Zeitoni M.

Narvaez Date of Experiment: September 8, 2017

Experiment 1: Solution Polymerization of Date of Submission: September 15, 2017
Styrene
Introduction
Polystyrene is a thermoplastic composed of styrene monomers with the general formula (C8H8)
n. Because of the alternating phenyl group attached to the hydrocarbon backbone of polystyrene, its
structure is non-crystalline and intermolecular interactions between the polymeric chains are governed
by weak Van der Waals forces. As a result, polystyrene has a low glass transition temperature. This
then makes this polymer flexible and easy to process; making it one of the most used plastics in the
world.
Polystyrene is manufactured through the radical polymerization of styrene, which is first
synthesized through the catalytic dehydrogenation of ethylbenzene (Wunsch, 2000). Radical
polymerization is used primarily because of the simplicity of the process; but aside from this technique,
other mechanisms can also be used to polymerize styrene to polystyrene, such as anionic and cationic
polymerization, and coordination propagation (Feldman and Barbalata, 1996). This is because styrene
can act both as an electron donor and acceptor.
Bulk polymerization is the most commonly used technique in industrial processes. In this
method, the initiator, a weakly-bonded molecule that promotes polymerization, will be added to the
pure monomer in liquid state. This procedure is simple and can generate large quantities of the product.
It also decreases the possibilities of contamination. However, bulk polymerization is known for
causing accidents and explosions. This is because of a phenomenon called auto-acceleration, wherein
increased entanglements of propagating polymeric chains cause localized increases in temperature
(Owolabi, Usman, and Kehinde, 2015). The absence of a medium results to inadequate heat
dissipation, resulting to uneven heat distribution through the reaction mixture. As a result, the
molecular weight and chain length of polymers produced through this method are non-uniform.
Other techniques include emulsion and pearl polymerization processes wherein the monomer
is only slightly or sometimes completely insoluble in the solvent. In the former, the reaction occurs in
monomer droplets with sizes ranging from 10 to 1000 microns. A stabilizer is used to mechanically
separate the polymer droplets. In emulsion polymerization, on the other hand, surfactants are used to
chemically disperse the polymer droplets. Because of the presence of a medium, efficient heat
transfer is possible in a suspension or an emulsion system, making these processes more controllable
than bulk polymerization. However, because of the presence of other substances such as the stabilizer
and the surfactant, these techniques are more complex and laborious.
In this experiment, a much simpler technique is used: solution polymerization. This method
offers advantages over bulk polymerization because a non-reactive medium is used which aids in heat
dissipation and prevents auto-acceleration.
The inhibitor, 4-tert-Butylcatechol, was first removed from styrene by washing it with sodium
hydroxide. Inhibitors are used to inhibit radical polymerization of monomers via radiation or heat when
in storage. However, aside from this, inhibitors like 4-tert-Butylcathecol also function as a terminator
in polymerization processes. Thus, this was removed.
The initiator for the reaction was benzoyl peroxide. Peroxides are commonly used as initiators
because these substances are unstable and can easily break off to free radicals. Benzoyl peroxide, for
instance, readily dissociates to two symmetrical benzoyloxy radicals when heated at around 80-90 C,
the temperature at which BPO decomposes into radicals.
In Figure 1, the polymerization mechanism for styrene is shown. In this reaction, the radical
attacks the double bond of styrene, giving rise to a benzyl-type radical (Vinod et al, 2012). This will
then add to another styrene monomerrepeating the process until a long chain of polystyrene is
synthesized. Termination of polystyrene can occur through combination (coupling) or through
disproportionation. With the former, two chains with radical ends combine; while with the latter, a
double bond forms on one chain while the other donates an H+. Between these, combination occurs
more frequently.
Initiation

Propagation

Terminatio
n

Figure 1. Polymerization of styrene (from Penn State Department of Chemistry. (n.d.). Syntheses of Nylon &
Polystyrene[PDF]. Pennsylvania: Pennsylvania State University.)

Materials and Apparatus

Reaction mixture
Styrene was Precipitate
was placed in a Mixture was transferred
washed with was filtered
round bottom to methanol to
NaOH and using a
flask and heated precipitate.
separated from Buchner
and stirred in a
inhibitor using a funnel and
silicon bath using
separatory dried in a petri
a magnetic stirrer
funnel dish.

Procedure
Inhibitor was first removed by washing 7 mL of inhibited styrene with 7 mL of 10% NaOH three times.
Then, styrene was separated from the separatory funnel and dried with 15 g of calcium carbonate. After
this, 5 mL of inhibitor-free styrene was transferred to a round bottom flask with 7 mL of toluene and
0.3 g benzoyl peroxide. This was stirred, covered with a rubber septum and placed in a beaker with
silicone oil on a hot plate. Temperature of silicone oil was elevated to 90 C prior to placing the flask.
Temperature was maintained between 80-90 C during the reaction. After 1 hours, heating was
stopped. When cool enough, the solution was poured to 200 mL of methanol. White precipitate of
polystyrene formed and this was collected via filtration using a Buchner funnel. Remaining sample
inside the round bottom flask was obtained by washing the flask with dichloromethane. After this, the
precipitate was removed from the funnel and spread out to dry on a petri dish.

