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Emulsion polymerization of styrene

Theoretical background
The definition for emulsion is:
A stable colloidal suspension as milk, consisting of an immiscible liquid dispersed and
held in another liquid by a substance called an emulsifier.
Emulsion polymerization is a heterogeneous polymerization technique. Initially the
monomer molecules are dispersed in water, forming small drops with diameter of about
1-10 m. The final polymerization system is also an emulsion with een smaller particles
!0.0"-0.1" m#$ the stability of the latter is higher when compared to the initial micro-
heterogeneous system.
Typically, the emulsion polymerization system comprises four basic ingredients% 1#
monomer, &# reaction'dispersion medium, (# emulsifier, )# initiator.
!1# The monomer forms the dispersed phase. The monomer should be polymerizable
through free radical polymerization.
!&# The reaction medium !the continuous phase# for monomer droplets and polymer
particles may be% !i# water !widely used due to inertness and other e*ceptional properties
such as high specific heat and thermal conductiity, non-to*icity, large aailability and
low price# or !ii# an organic solent !less used, if the monomer is hydrosoluble$ such
system is +nown as ,reersed emulsion-#.
!(# The surfactant/emulsifier contains two ends of different solubility%
the tail - a long hydrocarbon chain soluble in nonpolar, organic
the head . usually a sodium or potassium salt of a carbo*ylic acid or
sulfonic acid, water soluble.
The surfactant has different roles%
(i) to reduce the interfacial tension between the monomer phase and the water phase
so that, with agitation, the monomer is dispersed !or emulsified# in the water phase and to
stabilize the monomer droplets in an emulsion form.
(ii) to generate micelles. If these substances are used aboe the critical micelle
concentration !/0/'cmc#, they will form micelles which are ordered clusters of
emulsifier molecules, with the oil-soluble part of the molecule oriented toward the center
of the cluster and the water-soluble part of the molecule toward the water.
(iii) to solubilize the monomer within emulsifier micelles.
(iv) to stabilize the growing late* particles and to stabilize the particles of the final
Emulsifiers% sodium dodecyl sulfate !121#, sodium lauryl sulfate !131#

121 131
!)# The initiator should be soluble in the reaction medium.
4ydrosoluble initiators% 5I67, ammonium persulfate, potassium persulfate

Emulsion Polymerization
In an emulsion polymerization, the surfactant is dissoled in water until the critical
micelle concentration !/0/# is reached. The interior of the micelle !"-10 nm# proides
the site necessary for the occurrence of the polymerization. The monomer !li+e styrene or
methyl methacrylate# and the water soluble free radical initiator are added and the whole
batch is stirred. The monomer initially forms droplets !1-10 8m#. The emulsion
polymerization always occurs through a free radical mechanism.
!5nionic and cationic chain ends would be rapidly quenched by the water.#
The product of an emulsion polymerization is called latex.
9nce the polymerization mi*ture is prepared, the monomer can be found%
in large monomer droplets
a ery small amount dissoled in water : emulsifier
in micelles.
The emulsion polymerization is a comple* process still not completely understood.
1chematic representation of emulsion polymerization according to ;i+entscher and
Initiation ta+es place in two stages% first the initiator decomposes, to generate free
radicals, and then the radicals migrate and they react with monomer molecules. <ater
soluble initiators, such as persulfates, are commonly used !this also preents
polymerization in the big monomer droplets#. 9nce polymerization starts, the micelle is
referred to as a particle. =olymer particles can grow to e*tremely high molecular weights,
especially if the initiator concentration is low. That ma+es the radical concentration and
the rate of termination low as well.
0onomer molecules migrate from the large monomer droplets to the micelles to sustain
polymerization. 3ate* particles grow until the monomer drops are gone from the reaction
medium. 2ue to the increase in size of the late* particles, more emulsifier molecules are
adsorbed onto their surface and the micelles as such disappear. =ractically all the
monomer is consumed in emulsion polymerizations, meaning the late* can be used
without purification. This is a ery important practical aspect for paints and coatings.
4ere>s the neat aspect of emulsion polymerization% each micelle can be considered as a
bulk polymerization micro-reactor. ?nli+e traditional bul+ polymerizations there is no
unreacted monomer leftoer, and no thermal @hot spots@ form.
In bul+ polymerizations !no solent, Aust monomer and initiator#, thermal hot spots lead
to degradation and discoloration$ chain transfer broadens the molecular weight
distribution. 5n increase in temperature sometimes causes the rate of polymerization to
increase e*plosiely. In emulsion polymerization the water acts as a heat e*changer for
all the micro-reactors and preents oer-heating.
Molecular Weight
The rate of polymerization is the same as the rate of disappearance of monomer.
0onomer disappears faster when there are more particles. In order to hae more particles
there must be more micelles. If the surfactant concentration is increased, this ought to
gie more micelles. If the concentration of the initiator is +ept the same, this gies more
particles and less radicals. 5ccordingly, the number of radicals per micelle B 1. This
leads to a decrease of the termination rate since there are less radicals.
Decreasing the initiator concentration increases molecular weight and rate of
This is different when compared to bul+ and solution polymerization. To increase the rate
of polymerization for those you hae to heat the reaction or increase the initiator
concentration, both of which increase the rate of termination and lower the molecular
Polymerization type : -
6ul+ 9nly monomer : initiator,
eentually crosslin+er 4igh
molecular weights
Thermal hotspots, high
iscosity, residual monomer
1olution The solent allows
temperature control.
The solent should be
remoed$ chain transfer to
Emulsion 5ll the monomer is
consumed$ the late* can be
used as such !no residual
- temperature control
Experimental part
- 5 three nec+s round-bottom flas+, equipped with stirring unit, thermometer and
- 4eating water bath !temperature range% 0 - 100
- ;iltration funnels, bea+ers and Erlenmeyer flas+
- =ipettes
- Cradual cylinders
- 1olent% distilled water% D0 ml
- 0onomer% styrene% &0 g !d
E 0.F0" g'cm
- 1urfactant% sodium lauryl sulfate, sodium dodecyl sulfate
- Initiator !ammonium persulfate - 5=1#
- /a/l
or methanol.
The distilled water is poured in the round bottom flas+. The surfactant is dissoled under
stirring. The temperature is then raised to G0
/ and the monomer is added under
continuous stirring. <hen the wor+ing temperature is reached, the initiator is added !this
is the ,zero- moment of the polymerization#. It is recommended to dissole the initiator
in a small amount of water !this olume should be calculated from the total amount of
water to be used in this procedure#. The polymerization time starts to be measured after "
minutes from the addition of the initiator !considered as the real initial moment of the
polymerization#. 1amples !appro*imately " ml# will be withdrawn at regular time
interals !1" minutes# with a pipette, in order to follow the monomer conersion by
graimetry. The first )-" samples should be remoed at lower time interals !"-10
minutes#. The polymerization time needed to reach a complete monomer conersion is
usually ( h.
To determine the monomer conersion each emulsion should be ,bro+en-. To do this, the
emulsion is poured in an aqueous solution of an electrolyte !/a/l
or methanol,
appro*imately (0-"0 ml#. The separated polymer will be filtered, washed and dried !to
constant mass# and then weighed.
5t the end of the reaction, the whole reaction mass will be precipitated. 5 sample will be
+ept for the measurement of the aerage molecular weight.
1# The dependence conersion . polymerization time should be graphically
&# The cure reaction rate . polymerization time should be drawn.
0orphology of late* particles as obtained by scanning electron microscopy%

=olystyrene particles