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Emulsions Polymer Is at I On
Emulsions Polymer Is at I On
Objective
Styrene is polymerized in an emulsion using dodecyl hydrogen sulfate sodium salt as an emulsifier
and potassium persulfate as the initiator. Samples are drawn from the reactant solution in regular
intervals in order to generate diagrams of the conversion as well as the reaction rate versus the
reaction time.
References
1) H.‐G. Elias, Makromoleküle Bd. 1, Edition 6, Wiley‐VCH Verlag, Weinheim, 1999
2) P. J. Flory, Principles of Polymer Chemistry, Cornell, University Press, Ithaca, 1953
3) B. Tieke, Makromolekulare Chemie, Edition 2, Wiley‐VCH Verlag, Weinheim, 2005
4) W. V. Smith, H. Ewart, J. Chem. Phys. 16(6), 592 (1948)
5) W. D. Harkins, J. Am. Chem. Soc. 69, 1428 (1947)
Content
1. Theoretical Background
2. Experimental Part
3. Questions
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1. Theoretical Background
The process of emulsion polymerization is of vital significance for the fabrication of various industrial
polymers such as polychloroprene, poly(vinyl acetate), polytetrafluoroethylene and poly(vinyl
chloride) as well as “cold rubber” (styrene/butadiene copolymers). The technological development
of this method started in the 1920s and has since gained ever‐increasing importance resulting in a
recent global production of several million tons per year.
The essential components of an emulsion polymerization are the following.
Monomer (insoluble in water)
Water
Surfactant
Initiator (radical forming agent, soluble in water)
In most cases anionic surfactants (e.g. salts of fatty acids, salts of alkyl hydrogen sulfates, salts of
alkyl sulfonic acids) are used, while cationic (quaternary ammonium salts, e.g. cetyltrimethyl
ammonium bromide) or non‐ionic surfactants (often high molecular weight) are rarely applied. All
types of surfactants comprise both hydrophilic and hydrophobic groups. When highly diluted, the
surfactants can be completely dissolved in water. However, at concentrations above the critical
micelle concentration (cmc), the molecules of the emulsifier aggregate into micelles. This process,
which is driven by thermodynamic principles, is accompanied by a significant drop in the surface
tension of the system. The emulsion polymerization is generally performed at surfactant
concentrations above the cmc.
Water‐soluble peroxo salts (e.g. potassium persulfate) are the classical choice for the initiator of the
polymerization reaction, even though organic hydroperoxides (e.g. cumene hydroperoxide) are also
frequently used. Redox initiators are of particular importance in industrial processes, since these
compounds can induce polymerization even at low temperatures.
The progress of a typical emulsion polymerization can be divided into three phases distinguished by
their characteristic profiles of the reaction rate over time (see Figure 1):
(I) increasing reaction rate
(II) constant reaction rate
(III) decreasing reaction rate.
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Figure 11 further illustrates tha
at the surfaace tension of the system drasticaally increase
es at the
transitio
on between tthe first and the second pphase.
Figure 1: D
Development o
of the reaction rate (vp) and thhe surface tenssion (γ) as a fun
nction of the poolymerization ttime (t).
Harkin as well as Smith and Ewarts were the first to prop
pose correct interpretatioons of the un
nderlying
processees occurring at a molecular level duuring an em merization [44, 5]. Despite some
mulsion polym
initial reservations, tthe essential aspects of tthese concep
pts are widely accepted ttoday.
At the b
beginning off the polyme
erization reaaction, the system
s ains “emptyy” micelles (diameter
conta
~4.3 nm) as well as m
micelles swo
ollen by monnomer incorp
poration (dia
ameter ~5 nm
m). The vastt amount
omer, howevver, is initiallyy bound in m
of mono monomer droplets (diam
meter ~1000 nm) stabilize
ed by the
ure 2). Mon
emulsifieer (see Figu nomer moleecules can be
b transferre
ed from theese droplets into the
micelles by diffusion
n. The waterr‐soluble inittiator decom
mposes in the
e aqueous phhase and the
e radicals
formed in this proceess can, in principle, starrt a polymerrization eithe
er in the mo nomer droplets or in
the miceelles. Howevver, the reacction is far leess likely to begin within
n the monom
mer dropletss, as their
number (~1010 per cm
c 3 emulsion) is significcantly lower than the am
mount of miccelles (~10188 per cm3
n) present in
emulsion n the system
m, which corrresponds to a surface arrea ratio of ~~1:1000 betw
ween the
monomeer droplets aand the mice
elles. Polym
merization in the aqueous phase, on the other ha
and, is of
t water‐insoluble! moonomer. Du
no relevvance due to the very low concenntration of the uring the
polymerrization the monomer is
i depleted within the micelles, which
w each contain aro
ound 100
monomeer moleculess. This effecct is compennsated by mo
onomers difffusing into tthe micelles from the
monomeer droplets leading to a
a constant m
monomer co
oncentration in the nanoo‐reactors (d
diffusion‐
limited conditions). As a result of the onngoing polym
merization reaction,
r thee micelles grow
g and
m into so‐caalled latex pa
transform articles. Morre and more
e polymer chains are starrted in this first stage
of the reeaction and tthe reaction rate increasees.