Results
Mass of polystyrene 2.00 0.01 g
Percent yield 44 %
Discussion
When the reaction mixture was transferred to methanol, some of the crystals remained
suspended, while some aggregated and formed clumps of white solid. The differences in the
behavior of the precipitate show polydispersity and indicate differences in the molecular weight and
length of the polymeric chains. One factor that could have caused polydispersity in this experiment is
the minimal control of the reaction. Heating and cooling, for example, are non-uniform, thus resulting
to different rates of propagation and/or termination within the mixture. This then resulted to different
chain lengths for the polymerswhere those exposed to more heating had longer reaction/propagation
time than those that are not exposed as long. Another factor could be the incomplete purification of
styrene, resulting to the presence of impurities like 4-tert-Butylcatechol, which, as mentioned earlier,
could act as a terminator and produce shorter polymeric chains. Other factors could be cage effect,
which could hinder the initiation process because the caged radicals bond together instead of
initiating polymerization; and chain transfer, where instead of terminating the reaction, the resulting
chain allows re-initiation, thus making that particular chain longer and the over-all molecular weight
non-uniform. The polydispersity index, a value that gives information on the distribution of molecular
mass in the polymer, can actually be calculated; but since methods of obtaining average molecular
weight values of the product were not done (i.e. light scattering, gel permeation, osmotic pressure, and
viscosity measurements), it is not possible to calculate the PDI.
In figure 2, it can be seen that there are white flakes of polystyrene and there are also large
clumps of the polymer (boxed area). Before the product was dried, the large clumps were viscous,
indicating that this part of the polymer has high molecular weight. Polystyrene is a long and linear
hydrocarbon chain. Despite the presence of a phenyl group in polystyrene, crosslinking or simple Van
der Waals interaction can occur in sites where there is less steric hindrance. Thus, these chains can
entangle and form viscous clumps.

Figure 2. Product of Experiment

The percent yield of the reaction is 44 %. The low yield for the product can be attributed to the
incomplete reaction process. When the product was collected using Buchner funnel, white precipitate
formed in the filtrate. The continued formation of polystyrene, even in the filtrate, shows that two
hours was not enough to complete the polymerization of styrene. (However, the polystyrene from the
filtrate was not collected as it could have already been contaminated.)
To have a deeper understanding of the radical polymerization of styrene, characterization
methods like the ones mentioned (i.e. light scattering, gel permeation, osmotic pressure, and viscosity
measurements) can be done to obtain quantitative results.

Answers to Post-Laboratory Questions

1. It is necessary to purge the reaction system with N2 to remove oxygen. Oxygen can act both as an
inhibitor and a retarder in the reactionwhich means that it could contribute to the non-uniformity of
chain length and it could also slow the reaction down. When oxygen is present in the reaction, the
propagating chain can react with O2, producing a radical which is much more reactivethus slowing
the polymerization process.
2.
Initiator Solvent
Lauroyl peroxide Benzene
tert-Butyl peroxide Benzene

3. If the amount of the initiator is reduced, the polymer chains will increase in length because the
monomers have only few of the initiator to interact with (thus, they will interact with themselves,
promoting propagation). Consequently, if there is an increase in length, there will be a decrease in the
solubility of the material. This is because of the increase in the interaction of the polymer chains with
each other, given that the chains are longer and can easily entangle/intertwine.
This is a general case; however, this is not true at all times, because styrene can self-polymerize even
without an initiator and with heat alone (Wunsch, 2000). Thus, at elevated temperatures, styrene can
produce free radicals that can initiate polymerization and might result to shorter chains despite adding
only a few or no initiator at all (See figure 3).
In short, it will not be that predictable if there will be an increase or decrease in solubility, because the
amount of initiator is not the only determinant for chain length and solubility.

Figure 3. Spontaneous, thermally initiated polymerization of styrene

Conclusion
The difference in the behavior of the product (settling vs. floating/ being suspended) upon
precipitation indicates differences on the molecular weight and chain length of the resulting polymer.
A part of the product clumped together and was viscous while the other resemble white flakesfurther
demonstrates non-uniform molecular weight distribution in the product. The percent yield was 44 %.
The low yield is attributed to the incomplete polymerization process, which was crammed to two hours.
For better understanding of the process and more accurate interpretation of data, characterization
methods like dynamic light scattering, gel permeation, osmotic pressure, and viscosity measurements
can be done.

References
Feldman, D., & Barbalata, A. (1996). Synthetic polymers: technology, properties, applications.
London (etc.): Chapman.
Penn State Department of Chemistry. (n.d.). Syntheses of Nylon & Polystyrene [PDF]. Pennsylvania:
Pennsylvania State University.
Owolabi, R., Usman, M., & Kehinde, A. (2015). Process Safety in the Radical Polymerization of
Styrene: From Bulk to Solution/Emulsion Process. Journal of Science, Engineering and
Technology, 11(2), 1-14.
Wunsch, J. R. (2000). Polystyrene: synthesis, production and applications. Shawbury, Shrewsbury,
Shropshire, UK: Rapra Technology Ltd.