bladed Teflon stirrer and a dropping funnel. Deionised
industrial 50 litre semi-batch pilot plant reactor water, protective colloids and emulsifiers and buffer
involving emulsion homo-polymerization of vinyl are initially charged and maintained under a constant
acetate in the presence of poly (vinyl alcohol) as the agitation of 90-100 RPM for 2 h to ensure
protective colloid, and potassium persulphate as the solubilization of the poly (vinyl alcohol). Then
initiator, is to demonstrate productivity improvement approximately 25% of the initiator dissolved in
in the process by increasing the monomer feed rate (or deionised water is added, followed by addition of 5%
reducing the monomer feed time). It is also shown of the total monomer. The initiation occurs after 10
that these strategy can be used to control the particle min. This stage is called the ‘seeding stage’. The
size and hence, the viscosity of the latexes. For new remaining part of the monomer is then added drop-wise
as well as existing processes, first principles over a period of 5-6 h. The remaining 75% initiator is
understanding is essential for optimizing and added in 3-12 parts after every 30 min to 2 h. This
improving product quality and enhancing the stage of monomer addition is called the ‘feeding stage’.
company’s cost position. Variations with time of the After feeding, the batch is held for 1 h at the
% solids content, particle size, viscosity, pH, free temperature of reaction and then cooled to 40-45°C and
monomer content and the reactor temperature are held for 30 min. The same process is scaled up to pilot
reported. Process knowledge of the variation of the scale and plant scale reactors.
polymerization rate, total number of particles and
The process that has been chosen can be described
average number of radicals per particle during the
as follows. Deionised water, along with poly (vinyl
course of polymerization of this system is also
alcohol) was charged in the reactor. The reactor was
developed in this work.
heated to 90-95°C with the help of steam and held for
Process description 2 h. The monomer vinyl acetate was charged into the
Vinyl acetate is highly flammable, and its vapor is monomer tank from the monomer storage tank. At 80-
explosive in most concentrations and hence safety 82°C, sodium dodecyl sulphate (emulsifier) and
factors must be carefully considered. Vinyl acetate sodium bicarbonate (buffer) were added. The pH was
has one of the highest heats of polymerization of the checked (7.5-8.2). If necessary, extra sodium
SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY 37
while meeting the heat transfer and safety constraints. Ingredients Amount (% of total mass)
This strategy was tested in a 50 L pilot plant reactor, Deionised water 46.645
then newly constructed, in the plant of Jubilant Vinyl acetate (monomer) 47.0
Poly (vinyl alcohol) (88% 5.0
Organosys Limited, situated in Gajraula, Uttar hydrolyzed)
Pradesh, India. The above product was chosen as it (protective colloid)
had the highest viscosity among all the homo-polymer Potassium persulphate (initiator) 0.176
products that were being manufactured and thus, Sodium bicarbonate (buffer) 0.132
provided the maximum limitation to heat transfer. Formaldehyde (fungicide) 1.047
Since, the product specifications were not to be Table 2−Specifications of the product
disturbed, the initial seeding stage and initial feeding Property Nature/Value
of the monomer at slower rate for 30 min was not Appearnce Milky white
changed in any of the runs; these stages define the Solid (%) 50±1
particle nucleation stage which determines most of the pH 4-6
end-use properties of the final product. It was decided Viscosity (poise) 300-500
Particle size (micron) 1-3
to change the feeding time of the monomer from 5 h Film Hazy
to 4 h to 3 h to 2 h. Thus, in different runs, the total Free monomer <3%
feed time of the monomer varied from 2.5 h to 5.5 h. 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 from feed time of 5.5 h. Also the viscosity was lower for the
cotton cloth. These pieces were padded after dipping feed time of 4.5 h which could be attributed to larger
them in the 10% aqueous dispersion by using rollers. particle size, and hence, larger interparticle distance.