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The rem dustrial relevvance of thhe emulsion polymerization processs is a result of the
markable ind
followingg advantages:
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a) The aqueous phase enables temperature regulation during the polymerization reaction.
b) Redox initiators can be applied, which enable polymerization reactions to proceed at comparably
low temperatures, yet keeping the reaction rate relatively high.
c) High degrees of polymerization can be achieved due to the small probability of chain termination.
This can be further regulated by the controlled addition of chain transfer agents.
d) Remaining monomer can be removed by steam distillation.
e) The obtained latex can be directly subjected to further applications (paints, glues, coatings).
On the downside, however, a frequently problematic extraction of the emulsifier as well as the
potentially high degree of branching of the polymer chains have to be taken into account as major
disadvantages of the method.
Kinetics and Mechanism
A hallmark of the emulsion polymerization process is that this method yields higher degrees of
polymerization than those accessible under comparable conditions in bulk or suspension
polymerization reactions. The kinetics and the mechanism of emulsion polymerization are,
therefore, distinct from other radical polymerization methods. The reaction rate vw(L) in an individual
latex particle is given by equation (1).
vw(L): reaction rate of the polymerization in the latex particle
kw: rate constant of the polymerization
[M]: concentration of monomer in the latex particle
[P*]: concentration of radicals in the latex particle
The measurable reaction rate vw of the entire reaction batch is represented by the sum of the
reaction rates in all isolated latex particles. Assuming a narrow size distribution of the latex particles
the reaction rate can be described as follows:
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nN
(2) v w k w [M]
NA
vw: reaction rate of the polymerization
n: average number of free radicals per latex particle
N: number of latex particles per unit volume of the emulsion
NA: Avogadro constant
In equation (2), it is further assumed that the polymerization occurs exclusively within the latex
particles, i.e. there is no considerable amount of polymer forming either in the aqueous phase or in
the monomer droplets. For the determination of vW the factors included in equation (2) have to be
expressed as properties, which are experimentally accessible. This is particularly difficult in the case
of N and n. The most established quantitative model for the description of the kinetics and the
mechanism of the emulsion polymerization was derived by Smith and Ewart. It is particularly well‐
suited for systems showing a behavior consistent with the Harkin model.
The Harkin model is based on the following considerations: After a short phase of particle generation
(phase I) the reaction rate becomes constant in phase (II). Therefore, regarding the factors included
in equation (2), not only the monomer concentration [M] and the number of latex particles per unit
volume [N], but also the number of free radicals within the latex particles have to be constant.
However, according to the steady state approximation the number of these radicals will only remain
constant, when equal amounts of radicals are formed and consumed in a given period of time.
The following assumptions will be made: Once a radical is located within a latex particle, it cannot
leave this environment again. If a second radical enters the same latex particle, an immediate
recombination of the two will take place due to the small radius of the latex particle. An individual
latex particle, therefore, contains either one or no radical at any given time, corresponding to an
average number of radicals per latex particle of n = ½. With additional assumptions regarding the
number of latex particles equation (3) can be derived:
1 σ 25 3
(3) v w k w [M] b( ) (aS [S]) 5
2 NA
b: system constant in the range of 0.37‐0.53
σ: inflow/intake velocity of the radical into the latex particle
µ: constant volume increase of the latex particle
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aS: surface area required by one surfactant molecule
[S]: concentration of the emulsifier
Combining all constant parameters included in equation (3) into a single constant K leads to a
simplified representation as given by equation (4):
3
(4) v w K[M]([S]) 5
On closer examination of equation (4) it becomes obvious, that the reaction rate of the emulsion
polymerization can be raised even without increasing the temperature, monomer concentration or
initiator concentration – simply by adding a higher amount of the surfactant.
