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Chem 35.

1 - TEG

Espiritu, Walter Aljhon


Silong, Rafaelle
Tumimbang, Glenn Vincent

I. Abstract
Styrene is an important precursor in the production of industrial products and resins. Through free-radical
polymerization involving multiple steps, which are initiation, chain propagation, chain transfer, and
termination, polymers can be produced from the monomers of the said compound. In this experiment, two
major steps were observed. First was the removal of the inhibitor, tert-butyl-catechol, in commercial styrene
by means of acid-base extraction in order to initiate the chain reaction, which is then followed by the actual
polymerization with the addition of an initiator, tert-butyl-peroxybenzoate. A translucent, white substance
was formed, having an odor similar to rugby, believed to be polystyrene.
II. Keywords: free radicals, polymerization, styrene, polystyrene, inhibitor
III. Introduction
In nature, elements bond ionically or
covalently to form compounds. On the other hand,
chemical bonds are broken down either
heterolytically or homolytically. Heterolytic bond
cleavage forms ions back while hemolytic bond
cleavage forms radicals, where only one electron
is associated. Radicals are important in certain
synthesis such as halogenations of alkanes in
which in ordinary reactions cannot be produced.
In this experiment, radicals play an important part
in achieving a desired product of a process called
polymerization. It is a process of reacting
monomer molecules together to form polymer
chains. It is a widely used process in most
industries, and these polymers have a wide
variety of uses.
Styrene, also known as ethenylbenzene,
vinyl benzene, or phenylethene, is primarily used
in the production of polystyrene plastics and
resins. In the experiment, the free-radical
polymerization of styrene is used to produce
polystyrene. This method is widely observed to
induce chain-reaction polymerization.
Freeradical polymerization proceeds via multiple
steps: chain initiation, chain propagation, chain
transfer, and chain termination. Chain initiation
involves formation of reactive radicals. Initiating
radicals may be provided via thermal
decomposition of added initiators. Typical

initiators of this type include dialkyl peroxides,


diacylperoxides, and azo compounds.
IV. Methodology
There were two major methods observed
in this experiment. The first one involves the
removal of inhibitor from commercial styrene. This
was done by adding 4 mL of 3M NaOH and 15 mL
water. The mixture was allowed to separate in
layers for the aqueous layer to be removed. This
was done sequentially to obtain the needed
compound in the experiment. After drying in an
Erlenmeyer flask containing anhydrous CaCl 2, the
dried styrene is used on the second part of the
experiment.
The polymerization of pure styrene was
done on a small-glass test tube. Tert-butylperoxybenzoate was added. The test tube was
heated until the temperature reaches 140 C.
After the temperature reached 180 190 C, the
boiling liquid was transferred to a watch glass.
Formation of fibers was observed until the
polystyrene solidified.
V. Results and Discussion
Commercial styrene contains a radical
scavenger, usually tert-butyl-catechol, to prevent
styrene from polymerizing. Tert-butyl-catechol
stabilizes styrene by donating a hydrogen atom to
free radicals present to convert them to nonradical, and, thus, non-reactive species. Tert-

Experiment 4: Free-Radical Polymerization of Styrene

Chem 35.1 - TEG

butyl-catechol,
acting
as
inhibitor
of
polymerization was removed by drying the styrene
with anhydrous CaCl. The reaction proceeds as:

peroxy and benzoate radicals. These radicals


react with styrene monomer to give a carbon
radical.

Figure 3. Propagation stage.

The process is then repeated in the


propagation stage. The carbon radical reacts with
another styrene monomer, building up the
polymer chain.

Figure 1. Removal reaction of tert-butyl-catechol


via extraction with NaOH.

The deprotonated tert-butyl-catechol is


then separated from the styrene (in organic layer)
because it is soluble to the aqueous layer.
After the removal of inhibitor, the
polymerization of pure styrene was initialized by
tert-butyl-peroxide, either the tert-butyl peroxide or
the
benzoate
radical
can
initiate
the
polymerization of styrene. The free-radical
polymerization of styrene has three steps,

Figure 2. Initiation stage.

During the propagation stage, the tert-butylperoxybenzoate is broken down into tert-butyl-

Figure 4. Termination stage.

The process continues until there are no more


monomer to be reacted upon. Each of these
coupling reactions destroys radicals, and
therefore an example of termination.
High temperature is needed because heat
can
destroy
the
bonds
in
tert-butylperoxybenzoate and thus initiate the reaction.
Polystyrene products are recycled to be
used in Styrofoam packaging materials, coat
hangers, trash bins, etc.
Polymers are can be classified by reaction
type, mode of assembly, structure, or by
properties. It can also be produced by freeradical, cationic or anionic addition.
Mode of assembly is defined by how
polymers are generated. Chain growth polymers
are formed under conditions in which the