They were weighed. These pieces were dried in oven at Then, it was decided to change the total monomer
105°C for 5 min and again weighed. These pieces were feed time to 3.5 h and 2.5 h. The comparison of the key
then ironed and their bending length was measured properties of final samples obtained with different feed
using a bending meter. times are given in Table 4. It can be seen that as the feed
Results and Discussion time is reduced, there is an improvement in the
In the beginning the final product obtained with the application property i.e. bending length and there is
feed time of 5.5 h, manufactured in the 50 L pilot plant decrease in the viscosity which is the result of increase
reactor and 5 ton plant reactor was tested. The in the particle size (and hence larger interparticle
comparison of their properties is given in Table 3. As distance). It must be mentioned that latex exhibit
can be seen, the various properties are comparable. The thixotropic behaviour i.e. their viscosity decreases with
viscosity of the pilot plant sample is higher than the time at constant shear rate. In Table 5, the viscosities
plant sample because in the pilot runs double the after 1 min and 5 min of shear at 30°C, 20 RPM have
amount of poly (vinyl alcohol) (total mass percent been recorded with Brookfield viscometer with 7RVT
basis) was used as compared to plant runs. spindle. It can be seen that viscosity decreases with time
at constant RPM. All the viscosities reported in this
Then, it was decided to change the total feed time
work (except those in the third column of Table 5) were
of the monomer to 4.5 h in the pilot plant run. Table 4
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 sensitive Hazy, 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
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
Fig. 2−Variation of %solids with time for the runs with monomer time (4.5 h). Since the particle size before 2.5 h could
feed time of 3.5 h (rectangles) and 4.5 h (diamonds) not be measured, they were obtained by fitting a
feeding was stopped, for the runs with 5.5 h, 4.5 h, 3.5 linear regression line through the data for each of
h and 2.5 h feeding time, respectively, is given. As these runs with intercept equal to zero (the particle
can be seen, the temperature could be maintained size at the start of monomer feed will be zero). The
between 76-80°C during monomer feeding. plots are given in Fig. 2. As can be seen, the particle
It was then decided to gain process understanding grows at a faster rate at higher monomer feed rate as
by withdrawing samples during the course of the expected. The variations of % solids with time, for
run after every 0.5 to 1 h from the beginning of the both the runs, are plotted in Fig. 3. In Fig. 4, the
monomer feeding. The samples were quenched by variation of viscosity during the course of reaction is
putting them in an ice-filled container and also by plotted with respect to time, for both the runs. The
adding hydroquinone. The samples were withdrawn 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 reaction kinetics of this process builds up during the
monomer feed time of 3.5 h (rectangles) and 4.5 h (diamonds)
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
Fig. 4−Variation of viscosity with time for the runs with monomer monomer feed rate as is the characteristic of the
feed time of 3.5 h (rectangles) and 4.5 h (diamonds) monomer-starved semi-batch operations.
is plotted in Fig. 5. A second order polynomial curve In Table 8, the mass of solid formed at the end of a
is fitted to the data points as shown in Fig. 5. The given time duration (msolid), the particle size and the
polymerization rate was calculated as follows. During number of particles are given, for the run with
every time interval, total mass of the recipe monomer feed time of 3.5 h. The number of particles
components in the reactor till that time (mtot) was (Np) were calculated using the formula: Np = msolid/(ρP
calculated. Also, the mass of water (mW) and the ×π/6dp3 ). Here, ρP is the density of the polymer (=
monomer fed (mM) was calculated. The mass of other 1.15 g/cm3) and dp is the particle diameter. The
components (moc) was calculated from moc = mtot- particle sizes at 0.5 h and 1.5 h were obtained from
(mW + mM). The total solids in the reactor till that time the equation of the fitted regression line. In Fig. 6, the
variation of number of particles with time is plotted.
(msolid) were calculated from the measured value of
From initial trends, it can be concluded that a
%solid and mtot as msolid = %solid/100×mtot. The mass
coagulative nucleation mechanism is operative in this
of polymer formed upto that time (mP) was calculated
process. As can be seen, there is continuous
from mP = msolid – moc. The mass of polymer formed coagulation during the course of polymerization and
(ΔmP) in a given time interval (Δt) was calculated by even after monomer feeding is stopped. As the
subtracting the mass of polymer formed after the end particles grow there is a tendency to reduce the
of this time interval (mP)t+Δt from that formed after the surface area to maintain stability. The development of
end of previous time interval (mP)t. The rate of viscosity during the course of polymerization is a
polymerization (RP) in a given time interval was result of competition between increase in viscosity
calculated from RP = ΔmP/Δt. The rate of due to increase in dispersed phase volume fraction
polymerization which provides information about the due to polymerization and decrease in viscosity due to
SOOD: INCREASING PVAc EMULSION POLYMERIZATION PRODUCTIVITY 41