The degree of polymerization Pn of a polymerization reaction is defined as the ratio between the sum
of all reaction rates associated with processes leading to an increase in the chain length and the sum
of reaction rates ascribed to those processes resulting in the termination of an individual chain. The
latter can occur either by direct termination or by chain transfer to monomer, solvent, or initiator
molecules (but not to polymer chains!).
vw
(5) Pn
(v A v T )
vA: sum of the reaction rates of all processes terminating the chain
vT: sum of the rates of all chain transfer reactions
As the concentration of the emulsifier directly influences vw, it also has an immediate effect on the
degree of polymerization. In contrast to all other radical polymerization processes, the
recombination of radical chain ends is inhibited in emulsion polymerization, since the chains exist in
isolated latex particles and are therefore effectively separated from each other.
Moreover, in its final stages the process of emulsion polymerization shows a behavior analogous to
the Norrish‐Trommsdorf effect, which is known from bulk polymerization. As a result, the reaction
rate and the degree of polymerization are comparably higher.
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2. Experimental Part
The goal of this experiment is to prepare polystyrene by polymerization of styrene in emulsion. For
that purpose, dodecyl hydrogen sulfate sodium salt and potassium persulfate are used as the
surfactant and initiator, respectively. Plots of the conversion as well as the reaction rate versus the
reaction time should be obtained. The conversion is determined gravimetrically at various stages of
the reaction. The results shall be discussed with a special emphasis on the kinetics of the reaction.
Chemicals:
‐ Styrene (destabilized and freshly distilled)
‐ Water
‐ Dodecyl hydrogen sulfate sodium salt
‐ Potassium persulfate
‐ Hydroquinone (0.02% in water)
Equipment:
‐ Oil bath
‐ Round‐bottomed flask
‐ Hot‐plate magnetic‐stirrer device
‐ Reflux condenser
‐ Thermometer
‐ Magnetic stirring bars
‐ Sample dishes
‐ Glass vials
‐ Syringes and needles
‐ Plastic pipettes
‐ Analytical balance
‐ Vacuum drying oven
Procedure:
Water (50 mL), emulsifier (1 g) and styrene (5 g) are filled into a round‐bottomed flask of 100 mL
capacity. The mixture is heated to 70°C under stirring in an oil bath. After an equilibration period of
approximately 30 minutes the polymerization is started by the addition of the initiator dissolved in 4
95
mL water (t = 0 min). During the course of the next two hours, samples of 2 mL reactant solution
each are drawn in regular intervals according to the specifications in table 1.
Table 1. Sample identifier and reaction time at which the sample was taken.
Sample
E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11
identifier
These samples are immediately pipetted into glass vials containing 2 mL hydroquinone solution for
stabilization and are subsequently transferred to a vacuum drying oven to remove all volatile
components. Afterwards, the solid content is determined by gravimetric analysis. All relevant
masses and mass differences are calculated and documented according to table 2.
Table 2. Evaluation of the obtained sample weights and determination of the conversion.
m2
m3
m1
m0 (dish + m3‐m0
Sample m2‐m1
hydroquinone (dish + Conversion
identifier (dish + (msample)
(dish) + dispersion dispersion (msolid)
hydroquinone)
before after drying)
drying)
E1
E2
E3
E4
E5
E6
E7
E8
E9
E10
E11
Evaluation:
Plots of conversion versus time.
1) Besides the polymer molecules the isolated solid additionally contains residual emulsifier. In order
to determine the conversion (conv) of the reaction accurately, the surfactant content has to be
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subtracted from the total weight of the solid material. This calculation can be performed according
to the following equation:
msolid 1 mtot
conv = · m · ·100%
mM0 1+ E0 msample
mM0
msolid: weight of the solid
mE0: weight of emulsifier used in the reaction batch
mM0: weight of monomer used in the reaction batch
mtot: total weight of the reaction batch
msample: weight of the sample
2) Calculate conversions for all samples taken during the reaction and plot the results over the
reaction time.
Plots of reaction rate versus time.
3) Determine the reaction rates at the various time steps by constructing tangents on the conversion
vs. time curve. List the obtained reaction rates in a table, plot and discuss the results.
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3. Questions
1) Which effects can be potentially caused by the presence of oxygen traces in the emulsion? What
could be an explanation for another increase in the reaction rate during the final stages of the
polymerization (Take into account that the reaction is a radical polymerization)?
2) Why is the coagulation of latex particles inhibited?
3) What is the average radical concentration in the latex particles under the following assumptions?
The radicals reach the latex particles by diffusion. This process determines the reaction rate.
Whenever two radicals are located in the same latex particle they will recombine
immediately.
4) Describe the principle of a redox initiator and list a number of examples.
5) Compare the characteristics of emulsion polymerization and suspension polymerization. Name
further examples for technologically relevant polymerization procedures.
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