Experiment 4: Free-Radical Polymerization of Styrene

Chem 35.1 - TEG

monomers do not directly react with each other,


rather, each monomer is added to a growing
chain. The best example of this is styrene
polymerization. On the other hand, Step-growth
polymers are formed in the conditions in which the
individual monomers react with each other to form
oligomers (compounds constructed from just a
few monomers), which are then joined together to
form polymers. An example is the formation of
PET or poly(ethylene terephthalate) .
Also, polymers are classified according to
structure. Branched polymers contain large
number of branches connected to the main chain
of polymer. Linear polymers have minimal amount
of branches or no branches at all.
Polymers are sometimes classified by
properties. Thermoplastics are polymers that are
hard at room temperature but soft when heated.
These are commonly used in manufacturing of
toys and storage containers. Examples include
PET, polystyrene, and poly(vinylchloride) (PVC).
Elastomers are polymers that return to
their original shape when stretched. Fibers are
obtained from polymers that are heated, forced
into small holes, then cooled. These are polymers
with significant tensile strength. Examples are
Nylon, and polyethylene. Thermosetting resins
are highly cross-linked polymers that are
generally hard and insoluble.

water and methanol separates from the polymers


upon their combination. It is a process that
involves two different types of di-functional
monomers (end groups) that reacts with one
another to form a chain. This reaction produces
low-molecular-weight polymers.
2. Discuss the types of polymerization processes.
Free-radical is initiated with radical
species. Cationic addition is initiated in the
presence of an acid which reacts with a bond,
thereby creating a carbocation. Whereas, anionic
polymerization is initiated with a highly reactive
anion, such as butyl lithium, which functions as a
nucleophile and attacks the bond of a
monomer, then creating a new carbanion. On the
other hand, coordination polymerization is when a
monomer adds to a growing polymer with an
organometallic active center.
3. The use of phenols, such as tert-butyl-catechol,
as free-radical scavenger are based on the fact
that phenolic hydrogens are readily abstracted by
radicals, producing relatively stable phenoxy
radicals, which interrupt chain processes of
oxidation and polymerization. Alcohols such as
cyclohexanol, on the other hand, do not function
as radical scavengers. Explain why the two types
of molecules differ in their ability to donate a
hydrogen atom to a radical, R.

VI. Guide Questions


1. Differentiate Chain Polymerization from
Condensation Polymerization.
Chain-growth polymerization is a reaction
initiated by anions, cations or free radicals in
which large numbers of monomer units are added
rapidly until it is terminated by another
mechanism. It is a three-step process that
involves two chemical entities. The first a
monomer which have at least one carbon-carbon
double bond, the other a catalyst. It usually
produces high-molecular-weight polymers.
On the other hand, step-reaction
polymerization or Condensation Polymerizations
is a process wherein small molecules such as

The stability of the phenoxy radical is


higher than that of the alkoxy radical. Radical
abstraction from t-butylcatechol produces a
phenoxy radical that is stabilized by resonance.
On the other hand, cyclohexanol only produces a
2 alkoxy radical.
4. Write an equation for the reaction involved in
the removal of tert-butyl-catechol from styrene by
extraction with NaOH.
C10H14O2 + 2 NaOH Na2C10H12O2 + 2 H2O.
5. In principle, radicals could add to styrene at the
carbon atom bearing a phenyl group rather than

Experiment 4: Free-Radical Polymerization of Styrene

Chem 35.1 - TEG

the other one, yet do not. Explain the basis for this
selectivity.
The oxygen radical, an initiator, tends to
add on the phenyl-bearing carbon because the
lone pair of the oxygen can form conjugated pi
bonds with the aromatic ring. This creates a very
stable molecule and leaves the other carbon open
for radical addition by other styrene units.
6. Would you expect the polystyrene generated in
this experiment to be atactic, syndioatactic or
istactic. Explain.
In the experiment, the basis for tacticity
was the over-all appearance of the formed
polystyrene, which was amorphous and noncrystalline, and atactic polymers usually appear
this way.
7. What are thermosetting polymers? What is the
difference versus thermoplastic polymers?
Thermosetting polymers or thermosets is
a polymer that cannot be irreversibly cured, once
they have molded to their final form they can
never be melted or shaped differently. These type
of polymers have crosslinks between its chains
which form an irreversible chemical bond between
chains preventing the movement of chains. The
only difference of thermoset polymers with
thermoplastic polymers is the structure.
Thermoplastic polymers do not have cross-link
between chains so when it is subjected to heat its
chains are free to move past each other.

observed to produce the desired product under


polymerization.
VIII. References
Klein, D. (2012). Organic Chemistry. Chapter
11: Radical Reactions
Styrene. Retrieved from:
http://www.epa.gov/ttn/atw/hlthef/styrene.html
Polymers. Retrieved from:
http://chemistry2.csudh.edu/rpendarvi/Polymer
.html
Thermoset vs. Thermoplastics. Retrieved from:
http://www.modorplastics.com/thermoset-vsthermoplastics
Condensation Polymerization. Retrieved from:
http://www.ask.com/question/what-iscondensation-polymerization
Scientific Principles. Retrieved from:
http://matse1.matse.illinois.edu/polymers/prin.
html

VII. Conclusion and Recommendation


The experiment shows that polymerization
of styrene proceeds in a step-wise process. Freeradical polymerization induces the chain reaction,
which includes initiation, propagation, and
termination stages, which results to the desired
product, polystyrene. The inhibitor, in this case,
tert-butyl-catechol, was removed for the chain
reaction to proceed. Tert-butyl-peroxybenzoate
initiates the polymerization reaction.
It is recommended to use a different
method in removing the inhibitor, including the
chemicals used and the reaction mechanisms

Experiment 4: Free-Radical Polymerization of Styrene